CN119522219A - (5s)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4h-1,2,4-噁二嗪的晶型 - Google Patents
(5s)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4h-1,2,4-噁二嗪的晶型 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
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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
- A01N43/88—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 six-membered rings with three ring hetero atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mycology (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及式(I)的(5S)‑3‑[3‑(3‑氯‑2‑氟苯氧基)‑6‑甲基哒嗪‑4‑基]‑5‑(2‑氯‑4‑甲基苄基)‑5,6‑二氢‑4H‑1,2,4‑噁二嗪的新晶型、其制备方法、包含该新晶型的农用化学制剂,以及其在植物保护应用中的用途,尤其涉及其作为杀真菌剂(I)的用途。
Description
技术领域
本发明涉及式(I)的(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的新晶型、其制备方法、包含该新型晶型B的农用化学制剂以及其在植物保护应用中的用途,尤其涉及其作为杀真菌剂的用途。
(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪及其制备方法由WO 2020/127780得知。由现有技术已知的方法得到的(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪为无定形固体。
背景技术
多晶型性(polymorphism)是化合物以晶格中不同的分子排列和/或构象在不同晶相中进行结晶的能力。因此,多晶型物是相同的化学化合物的不同晶型。由于分子的不同排列和/或构象,多晶型物可以表现出不同的物理、化学和/或生物学性质。可受影响的性质包括但不限于溶解度、溶解速率、稳定性、光学性质和机械性质等。多晶型物的相对稳定性取决于其自由能,即更稳定的多晶型物具有更低的自由能。在一组确定的实验条件下,只有一种多晶型物具有最低的自由能。该多晶型物是热力学稳定形式,所有其它多晶型物被称为亚稳态形式。亚稳态形式是在热力学上不稳定但由于其相对慢的转化速率而仍然可以制备、分离和分析的形式。
不同的多晶型(本文也称为多晶型物或晶型)的活性物质的出现对于工业规模的制备以及含有该活性物质的制剂的开发至关重要,因为不期望的相变可导致制剂和/或大晶体的增稠和潜在的固化,这可导致施用设备(例如农业施用机械中的喷嘴)堵塞。因此,了解结晶变体的存在及其性质是高度相关的。每种多晶型物的特征在于固态下分子特定的、均匀的堆积和排列。然而,通常完全无法预测给定化学化合物是否形成多晶型物,以及如果形成,那不同的多晶型物可能具有哪些物理和生物学性质。
此外,可以存在有称为水合物或溶剂化物的假多晶型。溶剂化物是结晶的分子化合物,其中结晶溶剂的分子掺入到由未溶剂化的分子组成的主晶格中。水合物是溶剂化物的一个特例,此时所掺入的溶剂是水。晶格中溶剂分子的存在影响分子间相互作用,并赋予每种溶剂化物独特的物理性质。因此,溶剂化物具有其自身的内能、焓、熵、吉布斯自由能和热力学活性的特征值。
附图说明
图1a:(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型B的X射线粉末衍射图。
图1b:(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型B的FT拉曼光谱。
图1c:(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型B的IR光谱。
图2a:(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型A的X射线粉末衍射图。
图3a:浆液实验3(8d/80℃CH3CN/H2O)后的X射线粉末衍射图。
具体实施方式
在一个实施方案中,本发明涉及式(I)的(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的新晶型B,
根据WO 2020/127780的方法得到不想要的无定形形式的(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪。
因此,本发明的目的是提供一种具有优异的施用性质的多晶型,特别是具有优异的生理化学性质,例如在悬浮浓缩剂(SC)制剂中的高稳定性。
式(I)的化合物以A和B两种变体进行结晶。多晶型A和B在对映体上相关,呈现出在49℃和66℃之间的临界转变温度。该温度范围可以在制取过程中达到,并且可以导致从多晶型B到多晶型A的固-固相变(solid solid transformation),多晶型A可以在室温下重结晶成型B,从而在基于固体的制剂类型中引发团聚。
现已令人惊讶地发现,式(I)化合物的多晶型B具有优异的性质。与现有技术中已知的无定形形式相比,多晶型B表现出用于制备制剂的改善有益性质。特别地,多晶型B在悬浮浓缩剂(SC)制剂中表现出高稳定性,例如高稀释稳定性,特别是悬浮性,从而确保防止不想要地转化为式(I)化合物的另一种多晶型。已知多晶型物转变预计会导致SC制剂中的不稳定性(J.Weiss等人,J.Am.Oil Chem.Soc.2008,85,501-511;D.J.Burgess等人,Int.J.Pharmaceutics,2014,Vol.466,223-232),例如颗粒聚集从而导致较低悬浮性。另外,多晶型B在经历长时间的高于转变温度范围进行的浆液实验中表现出令人惊讶的高稳定性。未观察到重结晶现象。高稳定性确保了不会发生上述性质的相关变化,并因此提高了包含式(I)化合物的多晶型B的制剂和/或组合物的安全性和质量。
(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型B可以通过X射线粉末衍射法基于相应的衍射图表征,所述衍射图在25℃下记录,使用Cu-Kα1辐射本发明的多晶型B显示至少3个、通常至少5个、特别地至少7个、更特别地至少10个、并且尤其是下文中以值引用的所有反射:
表1:多晶型B的X射线反射
反射[2θ值] |
x±0.2° |
5.3 |
6.7 |
8.5 |
10.6 |
14.5 |
15.8 |
17.2 |
19.0 |
19.4 |
20.2 |
21.1 |
22.1 |
22.7 |
22.9 |
23.3 |
24.2 |
25.1 |
26.6 |
27.3 |
27.7 |
29.0 |
29.2 |
31.1 |
31.5 |
32.0 |
32.4 |
33.1 |
34.3 |
35.0 |
本发明的多晶型B通过图1a中所示的X射线粉末衍射图进一步表征。
式(I)化合物的多晶型B的特征在于,在25℃下使用Cu-Kα1辐射的X射线粉末衍射图具有至少以下反射:20.2、23.3和25.1,优选至少以下反射:20.2、23.3、25.1、14.5和19.4,更优选至少以下反射:20.2、23.3、25.1、14.5、19.4、23.4和10.6。
(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型B还可以通过拉曼光谱基于相应的光谱表征,所述光谱在25℃下记录,使用1064nm的激光波长和2cm-1的分辨率。本发明的多晶型B显示至少3个、通常至少5个,特别是至少7个、并且尤其是下文中以峰最大值引用的所有谱带:
表2:型B的拉曼谱带
式(I)化合物的多晶型B的特征在于以下谱带:98、112和1585,优选至少在于以下谱带:98、112、1585、1279和2925,更优选至少在于以下谱带:98、112、1585、1279、2925、688和1609。
(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型B还可以通过红外光谱基于相应的光谱表征,所述光谱在25℃下记录,使用通用金刚石ATR装置和和2cm-1的分辨率。本发明的多晶型B显示至少3个、通常至少5个,特别是至少7个、并且尤其是下文中以峰最大值引用的所有谱带:
表3:型B的IR谱带
式(I)化合物的多晶型B的特征在于以下谱带:1403、819和806,优选至少在于以下谱带:1403、819、806、1476和1274,更优选至少在于以下谱带:1403、819、806、1476、1274、1383和921。
除了多晶型B之外,还鉴别了另一种多晶型A(图2a),其在下文中进一步表征。
在一个实施方案中,本发明涉及式(I)的(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的新晶型A,
(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型A可以通过X射线粉末衍射法基于相应的衍射图表征,所述衍射图在25℃下记录,使用Cu-Kα1辐射多晶型A显示至少3个、通常至少5个、特别地至少7个、更特别地至少10个、并且尤其是下文中以值引用的所有反射:
表4:多晶型A的X射线反射
式(I)化合物的多晶型A的特征在于,在25℃下使用Cu-Kα1辐射的X射线粉末衍射图具有至少以下反射:16.9、19.8和24.5,优选至少以下反射:16.9、19.8、24.5、14.2和24.7,更优选至少以下反射:16.9、19.8、24.5、14.2、24.7、20.8和21.8,更优选至少以下反射:16.9、19.8、24.5、14.2、24.7、20.8、21.8、38.9、38.3和29.5,每项引用为2θ值±0.2°。
多晶型A通过图2a中所示的X射线粉末衍射图进一步表征。
多晶型A和B的热力学稳定性高度复杂。这两种形式在对映体上相关,并具有49℃至66℃范围内的转变温度。低于这些温度,多晶型物B为在热力学上稳定的多晶型物。多晶型A在更高的温度下重结晶,但在更低的温度下表现出向多晶型物B的极快速转变。
在又一个实施方案中,本发明涉及用于制备多晶型B的方法,其包括以下步骤:
a)在合适的溶剂或溶剂混合物中稀释式(I)化合物,
b)将步骤a)的组合物加热至至少70℃的温度,以及
c)将来自步骤b)的溶液冷却至低于20℃的温度。
式(I)的(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的化学制备由WO 2020/127780已获知。因此,步骤a)中使用的式(I)化合物可以根据WO 2020/127780制备,在此对其完整引用。
步骤a)中的式(I)化合物基本上可以是(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的任何已知形式。这意味着(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪可以以无定形形式或以不同多晶型的混合物或以含有无定形和一种或多种不同多晶型的混合物使用。
可用于在步骤a)中稀释和/或悬浮式(I)化合物并且在步骤c)中从中以多晶型B获得式(I)化合物的合适的溶剂或溶剂混合物为甲苯、四氢呋喃、丙酮、乙酸乙酯、乙腈、甲醇、乙醇、异丙醇、N,N-二甲基甲酰胺、1,4-二噁烷或DMSO,优选甲苯、乙醇或1,4-二噁烷。
(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的溶液也可以通过将由化学反应获得的包含(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的反应混合物,必要时在移除试剂和/或副产物之后,转移至本发明的溶剂或溶剂混合物来制备。
在步骤b)中,通常将溶液或浆液加热至至少70℃的温度,优选至至少90℃的温度。在一个优选的实施方案中,将每种溶剂或溶剂混合物加热至其沸腾温度。
在步骤c)中,将溶液或浆液冷却至低于20℃,优选低于0℃的温度。
可以通过用型B的晶种进行引晶来促进或加速多晶型B的结晶。
通过本领域已知的常用技术,例如通过过滤、离心分离或倾析,从母液中分离多晶型B。
更优选地,通过使溶液或浆液在步骤c)的结晶条件下静置直至蒸发至少90重量%的溶剂或溶剂混合物,从溶剂或溶剂混合物中分离多晶型B。
分离出的多晶型B可以任选地使用任何溶剂洗涤,优选使用用于结晶的溶剂或溶剂混合物、使用水或使用溶剂或溶剂混合物与水的混合物。洗涤步骤可以任选地重复,由此用水洗涤通常是最后的洗涤步骤。洗涤通常在低于30℃,通常低于25℃,特别地低于20℃,任选地在0℃下进行。在进一步的任选步骤中,可以将多晶型B的晶体干燥,然后提供用于进一步加工。
通过本发明的结晶化,(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的型B以至少85%,特别地90%,并且最优选至少≥95%获得。
因此,本发明的一个具体实施方案涉及(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪,其由至少85%且通常至少90%或至少≥95%的多晶型B组成。
在另一个实施方案中,本发明涉及含有(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型B的常规制剂形式的植物保护剂。
在本发明的一个优选实施方案中,植物保护剂含有大于90重量%且优选大于95重量%的式(I)化合物的多晶型B,基于组合物中存在的式(I)化合物的所有形式的总量计。
现在令人惊讶地发现,多晶型B具有改善的处理和制剂性质,例如SC制剂的高稳定性,例如高稀释稳定性,特别是高悬浮性,特别是在较高温度,甚至是高于转变温度范围时。因此,在另一个实施方案中,本发明涉及式(I)化合物的多晶型B用于制备具有高稳定性,优选高稀释稳定性,更优选高悬浮性,特别是在高于转变温度范围的温度下时的制剂的用途。
用途
在另一个实施方案中,本发明涉及式(I)化合物的多晶型B用于防治不想要的微生物,优选不想要的真菌和病毒的用途。在一个具体实施方案中,本发明涉及防治植物上不想要的真菌。在本发明的一个具体实施方案中,有用植物是转基因植物。
在另一个实施方案中,本发明涉及一种用于防治不想要的微生物的方法,在其中将所述多晶型B或如上定义的含有多晶型B的植物保护剂施用于植物。
本发明的化合物和组合物具有潜在的杀微生物活性和/或植物防御调节潜力。可将它们用于防治植物上不想要的微生物,例如不想要的真菌和病毒。它们可特别是用于作物保护(它们防治造成植物病害的微生物)或用于保护下文更详细描述的材料(例如工业材料、木材、储存货物)。更具体地,本发明的化合物和本发明的组合物可用于保护种子、发芽中的种子、新出幼苗、植物、植物部位、果实、采收的物品和/或植物生长于其中的土壤免遭不想要的微生物的侵袭。
本文所述的防治(Control或controlling)包括对不想要的微生物的预防、治疗和消灭处理。不想要的微生物可为病原性病毒或病原真菌,更具体地是植物病原性病毒或植物病原性真菌。如下文的详细描述,这些植物病原性微生物是广谱植物病害的致病剂。
更具体地,本发明的化合物和本发明的组合物可以用作杀真菌剂。为本发明的目的,术语“杀真菌剂”是指可以在作物保护中使用以防治不想要的真菌的化合物或组合物,所述真菌例如根肿菌(Plasmodiophoromycetes)、壶菌(Chytridiomycetes)、接合菌(Zygomycetes)、子囊菌(Ascomycetes)、担子菌(Basidiomycetes)和半知菌(Deuteromycetes)。
本发明的化合物和组合物也可以在作物保护中用作抗病毒剂。例如,本发明的化合物和组合物可以对于由植物病毒带来的病害产生影响,所述植物病毒如烟草花叶病毒(tobacco mosaic virus)(TMV)、烟草脆裂病毒(tobacco rattle virus)、烟草矮化病毒(tobacco stunt virus)(TStuV)、烟草曲叶病毒(tobacco leaf curl virus)(VLCV)、烟草花叶病毒(tobacco nervilia mosaic virus)(TVBMV)、烟草坏死矮缩病毒(tobacconecrotic dwarf virus)(TNDV)、烟草条纹病毒(tobacco streak virus)(TSV)、马铃薯病毒X(potato virus X)(PVX)、马铃薯病毒Y、S、M和A、马铃薯针叶花叶病毒(potato acubamosaic virus)(PAMV)、马铃薯帚顶病毒(potato mop-top virus)(PMTV)、马铃薯卷叶病毒(potato leaf-roll virus)(PLRV)、苜蓿花叶病毒(alfalfa mosaic virus)(AMV)、黄瓜花叶病毒(cucumber mosaic virus)(CMV)、黄瓜绿斑驳花叶病毒(cucumber greenmottlemosaic virus)(CGMMV)、黄瓜黄化病毒(cucumber yellows virus)(CuYV)、西瓜花叶病毒(watermelon mosaic virus)(WMV)、番茄斑萎病毒(tomato spotted wilt virus)(TSWV)、番茄环斑病毒(tomato ringspot virus)(TomRSV)、甘蔗花叶病毒(sugarcanemosaic virus)(SCMV)、水稻矮缩病毒(rice drawf virus)、水稻条纹病毒(rice stripevirus)水稻黑条矮缩病毒(rice black-streaked drawf virus)、草莓斑点病毒(strawberry mottle virus)(SMoV)、草莓脉带病毒(strawberry vein banding virus)(SVBV)、草莓轻性黄边病毒(strawberry mild yellow edge virus)(SMYEV)、草莓皱缩病毒(strawberry crinkle virus)(SCrV)、蚕豆萎蔫病毒(broad beanwilt virus)(BBWV)和甜瓜坏死斑点病毒(melon necrotic spot virus)(MNSV)。
本发明还涉及防治植物上不想要的微生物(如不想要的真菌)的方法,其包括将本发明的式(I)化合物的多晶型B或至少一种本发明的组合物施用至微生物和/或其生境(施用至植物、植物部位、种子、果实或施用至植物生长于其中的土壤)的步骤。
通常,在将本发明的化合物和组合物用在防治植物病原性真菌的治疗性或保护性方法中时,将它们以有效且与植物相容的量施用于植物、植物部位、果实、种子或施用至植物生长于其中的土壤或基质。可用于栽培植物的合适的基质包括基于无机的基质,例如矿棉特别是石棉,珍珠岩,砂土或砾石;有机基质,例如泥炭、松树皮或锯末;以及基于石油的基材,例如聚合物泡沫或塑料珠。有效且与植物相容的量意指这样的量,其足以防治或破坏农田上存在或易于出现的真菌,并且不会引起所述作物产生任何明显的植物毒性症状。该量可以在较大范围内变化,这取决于要防治的真菌、作物的类型、作物的生长阶段、气候条件以及所用的各个本发明的化合物或组合物。该量可以通过系统性田间试验确定,在本领域技术人员能力范围内。
植物和植物部位
本发明的化合物和组合物可施用于任何植物或植物部位。
植物意指所有的植物和植物种群,例如想要和不想要的野生植物或作物植物(包括天然存在的作物植物)。作物植物可以是可以通过常规育种和优化法或通过生物技术和基因工程方法或这些方法的结合而获得的植物,包括遗传修饰植物(GMO或转基因植物)以及受或不受植物育种权(plant breeders’rights)保护的植物栽培种。
植物栽培种应当理解为意指具有新特性(“性状”)并且已通过常规育种、诱变或重组DNA技术得到的植物。它们可为栽培种、变种、生物型或基因型。
植物部位应当理解为意指植物的地上及地下的所有部分及器官,如芽、叶、针叶、茎、干、花、果实体、果实、种子、根、块茎和根茎。植物部位也包括采收材料以及无性与有性繁殖材料,例如插枝、块茎、根茎、分株及种子。
植物和植物部位
本发明的化合物和组合物可施用于任何植物或植物部位。
植物意指所有的植物和植物种群,例如想要和不想要的野生植物或作物植物(包括天然存在的作物植物)。作物植物可以是可以通过常规育种和优化法或通过生物技术和基因工程方法或这些方法的结合而获得的植物,包括遗传修饰植物(GMO或转基因植物)以及受或不受植物育种权(plant breeders’rights)保护的植物栽培种。
植物栽培种应当理解为意指具有新特性(“性状”)并且已通过常规育种、诱变或重组DNA技术得到的植物。它们可为栽培种、变种、生物型或基因型。
植物部位应当理解为意指植物的地上及地下的所有部分及器官,如芽、叶、针叶、茎、干、花、果实体、果实、种子、根、块茎和根茎。植物部位也包括采收材料以及无性与有性繁殖材料,例如插枝、块茎、根茎、分株及种子。
可根据本文所述的方法处理的植物包括以下:棉花、亚麻、葡萄藤、水果、蔬菜,如蔷薇科属种(Rosaceae sp.)(例如仁果类,如苹果和梨,以及核果,例如杏、樱桃、扁桃和桃,以及无核小水果,例如草莓)、Ribesioidae sp.、胡桃科属种(Juglandaceae sp.)、桦木科属种(Betulaceaesp.)、漆树科属种(Anacardiaceae sp.)、壳斗科属种(Fagaceae sp.)、桑科属种(Moraceae sp.)、木犀科属种(Oleaceae sp.)、猕猴桃科属种(Actinidaceae sp.)、樟科属种(Lauraceae sp.)、芭蕉科属种(Musaceaesp.)(例如香蕉树和香蕉种植园)、茜草科属种(Rubiaceae sp.)(例如咖啡)、山茶科属种(Theaceae sp.)、梧桐科属种(Sterculiceae sp.)、芸香科属种(Rutaceae sp.)(例如柠檬、橙子和葡萄柚)、茄科属种(Solanaceae sp.)(例如马铃薯和番茄)、百合科属种(Liliaceae sp.)、紫菀科属种(Asteraceae sp.)(例如莴苣)、伞形科属种(Umbelliferae sp.)、十字花科属种(Cruciferae sp.)、藜科属种(Chenopodiaceae sp.)、葫芦科属种(Cucurbitaceae sp.)(例如黄瓜)、葱科属种(Alliaceae sp.)(例如韭菜、洋葱)、蝶形花科属种(Papilionaceaesp.)(例如豌豆);主要作物植物,如禾本科属种(Gramineae sp.)(例如玉米、草坪草、谷类(如小麦、黑麦、稻、大麦、燕麦、黍和黑小麦))、菊科属种(Asteraceae sp.)(例如向日葵)、十字花科属种(Brassicaceae sp.)(例如白球甘蓝、红球甘蓝、花茎甘蓝、花椰菜、抱子甘蓝、小白菜、球茎甘蓝、小红萝卜,以及油菜、芥菜、辣根和水芹)、豆科属种(Fabacae sp.)(例如菜豆、花生)、蝶形花科属种(Papilionaceae sp.)(例如大豆)、藜科属种(Chenopodiaceae sp.)(例如糖用甜菜、饲用甜菜、瑞士甜菜、甜菜根);园林和森林中的有用植物和观赏植物;以及这些植物各自的基因修饰的变种。
可以通过上述公开的方法处理的植物和植物栽培种包括对一种或多种生物胁迫具有抗性的植物和植物栽培种,即所述植物对动物或微生物有害物(如对线虫、昆虫、螨类、植物病原性真菌、细菌、病毒和/或类病毒)具有更好的防御。
可以通过上述公开的方法处理的植物和植物栽培种包括那些对一种或多种非生物胁迫具有抗性的植物。非生物胁迫条件可包括例如干旱、低温暴露、热暴露、渗透胁迫、水涝、提高的土壤含盐度、增强的矿物暴露、臭氧暴露、强光暴露、有限的氮营养素利用率、有限的磷营养素利用率、避荫。
可以通过上述公开的方法处理的植物和植物栽培种包括那些以提高的产量特性为特征的植物。所述植物中提高的产量可为以下因素的结果:例如,改良的植物生理机能、生长和发育,如水利用效率、持水效率、改善的氮利用率、增强的碳同化作用、改善的光合作用、提高的发芽率和加速的成熟。产率还可受到改进的植物体系结构(plantarchitecture)的影响(在胁迫和非胁迫条件下),所述植物体系结构包括但不限于:提早开花、对杂交种子生产的开花控制、秧苗活力、植株大小、节间数和节间距、根系生长、种子大小、果实大小、荚果大小、荚果数或穗数、每个荚果或穗的种子数量、种子质量、增强的种子饱满度、减少的种子散布、减少的荚开裂以及抗倒伏。其他的产量性状包括种子组成,如碳水化合物含量和组成,例如棉花或淀粉、蛋白质含量、油含量和组成、营养价值、抗营养化合物减少、改善的可加工性和更好的贮存稳定性。
可以通过上述公开的方法处理的植物和植物栽培种包括为杂种植物的植物和植物栽培种,该杂种植物已表达出杂种优势或杂种活力的特征,这通常导致更高的产量、活力、健康和对生物和非生物胁迫的抗性。
转基因植物、种子处理和整合株系(event)
本发明的式(I)化合物的多晶型B可有利地用于处理接受了遗传物质的转基因植物、植物栽培种或植物部位,这些遗传物质赋予这些植物、植物栽培种或植物部位有利和/或有用的特性(性状)。因此,可以考虑将本发明与一个或多个重组性状或转基因株系(transgenic event)或其结合相结合。为本申请的目的,转基因株系是通过将特定的重组DNA分子插入到植物基因组染色体的特定位置(位点)而产生的。该插入创造了一个被称为“株系”的新的DNA序列,其特征是插入的重组DNA分子和一定量的基因组DNA紧邻插入DNA的两端/在插入DNA的两端旁侧。这种性状或转基因株系包括但不限于抗病虫害、水利用效率、产量表现、耐旱性、种子质量、改善营养质量、杂交种子生产和耐除草剂,其中该性状是相对于缺乏这种性状或转基因株系的植物而判定的。这种有利和/或有用的特性(性状)的具体实例是更好的植物生长、活力、胁迫耐受性、林分生长能力、耐倒伏性、营养吸收、植物营养和/或产量,特别是改善生长、提高对高温或低温的耐受性、提高对干旱或对水或土壤含盐度水平的耐受性、增强的开花性能、更容易收获、加速成熟、更高的产量、更高的质量和/或更高的收获产品的营养价值、更好的储存期和/或收获产品的可加工性,以及增强对动物和微生物害虫(例如昆虫、蛛形纲动物、线虫、螨虫、蛞蝓和蜗牛)的抵抗力。
在编码赋予这些动物或微生物害虫(特别是昆虫)具有耐受性性状的蛋白质的DNA序列中,将特别提及由苏云金芽孢杆菌编码Bt蛋白组成的遗传物质,所述物质详细记载于文献中,并为本领域的技术人员所熟知。还将提到从细菌中提取的蛋白,如发光杆菌属(Photorhabdus)(WO97/17432和WO98/08932)。特别是将提及由Bt Cry或包括CrylA、CryIAb、CryIAc、CryIIA、CryIIIA、CryIIIB2、Cry9c、Cry2Ab、Cry3Bb和CryIF蛋白或其毒性片段的VIP蛋白,以及其杂交体或组合,特别是Cry1F蛋白或来自Cry1F蛋白的杂交体(如杂交的Cry1A-Cry1F蛋白或其毒性片段),Cry1A型蛋白或其毒性片段,优选Cry1Ac蛋白或来自Cry1Ac蛋白的杂交体(如杂交的Cry1Ab-Cry1Ac蛋白)或Cry1Ab或Bt2蛋白或其毒性片段,Cry2Ae、Cry2Af或Cry2Ag蛋白或其毒性片段,Cry1A.105蛋白或其毒性片段,在COT202或COT203棉花株系中产生的VIP3Aa19蛋白、VIP3Aa20蛋白、VIP3A蛋白,记载于Estruch等人(1996),Proc Natl Acad Sci US A.28;93(11):5389-94中的VIP3Aa蛋白或其毒性片段,记载于WO2001/47952中的Cry蛋白,来自致病杆菌属(Xenorhabdus)(如WO98/50427中所记载的)、沙雷氏菌属(Serratia)(特别是来自嗜虫沙雷氏菌(S.entomophila))或发光杆菌物种菌株的杀虫蛋白,例如记载于WO98/08932中的来自发光杆菌的Tc蛋白。此外,本文还包括在一些氨基酸(1-10,优选1-5)上与上述列出的任何序列(特别是它们的毒性片段的序列)不同的上述任一种蛋白的所有变体或突变体,或者,上述蛋白与转运肽(如质体转运肽)或另一种蛋白或肽融合的任何变体或突变体。
这种特性的另一个且特别强调的实例是赋予对一种或多种除草剂(例如咪唑啉酮类、磺酰脲类、草甘膦或草丁膦)具有耐受性。在编码赋予转化的植物细胞和植物对某些除草剂具有耐受性的蛋白质的DNA序列中,将特别提到在WO2009/152359中记载的赋予对草铵膦除草剂具有耐受性的bar或PAT基因或天蓝色链霉菌(Streptomyces coelicolor)基因,编码赋予对以EPSPS为目标的除草剂(特别是对草甘膦及其盐类等除草剂)具有耐受性的合适的EPSPS(5-烯醇化丙酮基莽草酸-3-磷酸-合酶)基因,编码草甘膦-n-乙酰转移酶的基因,或编码草甘膦氧化还原酶的基因。其他合适的除草剂耐受性状包括至少一种ALS(乙酰乳酸合酶)抑制剂(例如WO2007/024782)、突变的拟南芥ALS/AHAS基因(例如美国专利号6,855,533),编码2,4-D-单氧酶赋予对2,4-D(2,4-二氯苯氧乙酸)具有耐受性的基因,编码Dicamba单氧酶赋予对Dicamba(3,6-二氯-2-甲氧基苯甲酸)具有耐受性的基因。
然而这种特性的另一个实例是对一种或多种植物病原性真菌(例如亚洲大豆锈病(Asian Soybean Rust))的抗性。在编码赋予对此类病害的抗性的蛋白质的DNA序列中,将特别提到来自短绒野大豆(glycine tomentella)的遗传物质,例如在WO2019/103918中记载的任何一个公开可获得的登记系列:PI441001、PI483224、PI583970、PI446958、PI499939、PI505220、PI499933、PI441008、PI505256或PI446961。
这种特性的进一步和特别强调的实例为,由于例如系统获得性抗性(SAR)、系统素、植物抗毒素、诱导剂以及抗性基因和相应表达的蛋白质和毒素,对细菌和/或病毒的抗性增加。
根据本发明可以优先处理的转基因植物或植物栽培种中特别有用的转基因株系包括株系531/PV-GHBK04(棉花,昆虫防治,记载于WO2002/040677中),株系1143-14A(棉花,昆虫防治,未保藏,记载于WO2006/128569中);株系1143-51B(棉花,昆虫防治,未保藏,记载于WO2006/128570中);株系1445(棉花,除草剂耐性,未保藏,记载于US-A 2002-120964或WO2002/034946中);株系17053(稻,除草剂耐性,作为PTA-9843保藏,记载于WO2010/117737中);株系17314(稻,除草剂耐性,作为PTA-9844保藏,记载于WO2010/117735中);株系281-24-236(棉花,昆虫防治-除草剂耐性,作为PTA-6233保藏,记载于WO2005/103266或US-A2005-216969中);株系3006-210-23(棉花,昆虫防治-除草剂耐性,作为PTA-6233保藏,记载于US-A 2007-143876或WO2005/103266中);株系3272(玉米,质量性状,作为PTA-9972保藏,记载于WO2006/098952或US-A 2006-230473中);株系33391(小麦,除草剂耐性,作为PTA-2347保藏,记载于WO2002/027004),株系40416(玉米,昆虫防治-除草剂耐性,作为ATCCPTA-11508保藏,记载于WO 11/075593中);株系43A47(玉米,昆虫防治-除草剂耐性,作为ATCC PTA-11509保藏,记载于WO2011/075595中);株系5307(玉米,昆虫防治,作为ATCCPTA-9561保藏,记载于WO2010/077816中);株系ASR-368(水糠草(bent grass),除草剂耐性,作为ATCC PTA-4816保藏,记载于US-A 2006-162007或WO2004/053062中);株系B16(玉米,除草剂耐性,未保藏,记载于US-A 2003-126634中);株系BPS-CV127-9(大豆,除草剂耐性,作为NCIMB号41603保藏,记载于WO2010/080829中);株系BLRl(油菜,恢复雄性不育,作为NCIMB 41193保藏,记载于WO2005/074671中),株系CE43-67B(棉花,昆虫防治,作为DSMACC2724保藏,记载于US-A 2009-217423或WO2006/128573中);株系CE44-69D(棉花,昆虫防治,未保藏,记载于US-A 2010-0024077中);株系CE44-69D(棉花,昆虫防治,未保藏,记载于WO2006/128571中);株系CE46-02A(棉花,昆虫防治,未保藏,记载于WO2006/128572中);株系COT102(棉花,昆虫防治,未保藏,记载于US-A 2006-130175或WO2004/039986中);株系COT202(棉花,昆虫防治,未保藏,记载于US-A 2007-067868或WO2005/054479中);株系COT203(棉花,昆虫防治,未保藏,记载于WO2005/054480中);株系DAS21606-3/1606(大豆,除草剂耐性,作为PTA-11028保藏,记载于WO2012/033794中),株系DAS40278(玉米,除草剂耐性,作为ATCC PTA-10244保藏,记载于WO2011/022469中);株系DAS-44406-6/pDAB8264.44.06.l(大豆,除草剂耐性,作为PTA-11336保藏,记载于WO2012/075426中),株系DAS-14536-7/pDAB8291.45.36.2(大豆,除草剂耐性,作为PTA-11335保藏,记载于WO2012/075429中),株系DAS-59122-7(玉米,昆虫防治-除草剂耐性,作为ATCC PTA 11384保藏,记载于US-A 2006-070139中);株系DAS-59132(玉米,昆虫防治-除草剂耐性,未保藏,记载于WO2009/100188中);株系DAS68416(大豆,除草剂耐性,作为ATCC PTA-10442保藏,记载于WO2011/066384或WO2011/066360中);株系DP-098140-6(玉米,除草剂耐性,作为ATCCPTA-8296保藏,记载于US-A 2009-137395或WO 08/112019中);株系DP-305423-1(大豆,质量性状,未保藏,记载于US-A 2008-312082或WO2008/054747中);株系DP-32138-1(玉米,杂交体系,作为ATCC PTA-9158保藏,记载于US-A 2009-0210970或WO2009/103049中);株系DP-356043-5(大豆,除草剂耐性,作为ATCC PTA-8287保藏,记载于US-A 2010-0184079或WO2008/002872中);株系EE-I(茄子,昆虫防治,未保藏,记载于WO 07/091277中);株系Fil17(玉米,除草剂耐性,作为ATCC 209031保藏,记载于US-A 2006-059581或WO 98/044140中);株系FG72(大豆,除草剂耐性,作为PTA-11041保藏,记载于WO2011/063413中),株系GA21(玉米,除草剂耐性,作为ATCC 209033保藏,记载于US-A2005-086719或WO 98/044140中);株系GG25(玉米,除草剂耐性,作为ATCC 209032保藏,记载于US-A 2005-188434或WO98/044140中);株系GHB119(棉花,昆虫防治-除草剂耐性,作为ATCC PTA-8398保藏,记载于WO2008/151780中);株系GHB614(棉花,除草剂耐性,作为ATCC PTA-6878保藏,记载于US-A 2010-050282或W02007/017186中);株系GJ11(玉米,除草剂耐性,作为ATCC 209030保藏,记载于US-A2005-188434或WO98/044140中);株系GM RZ13(糖用甜菜,抗病毒性,作为NCIMB-41601保藏,记载于WO2010/076212中);株系H7-l(糖用甜菜,除草剂耐性,作为NCIMB41158或NCIMB 41159保藏,记载于US-A 2004-172669或WO 2004/074492中);株系JOPLINl(小麦,抗病性,未保藏,记载于US-A 2008-064032中);株系LL27(大豆,除草剂耐性,作为NCIMB41658保藏,记载于WO2006/108674或US-A2008-320616中);株系LL55(大豆,除草剂耐性,作为NCIMB 41660保藏,记载于WO 2006/108675或US-A 2008-196127中);株系LLcotton25(棉花,除草剂耐性,作为ATCC PTA-3343保藏,记载于WO2003/013224或US A2003-097687中);株系LLRICE06(稻,除草剂耐性,作为ATCC 203353保藏,记载于US 6,468,747或WO2000/026345中);株系LLRice62(稻,除草剂耐性,作为ATCC 203352保藏,记载于WO2000/026345),株系LLRICE601(稻,除草剂耐性,作为ATCC PTA-2600保藏,记载于US-A2008-2289060或WO2000/026356中);株系LY038(玉米,质量性状,作为ATCC PTA-5623保藏,记载于US-A 2007-028322或WO2005/061720中);株系MIR162(玉米,昆虫防治,作为PTA-8166保藏,记载于US-A 2009-300784或WO2007/142840中);株系MIR604(玉米,昆虫防治,未保藏,记载于US-A 2008-167456或WO2005/103301中);株系MON15985(棉花,昆虫防治,作为ATCC PTA-2516保藏,记载于US-A 2004-250317或WO2002/100163中);株系MON810(玉米,昆虫防治,未保藏,记载于US-A 2002-102582中);株系MON863(玉米,昆虫防治,作为ATCCPTA-2605保藏,记载于WO2004/011601或US-A 2006-095986中);株系MON87427(玉米,授粉控制,作为ATCC PTA-7899保藏,记载于WO2011/062904中);株系MON87460(玉米,抗逆性,作为ATCC PTA-8910保藏,记载于WO2009/111263或US-A2011-0138504中);株系MON87701(大豆,昆虫防治,作为ATCC PTA-8194保藏,记载于US-A 2009-130071或WO2009/064652中);株系MON87705(大豆,质量性状-除草剂耐性,作为ATCC PTA-9241保藏,记载于US-A2010-0080887或WO2010/037016中);株系MON87708(大豆,除草剂耐性,作为ATCC PTA-9670保藏,记载于WO2011/034704中);株系MON87712(大豆,产量,作为PTA-10296保藏,记载于WO2012/051199中),株系MON87754(大豆,质量性状,作为ATCC PTA-9385保藏,记载于WO2010/024976中);株系MON87769(大豆,质量性状,作为ATCC PTA-8911保藏,记载于US-A 2011-0067141或WO2009/102873中);株系MON88017(玉米,昆虫防治-除草剂耐性,作为ATCC PTA-5582保藏,记载于US-A 2008-028482或WO2005/059103中);株系MON88913(棉花,除草剂耐性,作为ATCC PTA-4854保藏,记载于WO2004/072235或US-A 2006-059590中);株系MON88302(油菜,除草剂耐性,作为PTA-10955保藏,记载于WO2011/153186中),株系MON88701(棉花,除草剂耐性,作为PTA-11754保藏,记载于WO2012/134808中),株系MON89034(玉米,昆虫防治,作为ATCC PTA-7455保藏,记载于WO 07/140256或US-A 2008-260932中);株系MON89788(大豆,除草剂耐性,作为ATCC PTA-6708保藏,记载于US-A 2006-282915或WO2006/130436中);株系MSl 1(油菜,授粉控制-除草剂耐性,作为ATCC PTA-850或PTA-2485保藏,记载于WO2001/031042中);株系MS8(油菜,授粉控制-除草剂耐性,作为ATCC PTA-730保藏,记载于WO2001/041558或US-A 2003-188347中);株系NK603(玉米,除草剂耐性,作为ATCC PTA-2478保藏,记载于US-A 2007-292854中);株系PE-7(稻,昆虫防治,未保藏,记载于WO2008/114282中);株系RF3(油菜,授粉控制-除草剂耐性,作为ATCC PTA-730保藏,记载于WO2001/041558或US-A 2003-188347中);株系RT73(油菜,除草剂耐性,未保藏,记载于WO2002/036831或US-A 2008-070260中);株系SYHT0H2/SYN-000H2-5(大豆,除草剂耐性,作为PTA-11226保藏,记载于WO2012/082548中),株系T227-1(糖用甜菜,除草剂耐性,未保藏,记载于WO2002/44407或US-A 2009-265817中);株系T25(玉米,除草剂耐性,未保藏,记载于US-A 2001-029014或WO2001/051654中);株系T304-40(棉花,昆虫防治-除草剂耐性,作为ATCC PTA-8171保藏,记载于US-A 2010-077501或WO2008/122406中);株系T342-142(棉花,昆虫防治,未保藏,记载于WO2006/128568中);株系TC1507(玉米,昆虫防治-除草剂耐性,未保藏,记载于US-A 2005-039226或WO2004/099447中);株系VIP1034(玉米,昆虫防治-除草剂耐性,作为ATCC PTA-3925保藏,记载于WO2003/052073中),株系32316(玉米,昆虫防治-除草剂耐性,作为PTA-11507保藏,记载于WO2011/084632中),株系4114(玉米,昆虫防治-除草剂耐性,作为PTA-11506保藏,记载于WO2011/084621中),任选地与株系EE-GM1/LL27或株系EE-GM2/LL55(WO2011/063413A2)叠加的株系EE-GM3/FG72(大豆,除草剂耐性,ATCC登记号PTA-11041),株系DAS-68416-4(大豆,除草剂耐性,ATCC登记号PTA-10442,WO2011/066360A1),株系DAS-68416-4(大豆,除草剂耐性,ATCC登记号PTA-10442,WO2011/066384A1),株系DP-040416-8(玉米,昆虫防治,ATCC登记号PTA-11508,WO2011/075593A1),株系DP-043A47-3(玉米,昆虫防治,ATCC登记号PTA-11509,WO2011/075595A1),株系DP-004114-3(玉米,昆虫防治,ATCC登记号PTA-11506,WO2011/084621A1),株系DP-032316-8(玉米,昆虫防治,ATCC登记号PTA-11507,WO2011/084632A1),株系MON-88302-9(油菜,除草剂耐性,ATCC登记号PTA-10955,WO2011/153186A1),株系DAS-21606-3(大豆,除草剂耐性,ATCC登记号PTA-11028,WO2012/033794A2),株系MON-87712-4(大豆,质量性状,ATCC登记号PTA-10296,WO2012/051199A2),株系DAS-44406-6(大豆,叠加的除草剂耐性,ATCC登记号PTA-11336,WO2012/075426A1),株系DAS-14536-7(大豆,叠加的除草剂耐性,ATCC登记号PTA-11335,WO2012/075429A1),株系SYN-000H2-5(大豆,除草剂耐性,ATCC登记号PTA-11226,WO2012/082548A2),株系DP-061061-7(油菜,除草剂耐性,无可用保藏号,WO2012071039A1),株系DP-073496-4(油菜,除草剂耐性,无可用保藏号,US2012131692),株系8264.44.06.1(大豆,叠加的除草剂耐性,登记号PTA-11336,WO2012075426A2),株系8291.45.36.2(大豆,叠加的除草剂耐性,登记号PTA-11335,WO2012075429A2),株系SYHT0H2(大豆,ATCC登记号PTA-11226,WO2012/082548A2),株系MON88701(棉花,ATCC登记号PTA-11754,WO2012/134808A1),株系KK179-2(苜蓿,ATCC登记号PTA-11833,WO2013/003558A1),株系pDAB8264.42.32.1(大豆,叠加的除草剂耐性,ATCC登记号PTA-11993,WO2013/010094A1),株系MZDT09Y(玉米,ATCC登记号PTA-13025,WO2013/012775A1中)。
此外,美国农业部(USDA)动植物卫生检验局(APHIS)提供了一份此类转基因株系的清单,可以在互联网上他们的网站上aphis.usda.gov找到。就本申请而言,该清单在本申请提交日的状态是相关的。
赋予所需性状的基因/株系也可以在转基因植物中以相互组合的方式存在。可以提及的转基因植物的实例是重要的作物植物,如谷类(小麦、稻、黑小麦、大麦、黑麦、燕麦)、玉米、大豆、马铃薯、糖用甜菜、甘蔗、番茄、豌豆和其他类型的蔬菜、棉花、烟草、油菜以及水果植物(包括苹果、梨、柑橘类水果和葡萄),特别强调玉米、大豆、小麦、稻、马铃薯、棉花、甘蔗、烟草和油菜。特别强调的性状是提高植物对昆虫、蛛形纲动物、线虫和蛞蝓及蜗牛的抗性,以及提高植物对一种或多种除草剂的抗性。
可根据本发明优先处理的此类植物、植物部位或植物种子的市售实例包括以 ROUNDUPVTVT TRIPLEBOLLGARDROUNDUP READY 2 ROUNDUP2XTENDTM、INTACTA RR2VISTIVE和/或XTENDFLEXTM商品名出售或分销的市售产品,如植物种子。
病原体
式(I)化合物的多晶型B可优选用作杀真菌剂。上述疾病包括:
由白粉病病原体引起的病害,所述病原体为例如布氏白粉菌属(Blumeria)属种,如禾本科布氏白粉菌(Blumeria graminis);内丝白粉菌属(Leveillula)属种,如鞑靼内丝白粉菌(Leveillula Taurica);叉丝单囊壳属(Podosphaera)属种,如白叉丝单囊壳(Podosphaera leucotricha)或苍耳单囊壳白粉菌(Podosphaera xanthii);单囊壳属(Sphaerotheca)属种,如单囊壳白粉菌(Sphaerotheca fuliginea);白粉菌属(Erysiphe)属种,如甜菜白粉菌(Erysiphe betae)和葡萄白粉菌(Erysiphe necator);
由锈病病原体引起的病害,所述病原体为例如胶锈菌属(Gymnosporangium)属种,如褐色胶锈菌(Gymnosporangium sabinae);驼孢锈属(Hemileia)属种,如咖啡驼孢锈菌(Hemileia vastatrix);层锈菌属(Phakopsora)属种,如豆薯层锈菌(Phakopsorapachyrhizi)或山马蝗层锈菌(Phakopsora meibomiae);柄锈菌属(Puccinia)属种,如隐匿柄锈菌(Puccinia recondita)、小麦杆锈菌(Puccinia graminis)或小麦条锈菌(Pucciniastriiformis);单胞锈菌属(Uromyces)属种,如疣顶单胞锈菌(Uromycesappendiculatus);
由以下病原体引起的叶斑枯病和叶萎蔫病病害:例如链格孢属(Alternaria)属种,例如茄链格孢(Alternaria solani)或苹果链格孢(Alternaria mali)或赤星霉(Alternaria alternata);尾孢属(Cercospora)属种,例如菾菜生尾孢(Cercosporabeticola);枝孢属(Cladiosporum)属种,例如黄瓜枝孢(Cladiosporium cucumerinum);旋孢腔菌属(Cochliobolus)属种,例如禾旋孢腔菌(Cochliobolus sativus)(分生孢子形式:内脐蠕孢属(Drechslera),同义词:长蠕孢属(Helminthosporium))或宫部旋孢霉(Cochliobolus miyabeanus);炭疽菌属(Colletotrichum)属种,例如菜豆炭疽菌(Colletotrichum lindemuthanium)或辣椒炭疽菌(Colletotrichum capsica)或尖孢炭疽菌(Colletotrichum acutatum);暗双孢属(Cordana)属种,例如香蕉暗双孢菌(Cordanamusae);棒孢属(Corynespora)属种,例如山扁豆生棒孢(Corynespora cassiicola);锈斑病菌属(Cycloconium)属种,例如油橄榄孔雀斑病菌(Cycloconium oleaginum);间座壳属(Diaporthe)属种,例如柑桔间座壳(Diaporthe citri);痂囊腔菌属(Elsinoe)属种,例如柑桔痂囊腔菌(Elsinoe fawcettii);盘长孢属(Gloeosporium)属种,例如悦色盘长孢(Gloeosporium laeticolor);小丛壳属(Glomerella)属种,例如围小丛壳(Glomerellacingulata);球座菌属(Guignardia)属种,例如葡萄球座菌(Guignardia bidwelli);小球腔菌属(Leptosphaeria)属种,例如斑污小球腔菌(Leptosphaeria maculans);大毁壳属(Magnaporthe)属种,例如灰色大毁壳(Magnaporthe grisea);盘二孢属(Marsonina)属种,例如苹果褐斑病菌(Marsonina mali);微座孢属(Microdochium)属种,例如雪霉微座孢(Microdochium nivale);球腔菌属(Mycosphaerella)属种,例如禾生球腔菌(Mycosphaerella graminicola)、落花生球腔菌(Mycosphaerella arachidicola)和斐济球腔菌(Mycosphaerella fijiensis);暗球腔菌属种(Phaeosphaeria)属种,例如颖枯暗球腔菌(Phaeosphaeria nodorum);核腔菌属(Pyrenophora)属种,例如圆核腔菌(Pyrenophora teres)、偃麦草核腔菌(Pyrenophora tritici repentis);柱隔孢属(Ramularia)属种,例如辛加柱隔孢(Ramularia collo-cygni)或白斑柱隔孢(Ramulariaareola);喙孢属(Rhynchosporium)属种,例如黑麦喙孢(Rhynchosporium secalis);针孢属(Septoria)属种,例如芹菜小壳针孢(Septoria apii)、番茄壳针孢(Septorialycopersii);毛座腔菌属(Setosphaeria)属种,例如玉米大斑病菌(Setosphaeriaturcica);核盘菌属(Sclerotinia)属种,例如核盘菌(Sclerotinia sclerotiorum);壳多孢属(Stagonospora)属种,例如颖枯壳针孢(Stagonospora nodorum);匍柄霉属(Stemphylium)属种,例如膨胀匐柄霉(Stemphylium vesicarium);核瑚菌属(Typhula)属种,例如肉孢核瑚菌(Typhula incarnata);黑星菌属(Venturia)属种,例如苹果黑星病菌(Venturia inaequalis);
由下述病原体引起的根和茎病害:例如伏革菌属(Corticium)属种,例如禾伏革菌(Corticium graminearum);镰孢属(Fusarium)属种,例如尖镰孢(Fusarium oxysporum);顶囊壳菌属(Gaeumannomyces)属种,例如禾顶囊壳(Gaeumannomyces graminis);盘二孢属(Marsonina)属种,例如苹果褐斑病菌(Marsonina mali);丝核菌属(Rhizoctonia)属种,例如立枯丝核菌(Rhizoctonia solani);帚枝杆孢属(Sarocladium),例如稻帚枝杆孢(Sarocladium oryzae)、小核菌属(Sclerotium),例如稻腐小核菌(Sclerotium oryzae)、Tapesia属种,例如Tapesia acuformis;根串珠霉属(Thielaviopsis)属种,例如根串珠霉(Thielaviopsis basicola);
由下述病原体引起的肉穗花序或圆锥花序病害(包括玉米穗轴):例如链格孢属(Alternaria)属种,例如链格孢属(Alternaria spp.);曲霉属(Aspergillus)属种,例如黄曲霉(Aspergillus flavus);枝孢属(Cladosporium)属种,例如枝孢样枝孢霉(Cladosporiumcladosporioides);麦角菌属(Claviceps)属种,例如麦角菌(Clavicepspurpurea);镰孢属(Fusarium)属种,例如黄色镰孢(Fusariumculmorum);赤霉属(Gibberella)属种,例如玉蜀黍赤霉(Gibberella zeae);小画线壳属(Monographella)属种,例如雪腐小画线壳(Monographella nivalis);Stagnospora属种,例如Stagnosporanodorum;
由黑粉菌引起的病害,所述黑粉菌为例如:轴黑粉菌属(Sphacelotheca)属种,例如丝孢堆黑粉菌(Sphacelotheca reiliana);腥黑粉菌属(Tilletia)属种,例如小麦网腥黑粉菌(Tilletia caries)或小麦矮腥黑粉菌(Tilletia controversa);条黑粉菌属(Urocystis)属种,例如隐条黑粉菌(Urocystis occulta);黑粉菌属(Ustilago)属种,例如裸黑粉菌(Ustilago nuda);
由以下病原体引起的果腐病:例如,曲霉属(Aspergillus)属种,例如黄曲霉(Aspergillus flavus);葡萄孢属(Botrytis)属种,例如灰霉菌(Botrytis cinerea);链核盘菌属(Monilinia)属种,例如核果链核盘菌(Monilinia laxa);青霉属(Penicillium)属种,例如扩展青霉(Penicillium expansum)或产紫青霉(Penicillium purpurogenum);拟茎点霉属(Phomopsis)属种,例如葡萄拟茎点霉菌(Phomopsis viticola);根霉属(Rhizopus)属种,例如葡茎根霉菌(Rhizopus stolonifer);核盘菌属(Sclerotinia)属种,例如核盘菌(Sclerotinia sclerotiorum);轮枝孢属(Verticilium)属种,例如黑白轮枝菌(Verticilium alboatrum);
由下述病原体引起的种传腐烂和土传腐烂和萎蔫病害,以及幼苗病害:例如链格孢属(Alternaria)属种,例如芸薹链格孢(Alternaria brassicicola);丝囊霉属(Aphanomyces)属种,例如根霉丝囊霉(Aphanomyces euteiches);壳二胞属(Ascochyta)属种,例如兵豆壳二孢(Ascochyta lentis);曲霉属属种,例如黄曲霉;枝孢属(Cladosporium)属种,例如草本枝孢霉(Cladosporium herbarum);旋孢腔菌属(Cochliobolus)属种,例如禾旋孢腔菌(Cochliobolus sativus)(分生孢子形式:内脐蠕孢属(Drechslera),离蠕孢属(Bipolaris)同义词:长蠕孢菌(Helminthosporium));炭疽菌属(Colletotrichum)属种,例如毛核炭疽菌(Colletotrichum coccodes);镰孢属(Fusarium)属种,例如黄色镰孢(Fusarium culmorum);赤霉属(Gibberella)属种,例如玉蜀黍赤霉(Gibberella zeae);壳球孢属(Macrophomina)属种,例如菜豆壳球孢(Macrophominaphaseolina);微座孢属(Microdochium)属种,例如雪霉微座孢(Microdochium nivale);小画线壳属(Monographella)属种,例如雪腐小画线壳(Monographella nivalis);青霉属(Penicillium)属种,例如扩展青霉(Penicillium expansum);茎点霉属(Phoma)属种,例如黑胫茎点霉(Phoma lingam);拟茎点霉属(Phomopsis)属种,例如大豆拟茎点霉(Phomopsissojae);核腔菌属(Pyrenophora)属种,例如麦类核腔菌(Pyrenophora graminea);梨孢属(Pyricularia)属种,例如稻梨孢(Pyricularia oryzae);丝核菌属(Rhizoctonia)属种,例如立枯丝核菌(Rhizoctonia solani);根霉属(Rhizopus)属种,例如稻根霉菌(Rhizopusoryzae);小核菌属(Sclerotium)属种,例如齐整小核菌(Sclerotium rolfsii);壳针孢属(Septoria)属种,例如颖枯壳针孢(Septoria nodorum);核瑚菌属(Typhula)属种,例如肉孢核瑚菌(Typhula incarnata);轮枝菌属(Verticillium)属种,例如大丽花轮枝孢(Verticillium dahliae);
由下述病原体引起的癌性病害、菌瘿和扫帚病:例如丛赤壳属(Nectria)属种,例如仁果干癌丛赤壳菌(Nectria galligena);
由下述病原体引起的萎蔫病害:例如轮枝菌属(Verticillium)属种,例如Verticillium longisporum;镰刀菌属(Fusarium)属种,例如(尖镰孢(Fusariumoxysporum);
由下述病原体引起的叶、花和果实的畸形:例如,外担菌属(Exobasidium)属种,例如坏损外担菌(Exobasidium vexans);外囊菌属(Taphrina)属种,例如畸形外囊菌(Taphrina deformans);
由下述病原体引起的木本植物退行性病害:例如依科属(Esca)属种,例如根霉格孢菌(Phaemoniella chlamydospora)、鸡腿蘑丝孢菌(Phaeoacremonium aleophilum)或地中海孢孔菌(Fomitiporia mediterranea);例如灵芝属(Ganoderma)属种,例如狭长孢灵芝(Ganoderma boninense);
由下述病原体引起的植物块茎的病害:例如丝核菌属(Rhizoctonia)属种,例如立枯丝核菌(Rhizoctonia solani);长蠕孢菌属(Helminthosporium)属种,例如茄病长蠕孢(Helminthosporium solani);
大豆病害:
由以下病原体引起的叶、茎、荚和种子的真菌病害:例如链格孢属叶斑病(Alternaria leaf spot)(Alternaria spec.atrans tenuissima)、炭疽病(Anthracnose)(Colletotrichum gloeosporoides dematium var.truncatum)、褐斑病(大豆壳针孢(Septoria glycines))、尾孢菌叶斑病和叶枯病(Cercospora leaf spot and blight)(菊池尾孢(Cercospora kikuchii))、笄霉属叶枯病(Choanephora leaf blight)(Choanephora infundibulifera trispora(同义词))、Dactuliophora叶斑病(Dactuliophora glycines)、大豆霜霉病(downy mildew)(东北霜霉(Peronosporamanshurica))、内脐蠕孢属枯萎病(Drechslera blight)(Drechslera glycini)、大豆灰斑病(frogeye leaf spot)(大豆尾孢(Cercospora sojina))、小光壳属叶斑病(Leptosphaerulina leaf spot)(三叶草小光壳(Leptosphaerulina trifolii))、白粉病(Leveillula powdery mildew)(鞑靼内丝白粉菌(Leveillula Taurica))、叶点霉属叶斑病(Phyllostica leaf spot)(大豆生叶点霉(Phyllosticta sojaecola))、荚和茎枯萎病(大豆拟茎点霉(Phomopsis sojae))、白粉病(Microsphaera diffusa)、棘壳孢属叶斑病(Pyrenochaeta leaf spot)(大豆红叶斑病菌(Pyrenochaeta glycines)、气生丝核菌(rhizoctonia aerial)、叶枯病和立枯病(foliage and web blight)(立枯丝核菌(Rhizoctonia solani))、锈病(豆薯层锈菌(Phakopsora pachyrhizi)、山蚂蝗层锈菌(Phakopsora meibomiae))、疮痂病(scab)(大豆痂圆孢(Sphaceloma glycines))、匍柄霉属叶枯病(stemphylium leaf blight)(匍柄霉(Stemphylium botryosum))、猝死综合征(Fusarium virguliforme)、靶斑病(山扁豆生棒孢(Corynespora cassiicola));
由以下病原体引起的根部和茎部的真菌病害:例如黑色根腐病(black root rot)(野百合丽赤壳菌(Calonectria crotalariae))、炭腐病(菜豆生壳球孢(Macrophominaphaseolina))、镰孢枯萎病或萎蔫病、根腐病以及荚和根颈腐烂病(尖镰孢(Fusariumoxysporum)、直喙镰孢(Fusarium orthoceras)、半裸镰孢(Fusarium semitectum)、木贼镰孢(Fusarium equiseti)、mycoleptodiscus根腐病(Mycoleptodiscus terrestris)、新赤壳属病(neocosmospora)(侵菅新赤壳(Neocosmopspora vasinfecta))、荚和茎枯萎病(菜豆间座壳(Diaporthe phaseolorum))、茎溃疡(stemcanker)(大豆北方茎溃疡病菌(Diaporthe phaseolorum var.caulivora))、茎褐腐病(大豆茎褐腐病菌(Phialophoragregata))、丝核菌属根腐病、茎腐病和立枯病(立枯丝核菌(Rhizoctonia solani))、核盘菌属茎腐病(核盘菌(Sclerotinia sclerotiorum))、核盘菌属白绢病(Sclerotiniarolfsii)、根串珠霉属根腐病(thielaviopsis root rot)(根串珠霉(Thielaviopsisbasicola))。
优选地,本发明涉及式(I)化合物的多晶型B用于防治以下病害的用途:由白粉病病原体引起的病害,所述病原体为例如布氏白粉菌属(Blumeria)属种,如禾本科布氏白粉菌(Blumeria graminis);内丝白粉菌属(Leveillula)属种,如鞑靼内丝白粉菌(Leveillula Taurica);叉丝单囊壳属(Podosphaera)属种,如白叉丝单囊壳(Podosphaeraleucotricha)或苍耳单囊壳白粉菌(Podosphaera xanthii);单囊壳属(Sphaerotheca)属种,如单囊壳白粉菌(Sphaerotheca fuliginea);白粉菌属(Erysiphe)属种,如甜菜白粉菌(Erysiphe betae)和葡萄白粉菌(Erysiphe necator);
由锈病病原体引起的病害,所述病原体为例如胶锈菌属(Gymnosporangium)属种,如褐色胶锈菌(Gymnosporangium sabinae);驼孢锈属(Hemileia)属种,如咖啡驼孢锈菌(Hemileia vastatrix);层锈菌属(Phakopsora)属种,如豆薯层锈菌(Phakopsorapachyrhizi)或山马蝗层锈菌(Phakopsora meibomiae);柄锈菌属(Puccinia)属种,如隐匿柄锈菌(Puccinia recondita)、小麦杆锈菌(Puccinia graminis)或小麦条锈菌(Pucciniastriiformis);单胞锈菌属(Uromyces)属种,如疣顶单胞锈菌(Uromycesappendiculatus);
由以下病原体引起的叶斑枯病和叶萎蔫病病害:例如链格孢属(Alternaria)属种,例如茄链格孢(Alternaria solani)或苹果链格孢(Alternaria mali)或赤星霉(Alternaria alternata);尾孢属(Cercospora)属种,例如菾菜生尾孢(Cercosporabeticola);枝孢属(Cladiosporum)属种,例如黄瓜枝孢(Cladiosporium cucumerinum);旋孢腔菌属(Cochliobolus)属种,例如禾旋孢腔菌(Cochliobolus sativus)(分生孢子形式:内脐蠕孢属(Drechslera),同义词:长蠕孢属(Helminthosporium))或宫部旋孢霉(Cochliobolus miyabeanus);炭疽菌属(Colletotrichum)属种,例如菜豆炭疽菌(Colletotrichum lindemuthanium)或辣椒炭疽菌(Colletotrichum capsica)或尖孢炭疽菌(Colletotrichum acutatum);棒孢属(Corynespora)属种,例如山扁豆生棒孢(Corynespora cassiicola);锈斑病菌属(Cycloconium)属种,例如油橄榄孔雀斑病菌(Cycloconium oleaginum);间座壳属(Diaporthe)属种,例如柑桔间座壳(Diaporthecitri);痂囊腔菌属(Elsinoe)属种,例如柑桔痂囊腔菌(Elsinoe fawcettii);白粉菌属(Erysiphe)属种,如甜菜白粉菌(Erysiphe betae)和葡萄白粉菌(Erysiphe necator)盘长孢属(Gloeosporium)属种,例如悦色盘长孢(Gloeosporium laeticolor);小丛壳属(Glomerella)属种,例如围小丛壳(Glomerella cingulata);球座菌属(Guignardia)属种,例如葡萄球座菌(Guignardia bidwelli);小球腔菌属(Leptosphaeria)属种,例如斑污小球腔菌(Leptosphaeria maculans);大毁壳属(Magnaporthe)属种,例如灰色大毁壳(Magnaporthe grisea);盘二孢属(Marsonina)属种,例如苹果褐斑病菌(Marsoninamali);微座孢属(Microdochium)属种,例如雪霉微座孢(Microdochium nivale);球腔菌属(Mycosphaerella)属种,例如禾生球腔菌(Mycosphaerella graminicola)、落花生球腔菌(Mycosphaerella arachidicola)和斐济球腔菌(Mycosphaerella fijiensis);暗球腔菌(Phaeosphaeria)属种,例如颖枯暗球腔菌(Phaeosphaeria nodorum);黑痣菌属(Phyllachora)属种,例如黑痣菌(Phyllachora maydis);核腔菌属(Pyrenophora)属种,例如圆核腔菌(Pyrenophora teres)、偃麦草核腔菌(Pyrenophora tritici repentis);柱隔孢属(Ramularia)属种,例如辛加柱隔孢(Ramularia collo-cygni)或白斑柱隔孢(Ramularia areola);喙孢属(Rhynchosporium)属种,例如黑麦喙孢(Rhynchosporiumsecalis);针孢属(Septoria)属种,例如芹菜小壳针孢(Septoria apii)、番茄壳针孢(Septoria lycopersii);毛座腔菌属(Setosphaeria)属种,例如玉米大斑病菌(Setosphaeria turcica);核盘菌属(Sclerotinia)属种,例如核盘菌(Sclerotiniasclerotiorum);壳多孢属(Stagonospora)属种,例如颖枯壳针孢(Stagonosporanodorum);匍柄霉属(Stemphylium)属种,例如膨胀匐柄霉(Stemphylium vesicarium);核瑚菌属(Typhula)属种,例如肉孢核瑚菌(Typhula incarnata);黑星菌属(Venturia)属种,例如苹果黑星病菌(Venturia inaequalis);
由下述病原体引起的根和茎病害:例如伏革菌属(Corticium)属种,例如禾伏革菌(Corticium graminearum);镰孢属(Fusarium)属种,例如尖镰孢(Fusarium oxysporum);顶囊壳菌属(Gaeumannomyces)属种,例如禾顶囊壳(Gaeumannomyces graminis);盘二孢属(Marsonina)属种,例如苹果褐斑病菌(Marsonina mali);丝核菌属(Rhizoctonia)属种,例如立枯丝核菌(Rhizoctonia solani);帚枝杆孢属(Sarocladium),例如稻帚枝杆孢(Sarocladium oryzae)、小核菌属(Sclerotium),例如稻腐小核菌(Sclerotium oryzae)、Tapesia属种,例如Tapesia acuformis;根串珠霉属(Thielaviopsis)属种,例如根串珠霉(Thielaviopsis basicola);
由下述病原体引起的肉穗花序或圆锥花序病害(包括玉米穗轴):例如链格孢属(Alternaria)属种,例如链格孢属(Alternaria spp.);曲霉属(Aspergillus)属种,例如黄曲霉(Aspergillus flavus);枝孢属(Cladosporium)属种,例如枝孢样枝孢霉(Cladosporiumcladosporioides);麦角菌属(Claviceps)属种,例如麦角菌(Clavicepspurpurea);镰孢属(Fusarium)属种,例如黄色镰孢(Fusariumculmorum);赤霉属(Gibberella)属种,例如玉蜀黍赤霉(Gibberella zeae);小画线壳属(Monographella)属种,例如雪腐小画线壳(Monographella nivalis);Stagnospora属种,例如Stagnosporanodorum;
由黑粉菌引起的病害,所述黑粉菌为例如:轴黑粉菌属(Sphacelotheca)属种,例如丝孢堆黑粉菌(Sphacelotheca reiliana);腥黑粉菌属(Tilletia)属种,例如小麦网腥黑粉菌(Tilletia caries)或小麦矮腥黑粉菌(Tilletia controversa);条黑粉菌属(Urocystis)属种,例如隐条黑粉菌(Urocystis occulta);黑粉菌属(Ustilago)属种,例如裸黑粉菌(Ustilago nuda);
由以下病原体引起的果腐病:例如,曲霉属(Aspergillus)属种,例如黄曲霉(Aspergillus flavus);葡萄孢属(Botrytis)属种,例如灰霉菌(Botrytis cinerea);链核盘菌属(Monilinia)属种,例如核果链核盘菌(Monilinia laxa);青霉属(Penicillium)属种,例如扩展青霉(Penicillium expansum)或产紫青霉(Penicillium purpurogenum);拟茎点霉属(Phomopsis)属种,例如葡萄拟茎点霉菌(Phomopsis viticola);根霉属(Rhizopus)属种,例如葡茎根霉菌(Rhizopus stolonifer);核盘菌属(Sclerotinia)属种,例如核盘菌(Sclerotinia sclerotiorum);轮枝孢属(Verticilium)属种,例如黑白轮枝菌(Verticilium alboatrum);
由下述病原体引起的种传腐烂和土传腐烂和萎蔫病害,以及幼苗病害:例如链格孢属(Alternaria)属种,例如芸薹链格孢(Alternaria brassicicola);丝囊霉属(Aphanomyces)属种,例如根霉丝囊霉(Aphanomyces euteiches);壳二胞属(Ascochyta)属种,例如兵豆壳二孢(Ascochyta lentis);曲霉属(Aspergillus)属种,例如黄曲霉(Aspergillus flavus);枝孢属(Cladosporium)属种,例如草本枝孢霉(Cladosporiumherbarum);旋孢腔菌属(Cochliobolus)属种,例如禾旋孢腔菌(Cochliobolus sativus)(分生孢子形式:内脐蠕孢属(Drechslera),离蠕孢属(Bipolaris)同义词:长蠕孢菌(Helminthosporium));炭疽菌属(Colletotrichum)属种,例如毛核炭疽菌(Colletotrichum coccodes);镰孢属(Fusarium)属种,例如黄色镰孢(Fusariumculmorum);赤霉属(Gibberella)属种,例如玉蜀黍赤霉(Gibberella zeae);壳球孢属(Macrophomina)属种,例如菜豆壳球孢(Macrophomina phaseolina);微座孢属(Microdochium)属种,例如雪霉微座孢(Microdochium nivale);小画线壳属(Monographella)属种,例如雪腐小画线壳(Monographella nivalis);青霉属(Penicillium)属种,例如扩展青霉(Penicillium expansum);茎点霉属(Phoma)属种,例如黑胫茎点霉(Phoma lingam);拟茎点霉属(Phomopsis)属种,例如大豆拟茎点霉(Phomopsissojae);核腔菌属(Pyrenophora)属种,例如麦类核腔菌(Pyrenophora graminea);梨孢属(Pyricularia)属种,例如稻梨孢(Pyricularia oryzae);丝核菌属(Rhizoctonia)属种,例如立枯丝核菌(Rhizoctonia solani);根霉属(Rhizopus)属种,例如稻根霉菌(Rhizopusoryzae);小核菌属(Sclerotium)属种,例如齐整小核菌(Sclerotium rolfsii);壳针孢属(Septoria)属种,例如颖枯壳针孢(Septoria nodorum);核瑚菌属(Typhula)属种,例如肉孢核瑚菌(Typhula incarnata);轮枝菌属(Verticillium)属种,例如大丽花轮枝孢(Verticillium dahliae);
由下述病原体引起的癌性病害、菌瘿和扫帚病:例如丛赤壳属(Nectria)属种,例如仁果干癌丛赤壳菌(Nectria galligena);
由下述病原体引起的萎蔫病害:例如轮枝菌属(Verticillium)属种,例如Verticillium longisporum;镰刀菌属(Fusarium)属种,例如(尖镰孢(Fusariumoxysporum);
由下述病原体引起的叶、花和果实的畸形:例如,外担菌属(Exobasidium)属种,例如坏损外担菌(Exobasidium vexans);外囊菌属(Taphrina)属种,例如畸形外囊菌(Taphrina deformans);
由下述病原体引起的木本植物退行性病害:例如依科属(Esca)属种,例如根霉格孢菌(Phaemoniella chlamydospora)、鸡腿蘑丝孢菌(Phaeoacremonium aleophilum)或地中海孢孔菌(Fomitiporia mediterranea);例如灵芝属(Ganoderma)属种,例如狭长孢灵芝(Ganoderma boninense);
由下述病原体引起的植物块茎的病害:例如丝核菌属(Rhizoctonia)属种,例如立枯丝核菌(Rhizoctonia solani);长蠕孢菌属(Helminthosporium)属种,例如茄病长蠕孢(Helminthosporium solani);
大豆病害:
由以下病原体引起的叶、茎、荚和种子的真菌病害:例如链格孢属叶斑病(Alternaria leaf spot)(Alternaria spec.atrans tenuissima)、炭疽病(Anthracnose)(Colletotrichum gloeosporoides dematium var.truncatum)、褐斑病(大豆壳针孢(Septoria glycines))、尾孢菌叶斑病和叶枯病(Cercospora leaf spot and blight)(菊池尾孢(Cercospora kikuchii))、笄霉属叶枯病(Choanephora leaf blight)(Choanephora infundibulifera trispora(同义词))、Dactuliophora叶斑病(Dactuliophora glycines)、大豆霜霉病(downy mildew)(东北霜霉(Peronosporamanshurica))、内脐蠕孢属枯萎病(Drechslera blight)(Drechslera glycini)、大豆灰斑病(frogeye leaf spot)(大豆尾孢(Cercospora sojina))、小光壳属叶斑病(Leptosphaerulina leaf spot)(三叶草小光壳(Leptosphaerulina trifolii))、白粉病(Leveillula powdery mildew)(鞑靼内丝白粉菌(Leveillula Taurica))、叶点霉属叶斑病(Phyllostica leaf spot)(大豆生叶点霉(Phyllosticta sojaecola))、荚和茎枯萎病(大豆拟茎点霉(Phomopsis sojae))、白粉病(Microsphaera diffusa)、棘壳孢属叶斑病(Pyrenochaeta leaf spot)(大豆红叶斑病菌(Pyrenochaeta glycines)、气生丝核菌(rhizoctonia aerial)、叶枯病和立枯病(foliage and web blight)(立枯丝核菌(Rhizoctonia solani))、锈病(豆薯层锈菌(Phakopsora pachyrhizi)、山蚂蝗层锈菌(Phakopsora meibomiae))、疮痂病(scab)(大豆痂圆孢(Sphaceloma glycines))、匍柄霉属叶枯病(stemphylium leaf blight)(匍柄霉(Stemphylium botryosum))、猝死综合征(Fusarium virguliforme)、靶斑病(山扁豆生棒孢(Corynespora cassiicola));
由以下病原体引起的根部和茎部的真菌病害:例如黑色根腐病(black root rot)(野百合丽赤壳菌(Calonectria crotalariae))、炭腐病(菜豆生壳球孢(Macrophominaphaseolina))、镰孢枯萎病或萎蔫病、根腐病以及荚和根颈腐烂病(尖镰孢(Fusariumoxysporum)、直喙镰孢(Fusarium orthoceras)、半裸镰孢(Fusarium semitectum)、木贼镰孢(Fusarium equiseti)、mycoleptodiscus根腐病(Mycoleptodiscus terrestris)、新赤壳属病(neocosmospora)(侵菅新赤壳(Neocosmopspora vasinfecta))、荚和茎枯萎病(菜豆间座壳(Diaporthe phaseolorum))、茎溃疡(stemcanker)(大豆北方茎溃疡病菌(Diaporthe phaseolorum var.caulivora))、茎褐腐病(大豆茎褐腐病菌(Phialophoragregata))、丝核菌属根腐病、茎腐病和立枯病(立枯丝核菌(Rhizoctonia solani))、核盘菌属茎腐病(核盘菌(Sclerotinia sclerotiorum))、核盘菌属白绢病(Sclerotiniarolfsii)、根串珠霉属根腐病(thielaviopsis root rot)(根串珠霉(Thielaviopsisbasicola))。
更优选地,本发明涉及式(I)化合物的多晶型B用于防治以下病害的用途:由白粉病病原体引起的病害,所述病原体为例如布氏白粉菌属(Blumeria)属种,如禾本科布氏白粉菌(Blumeria graminis);内丝白粉菌属(Leveillula)属种,如鞑靼内丝白粉菌(Leveillula Taurica);叉丝单囊壳属(Podosphaera)属种,如白叉丝单囊壳(Podosphaeraleucotricha)或苍耳单囊壳白粉菌(Podosphaera xanthii);单囊壳属(Sphaerotheca)属种,如单囊壳白粉菌(Sphaerotheca fuliginea);钩丝壳属(Uncinula)属种,如葡萄白粉病菌(Uncinula necator);
由以下病原体引起的叶斑枯病和叶萎蔫病病害:例如链格孢属(Alternaria)属种,例如茄链格孢(Alternaria solani)或苹果链格孢(Alternaria mali)或赤星霉(Alternaria alternata);尾孢属(Cercospora)属种,例如菾菜生尾孢(Cercosporabeticola);枝孢属(Cladiosporum)属种,例如黄瓜枝孢(Cladiosporium cucumerinum);旋孢腔菌属(Cochliobolus)属种,例如禾旋孢腔菌(Cochliobolus sativus)(分生孢子形式:内脐蠕孢属(Drechslera),同义词:长蠕孢属(Helminthosporium))或宫部旋孢霉(Cochliobolus miyabeanus);炭疽菌属(Colletotrichum)属种,例如菜豆炭疽菌(Colletotrichum lindemuthanium)或辣椒炭疽菌(Colletotrichum capsica)或尖孢炭疽菌(Colletotrichum acutatum);棒孢属(Corynespora)属种,例如山扁豆生棒孢(Corynespora cassiicola);锈斑病菌属(Cycloconium)属种,例如油橄榄孔雀斑病菌(Cycloconium oleaginum);间座壳属(Diaporthe)属种,例如柑桔间座壳(Diaporthecitri);痂囊腔菌属(Elsinoe)属种,例如柑桔痂囊腔菌(Elsinoe fawcettii);白粉菌属(Erysiphe)属种,如甜菜白粉菌(Erysiphe betae)和葡萄白粉菌(Erysiphe necator)盘长孢属(Gloeosporium)属种,例如悦色盘长孢(Gloeosporium laeticolor);小丛壳属(Glomerella)属种,例如围小丛壳(Glomerella cingulata);球座菌属(Guignardia)属种,例如葡萄球座菌(Guignardia bidwelli);小球腔菌属(Leptosphaeria)属种,例如斑污小球腔菌(Leptosphaeria maculans);大毁壳属(Magnaporthe)属种,例如灰色大毁壳(Magnaporthe grisea);盘二孢属(Marsonina)属种,例如苹果褐斑病菌(Marsoninamali);微座孢属(Microdochium)属种,例如雪霉微座孢(Microdochium nivale);球腔菌属(Mycosphaerella)属种,例如禾生球腔菌(Mycosphaerella graminicola)、落花生球腔菌(Mycosphaerella arachidicola)和斐济球腔菌(Mycosphaerella fijiensis);暗球腔菌(Phaeosphaeria)属种,例如颖枯暗球腔菌(Phaeosphaeria nodorum);核腔菌属(Pyrenophora)属种,例如圆核腔菌(Pyrenophora teres)、偃麦草核腔菌(Pyrenophoratritici repentis);柱隔孢属(Ramularia)属种,例如辛加柱隔孢(Ramularia collo-cygni)或白斑柱隔孢(Ramularia areola);喙孢属(Rhynchosporium)属种,例如黑麦喙孢(Rhynchosporium secalis);针孢属(Septoria)属种,例如芹菜小壳针孢(Septoriaapii)、番茄壳针孢(Septoria lycopersii);毛座腔菌属(Setosphaeria)属种,例如玉米大斑病菌(Setosphaeria turcica);核盘菌属(Sclerotinia)属种,例如核盘菌(Sclerotiniasclerotiorum);壳多孢属(Stagonospora)属种,例如颖枯壳针孢(Stagonosporanodorum);匍柄霉属(Stemphylium)属种,例如膨胀匐柄霉(Stemphylium vesicarium);核瑚菌属(Typhula)属种,例如肉孢核瑚菌(Typhula incarnata);黑星菌属(Venturia)属种,例如苹果黑星病菌(Venturia inaequalis);
由下述病原体引起的根和茎病害:例如伏革菌属(Corticium)属种,例如禾伏革菌(Corticium graminearum);镰孢属(Fusarium)属种,例如尖镰孢(Fusarium oxysporum);顶囊壳菌属(Gaeumannomyces)属种,例如禾顶囊壳(Gaeumannomyces graminis);盘二孢属(Marsonina)属种,例如苹果褐斑病菌(Marsonina mali);丝核菌属(Rhizoctonia)属种,例如立枯丝核菌(Rhizoctonia solani);帚枝杆孢属(Sarocladium),例如稻帚枝杆孢(Sarocladium oryzae)、小核菌属(Sclerotium),例如稻腐小核菌(Sclerotium oryzae)、Tapesia属种,例如Tapesia acuformis;根串珠霉属(Thielaviopsis)属种,例如根串珠霉(Thielaviopsis basicola);
由下述病原体引起的肉穗花序或圆锥花序病害(包括玉米穗轴):例如链格孢属(Alternaria)属种,例如链格孢属(Alternaria spp.);曲霉属(Aspergillus)属种,例如黄曲霉(Aspergillus flavus);枝孢属(Cladosporium)属种,例如枝孢样枝孢霉(Cladosporiumcladosporioides);麦角菌属(Claviceps)属种,例如麦角菌(Clavicepspurpurea);镰孢属(Fusarium)属种,例如黄色镰孢(Fusariumculmorum);赤霉属(Gibberella)属种,例如玉蜀黍赤霉(Gibberella zeae);小画线壳属(Monographella)属种,例如雪腐小画线壳(Monographella nivalis);Stagnospora属种,例如Stagnosporanodorum;
由以下病原体引起的果腐病:例如,曲霉属(Aspergillus)属种,例如黄曲霉(Aspergillus flavus);葡萄孢属(Botrytis)属种,例如灰霉菌(Botrytis cinerea);链核盘菌属(Monilinia)属种,例如核果链核盘菌(Monilinia laxa);青霉属(Penicillium)属种,例如扩展青霉(Penicillium expansum)或产紫青霉(Penicillium purpurogenum);拟茎点霉属(Phomopsis)属种,例如葡萄拟茎点霉菌(Phomopsis viticola);根霉属(Rhizopus)属种,例如葡茎根霉菌(Rhizopus stolonifer);核盘菌属(Sclerotinia)属种,例如核盘菌(Sclerotinia sclerotiorum);轮枝孢属(Verticilium)属种,例如黑白轮枝菌(Verticilium alboatrum);
由下述病原体引起的种传腐烂和土传腐烂和萎蔫病害,以及幼苗病害:例如链格孢属(Alternaria)属种,例如芸薹链格孢(Alternaria brassicicola);丝囊霉属(Aphanomyces)属种,例如根霉丝囊霉(Aphanomyces euteiches);壳二胞属(Ascochyta)属种,例如兵豆壳二孢(Ascochyta lentis);曲霉属(Aspergillus)属种,例如黄曲霉(Aspergillus flavus);枝孢属(Cladosporium)属种,例如草本枝孢霉(Cladosporiumherbarum);旋孢腔菌属(Cochliobolus)属种,例如禾旋孢腔菌(Cochliobolus sativus)(分生孢子形式:内脐蠕孢属(Drechslera),离蠕孢属(Bipolaris)同义词:长蠕孢菌(Helminthosporium));炭疽菌属(Colletotrichum)属种,例如毛核炭疽菌(Colletotrichum coccodes);镰孢属(Fusarium)属种,例如黄色镰孢(Fusariumculmorum);赤霉属(Gibberella)属种,例如玉蜀黍赤霉(Gibberella zeae);壳球孢属(Macrophomina)属种,例如菜豆壳球孢(Macrophomina phaseolina);微座孢属(Microdochium)属种,例如雪霉微座孢(Microdochium nivale);小画线壳属(Monographella)属种,例如雪腐小画线壳(Monographella nivalis);青霉属(Penicillium)属种,例如扩展青霉(Penicillium expansum);茎点霉属(Phoma)属种,例如黑胫茎点霉(Phoma lingam);拟茎点霉属(Phomopsis)属种,例如大豆拟茎点霉(Phomopsissojae);核腔菌属(Pyrenophora)属种,例如麦类核腔菌(Pyrenophora graminea);梨孢属(Pyricularia)属种,例如稻梨孢(Pyricularia oryzae);丝核菌属(Rhizoctonia)属种,例如立枯丝核菌(Rhizoctonia solani);根霉属(Rhizopus)属种,例如稻根霉菌(Rhizopusoryzae);小核菌属(Sclerotium)属种,例如齐整小核菌(Sclerotium rolfsii);壳针孢属(Septoria)属种,例如颖枯壳针孢(Septoria nodorum);核瑚菌属(Typhula)属种,例如肉孢核瑚菌(Typhula incarnata);轮枝菌属(Verticillium)属种,例如大丽花轮枝孢(Verticillium dahliae);
镰刀菌属(Fusarium)属种,例如金黄尖镰孢(Fusarium oxysporum);
大豆病害:
由以下病原体引起的叶、茎、荚和种子的真菌病害:例如链格孢属叶斑病(Alternaria leaf spot)(Alternaria spec.atrans tenuissima)、炭疽病(Anthracnose)(Colletotrichum gloeosporoides dematium var.truncatum)、褐斑病(大豆壳针孢(Septoria glycines))、尾孢菌叶斑病和叶枯病(Cercospora leaf spot and blight)(菊池尾孢(Cercospora kikuchii))、笄霉属叶枯病(Choanephora leaf blight)(Choanephora infundibulifera trispora(同义词))、Dactuliophora叶斑病(Dactuliophora glycines)、大豆霜霉病(downy mildew)(东北霜霉(Peronosporamanshurica))、内脐蠕孢属枯萎病(Drechslera blight)(Drechslera glycini)、大豆灰斑病(frogeye leaf spot)(大豆尾孢(Cercospora sojina))、小光壳属叶斑病(Leptosphaerulina leaf spot)(三叶草小光壳(Leptosphaerulina trifolii))、白粉病(Leveillula powdery mildew)(鞑靼内丝白粉菌(Leveillula Taurica))、叶点霉属叶斑病(Phyllostica leaf spot)(大豆生叶点霉(Phyllosticta sojaecola))、荚和茎枯萎病(大豆拟茎点霉(Phomopsis sojae))、白粉病(Microsphaera diffusa)、棘壳孢属叶斑病(Pyrenochaeta leaf spot)(大豆红叶斑病菌(Pyrenochaeta glycines)、气生丝核菌(rhizoctonia aerial)、叶枯病和立枯病(foliage and web blight)(立枯丝核菌(Rhizoctonia solani))、疮痂病(scab)(大豆痂圆孢(Sphaceloma glycines))、匍柄霉属叶枯病(stemphylium leaf blight)(匍柄霉(Stemphylium botryosum))、猝死综合征(Fusarium virguliforme)、靶斑病(山扁豆生棒孢(Corynespora cassiicola));
由以下病原体引起的根部和茎部的真菌病害:例如黑色根腐病(black root rot)(野百合丽赤壳菌(Calonectria crotalariae))、炭腐病(菜豆生壳球孢(Macrophominaphaseolina))、镰孢枯萎病或萎蔫病、根腐病以及荚和根颈腐烂病(尖镰孢(Fusariumoxysporum)、直喙镰孢(Fusarium orthoceras)、半裸镰孢(Fusarium semitectum)、木贼镰孢(Fusarium equiseti)、mycoleptodiscus根腐病(Mycoleptodiscus terrestris)、新赤壳属病(neocosmospora)(侵菅新赤壳(Neocosmopspora vasinfecta))、荚和茎枯萎病(菜豆间座壳(Diaporthe phaseolorum))、茎溃疡(stemcanker)(大豆北方茎溃疡病菌(Diaporthe phaseolorum var.caulivora))、茎褐腐病(大豆茎褐腐病菌(Phialophoragregata))、丝核菌属根腐病、茎腐病和立枯病(立枯丝核菌(Rhizoctonia solani))、核盘菌属茎腐病(核盘菌(Sclerotinia sclerotiorum))、核盘菌属白绢病(Sclerotiniarolfsii)、根串珠霉属根腐病(thielaviopsis root rot)(根串珠霉(Thielaviopsisbasicola))。
最优选地,本发明涉及式(I)化合物的多晶型B用于防治以下病害的用途:由白粉病病原体引起的病害,所述病原体为单囊壳属(Sphaerotheca)属种,如单囊壳白粉菌(Sphaerotheca fuliginea);
由以下病原体引起的叶斑枯病和叶萎蔫病病害:例如链格孢属(Alternaria)属种,例如茄链格孢(Alternaria solani)或苹果链格孢(Alternaria mali)或赤星霉(Alternaria alternata);尾孢属(Cercospora)属种,例如菾菜生尾孢(Cercosporabeticola);炭疽菌属(Colletotrichum)属种,例如菜豆炭疽菌(Colletotrichumlindemuthanium)或辣椒炭疽菌(Colletotrichum capsica)或尖孢炭疽菌(Colletotrichum acutatum);间座壳属(Diaporthe)属种,例如柑桔间座壳(Diaporthecitri);暗球腔菌(Phaeosphaeria)属种,例如颖枯暗球腔菌(Phaeosphaeria nodorum);核腔菌属(Pyrenophora)属种,例如圆核腔菌(Pyrenophora teres)、偃麦草核腔菌(Pyrenophora tritici repentis);针孢属(Septoria)属种,例如芹菜小壳针孢(Septoriaapii)、番茄壳针孢(Septoria lycopersii);
由下述病原体引起的根和茎病害:例如镰孢属(Fusarium)属种,例如尖镰孢(Fusarium oxysporum);
由下述病原体引起的肉穗花序或圆锥花序病害(包括玉米穗轴):例如链格孢属(Alternaria)属种,例如链格孢属(Alternaria spp.);镰孢属(Fusarium)属种,例如黄色镰孢(Fusarium culmorum);
葡萄孢属(Botrytis)属种,例如灰霉菌(Botrytis cinerea);由下述病原体引起的种传腐烂和土传腐烂和萎蔫病害,以及幼苗病害:例如链格孢属(Alternaria)属种,例如芸薹链格孢(Alternaria brassicicola);炭疽菌属(Colletotrichum)属种,例如毛核炭疽菌(Colletotrichum coccodes);镰孢属(Fusarium)属种,例如黄色镰孢(Fusariumculmorum);核腔菌属(Pyrenophora)属种,例如麦类核腔菌(Pyrenophora graminea);梨孢属(Pyricularia)属种,例如稻梨孢(Pyricularia oryzae);
镰刀菌属(Fusarium)属种,例如金黄尖镰孢(Fusarium oxysporum)。
真菌毒素
此外,式(I)化合物的多晶型B和包含其的组合物可减少采收材料以及由其所制得的食品和饲料中的真菌毒素的含量。特别地,真菌毒素包括但不限于以下:脱氧雪腐镰刀菌烯醇(deoxynivalenol,DON)、瓜萎镰菌醇(nivalenol)、15-Ac-DON、3-Ac-DON、T2-毒素和HT2-毒素、伏马菌素(fumonisin)、玉米赤霉烯酮(zearalenon)、串珠镰刀菌素(moniliformin)、镰刀菌素(fusarin)、蛇形菌素(diaceotoxyscirpenol,DAS)、白僵菌素(beauvericin)、恩镰孢菌素(enniatin)、层出镰孢菌素(fusaroproliferin)、镰刀菌醇(fusarenol)、赭曲毒素(ochratoxins)、棒曲霉素(patulin)、麦角生物碱(ergotalkaloid)和黄曲霉毒素(aflatoxin),所述毒素可由例如以下真菌产生:镰孢菌属(Fusarium)属种,例如锐顶镰刀菌(F.acuminatum)、F.asiaticum、燕麦镰刀菌(F.avenaceum)、克地镰刀菌(F.crookwellense)、黄色镰孢菌(F.culmorum)、禾谷镰刀菌(F.graminearum)(玉米赤霉(Gibberella zeae))、木贼镰刀菌(F.equiseti)、F.fujikoroi、香蕉镰刀菌(F.musarum)、尖孢镰刀菌(F.oxysporum)、再育镰刀菌(F.proliferatum)、梨孢镰刀菌(F.poae)、F.pseudograminearum、接骨木镰刀菌(F.sambucinum)、藤草镰刀菌(F.scirpi)、半裸镰刀菌(F.semitectum)、茄病镰刀菌(F.solani)、拟枝孢镰刀菌(F.sporotrichoides)、F.langsethiae、胶孢镰刀菌(F.subglutinans)、三线镰刀菌(F.tricinctum)、串珠镰刀菌(F.verticillioides)等;以及曲霉属属种,例如黄曲霉(A.flavus)、寄生曲霉(A.parasiticus)、红绶曲霉(A.nomius)、赭曲霉(A.ochraceus)、棒曲霉(A.clavatus)、土曲霉(A.terreus)、杂色曲霉(A.versicolor);青霉属(Penicillium)属种,例如疣孢青霉(P.verrucosum)、鲜绿青霉(P.viridicatum)、橘青霉(P.citrinum)、扩展青霉(P.expansum)、棒形青霉(P.claviforme)、娄地青霉(P.roqueforti);麦角菌属(Claviceps)属种,例如紫麦角菌(C.purpurea)、梭形麦角菌(C.fusiformis)、雀稗麦角菌(C.paspali)、C.africana;葡萄穗霉属(Stachybotrys)属种及其他。
材料保护
式(I)化合物的多晶型B和包含其的组合物还可用于材料保护中,尤其是用于保护工业材料免受植物病原性真菌的攻击和破坏。
此外,式(I)化合物的多晶型B和包含其的组合物可单独或与其他活性成分结合用作防污组合物。
在本文中,工业材料应理解为意指为了工业应用而制备的无生命材料。例如,可以被保护免受微生物蚀变或破坏的工业材料可为粘着剂、胶水、纸张、壁纸和木板/硬纸板、纺织品、地毯、皮革、木材、纤维和薄纱、油漆和塑料制品、冷却润滑剂和可被微生物侵染或破坏的其他材料。可被微生物的增殖损害的生产设备和建筑物的部件(例如冷却水回路、冷却和加热系统以及通风和空调单元)也包括在待保护的材料的范围内。在本发明的范围内,工业材料优选包括粘着剂、胶料(size)、纸张和卡片、皮革、木材、油漆、冷却润滑剂和传热流体,更优选木材。
式(I)化合物的多晶型B和包含其的组合物可预防多种不良影响,例如腐烂、腐坏、变色、褪色或发霉。
在处理木材的情况下,式(I)化合物的多晶型B和包含其的组合物还可用来抵抗易在木材表面或内部生长的真菌病害。
木材意指所有类型的木材品种以及用于建造的该木材的所有类型的加工品,例如实木、高密度木材、叠层木板(laminated wood)和胶合板(plywood)。此外,式(I)化合物的多晶型B和包含其的组合物可用于保护会接触到盐水或苦咸水的物体免受污染,特别是船体、筛、网、建筑物、系泊设备和信号系统。
式(I)化合物的多晶型B和包含其的组合物也可用于保护贮存物。贮存物应当理解为意指植物来源或动物来源的天然物质或其加工产品,其为天然来源的并且需要长期保护。植物来源的贮存物例如植物或植物部位(如茎、叶、块茎、种子、果实、谷粒)可在刚采收或通过(预)干燥、湿润、粉碎、研磨、压榨或烘焙加工后进行保护。贮存物还包括木材,包括未加工的木材(例如建筑木材、电线杆和栅栏)或成品形式的木材(例如家具)。动物来源的贮存物为例如兽皮、皮革、毛皮和毛发。式(I)化合物的多晶型B和包含其的组合物可预防多种不良影响,例如腐烂、腐坏、变色、褪色或发霉。
能够降解或改变工业材料的微生物包括例如细菌、真菌、酵母、藻类及粘液生物(slime organism)。式(I)化合物的多晶型B和包含其的组合物优选作用于真菌,尤其是霉菌、使木材变色和破坏木材的真菌(子囊菌(Ascomycete)、担子菌(Basidiomycete)、半知菌(Deuteromycete)和接合菌(Zygomycete))以及作用于粘液生物和藻类。实例包括以下属的微生物:链格孢属(Alternaria),例如细链格孢(Alternaria tenuis);曲霉属(Aspergillus),例如黑曲霉(Aspergillus niger);毛壳菌属(Chaetomium),例如球毛壳菌(Chaetomium globosum);粉孢革菌属(Coniophora),例如粉孢革菌(Coniophorapuetana);香菇属(Lentinus),例如虎皮香菇(Lentinus tigrinus);青霉属(Penicillium),例如灰绿青霉(Penicillium glaucum);多孔菌属(Polyporus),例如变色多孔菌(Polyporus versicolor);短梗霉属(Aureobasidium),例如出芽短梗霉(Aureobasidium pullulans);核茎点属(Sclerophoma),例如Sclerophoma pityophila;木霉属(Trichoderma),例如绿色木霉;蛇口壳属(Ophiostoma spp.)、长喙壳属(Ceratocystis spp.)、腐质霉属(Humicola spp.)、彼得壳属(Petriella spp.)、毛束霉属(Trichurus spp.)、革盖菌属(Coriolus spp.)、粘褶菌属(Gloeophyllum spp.)、侧耳属(Pleurotus spp.)、卧孔菌属(Poria spp.)、干朽菌属(Serpula spp.)和干酪菌属(Tyromyces spp.)、枝孢属(Cladosporium spp.)、拟青霉属、毛霉属、埃希氏菌属(Escherichia),例如大肠杆菌(Escherichia coli);假单胞菌属(Pseudomonas),例如绿脓假单胞菌(Pseudomonas aeruginosa);葡萄球菌属(Staphylococcus),例如金黄色酿脓葡萄球菌(Staphylococcus aureus)、念珠菌属和酵母属(Saccharomyces spp.),例如酿酒酵母(Saccharomyces cerevisae)。植物保护剂可以另外包含一种或多种其他活性成分,如杀真菌剂、杀细菌剂、杀螨剂、杀线虫剂、杀昆虫剂、生物防治剂或除草剂。与肥料、生长调节剂、安全剂、硝化抑制剂、半化学物和/或其他农业上有益的制剂的混合物也是可能的。这可以使活性谱拓宽或者防止产生抗性。
在另一个实施方案中,本发明还涉及包含式(I)化合物的多晶型B的植物保护剂,其还包括一种或多种选自以下物质的其他活性物质:杀真菌剂、杀昆虫剂、除草剂、杀螨剂、安全剂和/或植物生长调节剂。
本文中以其通用名称描述的活性化合物是已知的,并且记载于例如《农药手册》(“The Pesticide Manual”第17版,British Crop Protection Council 2015)中,或者可在互联网(如http://www.alanwood.net/pesticides)上找到。
可以与本发明的化合物和组合物混合的杀真菌剂的实例为:
1)麦角固醇生物合成的抑制剂,例如(1.001)环丙唑醇(cyproconazole)、(1.002)苯醚甲环唑(difenoconazole)、(1.003)氟环唑(epoxiconazole)、(1.004)腈苯唑(fenbuconazole)、(1.005)环酰菌胺(fenhexamid)、(1.006)苯锈啶(fenpropidin)、(1.007)丁苯吗啉(fenpropimorph)、(1.008)胺苯吡菌酮(fenpyrazamine)、(1.009)氟吡菌唑(Fluoxytioconazole)、(1.010)氟喹唑(fluquinconazole)、(1.011)粉唑醇(flutriafol)、(1.012)己唑醇(hexaconazole)、(1.013)抑霉唑(imazalil)、(1.014)抑霉唑硫酸盐(imazalil sulfate)、(1.015)种菌唑(ipconazole)、(1.016)伊芬三氟康唑(ipfentrifluconazole)、(1.017)氯氟醚菌唑(mefentrifluconazole)、(1.018)叶菌唑(metconazole)、(1.019)腈菌唑(myclobutanil)、(1.020)多效唑(paclobutrazol)、(1.021)戊菌唑(penconazole)、(1.022)咪鲜胺(prochloraz)、(1.023)丙环唑(propiconazole)、(1.024)丙硫菌唑(prothioconazole)、(1.025)啶菌噁唑(pyrisoxazole)、(1.026)螺环菌胺(spiroxamine)、(1.027)戊唑醇(tebuconazole)、(1.028)四氟醚唑(tetraconazole)、(1.029)三唑醇(triadimenol)、(1.030)十三吗啉(tridemorph)、(1.031)灭菌唑(triticonazole)、(1.032)(1R,2S,5S)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊醇、(1.033)(1S,2R,5R)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊醇、(1.034)(2R)-2-(1-氯环丙基)-4-[(1R)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.035)(2R)-2-(1-氯环丙基)-4-[(1S)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.036)(2R)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.037)(2S)-2-(1-氯环丙基)-4-[(1R)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.038)(2S)-2-(1-氯环丙基)-4-[(1S)-2,2-二氯环丙基]-1-(1H-1,2,4-三唑-1-基)丁-2-醇、(1.039)(2S)-2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-三唑-1-基)丙-2-醇、(1.040)(R)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.041)(S)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.042)[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(1.043)1-({(2R,4S)-2-[2-氯-4-(4-氯苯氧基)苯基]-4-甲基-1,3-二氧戊环-2-基}甲基)-1H-1,2,4-三唑、(1.044)1-({(2S,4S)-2-[2-氯-4-(4-氯苯氧基)苯基]-4-甲基-1,3-二氧戊环-2-基}甲基)-1H-1,2,4-三唑、(1.045)1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫氰酸酯、(1.046)1-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫氰酸酯、(1.047)1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑-5-基硫氰酸酯、(1.048)2-[(2R,4R,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.049)2-[(2R,4R,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.050)2-[(2R,4S,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.051)2-[(2R,4S,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.052)2-[(2S,4R,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.053)2-[(2S,4R,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.054)2-[(2S,4S,5R)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.055)2-[(2S,4S,5S)-1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.056)2-[1-(2,4-二氯苯基)-5-羟基-2,6,6-三甲基庚-4-基]-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.057)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、(1.058)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、(1.059)2-{[3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.060)2-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.061)2-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-2,4-二氢-3H-1,2,4-三唑-3-硫酮、(1.062)3-[2-(1-氯环丙基)-3-(3-氯-2-氟-苯基)-2-羟基-丙基]咪唑-4-腈、(1.063)5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊醇、(1.064)5-(烯丙基硫基)-1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑、(1.065)5-(烯丙基硫基)-1-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑、(1.066)5-(烯丙基硫基)-1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)环氧乙烷-2-基]甲基}-1H-1,2,4-三唑、(1.067)2-[2-氯-4-(4-氯苯氧基)苯基]-2-羟基-3-(1H-1,2,4-三唑-1-基)丙酸甲酯、(1.068)N'-(2,5-二甲基-4-(2-甲苄基)苯基)-N-乙基-N-甲脒甲酯、(1.069)N'-(2-氯-4-(4-氰苄基)-5-甲基-苯基)-N-乙基-N-氰苄基、(1.070)N'-(2-氯-4-(4-甲氧基-苄基)-5-甲苯基)-N-乙基-N-甲脒甲酯、(1.071)N'-(2-氯-5-甲基-4-苯氧基苯基)-N-乙基-N-甲基亚氨基甲酰胺,(1.072)N'-(4-苄基-2-氯-5-甲苯基)-N-乙基-N-甲脒甲酯、(1.073)N'-[2-氯-4-(2-氟苯氧基)-5-甲苯基]-N-乙基-N-甲基亚氨基甲酰胺、(1.074)N'-[5-溴-6-(2,3-二氢-1H-茚-2-基氧基)-2-甲基吡啶-3-基]-N-乙基-N-甲基亚氨基甲酰胺、(1.075)N'-{4-[(4,5-二氯-1,3-噻唑-2-基)氧基]-2,5-二甲基苯基}-N-乙基-N-甲基亚氨基甲酰胺、(1.076)N'-{5-溴-2-甲基-6-[(1-丙氧基丙-2-基)氧基]吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.077)N'-{5-溴-6-[(1R)-1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.078)N'-{5-溴-6-[(1S)-1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.079)N'-{5-溴-6-[(顺式-4-异丙基环己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.080)N'-{5-溴-6-[(反式-4-异丙基环己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.081)N'-{5-溴-6-[1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亚氨基甲酰胺、(1.082)N-异丙基-N'-[5-甲氧基-2-甲基-4-(2,2,2-三氟-1-羟基-1-苯基乙基)苯基]-N-甲基亚氨基甲酰胺、(1.083)对-甲苯基甲基4-[(E)-[乙基(甲基)氨基]亚甲基氨基]-2,5-二甲基-苯酸盐。
2)呼吸链复合物I或II的抑制剂,例如(2.001)苯并烯氟菌唑(benzovindiflupyr)、(2.002)联苯吡菌胺(bixafen)、(2.003)啶酰菌胺(boscalid)、(2.004)萎锈灵(carboxin)、(2.005)三氟吡啶胺(cyclobutrifluram)、(2.006)氟苯虫酰胺(flubeneteram)、(2.007)氟茚唑菌胺(fluindapyr)、(2.008)氟吡菌酰胺(fluopyram)、(2.009)氟酰胺(flutolanil)、(2.010)氟唑菌酰胺(fluxapyroxad)、(2.011)呋吡菌胺(furametpyr)、(2.012)inpyrfluxam、(2.013)噻吩酰菌酮(Isofetamid)、(2.014)isoflucypram、(2.015)吡唑萘菌胺(isopyrazam)、(2.016)氟唑菌苯胺(penflufen)、(2.017)吡噻菌胺(penthiopyrad)、(2.018)氟唑菌酰羟胺(pydiflumetofen)、(2.019)pyrapropoyne、(2.020)Pyraziflumid、(2.021)氟唑环菌胺(sedaxane)、(2.022)噻呋酰胺(Thifluzamide)(又名噻氟菌胺(trifluzamide))、(2.023)5,8-二氟-N-[2-(2-氟-4-{[4-(三氟甲基)吡啶-2-基]氧基}苯基)乙基]喹唑啉-4-胺、(2.024)5-氯-N-[2-[1-(4-氯苯基)吡唑-3-基]乙氧基]-6-乙基-嘧啶-4-胺、(2.025)N-[2-[1-(4-氯苯基)吡唑-3-基]乙氧基]喹唑啉-4-胺、(2.026)1,3-二甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺、(2.027)1,3-二甲基-N-[(3R)-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1H-吡唑-4-甲酰胺、(2.028)1,3-二甲基-N-[(3S)-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1H-吡唑-4-甲酰胺、(2.029)1-甲基-3-(三氟甲基)-N-[2'-(三氟甲基)联苯基-2-基]-1H-吡唑-4-甲酰胺、(2.030)2-氟-6-(三氟甲基)-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)苯甲酰胺、(2.031)3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺、(2.032)3-(二氟甲基)-1-甲基-N-[(3S)-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1H-吡唑-4-甲酰胺、(2.033)3-(二氟甲基)-N-[(3R)-7-氟-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲酰胺、(2.034)3-(二氟甲基)-N-[(3S)-7-氟-1,1,3-三甲基-2,3-二氢-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲酰胺、(2.035)N-[(1R,4S)-9-(二氯亚甲基)-1,2,3,4-四氢-1,4-桥亚甲基萘(methanonaphthalen)-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺、(2.036)N-[(1S,4R)-9-(二氯亚甲基)-1,2,3,4-四氢-1,4-桥亚甲基萘-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺、(2.037)N-[1-(2,4-二氯苯基)-1-甲氧基丙-2-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲酰胺、(2.038)N-[rac-(1S,2S)-2-(2,4-二氯苯基)环丁基]-2-(三氟甲基)烟酰胺。
3)呼吸链复合物III的抑制剂,例如(3.001)唑嘧菌胺(ametoctradin)、(3.002)吲唑磺菌胺(amisulbrom)、(3.003)嘧菌酯(azoxystrobin)、(3.004)甲香菌酯(coumethoxystrobin)、(3.005)丁香菌酯(coumoxystrobin)、(3.006)氰霜唑(cyazofamid)、(3.007)醚菌胺(dimoxystrobin)、(3.008)烯肟菌酯(enoxastrobin)、(3.009)噁唑菌酮(famoxadone)、(3.010)咪唑菌酮(fenamidone)、(3.011)fenpicoxamid、(3.012)florylpicoxamid、(3.013)氟菌螨酯(flufenoxystrobin)、(3.014)氟嘧菌酯(fluoxastrobin)、(3.015)醚菌酯(kresoxim-methyl)、(3.016)mandestrobin、(3.017)metarylpicoxamid、(3.018)苯氧菌胺(metominostrobin)、(3.019)metyltetraprole、(3.020)肟醚菌胺(orysastrobin)、(3.021)啶氧菌酯(picoxystrobin)、(3.022)唑菌胺酯(pyraclostrobin)、(3.023)唑胺菌酯(pyrametostrobin)、(3.024)唑菌酯(pyraoxystrobin)、(3.025)肟菌酯(trifloxystrobin)、(3.026)(2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-氟-2-苯基乙烯基]氧基}苯基)亚乙基]氨基}氧基)甲基]苯基}-2-(甲氧基亚氨基)-N-甲基乙酰胺、(3.027)(2E,3Z)-5-{[1-(4-氯-2-氟苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亚氨基)-N,3-二甲基戊-3-烯酰胺、(3.028)(2E,3Z)-5-{[1-(4-氯苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亚氨基)-N,3-二甲基戊-3-烯酰胺、(3.029)(2R)-2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙酰胺、(3.030)(2S)-2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙酰胺、(3.031)(Z,2E)-5-[1-(2,4-二氯苯基)吡唑-3-基]氧基-2-甲氧基亚氨基-N,3-二甲基戊-3-烯酰胺、(3.032)(Z)-2-(5-环己基-2-甲基-苯氧基)-3-甲氧基-丙-2-烯酸甲酯、(3.033)(Z)-2-(5-环戊基-2-甲基-苯氧基)-3-甲氧基-丙-2-烯酸甲酯、(3.034)(Z)-3-甲氧基-2-[2-甲基-5-(3-丙基吡唑-1-基)苯氧基]丙-2-烯酸甲酯、(3.035)(Z)-3-甲氧基-2-[2-甲基-5-[3-(三氟甲基)甲氧基]苯氧基]丙-2-烯酸甲酯、(3.036){5-[3-(2,4-二甲基苯基)-1H-吡唑-1-基]-2-甲基苄基}氨基甲酸甲酯、(3.037)(2S)-2-[(3-羟基-4-甲氧基-吡啶-2-羰基)氨基]丙酸[rac-2-(4-溴-7-氟-吲哚-1-基)-1-甲基-丙基]酯、(3.038)(2S)-2-[(3-乙酸基-4-甲氧基-吡啶-2-羰基)氨基]丙酸[rac-2-(7-溴-4-氟-吲哚-1-基)-1-甲基-丙基]酯、(3.039)(2S)-2-[(3-羟基-4-甲氧基-吡啶-2-羰基)氨基]丙酸[rac-2-(7-溴吲哚-1-基)-1-甲基-丙基]酯、(3.040)(2S)-2-[(3-羟基-4-甲氧基-吡啶-2-羰基)氨基]丙酸[rac-2-(3,5-二氯-2-吡啶基)-1-甲基-丙基]酯、(3.041)(2S)-2-[(3-乙酸基-4-甲氧基-吡啶-2-羰基)氨基]丙酸[(1S)-1-[1-(1-萘基)环丙基]乙基]酯、(3.042)(2S)-2-[(3-羟基-4-甲氧基-吡啶-2-羰基)氨基]丙酸[(1S)-1-[1-(1-萘基)环丙基]乙基]酯、(3.043)(2S)-2-[[3-(乙酸基甲氧基)-4-甲氧基-吡啶-2-羰基]氨基]丙酸[(1S)-1-[1-(1-萘基)环丙基]乙基]酯、(3.044)2-甲基丙酸[2-[[(1S)-2-[(1RS,2SR)-2-(3,5-二氯-2-吡啶基)-1-甲基-丙基]-1-甲基-2-氧代-乙基]氨基甲酰]-4-甲氧基-3-吡啶基]氧基甲基酯、(3.045)N-(3-乙基-3,5,5-三甲基环己基)-3-甲酰胺基-2-羟基苯甲酰胺。
4)有丝分裂和细胞分裂的抑制剂,例如(4.001)多菌灵(carbendazim)、(4.002)乙霉威(diethofencarb)、(4.003)噻唑菌胺(ethaboxam)、(4.004)氟吡菌胺(fluopicolide)、(4.005)氟醚菌酰胺(fluopimomide)、(4.006)苯菌酮(metrafenone)、(4.007)戊菌隆(pencycuron)、(4.008)pyridachlometyl、(4.009)pyriofenone(chlazafenone)、(4.010)噻菌灵(thiabendazole)、(4.011)甲基硫菌灵(thiophanate-methyl)、(4.012)苯酰菌胺(zoxamide)、(4.013)3-氯-5-(4-氯苯基)-4-(2,6-二氟苯基)-6-甲基哒嗪、(4.014)3-氯-5-(6-氯吡啶-3-基)-6-甲基-4-(2,4,6-三氟苯基)哒嗪、(4.015)4-(2-溴-4-氟苯基)-N-(2,6-二氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.016)4-(2-溴-4-氟苯基)-N-(2-溴-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.017)4-(2-溴-4-氟苯基)-N-(2-溴苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.018)4-(2-溴-4-氟苯基)-N-(2-溴-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.019)4-(2-溴-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.020)4-(2-溴-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.021)4-(2-氯-4-氟苯基)-N-(2,6-二氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.022)4-(2-氯-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.023)4-(2-氯-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.024)4-(2-氯-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.025)4-(4-氯苯基)-5-(2,6-二氟苯基)-3,6-二甲基哒嗪、(4.026)N-(2-溴-6-氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.027)N-(2-溴苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(4.028)N-(4-氯-2,6-二氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺。
5)能够具有多位点作用的化合物,例如(5.001)波尔多混合剂(bordeauxmixture)、(5.002)敌菌丹(captafol)、(5.003)克菌丹(captan)、(5.004)百菌清(chlorothalonil)、(5.005)氢氧化铜、(5.006)环烷酸铜(copper naphthenate)、(5.007)氧化铜、(5.008)氯氧化铜(copper oxychloride)、(5.009)硫酸铜(2+)、(5.010)二噻农(dithianon)、(5.011)多果定(dodine)、(5.012)灭菌丹(folpet)、(5.013)代森锰锌(mancozeb)、(5.014)代森锰(maneb)、(5.015)代森联(metiram)、(5.016)代森联锌(metiram zinc)、(5.017)喹啉铜(oxine-copper)、(5.018)丙森锌(propineb)、(5.019)硫和包括多硫化钙的硫制剂、(5.020)福美双(thiram)、(5.021)代森锌(zineb)、(5.022)福美锌(ziram)、(5.023)6-乙基-5,7-二氧代-6,7-二氢-5H-吡咯并[3',4':5,6][1,4]二噻英并[2,3-c][1,2]噻唑-3-甲腈。
6)能诱导宿主防御的化合物,例如(6.001)苯并噻二唑(acibenzolar-S-methyl)、(6.002)三乙膦酸铝(fosetyl-aluminium)、(6.003)三乙膦酸钙(fosetyl-calcium)、(6.004)三乙膦酸钠(fosetyl-sodium)、(6.005)异噻菌胺(isotianil)、(6.006)亚磷酸及其盐、(6.007)烯丙苯噻唑(probenazole)、(6.008)噻酰菌胺(tiadinil)。
7)氨基酸和/或蛋白质生物合成的抑制剂,例如(7.001)嘧菌环胺(cyprodinil)、(7.002)春雷霉素(kasugamycin)、(7.003)春雷霉素盐酸盐水合物(kasugamycinhydrochloride hydrate)、(7.004)氧四环素(oxytetracycline)、(7.005)嘧霉胺(pyrimethanil)。
8)ATP产生的抑制剂,例如(8.001)硅噻菌胺(silthiofam)。
9)细胞壁合成的抑制剂,例如(9.001)苯噻菌胺(benthiavalicarb)、(9.002)烯酰吗啉(dimethomorph)、(9.003)氟吗啉(flumorph)、(9.004)异丙菌胺(iprovalicarb)、(9.005)双炔酰菌胺(mandipropamid)、(9.006)吡吗啉(pyrimorph)、(9.007)霜霉灭(valifenalate)、(9.008)(2E)-3-(4-叔丁基苯基)-3-(2-氯吡啶-4-基)-1-(吗啉-4-基)丙-2-烯-1-酮、(9.009)(2Z)-3-(4-叔丁基苯基)-3-(2-氯吡啶-4-基)-1-(吗啉-4-基)丙-2-烯-1-酮。
10)脂质合成或转运或膜合成的抑制剂,例如(10.001)fluoxapiprolin、(10.002)纳他霉素(natamycin)、(10.003)氟噻唑吡乙酮(oxathiapiprolin)、(10.004)霜霉威(propamocarb)、(10.005)霜霉威盐酸盐(propamocarb hydrochloride)、(10.006)霜霉威乙膦酸盐(propamocarb-fosetylate)、(10.007)甲基立枯磷(tolclofos-methyl)、(10.008)1-(4-{4-[(5R)-5-(2,6-二氟苯基)-4,5-二氢-1,2-噁唑-3-基]-1,3-噻唑-2-基}哌啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(10.009)1-(4-{4-[(5S)-5-(2,6-二氟苯基)-4,5-二氢-1,2-噁唑-3-基]-1,3-噻唑-2-基}哌啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(10.010)2-[3,5-双(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-丙-2-炔-1-基氧基)苯基]-4,5-二氢-1,2-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(10.011)2-[3,5-双(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氯-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氢-1,2-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(10.012)2-[3,5-双(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氟-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氢-1,2-噁唑-3-基}-1,3-噻唑-2-基)哌啶-1-基]乙酮、(10.013)2-{(5R)-3-[2-(1-{[3,5-双(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氢-1,2-噁唑-5-基}-3-氯苯基甲磺酸酯、(10.014)2-{(5S)-3-[2-(1-{[3,5-双(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氢-1,2-噁唑-5-基}-3-氯苯基甲磺酸酯、(10.015)2-{3-[2-(1-{[3,5-双(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-4,5-二氢-1,2-噁唑-5-基}苯基甲磺酸酯、(10.016)甲磺酸3-[2-(1-{[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-1,5-二氢-2,4-苯并二氮杂卓-6-基}酯、(10.017)甲磺酸9-氟-3-[2-(1-{[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-1,5-二氢-2,4-苯并二氧杂卓-6-基酯、(10.018)甲磺酸3-[2-(1-{[3,5-双(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-1,5-二氢-2,4-苯并二氧杂卓-6-基酯、(10.019)甲磺酸3-[2-(1-{[3,5-双(二氟甲基)-1H-吡唑-1-基]乙酰基}哌啶-4-基)-1,3-噻唑-4-基]-9-氟-1,5-二氢-2,4-苯并二氧杂卓-6-基酯。
11)黑色素生物合成的抑制剂,例如(11.001)tolprocarb、(11.002)三环唑(tricyclazole)。
12)核酸合成的抑制剂,例如(12.001)苯霜灵(benalaxyl)、(12.002)精苯霜灵(benalaxyl-M、kiralaxyl)、(12.003)甲霜灵(metalaxyl)、(12.004)高效甲霜灵(metalaxyl-M)(精甲霜灵(mefenoxam))。
13)信号转导的抑制剂,例如(13.001)咯菌腈(fludioxonil)、(13.002)异菌脲(iprodione)、(13.003)腐霉利(procymidone)、(13.004)丙氧喹啉(proquinazid)、(13.005)喹氧灵(quinoxyfen)、(13.006)乙烯菌核利(vinclozolin)。
14)能够作为解偶联剂的化合物,例如(14.001)氟啶胺(fluazinam)、(14.002)消螨多(meptyldinocap)。
15)其他杀真菌剂,例如(15.001)脱落酸(abscisic acid)、(15.002)aminopyrifen、(15.003)苯噻硫氰(benthiazole)、(15.004)bethoxazin、(15.005)卡巴西霉素(capsimycin)、(15.006)香芹酮(carvone)、(15.007)灭螨猛(chinomethionat)、(15.008)氯吲哚酰肼(chloroinconazide)、(15.009)硫杂灵(cufraneb)、(15.010)环氟菌胺(cyflufenamid)、(15.011)霜脲氰(cymoxanil)、(15.012)环丙磺酰胺(cyprosulfamide)、(15.013)dipymetitrone、(15.014)D-塔格糖(D-tagatose)、(15.015)flufenoxadiazam、(15.016)flumetylsulforim、(15.017)flutianil、(15.018)ipflufenoquin、(15.019)异硫氰酸甲酯、(15.020)米多霉素(mildiomycin)、(15.021)福美镍(nickel dimethyldithiocarbamate)、(15.022)酞菌酯(nitrothal-isopropyl)、(15.023)oxyfenthiin、(15.024)五氯苯酚及盐、(15.025)四唑吡氨酯(picarbutrazox)、(15.026)quinofumelin、(15.027)异丁乙氧喹啉(tebufloquin)、(15.028)叶枯酞(tecloftalam)、(15.029)甲磺菌胺(tolnifanide)、(15.030)2-(6-苄基吡啶-2-基)喹唑啉、(15.031)2-[6-(3-氟-4-甲氧基苯基)-5-甲基吡啶-2-基]喹唑啉、(15.032)2-苯基苯酚及盐、(15.033)4-氨基-5-氟嘧啶-2-醇(互变异构形式:4-氨基-5-氟嘧啶-2(1H)-酮)、(15.034)4-氧代-4-[(2-苯基乙基)氨基]丁酸、(15.035)5-氨基-1,3,4-噻二唑-2-硫醇、(15.036)5-氯-N'-苯基-N'-(丙-2-炔-1-基)噻吩-2-磺酰肼、(15.037)5-氟-2-[(4-氟苄基)氧基]嘧啶-4-胺、(15.038)5-氟-2-[(4-甲基苄基)氧基]嘧啶-4-胺、(15.039){6-[({[(Z)-(1-甲基-1H-四唑-5-基)(苯基)亚甲基]氨基}氧基)甲基]吡啶-2-基}氨基甲酸丁-3-炔-1-基酯、(15.040)(2Z)-3-氨基-2-氰基-3-苯基丙烯酸乙酯、(15.041)2-[乙酰基-[2-乙基磺酰基-4-(三氟甲基)苯甲酰基]氨基]-5-(三氟甲氧基)苯酸甲酯、(15.042)N-乙酰基-N-[2-溴-4-(三氟甲氧基)苯基]-2-乙基磺酰基-4-(三氟甲基)苯甲酰胺、(15.043)吩嗪-1-甲酸、(15.044)3,4,5-三羟基苯甲酸丙酯、(15.045)喹啉-8-醇、(15.046)喹啉-8-醇硫酸酯(2:1)、(15.047)(2R)-2-苄基-N-(8-氟-2-甲基-3-喹啉基)-2,4-二甲基-戊酰胺、(15.048)(2S)-2-苄基-N-(8-氟-2-甲基-3-喹啉基)-2,4-二甲基-戊酰胺、(15.049)1-(4,5-二甲基-1H-苯并咪唑-1-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.050)1-(4,5-二甲基苯并咪唑-1-基)-4,4,5-三氟-3,3-二甲基-异喹啉、(15.051)1-(5-(氟甲基)-6-甲基-吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.052)1-(5,6-二甲基吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.053)1-(6-(二氟甲基)-5-甲氧基-吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.054)1-(6-(二氟甲基)-5-甲基-吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.055)1-(6,7-二甲基吡唑并[1,5-a]吡啶-3-基)-4,4,5-三氟-3,3-二甲基-3,4-异喹啉、(15.056)1-(6,7-二甲基吡唑并[1,5-a]吡啶-3-基)-4,4-二氟-3,3-二甲基-3,4-二氢异喹啉、(15.057)2-{2-氟-6-[(8-氟-2-甲基喹啉-3-基)氧基]苯基}丙-2-醇、(15.058)3-(4,4,5-三氟-3,3-二甲基-3,4-二氢异喹啉-1-基)喹啉、(15.059)3-(4,4-二氟-3,3-二甲基-3,4-二氢异喹啉-1-基)-8-氟喹啉、(15.060)3-(4,4-二氟-5,5-二甲基-4,5-二氢噻吩并[2,3-c]吡啶-7-基)喹啉、(15.061)3-(5-氟-3,3,4,4-四甲基-3,4-二氢异喹啉-1-基)喹啉、(15.062)4,4-二氟-3,3-二甲基-1-(4-甲基苯并咪唑-1-基)异喹啉、(15.063)4,4-二氟-3,3-二甲基-1-(6-甲基吡唑并[1,5-a]吡啶-3-基)异喹啉、(15.064)5-溴-1-(5,6-二甲基吡啶-3-基)-3,3-二甲基-3,4-二氢异喹啉、(15.065)7,8-二氟-N-[rac-1-苄基-1,3-二甲基-丁基]喹啉-3-甲酰胺、(15.066)8-氟-3-(5-氟-3,3,4,4-四甲基-3,4-二氢异喹啉-1-基)喹啉、(15.067)8-氟-3-(5-氟-3,3-二甲基-3,4-二氢异喹啉-1-基)喹啉、(15.068)8-氟-N-(4,4,4-三氟-2-甲基-1-苯基丁-2-基)喹啉-3-甲酰胺、(15.069)8-氟-N-[(1R)-1-[(3-氟苯基)甲基]-1,3-二甲基-丁基]喹啉-3-甲酰胺、(15.070)8-氟-N-[(1S)-1-[(3-氟苯基)甲基]-1,3-二甲基-丁基]喹啉-3-甲酰胺、(15.071)8-氟-N-[(2S)-4,4,4-三氟-2-甲基-1-苯基丁-2-基]喹啉-3-甲酰胺、(15.072)8-氟-N-[rac-1-[(3-8-氟-N-[(2S)-4,4,4-三氟-2-甲基-1-苯基丁-2-基]喹啉-3-甲酰胺)甲基]-1,3-二甲基-丁基]喹啉-3-甲酰胺、(15.073)9-氟-2,2-二甲基-5-(喹啉-3-基)-2,3-二氢-1,4-苯并氧氮杂卓、(15.074)N-(2,4-二甲基-1-苯基戊-2-基)-8-氟喹啉-3-甲酰胺、(15.075)N-[(1R)-1-苄基-1,3-二甲基-丁基]-7,8-二氟-喹啉-3-甲酰胺、(15.076)N-[(1S)-1-苄基-1,3-二甲基-丁基]-7,8-二氟-喹啉-3-甲酰胺、(15.077)N-[(2R)-2,4-二甲基-1-苯基戊-2-基)-8-氟喹啉-3-甲酰胺、(15.078)rac-2-苄基-N-(8-氟-2-甲基-3-喹啉基)-2,4-二甲基-戊酰胺、(15.079)1,1-二乙基-3-[[4-[5-(三氟甲基}-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.080)1,3-二甲氧基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.081)1-[[3-氟-4-(5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]氮杂环庚烷-2-酮、(15.082)1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]哌啶-2-酮、(15.083)1-甲氧基-1-甲基-3-[[4-[5-(三氟甲基}-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.084)1-甲氧基-3-甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.085)1-甲氧基-3-甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]脲、(15.086)2-(二氟甲基)-5-[2-[1-(2,6-二氟苯基)环丙氧基]嘧啶-5-基]-1,3,4-噁二唑、(15.087)2,2-二氟-N-甲基-2-[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]乙酰胺、(15.088)3,3-二甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]哌啶-2-酮、(15.089)3-乙基-1-甲氧基-1-[[4-[5-(三氟甲基)噁二唑-3-基]苯基]甲基]脲、(15.090)4,4-二甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]吡咯烷-2-酮、(15.091)4,4-二甲基-2-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]异噁唑啉-3-酮、(15.092)二甲基氨基甲酸4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基酯、15.093)5,5-二甲基-2-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]异噁唑啉-3-酮、(15.094)5-[5-(二氟甲基)-1,3,4-噁二唑-2-基]-N-[(1R)-1-(2,6-二氟苯基)乙基]嘧啶-2-胺、(15.095)5-[5-(二氟甲基)-1,3,4-噁二唑-2-基]-N-[(1R)-1-(2,6-二氟苯基)丙基]嘧啶-2-胺、(15.096)5-[5-(二氟甲基)-1,3,4-噁二唑-2-基]-N-[(1R)-1-(2-氟苯基)乙基]嘧啶-2-胺、(15.097)5-[5-(二氟甲基)-1,3,4-噁二唑-2-基]-N-[(1R)-1-(2-氟苯基)乙基]嘧啶-2-胺、(15.098)5-[5-(二氟甲基)-1,3,4-噁二唑-2-基]-N-[(1R)-1-(3,5-二氟苯基)乙基]嘧啶-2-胺、(15.099)5-[5-(二氟甲基)-1,3,4-噁二唑-2-基]-N-[(1R)-1-苯基乙基]嘧啶-2-胺、(15.100)5-[5-(二氟甲基)-1,3,4-噁二唑-2-基]-N-[1-(2-氟苯基)环丙基]嘧啶-2-胺、(15.101)5-甲基-1-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]吡咯烷-2-酮、(15.102)1-{4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苄基}-1H-吡唑-4-羧酸乙酯、(15.103){4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基}氨基甲酸甲酯、(15.104)N-(1-甲基环丙基)-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.105)N-(2,4-二氟苯基)-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.106)N,2-二甲氧基-N-[[4-[5-(三氟甲基}-1,2,4-噁二唑-3-基]苯基]甲基]丙酰胺、(15.107)N,N-二甲基-1-{4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苄基}-1H-1,2,4-三唑-3-胺、(15.108)N-[(E)-甲氧基亚氨基甲基]-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.109)N-[(E)-N-甲氧基-C-甲基-碳亚氨基]-4-(5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.110)N-[(Z)-甲氧基亚氨基甲基]-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.111)N-[(Z)-N-甲氧基-C-甲基-碳亚氨基]-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.112)N-[[2,3-二氟-4-[5-(N-[[2,3-)-1,2,4-噁二唑-3-基]苯基]甲基]-3,3,3-三氟-丙酰胺、(15.113)N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]丙酰胺、(15.114)N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]环丙烷甲酰胺、(15.115)N-{2,3-二氟-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苄基}丁酰胺、(15.116)N-{4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苄基}环丙烷甲酰胺、(15.117)N-{4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基}丙酰胺、(15.118)N-烯丙基-N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基)苯基]甲基]乙酰胺、(15.119)N-烯丙基-N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]丙酰胺、(15.120)N-乙基-2-甲基-N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基]丙酰胺、(15.121)N-甲氧基-N-[[4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基]甲基)环丙烷甲酰胺、(15.122)N-甲基-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺、(15.123)N-甲基-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]硫代苯甲酰胺、(15.124)N-甲基-N-苯基-4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯甲酰胺。
上文所述的(1)至(15)类的所有命名的混合组分可以游离化合物的形式存在,或者,如果它们的官能团能够成盐,则可以其农业上可接受的活性盐的形式存在。
本发明的化合物和组合物也可以与一种或多种生物防治剂结合。
如本文所使用的,术语“生物防治”被定义为通过使用或利用生物防治剂来防治有害生物,如植物病原性真菌和/或昆虫和/或螨虫和/或线虫。
如本文所使用的,术语“生物防治剂”被定义为非有害生物的生物和/或由这种生物产生的为生物防治目的的蛋白质或次生代谢物。第二种生物的突变体应包括在生物防治剂的定义内。术语“突变体”是指亲本菌株的变体,以及获得突变体或变体的方法,其中农药活性大于亲本菌株所表达的农药活性。本文中“亲本菌株”被定义为诱变前的原始菌株。为了获得这样的突变体,可以用化学品如N-甲基-N'-硝基-N-亚硝基胍、乙基甲砜,或用伽马射线、x-射线或紫外线照射,或用本领域技术人员熟知的其他方法进行处理亲本菌株。已知的生物防治剂机制包含通过在根部表面竞争真菌的空间来防治根部腐烂的肠道细菌。细菌毒素(如抗生素)已被用于防治病原体。所述毒素可以被分离出来并直接施用到植物上,或者可以施用细菌物种,使其原位产生该毒素。
“变种”是指具有本文所示的NRRL或ATCC登记号的所有识别特征的菌株,可被识别为具有在高严谨条件下与NRRL或ATCC登记号的基因组杂交的基因组。
“杂交”是指一种反应,其中一个或多个多核苷酸反应以形成通过基于核苷酸残基之间的氢键稳定下来的复合物。氢键可以通过Watson-Crick碱基配对、Hoogstein结合或任何其他特定序列的方式发生。复合物可以包含形成双链结构的两条链,形成多链复合物的三条或多条链,单一的自杂交链,或这些的任何组合。杂交反应可以在不同的“严谨”条件下进行。通常,低严谨杂交反应是在10X SSC于约40℃下或同等离子强度/温度的溶液中进行的。普通严谨杂交通常在6X SSC中于约50℃下进行的,而高严谨杂交反应通常在1X SSC中于约60℃下进行的。
指明的NRRL或ATCC登记号的变体也可定义为与指明的NRRL或ATCC登记号的基因组相比,具有大于85%、更优选大于90%或更优选大于95%序列相同的基因组序列的菌株。一个多核苷酸或多核苷酸区域(或一个多肽或多肽区域)与另一个序列具有一定百分比(例如80%、85%、90%或95%)的“序列同一性”意指,当进行比对时,所比较的两个序列具有相同的该百分比的碱基(或氨基酸)。这种比对和同源性或序列同一性的百分比可以用本领域已知的软件程序来确定,例如,那些记载于Current Protocols in Molecular Biology(F.M.Ausubel等人,编辑,1987)中的程序。
NRRL是Agricultural Research Service Culture Collection的缩写,根据关于国际认可为专利程序目的保藏微生物的布达佩斯条约,该机构是为保藏微生物菌种目的而设立的国际保藏机构,其地址是National Center for Agricultural UtilizationResearch,Agricultural Research service,U.S.Department of Agriculture,1815North university Street,Peroira,Illinois 61604 USA。
ATCC是American Type Culture Collection的缩写,根据关于国际认可为专利程序目的保藏微生物的布达佩斯条约,该机构是为保藏微生物菌种目的而设立的国际保藏机构,其地址是ATCC Patent Depository,10801University Blvd.,Manassas,VA 10110USA。
可以与本发明的化合物和组合物结合的生物防治剂的实例为:
(A)选自以下的抗细菌剂:
(A1)细菌,如(A1.01)枯草芽孢杆菌(Bacillus subtilis),特别是菌株QST713/AQ713(可从Bayer CropScience LP,US以SERENADE OPTI或SERENADE ASO获得,NRRL登记号B21661,美国专利号6,060,051);(A1.02)芽孢杆菌属(Bacillus sp.),特别是菌株D747(可从Kumiai Chemical Industry Co.,Ltd.以DOUBLE获得),登记号FERM BP-8234,美国专利号7,094,592;(A1.03)短小芽孢杆菌(Bacillus pumilus),特别是菌株BUF-33,NRRL登记号50185(可从BASF以产品的部分获得,EPA登记号71840-19);(A1.04)Bacillus subtilis var.amyloliquefaciens菌株FZB24,登记号DSM 10271(可从Novozymes以或ECO(EPA登记号70127-5)获得);(A1.05)类芽孢杆菌属(Paenibacillus sp.)菌株,登记号NRRL B-50972或登记号NRRL B-67129,WO 2016/154297;(A1.06)枯草芽孢杆菌(Bacillus subtilis)菌株BU1814,(可从BASF SE以PLUS、FLEX和EXTRA获得);(A1.07)来自Certis USA LLC(Mitsui&Co.的子公司)的莫海威芽孢杆菌(Bacillusmojavensis)菌株R3B(登记号NCAIM(P)B001389)(WO 2013/034938);(A1.08)来自CertisUSA LLC(Mitsui&Co.的子公司)的枯草芽孢杆菌CX-9060;(A1.09)多粘类芽孢杆菌(Paenibacillus polymyxa),特别是菌株AC-1(例如来自Green Biotech Company Ltd.的);(A1.10)Pseudomonas proradix(例如来自Sourcon Padena的);(A1.11)成团泛菌(Pantoea agglomerans),特别是菌株E325(登记号NRRL B-21856)(可从Northwest Agri Products以BLOOMTIME BIOLOGICALTM FDBIOPESTICIDE获得);和
(A2)真菌,如(A2.01)出芽短梗霉菌(Aureobasidium pullulans),特别是菌株DSM14940的芽生孢子,菌株DSM14941的芽生孢子,或菌株DSM14940和DSM14941的芽生孢子的混合物(例如来自bio-ferm,CH的和BLOSSOM);(A2.02)Pseudozyma aphidis(如Yissum Research Development Company of the HebrewUniversity of Jerusalem在WO2011/151819中所公开的);(A2.03)酿酒酵母(Saccharomyces cerevisiae),特别是来自Lesaffre et Compagnie,FR的菌株CNCM号I-3936、CNCM号I-3937、CNCM号I-3938或CNCM号I-3939(WO 2010/086790);
(B)选自以下的生物杀真菌剂:
(B1)细菌,例如(B1.01)枯草芽孢杆菌,特别是菌株QST713/AQ713(可从BayerCropScience LP,US以SERENADE OPTI或SERENADE ASO获得,NRRL登记号B21661且记载于美国专利号6,060,051中);(B1.02)短小芽孢杆菌,特别是菌株QST2808(可从BayerCropScience LP,US以获得,NRRL登记号B-30087且记载于美国专利号6,245,551中);(B1.03)短小芽孢杆菌,特别是菌株GB34(可从Bayer AG,DE以Yield获得);(B1.04)短小芽孢杆菌,特别是菌株BU F-33,NRRL登记号50185(可从BASF以CARTISSA产品的部分获得,EPA登记号71840-19);(B1.05)解淀粉芽孢杆菌(Bacillusamyloliquefaciens),特别是菌株D747(可从Kumiai Chemical Industry Co.,Ltd.以Double NickelTM获得,登记号FERM BP-8234,美国专利号7,094,592);(B1.06)枯草芽孢杆菌Y1336(可从Bion-Tech,Taiwan,China以WP获得,在中国台湾以登记号4764、5454、5096和5277登记为生物杀真菌剂);(B1.07)枯草芽孢杆菌菌株MBI 600(可从BASF SE以SUBTILEX获得),登记号NRRL B-50595,美国专利号5,061,495;(B1.08)枯草芽孢杆菌菌株GB03(可从Bayer AG,DE以获得);(B1.09)Bacillus subtilisvar.amyloliquefaciens菌株FZB24,登记号DSM 10271(可从Novozymes以或ECO(EPA登记号70127-5)获得);(B1.10)蕈状芽孢杆菌(Bacillusmycoides),分离菌J,登记号B-30890(可从Certis USA LLC(Mitsui&Co.的子公司)以BMJ或WG and LifeGardTM获得);(B1.11)藓样芽胞杆菌(Bacillus licheniformis),特别是菌株SB3086,登记号ATCC 55406,WO 2003/000051(可从Novozymes以生物杀真菌剂和GREEN RELEAFTM获得);(B1.12)类芽孢杆菌属(Paenibacillus sp.)菌株,登记号NRRL B-50972或登记号NRRL B-67129,WO 2016/154297;(B1.13)枯草芽孢杆菌菌株BU1814,(可从BASF SE以PLUS、FLEX和EXTR获得);(B1.14)来自Certis USA LLC(Mitsui&Co.的子公司)的枯草芽孢杆菌CX-9060;(B1.15)解淀粉芽孢杆菌菌株F727(也称为菌株MBI110)(NRRL登记号B-50768;WO 2014/028521)(来自Marrone Bio Innovations的);(B1.16)解淀粉芽孢杆菌菌株FZB42,登记号DSM 23117(可从ABiTEP,DE以获得);(B1.17)藓样芽胞杆菌FMCH001和枯草芽孢杆菌FMCH002(来自FMC公司的(WG)和(WP));(B1.18)来自Certis USALLC(Mitsui&Co.的子公司)的莫海威芽孢杆菌菌株R3B(登记号NCAIM(P)B001389)(WO2013/034938);(B1.19)来自BASF SE的多粘类芽孢杆菌植物亚种(ssp.plantarum)(WO2016/020371);(B1.20)来自BASF SE的附生类芽孢杆菌(Paenibacillus epiphyticus)(WO2016/020371);(B.1.21)绿针假单胞菌(Pseudomonas chlororaphis)菌株AFS009,登记号NRRL B-50897,WO 2017/019448(例如来自AgBiome Innovations,US的HOWLERTM和);(B1.22)绿针假单胞菌,特别是菌株MA342(如,由Bioagri和Koppert提供的和);(B1.23)利迪链霉菌(Streptomyces lydicus)菌株WYEC108(也称为利迪链霉菌菌株WYCD108US)(来自Novozymes的和);(B1.24)放射形土壤杆菌(Agrobacterium radiobacter)菌株K84(例如来自AgBioChem,CA的);(B1.25)放射形土壤杆菌菌株K1026(例如来自BASF SE的NOGALLTM);(B1.26)枯草芽孢杆菌KTSB菌株(来自Donaghys的);(B1.27)枯草芽孢杆菌IAB/BS03(来自STK Bio-Ag Technologies的AVIVTM);(B1.28)枯草芽孢杆菌菌株Y1336(可从Bion-Tech,Taiwan,China以WP获得,在中国台湾以登记号4764、5454、5096和5277登记为生物杀真菌剂);(B1.29)解淀粉芽孢杆菌分离菌B246(例如来自University of Pretoria的AVOGREENTM);(B1.30)甲基营养型芽孢杆菌(Bacillus methylotrophicus)菌株BAC-9912(来自Chinese Academy of Sciences’Institute of Applied Ecology);(B1.31)Pseudomonas proradix(例如来自Sourcon Padena的);(B1.32)Streptomyces griseoviridis菌株K61(也称为鲜黄链霉菌(Streptomyces galbus)菌株K61)(登记号DSM 7206)(来自Verdera的来自BioWorks的参见Crop Protection 2006,25,468-475);(B1.33)荧光假单胞菌(Pseudomonas fluorescens)菌株A506(例如由NuFarm提供的);和
(B2)真菌,例如:(B2.01)盾壳霉(Coniothyrium minitans),特别是菌株CON/M/91-8(登记号DSM-9660;例如来自Bayer CropScience Biologics GmbH的);(B2.02)核果梅奇酵母(Metschnikowia fructicola),特别是菌株NRRL Y-30752;(B2.03)Microsphaeropsis ochracea;(B2.04)深绿木霉(Trichoderma atroviride),特别是菌株SC1(登记号CBS122089,WO 2009/116106和美国专利号8,431,120(来自Bi-PA))、菌株77B(来自Andermatt Biocontrol的T77)或菌株LU132(例如来自Agrimm TechnologiesLimited的Sentinel);(B2.05)哈茨木霉(Trichoderma harzianum)菌株T-22(例如来自Andermatt Biocontrol或Koppert的Trianum-P)或菌株Cepa Simb-T5(来自SimbioseAgro);(B2.06)Gliocladium roseum(也称为Clonostachys rosea f.rosea),特别是来自Adjuvants Plus的菌株321U,在Xue(Efficacy of Clonostachys rosea strain ACM941and fungicide seed treatments for controlling the root tot complex of fieldpea,Can Jour Plant Sci 83(3):519-524)中所公开的菌株ACM941,或菌株IK726(JensenDF等人Development of a biocontrol agent for plant disease control withspecial emphasis on the near commercial fungal antagonist Clonostachys roseastrain‘IK726’;Australas Plant Pathol.2007;36:95-101);(B2.07)黄色蠕形霉(Talaromyces flavus),菌株V117b;(B2.08)绿色木霉(Trichoderma viride),特别是菌株B35(Pietr等人,1993,Zesz.Nauk.A R w Szczecinie161:125-137);(B2.09)棘孢木霉(Trichoderma asperellum),特别是菌株SKT-1,登记号FERM P-16510(例如来自KumiaiChemical Industry的),菌株T34(例如由Biocontrol TechnologiesS.L.,ES提供的T34 Biocontrol)或来自Isagro的菌株ICC 012;(B2.10)深绿木霉,菌株CNCM I-1237(例如来自Agrauxine,FR的WP);(B2.11)深绿木霉,菌株号V08/002387;(B2.12)深绿木霉,菌株NMI号V08/002388;(B2.13)深绿木霉,菌株NMI号V08/002389;(B2.14)深绿木霉,菌株NMI号V08/002390;(B2.15)深绿木霉,菌株LC52(例如由Agrimm Technologies Limited提供的Tenet);(B2.16)深绿木霉,菌株ATCC 20476(IMI206040);(B2.17)深绿木霉,菌株T11(IMI352941/CECT20498);(B2.18);Trichodermaharmatum;(B2.19)哈茨木霉;(B2.20)哈茨木霉(Trichoderma harzianum rifai)T39(例如来自Makhteshim,US的);(B2.21)棘孢木霉,特别是菌株kd(例如来自Andermatt Biocontrol的T-Gro);(B2.22)哈茨木霉,菌株ITEM 908(例如来自Koppert的Trianum-P);(B2.23)哈茨木霉,菌株TH35(例如由Mycontrol提供的Root-Pro);(B2.24)绿木霉(Trichoderma virens)(也称为绿粘帚霉(Gliocladium virens)),特别是菌株GL-21(例如由Certis,US提供的SoilGard);(B2.25)绿色木霉,菌株TV1(例如由Koppert提供的Trianum-P);(B2.26)白粉寄生孢(Ampelomyces quisqualis),特别是菌株AQ 10(例如由IntrachemBio Italia提供的AQ);(B2.27)出芽短梗霉菌,特别是菌株DSM14940的芽生孢子;(B2.28)出芽短梗霉菌,特别是菌株DSM 14941的芽生孢子;(B2.29)出芽短梗霉菌,特别是菌株DSM14940和DSM 14941的芽生孢子的混合物(例如由bio-ferm,CH提供的);(B2.30)枝孢样枝孢霉(Cladosporium cladosporioides),菌株H39,登记号CBS122244,US2010/0291039(由Stichting Dienst Landbouwkundig Onderzoek提供);(B2.31)链孢粘帚霉(Gliocladiumcatenulatum)(同物异名:Clonostachys roseaf.catenulate)菌株J1446(例如由Lallemand提供的);(B2.32)蜡蚧轮枝孢(Lecanicillium lecanii)(先前称为Verticillium lecanii)菌株KV01的分生孢子(例如由Koppert/Arysta提供的);(B2.33)蠕形青霉(Penicillium vermiculatum);(B2.34)异常毕赤酵母(Pichia anomala),菌株WRL-076(NRRL Y-30842),美国专利号7,579,183;(B2.35)深绿木霉,菌株SKT-1(FERM P-16510),日本专利公布(Kokai)号11-253151A;(B2.36)深绿木霉,菌株SKT-2(FERM P-16511),日本专利公布(Kokai)号11-253151A;(B2.37)深绿木霉,菌株SKT-3(FERM P-17021),日本专利公布(Kokai)号11-253151A;(B2.38)盖姆斯木霉(Trichoderma gamsii)(先前是T.viride),菌株ICC080(IMICC 392151CABI,例如由AGROBIOSOL DE MEXICO,S.A.DE C.V.提供的BioDerma);(B2.39)哈茨木霉,菌株DB103(可由Dagutat Biolab提供T-Gro 7456获得);(B2.40)多孢木霉(Trichoderma polysporum),菌株IMI 206039(例如由BINAB Bio-Innovation AB,Sweden提供的Binab TF WP);(B2.41)Trichoderma stromaticum,登记号Ts3550(例如由CEPLAC,Brazil提供的Tricovab);(B2.42)Ulocladium oudemansii菌株U3,登记号NM 99/06216(例如由Botry-Zen Ltd,New Zealand提供的和来自BioWorks,Inc.的);(B2.43)黑白轮枝孢(Verticillium albo-atrum)(先前是V.dahliae),登记号为WCS850的菌株WCS850,保藏于Central Bureau for Fungi Cultures(例如由Tree Care Innovations提供的DUTCH);(B2.44)厚垣轮枝孢菌(Verticillium chlamydosporium);(B2.45)棘孢木霉菌株ICC 012(也称为哈茨木霉ICC012)(登记号CABI CC IMI 392716)和盖姆斯木霉菌株(先前是T.viride)菌株ICC080(登记号IMI 392151)的混合物(例如来自Isagro USA,Inc.的BIO-TAMTM和由Agrobiosolde Mexico,S.A.de C.V.提供的);(B2.46)Trichoderma asperelloidesJM41R(登记号NRRL B-50759)(来自BASF SE的TRICHO);(B2.47)黄曲霉(Aspergillus flavus)菌株NRRL 21882(来自Syngenta/ChemChina称为的产品);(B2.48)Chaetomium cupreum(登记号CABI 353812)(例如由AgriLife提供的BIOKUPRUMTM);(B2.49)酿酒酵母,特别是菌株LASO2(来自Agro-Levureset Dérivés),菌株LAS117细胞壁(来自Lesaffre的来自BASF SE的),来自Lesaffre et Compagnie,FR的菌株CNCM号I-3936、CNCM号I-3937、CNCM号I-3938、CNCM号I-3939(WO 2010/086790);(B2.50)绿木霉菌株G-41,先前也称为绿粘帚霉(登记号ATCC 20906)(例如,来自BioWorks,US的PLUS WP和PLUS WP);(B2.51)钩状木霉(Trichoderma hamatum),登记号ATCC28012;(B2.52)白粉寄生孢菌株AQ10,登记号CNCM I-807(例如,由IntrachemBio Italia提供的AQ);(B2.53)大伏革菌(Phlebiopsis gigantea)菌株VRA 1992(来自DanstarFerment的C);(B2.54)来自BASF SE的Penicillium steckii(DSM 27859;WO 2015/067800);(B2.55)球毛壳菌(Chaetomium globosum)(可由Rivale提供获得);(B2.56)Cryptococcus flavescens,菌株3C(NRRL Y-50378);(B2.57)Dactylaria candida;(B2.58)Dilophosphora alopecuri(可以TWIST获得);(B2.59)尖孢镰刀菌(Fusarium oxysporum),菌株Fo47(可由NaturalPlant Protection提供的获得);(B2.60)Pseudozyma flocculosa,菌株PF-A22 UL(可由Plant Products Co.,CA提供的L获得);(B2.61)盖姆斯木霉(先前是T.viride),菌株ICC 080(IMI CC 392151CABI)(可由AGROBIOSOL DEMEXICO,S.A.DE C.V.提供的获得);(B2.62)Trichoderma fertile(例如来自BASF的产品TrichoPlus);(B2.63)粉红产气霉(Muscodor roseus),特别是菌株A3-5(登记号NRRL 30548);(B2.64)Simplicillium lanosoniveum;
(C)具有改善植物生长和/或植物健康的效果的生物防治剂,其可与本发明的化合物组合进行组合,包括:
(C1)选自以下的细菌:(C1.01)短小芽孢杆菌,特别是菌株QST2808(登记号NRRL号B-30087);(C1.02)枯草芽孢杆菌,特别是菌株QST713/AQ713(NRRL登记号B-21661且记载于美国专利号6,060,051中;(C1.03)可从Bayer CropScience LP,US以OPTI或ASO获得);(C1.04)枯草芽孢杆菌,特别是菌株AQ30002(登记号NRRL B-50421且记载于美国专利申请号13/330,576中);(C1.05)枯草芽孢杆菌,特别是菌株AQ30004(NRRL B-50455且记载于美国专利申请号13/330,576中);(C1.06)苜蓿中华根瘤菌(Sinorhizobium meliloti)菌株NRG-185-1(来自Bayer CropScience的GOLD);(C1.07)枯草芽孢杆菌菌株BU1814,(可从BASF SE以获得);(C1.08)枯草芽孢杆菌rm303(来自Biofilm Crop Protection的);(C1.09)解淀粉芽孢杆菌pm414(来自Biofilm Crop Protection的);(C1.10)蕈状芽孢杆菌BT155(NRRL号B-50921),蕈状芽孢杆菌EE118(NRRL号B-50918),(C1.11)蕈状芽孢杆菌EE141(NRRL号B-50916),(C1.12)蕈状芽孢杆菌BT46-3(NRRL号B-50922),(C1.13)蜡状芽孢杆菌(Bacillus cereus)家族成员EE128(NRRL号B-50917),(C1.14)苏云金芽孢杆菌(Bacillus thuringiensis)BT013A(NRRL号B-50924)(也称为苏云金芽孢杆菌4Q7),(C1.15)蜡状芽孢杆菌家族成员EE349(NRRL号B-50928),(C1.16)解淀粉芽孢杆菌SB3281(ATCC#PTA-7542;WO 2017/205258),(C1.17)解淀粉芽孢杆菌TJ1000(可从Novozymes以获得);(C1.18)坚强芽孢杆菌(Bacillus firmus),特别是菌株CNMC I-1582(例如来自BASF SE的);(C1.19)短小芽孢杆菌,特别是菌株GB34(例如来自Bayer Crop Science,DE的YIELD);(C1.20)解淀粉芽孢杆菌,特别是菌株IN937a;(C1.21)解淀粉芽孢杆菌,特别是菌株FZB42(例如来自ABiTEP,DE的);(C1.22)解淀粉芽孢杆菌BS27(登记号NRRL B-5015);(C1.23)藓样芽胞杆菌FMCH001和枯草芽孢杆菌FMCH002的混合物(可从FMC公司以(WG)、(WP)获得);(C1.24)蜡状芽孢杆菌,特别是菌株BP01(ATCC 55675;例如来自Arysta Lifescience,US的);(C1.25)枯草芽孢杆菌,特别是菌株MBI 600(例如来自BASF SE的);(C1.26)慢生型大豆根瘤菌(Bradyrhizobium japonicum)(例如来自Novozymes的);(C1.27)Mesorhizobium cicer(例如,来自BASF SE的NODULATOR);(C1.28)Rhizobiumleguminosarium biovar viciae(例如,来自BASF SE的NODULATOR);(C1.29)食酸丛毛单胞菌(Delftia acidovorans),特别是菌株RAY209(例如来自Brett Young Seeds的);(C1.30)乳杆菌(Lactobacillus sp.)(例如来自LactoPAFI的);(C1.31)多粘类芽孢杆菌,特别是菌株AC-1(例如来自GreenBiotech Company Ltd.的);(C1.32)Pseudomonas proradix(例如来自Sourcon Padena的);(C1.33)巴西固氮螺菌(Azospirillum brasilense)(例如,来自KALO,Inc.的);(C1.34)生脂固氮螺菌(Azospirillum lipoferum)(例如,来自TerraMax,Inc.的VERTEX-IFTM);(C1.35)维氏固氮菌(Azotobactervinelandii)和巴氏固氮梭状芽孢杆菌(Clostridium pasteurianum)的混合物(可从Agrinos以获得);(C1.36)铜绿假单胞菌(Pseudomonas aeruginosa),特别是菌株PN1;(C1.37)豌豆根瘤菌(Rhizobium leguminosarum),特别是bv.viceae菌株Z25(登记号CECT 4585);(C1.38)茎瘤固氮根瘤菌(Azorhizobiumcaulinodans),特别是菌株ZB-SK-5;(C1.39)褐球固氮菌(Azotobacter chroococcum),特别是菌株H23;(C1.40)维氏固氮菌,特别是菌株ATCC12837;(C1.41)Bacillus siamensis,特别是菌株KCTC 13613T;(C1.42)特基拉芽胞杆菌(Bacillus tequilensis),特别是菌株NII-0943;(C1.43)粘质沙雷氏菌(Serratia marcescens),特别是菌株SRM(登记号MTCC 8708);(C1.44)硫杆菌属(Thiobacillus sp.)(例如来自Cropaid Ltd UK的);和
(C2)选自以下的真菌:(C2.01)淡紫拟青霉(Purpureocillium lilacinum)(先前称为淡紫拟青霉(Paecilomyces lilacinus))菌株251(AGAL 89/030550;例如来自BayerCropScience Biologics GmbH的BioAct)青霉菌(Penicillium bilaii),(C2.02)菌株ATCC22348(例如来自Acceleron BioAg的),(C2.03)黄色蠕形霉,菌株V117b;(C2.04)深绿木霉菌株CNCM I-1237(例如来自Agrauxine,FR的WP),(C2.05)绿色木霉,例如菌株B35(Pietr等人,1993,Zesz.Nauk.A Rw Szczecinie 161:125-137);(C2.06)深绿木霉菌株LC52(也称为深绿木霉菌株LU132;例如来自Agrimm TechnologiesLimited的Sentinel);记载于国际申请号PCT/IT2008/000196中的(C207.)深绿木霉菌株SC1;(C2.08)棘孢木霉菌株kd(例如来自Andermatt Biocontrol的T-Gro);(C2.09)棘孢木霉菌株Eco-T(Plant Health Products,ZA);(C2.10)哈茨木霉菌株T-22(例如来自Andermatt Biocontrol或Koppert的Trianum-P);(C2.11)疣孢漆斑菌(Myrotheciumverrucaria)菌株AARC-0255(例如来自Valent Biosciences的DiTeraTM);(C2.12)青霉菌菌株ATCC ATCC20851;(C2.13)寡雄腐霉(Pythium oligandrum)菌株M1(ATCC 38472;例如来自Bioprepraty,CZ的Polyversum);(C2.14)绿木霉菌株GL-21(例如来自Certis,USA的);(C2.15)黑白轮枝孢(先前是V.dahliae)菌株WCS850(CBS276.92;例如来自Tree Care Innovations的Dutch Trig);(C2.16)深绿木霉,特别是菌株号V08/002387、菌株号NMI号V08/002388、菌株号NMI号V08/002389、菌株号NMI号V08/002390;(C2.17)哈茨木霉菌株ITEM 908;(C2.18)哈茨木霉,菌株TSTh20;(C2.19)哈茨木霉菌株1295-22;(C2.20)寡雄腐霉菌株DV74;(C2.21)Rhizopogon amylopogon(例如包含在来自Helena ChemicalCompany的Myco-Sol中);(C2.22)Rhizopogon fulvigleba(例如包含在来自HelenaChemical Company的Myco-Sol中);和(C2.23)绿木霉菌株GI-3;
(D)杀虫活性生物防治剂,选自:
(D1)选自以下的细菌:(D1.01)苏云金芽孢杆菌鲇泽亚种(Bacillusthuringiensis subsp.aizawai),特别是菌株ABTS-1857(SD-1372;例如来自ValentBioSciences的);(D1.02)蕈状芽孢杆菌,分离菌J.(例如来自Certis USALLC(Mitsui&Co.的子公司)的BmJ);(D1.03)球形芽孢杆菌(Bacillus sphaericus),特别是血清型H5a5b菌株2362(菌株ABTS-1743)(例如来自Valent BioSciences,US的);(D1.04)来自Becker Microbial Products,IL的苏云金芽孢杆菌库尔斯塔克亚种(Bacillus thuringiensis subsp.kurstaki)菌株BMP 123;(D1.05)苏云金芽孢杆菌鲇泽亚种,特别是血清型H-7(例如来自Valent BioSciences,US的WG);(D1.06)苏云金芽孢杆菌库尔斯塔克亚种菌株HD-1(例如来自Valent BioSciences,US的ES);(D1.07)由Becker Microbial Products,IL提供的苏云金芽孢杆菌库尔斯塔克亚种菌株BMP 123;(D1.08)苏云金芽孢杆菌以色列(Bacillus thuringiensisisraelensis)菌株BMP 144(例如由Becker Microbial Products IL提供的);伯克霍尔德菌属(Burkholderia spp.),特别是(D1.09)Burkholderiarinojensis菌株A396(也称为Burkholderia rinojensis菌株MBI 305)(登记号NRRL B-50319;WO 2011/106491和WO 2013/032693;例如来自Marrone Bio Innovations的MBI-206TGAI和);(D1.10)活性紫色细菌(Chromobacterium subtsugae),特别是菌株PRAA4-1T(MBI-203;例如来自Marrone Bio Innovations的);(D1.11)乳白色致病细菌(Paenibacillus popilliae)(先前是蛴螬乳状菌(Bacillus popilliae);例如来自St.Gabriel Laboratories的MILKY SPORE POWDERTM和MILKY SPOREGRANULARTM);(D1.12)苏云金芽孢杆菌以色列亚种(Bacillus thuringiensissubsp.israelensis)(血清型H-14)菌株AM65-52(登记号ATCC 1276)(例如由ValentBioSciences,US提供的);(D1.13)Bacillus thuringiensisvar.kurstaki菌株EVB-113-19(例如,来自AEF Global的);(D1.14)苏云金芽孢杆菌拟步行甲亚种(B.thuringiensis subsp.tenebrionis)菌株NB 176(SD-5428;例如来自BioFa DE的FC);(D1.15)Bacillus thuringiensisvar.japonensis菌株Buibui;(D1.16)苏云金芽孢杆菌库尔斯塔克亚种菌株ABTS 351;(D1.17)苏云金芽孢杆菌库尔斯塔克亚种菌株PB 54;(D1.18)苏云金芽孢杆菌库尔斯塔克亚种菌株SA 11;(D1.19)苏云金芽孢杆菌库尔斯塔克亚种菌株SA 12;(D1.20)苏云金芽孢杆菌库尔斯塔克亚种菌株EG 2348;(D1.21)Bacillus thuringiensis var.Colmeri(例如由Changzhou Jianghai Chemical Factory提供的TIANBAOBTC);(D1.22)苏云金芽孢杆菌鲇泽亚种菌株GC-91;(D1.23)Serratia entomophila(例如由Wrightson Seeds提供的);(D1.24)粘质沙雷菌(Serratia marcescens),特别是菌株SRM(登记号MTCC8708);和(D1.25)Wolbachia pipientis ZAP菌株(例如,来自MosquitoMate的ZAP);和
(D2)选自以下的真菌:(D2.01)玫烟色棒束孢(Isaria fumosorosea)(先前称为玫烟色拟青霉(Paecilomyces fumosoroseus))菌株apopka 97;(D2.02)球孢白僵菌(Beauveria bassiana)菌株ATCC 74040(例如来自Intrachem Bio Italia的);(D2.03)球孢白僵菌菌株GHA(登记号ATCC74250;例如来自LaverlamInternational Corporation的ES和);(D2.04)Zoophtora radicans;(D2.05)罗伯茨绿僵菌(Metarhizium robertsii)15013-1(在NRRL登记号67073下保藏),(D2.06)罗伯茨绿僵菌23013-3(在NRRL登记号67075下保藏),和(D2.07)绿僵菌(Metarhizium anisopliae)3213-1(在NRRL登记号67074下保藏)(WO2017/066094;Pioneer Hi-Bred International);(D2.08)球孢白僵菌菌株ATP02(登记号DSM 24665);
(E)选自以下的病毒:棉褐带卷蛾(Adoxophyes orana)(夏季水果卷叶蛾(summerfruit tortrix))颗粒体病毒(GV),苹果皮小卷蛾(Cydia pomonella)(codling moth)颗粒体病毒(GV),棉铃虫(Helicoverpa armigera)(cotton bollworm)核多角体病毒(NPV),甜菜夜蛾(Spodoptera exigua)(beet armyworm)mNPV,草地贪夜蛾(Spodopterafrugiperda)(fall armyworm)mNPV和海灰翅夜蛾(Spodoptera littoralis)(非洲棉叶虫(African cotton leafworm)NPV;
(F)可以作为“接种剂(inoculant)”加入到植物或植物部位或植物器官并凭借其特定性能促进植物生长和植物健康的细菌和真菌。所述细菌和真菌的实例为:土壤杆菌属(Agrobacterium spp.),茎瘤固氮根瘤菌(Azorhizobium caulinodans),固氮螺菌属(Azospirillum spp.),固氮菌属(Azotobacter spp.),慢生根瘤菌属(Bradyrhizobiumspp.),伯克霍尔德菌属,特别是洋葱伯克霍尔德菌(Burkholderia cepacia)(先前称为洋葱假单胞菌(Pseudomonas cepacia)),巨孢囊霉属(Gigaspora spp.)或Gigasporamonosporum,球囊霉属(Glomus spp.),蜡蘑属(Laccaria spp.),布氏乳杆菌(Lactobacillus buchneri),类球囊霉属(Paraglomus spp.),Pisolithus tinctorus,假单胞菌属(Pseudomonas spp.),根瘤菌属(Rhizobium spp.),特别是三叶草根瘤菌(Rhizobium trifolii),须腹菌属(Rhizopogon spp.),硬皮马勃属(Scleroderma spp.),乳牛肝菌属(Suillus spp.)和链霉菌属(Streptomyces spp.);以及
(G)可用作生物防治剂的植物提取物和由微生物形成的产物(包括蛋白质和次生代谢物),例如大蒜(Allium sativum)、苦艾(Artemisia absinthium)、印楝素(azadirachtin)、Biokeeper WP、Cassia nigricans、苦皮藤(Celastrus angulatus)、Chenopodium anthelminticum、几丁质、Armour-Zen、欧洲鳞毛蕨(Dryopteris filix-mas)、问荆(Equisetum arvense)、Fortune Aza、Fungastop、Heads Up(藜麦皂苷提取物(Chenopodium quinoa saponin extract))、除虫菊(pyrethrum)/除虫菊酯(pyrethrins)、苏里南苦木(Quassia amara)、栎属(Quercus)、皂树(Quillaja)、Regalia、“RequiemTM杀昆虫剂”、鱼藤酮(rotenone)、鱼尼丁(ryania)/兰尼碱(ryanodine)、聚合草(Symphytumofficinale)、菊蒿(Tanacetum vulgare)、百里酚(thymol)、Triact 70、TriCon、Tropaeulum majus、大荨麻(Urtica dioica)、藜芦碱(Veratrin)、白果槲寄生(Viscumalbum)、十字花科(Brassicaceae)提取物(特别是油菜粉末或芥菜粉末),以及从橄榄油中获得的生物杀虫/杀螨活性物质,特别是碳链长度为C16-C20的不饱和脂肪/羧酸作为活性成分,例如如,包含在商品名为的产品中。
本发明的化合物和组合物可与一种或多种选自杀昆虫剂、杀螨剂和杀线虫剂的活性成分结合。
“杀昆虫剂(insecticides)”以及术语“杀昆虫的(insecticidal)”是指一种能够增加昆虫的死亡率或抑制其生长速度的物质。如本文所使用的,术语“昆虫纲(insects)”包括“昆虫纲(insecta)”类中的所有生物。
“杀线虫剂(nematicide)”和“杀线虫的(nematicidal)”是指一种能够增加线虫的死亡率或抑制其生长速度的物质。通常,术语“线虫”包含所述生物的卵、幼虫、幼年和成熟形式。
“杀螨剂(acaricide)”和“杀螨的(acaricidal)”是指一种能够增加属于蛛形纲、螨蜱亚纲的外寄生虫的死亡率或抑制其生长速度的物质。
可以与本发明的化合物和组合物混合的杀昆虫剂、杀螨剂和杀线虫剂的实例分别为:
(1)乙酰胆碱酯酶(AChE)抑制剂,优选氨基甲酸酯类,选自棉铃威(alanycarb)、涕灭威(aldicarb)、噁虫威(bendiocarb)、丙硫克百威(benfuracarb)、丁酮威(butocarboxim)、丁酮砜威(butoxycarboxim)、胺甲萘(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、乙硫苯威(ethiofencarb)、仲丁威(fenobucarb)、伐虫脒(formetanate)、呋线威(furathiocarb)、异丙威(isoprocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、速灭威(metolcarb)、杀线威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、久效威(thiofanox)、唑蚜威(triazamate)、混杀威(trimethacarb)、灭除威(XMC)和灭杀威(xylylcarb);或有机磷酸酯类,选自乙酰甲胺磷(acephate)、甲基吡噁磷(azamethiphos)、乙基谷硫磷(azinphos-ethyl)、甲基谷硫磷(azinphos-methyl)、硫线磷(cadusafos)、氯氧磷(chlorethoxyfos)、毒虫畏(chlorfenvinphos)、氯甲硫磷(chlormephos)、甲基毒死蜱(chloropyrifos-methyl)、蝇毒磷(coumaphos)、杀螟腈(cyanophos)、甲基内吸磷(demeton-S-methyl)、二嗪农(diazinon)、敌敌畏(dichlorvos/DDVP)、百治磷(dicrotophos)、乐果(dimethoate)、甲基毒虫畏(dimethylvinphos)、乙拌磷(disulfoton)、苯硫磷(EPN)、乙硫磷(ethion)、灭线磷(ethoprophos)、伐灭磷(famphur)、苯线磷(fenamiphos)、杀螟松(fenitrothion)、倍硫磷(fenthion)、噻唑磷(fosthiazate)、庚烯磷(heptenophos)、氰咪唑硫磷(imicyafos)、异柳磷(isofenphos)、O-(甲氧基氨基硫代磷酰基)水杨酸异丙酯、异噁唑磷(isoxathion)、马拉硫磷(malathion)、灭蚜磷(mecarbam)、甲胺磷(methamidophos)、杀扑磷(methidathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、二溴磷(naled)、氧乐果(omethoate)、亚砜磷(oxydemeton-methyl)、对硫磷甲酯(parathion-methyl)、稻丰散(phenthoate)、甲拌磷(phorate)、伏杀磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、肟硫磷(phoxim)、甲基吡啶磷(pirimiphos-methyl)、丙溴磷(profenofos)、胺丙畏(propetamphos)、丙硫磷(prothiofos)、吡唑硫磷(pyraclofos)、哒嗪硫磷(pyridaphenthion)、喹硫磷(quinalphos)、治螟磷(sulfotep)、丁基吡啶磷(tebupirimfos)、双硫磷(temephos)、特丁硫磷(terbufos)、杀虫畏(tetrachlorvinphos)、甲基乙拌磷(thiometon)、三唑磷(triazophos)、敌百虫(triclorfon)和蚜灭磷(vamidothion)。
(2)GABA-门控氯化物通道阻断剂,优选环戊二烯有机氯类,选自氯丹(chlordane)和硫丹(endosulfan);或苯基吡唑类(fiproles),选自乙虫腈(ethiprole)和氟虫腈(fipronil)。
(3)钠通道调节剂,优选拟除虫菊酯类(pyrethroid),选自氟丙菊酯(acrinathrin)、丙烯除虫菊酯(allethrin)、d-顺式-反式丙烯除虫菊酯(d-cis-transallethrin)、d-反式丙烯除虫菊酯(d-trans allethrin)、联苯菊酯(bifenthrin)、生物烯丙菊酯(bioallethrin)、生物烯丙菊酯s-环戊烯基异构体(bioallethrin s-cyclopentenyl isomer)、生物苄呋菊酯(bioresmethrin)、乙氰菊酯(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、β-氟氯氰菊酯(beta-cyfluthrin)、氯氟氰菊酯(cyhalothrin)、λ-氯氟氰菊酯(lambda-cyhalothrin)、γ-氯氟氰菊酯(gamma-cyhalothrin)、氯氰菊酯(cypermethrin)、α-氯氰菊酯(alpha-cypermethrin)、β-氯氰菊酯(beta-cypermethrin)、θ-氯氰菊酯(theta-cypermethrin)、ζ-氯氰菊酯(zeta-cypermethrin)、苯醚氰菊酯[(1R)-反式异构体](cyphenothrin[(1R)-trans-isomer])、溴氰菊酯(deltamethrin)、右旋烯炔菊酯[(EZ)-(1R)-异构体](empenthrin[(EZ)-(1R)-isomer])、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、氰戊菊酯(fenvalerate)、氟氰戊菊酯(flucythrinate)、氟氯苯菊酯(flumethrin)、τ-氟胺氰菊酯(tau-fluvalinate)、苄螨醚(halfenprox)、炔咪菊酯(imiprothrin)、噻嗯菊酯(kadethrin)、甲氧苄氟菊酯(momfluorothrin)、苄氯菊酯(permethrin)、苯醚菊酯[(1R)-反式异构体](phenothrin[(1R)-trans-isomer])、炔丙菊酯(prallethrin)、除虫菊酯(pyrethrine、pyrethrum)、苄呋菊酯(resmethrin)、氟硅菊酯(silafluofen)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、胺菊酯[(1R)-异构体](tetramethrin[(1R)-isomer])、四溴菊酯(tralomethrin)和四氟苯菊酯(transfluthrin);或DDT;或甲氧氯。
(4)烟碱乙酰胆碱受体(nAChR)竞争调节剂,优选新烟碱类(neonicotinoids),选自啶虫脒(acetamiprid)、噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、烯啶虫胺(nitenpyram)、噻虫啉(thiacloprid)和噻虫嗪(thiamethoxam)或尼古丁(nicotine)或或选自氟啶虫胺腈(sulfoxaflor)的亚砜亚胺类(sulfoximines);或选自氟吡呋喃酮(flupyradifurone)的丁烯酸内酯类(butenolids),或选自三氟苯嘧啶(triflumezopyrim)的介离子物(mesoionics)。
(5)烟碱乙酰胆碱受体(nAChR)变构调节剂(位点I),优选多杀菌素类(spinosyns),选自乙基多杀菌素(spinetoram)和多杀菌素(spinosad)。
(6)谷氨酸门控氯化物通道(GluCl)变构调节剂,优选阿凡曼维菌素类/米尔倍霉素类(avermectins/milbemycins),选自阿巴克丁(abamectin)、甲氨基阿维菌素苯甲酸盐(emamectin benzoate)、雷皮菌素(lepimectin)和灭螨菌素(milbemectin)。
(7)保幼激素模仿物,优选保幼激素类似物,选自烯虫乙酯(hydroprene)、烯虫炔酯(kinoprene)和烯虫酯(methoprene)或苯氧威(fenoxycarb)或蚊蝇醚(pyriproxyfen)。
(8)各种非特异性(多位点)抑制剂,优选烷基卤化物,选自甲基溴化物和其他烷基卤化物;或氯化苦(chloropicrine)或硫酰氟或硼砂或吐酒石(tartar emetic)或异氰酸甲酯生成剂,选自棉隆(diazomet)或威百亩(metam)。
(9)弦音器官TRPV通道调节剂,优选选自吡蚜酮(pymetrozine)的吡啶偶氮甲烷(pyridine azomethane)和氟虫吡喹(pyrifluquinazone),或选自双丙环虫酯(Afidopyropen)的pyropene。
(10)影响CHS1的螨生长抑制剂,选自四螨嗪(clofentezine)、噻螨酮(hexythiazox)和氟螨嗪(diflovidazin)或乙螨唑(etoxazole)。
(11)昆虫肠膜的微生物干扰剂,选自苏云金芽孢杆菌以色列亚种(Bacillusthuringiensis subspecies israelensis)、球形芽孢杆菌(Bacillus sphaericus)、苏云金芽胞杆菌鲇泽亚种(Bacillus thuringiensis subspecies aizawai)、苏云金芽孢杆菌库尔斯塔克亚种(Bacillus thuringiensis subspecies kurstaki)、苏云金芽孢杆菌拟步行甲亚种(Bacillus thuringiensis subspecies tenebrionis)和B.t.植物蛋白,选自Cry1Ab、Cry1Ac、Cry1Fa、Cry1A.105、Cry2Ab、Vip3A、mCry3A、Cry3Ab、Cry3Bb和Cry34Ab1/35Ab1。
(12)线粒体ATP合成酶的抑制剂,优选ATP干扰剂,选自丁醚脲或有机锡化合物,选自三唑锡、三环锡和苯丁锡(fenbutatin oxide)或克螨特(propargite)或四氯杀螨砜(tetradifon)。
(13)通过阻断质子梯度的氧化磷酸化的解偶联剂,选自虫螨腈(chlorfenapyr)、二硝甲酚(DNOC)和氟虫胺(sulphluramid)。
(14)烟碱乙酰胆碱受体通道阻断剂,选自杀虫磺(bensultap)、杀螟丹氢氯化物(cartap hydrochloride)、杀虫环(thiocyclam)和杀虫双(thiosultap-sodium)。
(15)几丁质生物合成抑制剂,影响CHS1,优选选自双三氟虫脲(bistrifluron)的苯甲酰脲(benzoylurea)类、定虫隆(chlofluazuron)、二氟苯隆(diflubenzuron)、氟环脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氯芬奴隆(lufenuron)、双苯氟脲(novaluron)、多氟脲(noviflumuron)、氟苯脲(teflubenzuron)和杀铃脲(triflumuron)。
(16)几丁质生物合成抑制剂,1型,选自噻嗪酮(buprofezin)。
(17)蜕皮干扰剂(特别是对于双翅目(Diptera),即双翅昆虫(dipteran)),选自灭蝇胺(cyromazine)。
(18)蜕皮激素受体激动剂,优选选自环虫酰胺(chromafenozide)的二酰基肼(diacylhydrazine)类、氯虫酰肼(halofenozide)、甲氧虫酰肼(methoxyfenozide)和虫酰肼(tebufenozide)。
(19)章鱼胺受体激动剂,选自双甲脒(amitraz)。
(20)线粒体复合物III电子传递抑制剂,选自氟蚁腙(hydramethylnone)、灭螨醌(acequinocyl)、嘧螨酯(fluacrypyrim)和联苯肼酯(bifenazate)。
(21)线粒体复合物I电子传递抑制剂,优选METI杀螨剂和杀昆虫剂,选自喹螨醚(fenazaquin)、唑螨酯(fenpyroximate)、嘧螨醚(pyrimidifen)、哒螨灵(pyridaben)、吡螨胺(tebufenpyrad)和唑虫酰胺(tolfenpyrad);或鱼藤酮(rotenone)(鱼藤属(Derris))。
(22)电压依赖型钠通道阻断剂,优选选自茚虫威(indoxacarb)的噁二嗪(oxadiazine)类和选自氰氟虫腙(metaflumizone)的缩氨脲(semicarbazone)。
(23)乙酰基CoA羧化酶的抑制剂,优选特窗酸(tetronic acid)和特特拉姆酸(tetramic acid)衍生物,选自螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、甲氧哌啶乙酯(spiropidion)和螺虫乙酯(spirotetramat)。
(24)线粒体复合物IV电子传递抑制剂,优选选自磷化铝、磷化钙、膦和磷化锌的磷化物,或选自氰化钙、氰化钾和氰化钠的氰化物。
(25)线粒体复合物II电子传递抑制剂,优选β-酮腈衍生物,选自腈吡螨酯(cyenopyrafen)和丁氟螨酯(cyflumetofen)或选自pyflubumide的甲酰苯胺。
(28)鱼尼丁受体调节剂,优选二酰胺类,选自氯虫苯甲酰胺(chlorantraniliprole)、溴氰虫酰胺(cyantraniliprole)、环溴虫酰胺(cyclaniliprole)、氟虫双酰胺(flubendiamide)和氟氰虫酰胺(tetraniliprole)。
(29)弦音器官调节剂(具有未定义的靶位点),选自氟啶虫酰胺(flonicamid)。
(30)GABA门控氯化物通道变构调节剂,优选选自溴氟苯胺的间二酰胺或选自fluxametamide的异噁唑。
(31)杆状病毒,优选选自苹果蠹蛾(Cydia pomonella GV)和Thaumatotibialeucotreta(GV)的颗粒病毒(GVs)或选自Anticarsia gemmatalis MNPV,Flucypyriprole和Helicoverpa armigera NPV的核型多角体病毒(NPV)。
(32)烟碱型乙酰胆碱受体的变构调节剂(位点II),其选自GS-ω/κ-HXTX-Hv1a肽。
(33)其他活性成分,选自:Acynonapyr、阿福拉纳(Afoxolaner)、印楝素(Azadirachtin)、Benclothiaz、苯螨特(Benzoximate)、Benzpyrimoxan、溴螨酯(Bromopropylate)、灭螨猛(Chinomethionat)、氯丙炔菊酯(Chloroprallethrin)、冰晶石(Cryolite)、Cyclobutrifluram、环氧虫啶(Cycloxaprid)、Cyetpyrafen、氯氟氰虫酰胺(Cyhalodiamide)、Cyproflanilide(CAS2375110-88-4)、Dicloromezotiaz、三氯杀螨醇(Dicofol)、Dimpropyridaz、ε-甲氧苄氟菊酯(epsilon-Metofluthrin)、ε-Momfluthrin、Flometoquin、Fluazaindolizine、Flucypyriprole(CAS 1771741-86-6)、联氟砜(Fluensulfone)、嘧虫胺(Flufenerim)、氟菌螨酯(Flufenoxystrobin)、丁虫腈(Flufiprole)、Fluhexafon、氟吡菌酰胺(Fluopyram)、Flupyrimin、氟雷拉纳(Fluralaner)、呋喃虫酰肼(Fufenozide)、Flupentiofenox、戊吡虫胍(Guadipyr)、Heptafluthrin、氯噻啉(Imidaclothiz)、异菌脲(Iprodione)、Isocycloseram、κ-联苯菊酯(kappa-Bifenthrin)、κ-七氟菊酯(kappa-Tefluthrin)、Lotilaner、氯氟醚菊酯(Meperfluthrin)、Nicofluprole(CAS1771741-86-6)、Oxazosulfyl、哌虫啶(Paichongding)、啶虫丙醚(Pyridalyl)、Pyrifluquinazon、嘧螨胺(Pyriminostrobin)、Sarolaner、Spidoxamat、Spirobudiclofen、四氟醚菊酯(Tetramethylfluthrin)、四氯虫酰胺(Tetrachlorantraniliprole)、Tigolaner、Tioxazafen、硫氟肟醚(Thiofluoximate)、Tyclopyrazoflor、碘甲烷iodomethane);以及基于坚强芽孢杆菌(Bacillus firmus)(I-1582,Votivo)印楝素(azadirachtin)(BioNeem)的制剂和,以及以下化合物:1-{2-氟-4-甲基-5-[(2,2,2-三氟乙基)亚磺酰基]苯基}-3-(三氟甲基)-1H-1,2,4-三唑-5-胺(由WO2006/043635已知)(CAS 885026-50-6)、2-氯-N-[2-{1-[(2E)-3-(4-氯苯基)丙-2-烯-1-基]哌啶-4-基}-4-(三氟甲基)苯基]异烟酰胺(由WO2006/003494已知)(CAS 872999-66-1)、3-(4-氯-2,6-二甲基苯基)-4-羟基-8-甲氧基-1,8-二氮杂螺[4.5]癸-3-烯-2-酮(由WO2010052161已知)(CAS1225292-17-0)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-2-氧代-1,8-二氮杂螺[4.5]癸-3-烯-4-基乙基碳酸酯(由EP2647626已知)(CAS1440516-42-6)、PF1364(由JP2010/018586已知)(CAS1204776-60-2)、(3E)-3-[1-[(6-氯-3-吡啶基)甲基]-2-吡啶亚基]-1,1,1-三氟-丙-2-酮(由WO2013/144213已知)(CAS1461743-15-6)、N-[3-(苄基氨基甲酰基)-4-氯苯基]-1-甲基-3-(五氟乙基)-4-(三氟甲基)-1H-吡唑-5-甲酰胺(由WO2010/051926已知)(CAS1226889-14-0)、5-溴-4-氯-N-[4-氯-2-甲基-6-(甲基氨基甲酰基)苯基]-2-(3-氯-2-吡啶基)吡唑-3-甲酰胺(由CN103232431已知)(CAS1449220-44-3)、4-[5-(3,5-二氯苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-2-甲基-N-(顺式-1-氧代-3-硫杂环丁基)-苯甲酰胺、4-[5-(3,5-二氯苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-2-甲基-N-(反式-1-氧代-3-硫杂环丁基)-苯甲酰胺和4-[(5S)-5-(3,5-二氯苯基)-4,5-二氢-5-(三氟甲基)-3-异噁唑基]-2-甲基-N-(顺式-1-氧代-3-硫杂环丁基)苯甲酰胺(由WO2013/050317 A1已知)(CAS1332628-83-7)、N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亚磺酰基]-丙酰胺、(+)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亚磺酰基]-丙酰胺和(-)-N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-N-乙基-3-[(3,3,3-三氟丙基)亚磺酰基]-丙酰胺(由WO 2013/162715 A2、WO2013/162716 A2、US2014/0213448A1已知)(CAS1477923-37-7)、5-[[(2E)-3-氯-2-丙烯-1-基]氨基]-1-[2,6-二氯-4-(三氟甲基)苯基]-4-[(三氟甲基)亚磺酰基]-1H-吡唑-3-甲腈(由CN 101337937 A已知)(CAS1105672-77-2)、3-溴-N-[4-氯-2-甲基-6-[(甲基氨基)硫代甲基]苯基]-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(Liudaibenjiaxuanan,由CN103109816 A已知)(CAS1232543-85-9);N-[4-氯-2-[[(1,1-二甲基乙基)氨基]羰基]-6-甲基苯基]-1-(3-氯-2-吡啶基)-3-(氟甲氧基)-1H-吡唑-5-甲酰胺(由WO 2012/034403 A1已知)(CAS 1268277-22-0)、N-[2-(5-氨基-1,3,4-噻二唑-2-基)-4-氯-6-甲基苯基]-3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(由WO 2011/085575 A1已知)(CAS 1233882-22-8)、4-[3-[2,6-二氯-4-[(3,3-二氯-2-丙烯-1-基)氧基]苯氧基]丙氧基]-2-甲氧基-6-(三氟甲基)-嘧啶(由CN 101337940 A已知)(CAS 1108184-52-6);(2E)-和2(Z)-2-[2-(4-氰基苯基)-1-[3-(三氟甲基)苯基]亚乙基]-N-[4-(二氟甲氧基)苯基]-肼甲酰胺(由CN101715774 A已知)(CAS 1232543-85-9);3-(2,2-二氯乙烯基)-2,2-二甲基-4-(1H-苯并咪唑-2-基)苯基环丙烷甲酸酯(由CN 103524422 A已知)(CAS1542271-46-4);(4aS)-7-氯-2,5-二氢-2-[[(甲氧基羰基)[4-[(三氟甲基)硫基]苯基]氨基]羰基]-茚并[1,2-e][1,3,4]噁二嗪-4a(3H)-甲酸甲酯(由CN 102391261 A已知)(CAS 1370358-69-2);6-脱氧-3-O-乙基-2,4-二-O-甲基-1-[N-[4-[1-[4-(1,1,2,2,2-五氟乙氧基)苯基]-1H-1,2,4-三唑-3-基]苯基]氨基甲酸酯]-α-L-吡喃甘露糖(由US2014/0275503 A1已知)(CAS1181213-14-8);8-(2-环丙基甲氧基-4-三氟甲基苯氧基)-3-(6-三氟甲基-哒嗪-3-基)-3-氮杂双环[3.2.1]辛烷(CAS1253850-56-4)、(8-反式)-8-(2-环丙基甲氧基-4-三氟甲基苯氧基)-3-(6-三氟甲基哒嗪-3-基)-3-氮杂双环[3.2.1]辛烷(CAS 933798-27-7)、(8-顺式)-8-(2-环丙基甲氧基-4-三氟甲基苯氧基)-3-(6-三氟甲基哒嗪-3-基)-3-氮杂双环[3.2.1]辛烷(由WO 2007040280 A1、WO 2007040282 A1已知)(CAS 934001-66-8)、N-[4-(氨基硫代甲基)-2-甲基-6-[(甲基氨基)羰基]苯基]-3-溴-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酰胺(由CN103265527 A已知)(CAS1452877-50-7)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-1,8-二氮杂螺[4.5]癸烷-2,4-二酮(由WO 2014/187846 A1已知)(CAS 1638765-58-8)、3-(4-氯-2,6-二甲基苯基)-8-甲氧基-1-甲基-2-氧代-1,8-二氮杂螺[4.5]癸-3-烯-4-基碳酸乙酯(由WO 2010/066780 A1,WO 2011151146A1已知)(CAS1229023-00-0)、N-[1-(2,6-二氟苯基)-1H-吡唑-3-yl]-2-(三氟甲基)苯甲酰胺(由WO 2014/053450 A1已知)(CAS1594624-87-9)、N-[2-(2,6-二氟苯基)-2H-1,2,3-三唑-4-yl]-2-(三氟甲基)苯甲酰胺(由WO 2014/053450A1已知)(CAS1594637-65-6)、N-[1-(3,5-二氟-2-吡啶)-1H-吡唑-3-yl]-2-(三氟甲基)苯甲酰胺(由WO 2014/053450 A1已知)(CAS 1594626-19-3)、(3R)-3-(2-氯-5-噻唑)-2,3-二氢-8-甲基-5,7-二氧杂-6-苯基-5H-噻唑并[3,2-a]嘧啶内盐(由WO 2018/177970A1已知)(CAS 2246757-58-2);3-(2-氯-5-噻唑)-2,3-二氢-8-甲基-5,7-二氧杂-6-苯基-5H-噻唑并[3,2-a]嘧啶内盐(由WO 2018/177970 A1已知)(CAS 2246757-56-0);N-[3-氯-1-(3-吡啶基)-1H-吡唑-4-基]-2-(甲磺酰)丙酰胺(由WO 2019/236274A1已知)(CAS2396747-83-2);N-[2-溴-4-[1,2,2,2-四氟-1-(三氟甲基)乙基]-6-(三氟甲基)苯基]-2-氟-3-[(4-氟苯甲基)氨基]苯甲酰胺(由WO 2019059412 A1已知)(CAS1207977-87-4);3-溴-1-(3-氯-2-吡啶基)-N-[4,6-二氯-3-氟-2-[(甲胺基)羰基]苯基]-1H-吡唑-5-甲酰胺(Fluchlorodiamide;由CN110835330 A,CN106977494 A已知)(CAS:2129147-03-9)。
可以与本发明的化合物和组合物混合的杀线虫剂的实例为:
(组N-1)乙酰胆碱酯酶(AChE)抑制剂,优选选自涕灭威、丙硫克百威、虫螨威、丁硫克百威和硫双威的(N-1A)氨基甲酸酯类,或(N-1B)选自硫线磷、ethoprofos、苯线磷、噻唑磷、氰咪唑硫磷、甲拌磷和特丁硫磷的有机磷酸酯类。
(组N-2)谷氨酸门控氯化物通道(GluCl)变构调节剂,优选选自阿巴克丁和甲氨基阿维菌素苯甲酸盐的阿凡曼维菌素类。
(组N-3)线粒体复合物II电子传递抑制剂,尤其是琥珀酸-辅酶Q还原酶抑制剂,优选选自氟吡菌酰胺的吡啶基甲基苯酰胺类。
(组N-4)脂质合成/生长调节调节剂,尤其是乙酰辅酶A羧化酶抑制剂,优选选自螺虫乙酯的季酮酸(tetronic acid)衍生物和四元酸(tetramic acid)衍生物。
(组N-UN)未知或不确定作用方式的带有各种化学性质的化合物,其选自氟噻虫砜、三氟咪啶酰胺、呋喃甲醛、异菌脲和tioxazafen。
(组N-UNX)未知或不确定作用方式的化合物:推测的多位点抑制剂,优选选自二硫化碳和二甲基二硫化物(DMDS)中的挥发性硫生成剂,或选自四硫代碳酸钠中的二硫化碳释放物,或选自甲基溴和甲基碘(碘甲烷)中的烷基卤化物,或选自1,2-二溴-3-氯丙烷(DBCP)和1,3-二氯丙烯的卤代烃,或氯化苦,或选自异硫氰酸烯丙酯、棉隆、威百亩钾(metampotassium)和威百亩钠的异硫氰酸甲酯生成剂。
(组N-UNB)未知或不确定作用方式的细菌剂(非-Bt),优选选自以下的细菌或细菌衍生物:伯克氏菌属(Burkholderia spp.),例如rinojensis A396;芽孢杆菌属(Bacillusspp.),例如坚强芽孢杆菌、地衣芽孢杆菌(Bacillus licheniformis)、解淀粉芽孢杆菌(Bacillus amyloliquefaciens)或枯草芽孢杆菌(Bacillus subtilis);巴斯德氏芽菌属(Pasteuria spp.),例如穿刺芽孢杆菌(Pasteuria penetrans)或Pasteuria nishizawae;假单胞菌属(Pseudomonas spp.),例如绿针假单胞菌(Pseudomonas chlororaphis)或荧光假单胞菌(Pseudomonas fluorescens);以及链霉菌属(Streptomyces spp.),例如利迪链霉菌(Streptomyces lydicus)、Streptomyces dicklowii或白浅灰链霉菌(Streptomycesalbogriseolus)。
(组N-UNF)未知或不确定作用方式的真菌剂,优选选自以下的真菌或真菌衍生物:放线菌属(Actinomyces spp.),例如放线菌链球菌(Actinomyces streptococcus);节丛孢属(Arthrobotrys spp.),例如少孢节丛孢菌(Arthrobotrys oligospora);曲霉菌属(Aspergillus spp.),例如黑曲霉(Aspergillus niger);麝香霉属(Muscodor spp.),例如Muscodor albus;漆斑菌属(Myrothecium spp.),例如疣孢漆斑菌(Myrotheciumverrucaria);拟青霉属(Paecilomyces spp.),例如淡紫拟青霉(Paecilomyces lilacinus(淡紫拟青霉菌(Purpureocillium lilacinum)))、肉色瓶梗青霉(Paecilomyces carneus)或玫烟色拟青霉(Paecilomyces fumosoroseus);轮枝孢属(Pochonia spp.),例如厚垣普可尼亚菌(Pochonia chlamydosporia);以及木霉属(Trichoderma spp.),例如哈茨木霉(Trichoderma harzianum)、绿色木霉(Trichoderma virens)、深绿木霉(Trichodermaatroviride)或绿色木霉(Trichoderma viride)。
(组N-UNE)未知或不确定作用方式的源自植物或动物的制剂,其包括合成提取物和未精炼油,优选选自以下的源自植物或动物的制剂:印楝素、山茶籽饼、精油、大蒜提取物、水黄皮属油(pongamia oil)、萜烯(如香芹酚(carvacrol))和皂树(Quillajasaponaria)提取物。
可以与本发明的化合物和组合物混合的除草剂的实例为:
乙草胺(acetochlor)、三氟羧草醚(acifluorfen)、三氟羧草醚甲酯(acifluorfen-methyl)、三氟羧草醚钠(acifluorfen-sodium)、苯草醚(aclonifen)、甲草胺(alachlor)、二丙烯草胺(allidochlor)、禾草灭(alloxydim)、禾草灭钠(alloxydim-sodium)、莠灭净(ametryn)、氨唑草酮(amicarbazone)、先甲草胺(amidochlor)、酰嘧磺隆(amidosulfuron)、4-氨基-3-氯-6-(4-氯-2-氟-3-甲基苯基)-5-氟吡啶-2-甲酸、环丙嘧啶酸(aminocyclopyrachlor)、环丙嘧啶酸钾(aminocyclopyrachlor-potassium)、环丙嘧啶酸甲酯(aminocyclopyrachlor-methyl)、氯氨吡啶酸(aminopyralid)、氯氨吡啶酸二甲基铵(aminopyralid-dimethylammonium)、aminopyralid-tripromine、杀草强(amitrole)、氨基磺酸铵(ammoniumsulfamate)、莎稗磷(anilofos)、磺草灵(asulam)、磺草灵钾(asulam-potassium)、磺草灵钠(asulam sodium)、莠去津(atrazine)、唑啶草酮(azafenidin)、四唑嘧磺隆(azimsulfuron)、氟丁酰草胺(beflubutamid)、(S)-(-)-氟丁酰草胺、精氟丁酰草胺(beflubutamid-M)、草除灵(benazolin)、草除灵乙酯(benazolin-ethyl)、草除灵二甲基铵(benazolin-dimethylammonium)、草除灵钾(benazolin-potassium)、乙丁氟灵(benfluralin)、呋草黄(benfuresate)、苄嘧磺隆(bensulfuron)、苄嘧磺隆(bensulfuron-methyl)、地散磷(bensulide)、灭草松(bentazone)、灭草松钠(bentazone-sodium)、双环磺草酮(benzobicyclon)、吡草酮(benzofenap)、氟吡草酮(bicyclopyrone)、甲羧除草醚(bifenox)、双丙氨膦(bilanafos)、双丙氨膦钠(bilanafos-sodium)、双唑草酮(bipyrazone)、双草醚(bispyribac)、双草醚钠(bispyribac-sodium)、二氯异噁草酮(bixlozone)、除草定(bromacil)、除草定锂(bromacil-lithium)、除草定钠(bromacil-sodium)、溴丁酰草胺(bromobutide)、溴酚肟(bromofenoxim)、溴苯腈(bromoxynil)、丁酰溴苯腈(bromoxynil-butyrate)、溴苯腈钾(bromoxynil-potassium)、庚酰溴苯腈(bromoxynil-heptanoate)和辛酰溴苯腈(bromoxynil-octanoate)、羟草酮(busoxinone)、丁草胺(butachlor)、氟丙嘧草酯(butafenacil)、抑草磷(butamifos)、丁烯草胺(butenachlor)、仲丁灵(butralin)、丁苯草酮(butroxydim)、丁草敌(butylate)、唑草胺(cafenstrole)、克草胺酯(cambendichlor)、双酰草胺(carbetamide)、唑酮草酯(carfentrazone)、唑酮草酯(carfentrazone-ethyl)、草灭畏(chloramben)、草灭畏铵(chloramben-ammonium)、草灭畏二乙醇胺(chloramben-diolamine)、草灭畏甲酯(chlroamben-methyl)、草灭畏甲基铵(chloramben-methylammonium)、草灭畏钠(chloramben-sodium)、氯溴隆(chlorbromuron)、伐草克(chlorfenac)、伐草克铵(chlorfenac-ammonium)、伐草克钠(chlorfenac-sodium)、燕麦酯(chlorfenprop)、燕麦酯(chlorfenprop-methyl)、氯芴素(chlorflurenol)、氯芴素(chlorflurenol-methyl)、氯草敏(chloridazon)、氯嘧磺隆(chlorimuron)、氯嘧磺隆(chlorimuron-ethyl)、氯酞酰亚胺(chlorophthalim)、绿麦隆(chlorotoluron)、氯磺隆(chlorsulfuron)、氯酞酸(chlorthal)、氯酞酸二甲酯(chlorthal-dimethyl)、氯酞酸单甲酯(chlorthal-monomethyl)、吲哚酮草酯(cinidon)、吲哚酮草酯(cinidon-ethyl)、环庚草醚(cinmethylin)、外-(+)-环庚草醚(即(1R,2S,4S)-4-异丙基-1-甲基-2-[(2-甲基苄基)氧基]-7-氧杂双环[2.2.1]庚烷)、外-(-)-环庚草醚(即(1R,2S,4S)-4-异丙基-1-甲基-2-[(2-甲基苄基)氧基]-7-氧杂双环[2.2.1]庚烷)、醚磺隆(cinosulfuron)、氯酰草膦(clacyfos)、烯草酮(clethodim)、炔草酸(clodinafop)、炔草酸乙酯(clodinafop-ethyl)、炔草酯(clodinafop-propargyl)、异噁草松(clomazone)、氯甲酰草胺(clomeprop)、二氯吡啶酸(clopyralid)、二氯吡啶酸甲酯(clopyralid-methyl)、二氯吡啶酸乙醇胺(clopyralid-olamine)、二氯吡啶酸钾(clopyralid-potassium)、clopyralid-tripomine、氯酯磺草胺(cloransulam)、氯酯磺草胺(cloransulam-methyl)、苄草隆(cumyluron)、氰胺(cyanamide)、氰草津(cyanazine)、环草敌(cycloate)、cyclopyranil、环哒嗪草酯(cyclopyrimorate)、环丙嘧磺隆(cyclosulfamuron)、噻草酮(cycloxydim)、氰氟草酸(cyhalofop)、氰氟草酯(cyhalofop-butyl)、环草津(cyprazine)、2,4-D(包括其以下的盐:2,4-D-铵、2,4-D-丁氧基乙酯(2,4-D-butotyl)、2,4-D-丁酯、2,4-D-胆碱(2,4-D-choline)、2,4-D-二乙基铵、2,4-D-二甲基铵、2,4-D-二乙醇胺(2,4-D-diolamine)、2,4-D-丙酯丁醚(2,4-D-doboxyl)、2,4-D-十二烷基铵、2,4-D-乙基己酯(2,4-D-etexyl)、2,4-D-乙酯、2,4-D-2-乙基己酯、2,4-D-庚基铵、2,4-D-异丁酯、2,4-D-异辛酯、2,4-D-异丙酯、2,4-D-异丙基铵、2,4-D-锂、2,4-D-甲基庚酯(2,4-D-meptyl)、2,4-D-甲酯、2,4-D-钾、2,4-D-十四烷基铵、2,4-D-三乙基铵、2,4-D-三异丙醇铵、2,4-D-三丙胺(2,4-D-tripromine)和2,4-D-三乙醇胺(2,4-D-trolamine))、2,4-DB、2,4-DB-丁酯、2,4-DB-二甲基铵、2,4-DB-异辛酯、2,4-DB-钾和2,4-DB-钠、杀草隆(daimuron(dymron))、茅草枯(dalapon)、茅草枯钙(dalapon-calcium)、茅草枯镁(dalapon-magnesium)、茅草枯钠(dalapon-sodium)、棉隆(dazomet)、棉隆钠(dazomet-sodium)、正癸醇、7-脱氧-D-景天庚酮糖(sedoheptulose)、甜菜安(desmedipham)、去甲苯磺酰基-吡唑特(detosyl-pyrazolate(DTP))、麦草畏及其盐(例如麦草畏二丙胺(dicamba-biproamine)、麦草畏-N,N-双(3-氨基丙基)甲基胺、麦草畏-丁氧基乙酯(dicamba-butotyl)、麦草畏-胆碱(dicamba-choline)、麦草畏-二乙二醇胺(dicamba-diglycolamine)、麦草畏-二甲基铵、麦草畏-二乙醇胺铵(dicamba-diethanolamine ammonium)、麦草畏-二乙基铵、麦草畏-异丙基铵、麦草畏-甲酯、麦草畏-单乙醇胺(dicamba-monoethanolamine)、麦草畏-乙醇胺(dicamba-olamine)、麦草畏钾(dicamba-potassium)、麦草畏钠(dicamba-sodium)、麦草畏-三乙醇胺(dicamba-triethanolamine))、敌草腈(dichlobenil)、2-(2,4-二氯苄基)-4,4-二甲基-1,2-噁唑烷-3-酮、2-(2,5-二氯苄基)-4,4-二甲基-1,2-噁唑烷-3-酮、2,4-滴丙酸(dichlorprop)、2,4-滴丙酸丁氧基乙酯(dichlorprop-butotyl)、2,4-滴丙酸二甲铵(dichlorprop-dimethylammonium)、2,4-滴丙酸乙基己酯(dichlorprop-etexyl)、2,4-滴丙酸乙基铵(dichlorprop-ethylammonium)、2,4-滴丙酸异辛酯(dichlorprop-isoctyl)、2,4-滴丙酸甲酯(dichlorprop-methyl)、2,4-滴丙酸钾(dichlorprop-potassium)、2,4-滴丙酸钠(dichlorprop-sodium)、精2,4-滴丙酸(dichlorprop-P)、精2,4-滴丙酸二甲基铵(dichlorprop-P-dimethylammonium)、精2,4-滴丙酸乙基己酯(dichlorprop-P-etexyl)、精2,4-滴丙酸钾(dichlorprop-P-potassium)、2,4-滴丙酸钠(dichlorprop-sodium)、禾草灵(diclofop)、禾草灵(diclofop-methyl)、精禾草灵(diclofop-P)、精禾草灵(diclofop-P-methyl)、双氯磺草胺(diclosulam)、野燕枯(difenzoquat)、野燕枯硫酸甲酯(difenzoquat-metilsulfate)、吡氟酰草胺(diflufenican)、二氟吡隆(diflufenzopyr)、二氟吡隆钠(diflufenzopyr-sodium)、噁唑隆(dimefuron)、哌草丹(dimepiperate)、dimesulfazet、二甲草胺(dimethachlor)、异戊乙净(dimethametryn)、二甲吩草胺(dimethenamid)、精二甲吩草胺(dimethenamid-P)、醚磺隆(dimetrasulfuron)、氨氟灵(dinitramine)、特乐酚(dinoterb)、特乐酯(dinoterb-acetate)、双苯酰草胺(diphenamid)、敌草快(diquat)、敌草快二溴化物(diquat-dibromid)、敌草快二氯化物(diquat-dichloride)、氟硫草定(dithiopyr)、敌草隆(diuron)、二硝酚(DNOC)、二硝酚铵(DNOC-ammonium)、二硝酚钾(DNOC-potassium)、二硝酚钠(DNOC-sodium)、茵多酸(endothal)、茵多酸二铵(endothal-diammonium)、茵多酸二钾(endothal-dipotassium)、茵多酸二钠(endothal-disodium)、Epyrifenacil(S-3100)、茵草敌(EPTC)、戊草丹(esprocarb)、乙丁烯氟灵(ethalfluralin)、胺苯磺隆(ethametsulfuron)、胺苯磺隆(ethametsulfuron-methyl)、乙嗪草酮(ethiozin)、乙氧呋草黄(ethofumesate)、氯氟草醚(ethoxyfen)、氯氟草醚乙酯(ethoxyfen-ethyl)、乙氧嘧磺隆(ethoxysulfuron)、乙氧苯草胺(etobenzanid)、F-5231(即N-[2-氯-4-氟-5-[4-(3-氟丙基)-4,5-二氢-5-氧代-1H-四唑-1-基]-苯基]-乙磺酰胺)、F-7967(即3-[7-氯-5-氟-2-(三氟甲基)-1H-苯并咪唑-4-基]-1-甲基-6-(三氟甲基)嘧啶-2,4(1H,3H)-二酮)、噁唑禾草灵(fenoxaprop)、精噁唑禾草灵(fenoxaprop-P)、噁唑禾草灵(fenoxaprop-ethyl)、精噁唑禾草灵(fenoxaprop-P-ethyl)、苯磺噁唑草(fenoxasulfone)、苯唑氟草酮(fenpyrazone)、fenquinotrione、四唑酰草胺(fentrazamide)、麦草氟(flamprop)、麦草氟异丙酯(flamprop-isoproyl)、麦草氟甲酯(flamprop-methyl)、精麦草氟异丙酯(flamprop-M-isopropyl)、精麦草氟甲酯(flamprop-M-methyl)、啶嘧磺隆(flazasulfuron)、双氟磺草胺(florasulam)、氯氟吡啶酸(florpyrauxifen)、氯氟吡啶酯(florpyrauxifen-benzyl)、吡氟禾草灵(fluazifop)、吡氟禾草灵丁酯(fluazifop-butyl)、吡氟禾草灵甲酯(fluazifop-methyl)、精吡氟禾草灵(fluazifop-P)、精吡氟禾草灵丁酯(fluazifop-P-butyl)、氟唑磺隆(flucarbazone)、氟唑磺隆钠(flucarbazone-sodium)、氟吡磺隆(flucetosulfuron)、氯乙氟灵(fluchloralin)、氟噻草胺(flufenacet)、氟哒嗪草酸(flufenpyr)、氟哒嗪草酯(flufenpyr-ethyl)、唑嘧磺草胺(flumetsulam)、氟烯草酸(flumiclorac)、氟烯草酯(flumiclorac-pentyl)、丙炔氟草胺(flumioxazin)、氟草隆(fluometuron)、抑草丁(flurenol)、芴醇丁酯(flurenol-butyl)、芴醇二甲基铵(flurenol-dimethylammonium)和芴醇甲酯(flurenol-methyl)、乙羧氟草醚(fluoroglycofen)、乙羧氟草醚(fluoroglycofen-ethyl)、四氟丙酸(flupropanate)、四氟丙酸钠(flupropanate-sdium)、氟啶嘧磺隆(flupyrsulfuron)、氟啶嘧磺隆(flupyrsulfuron-methyl)、氟啶嘧磺隆钠(flupyrsulfuron-methyl-sodium)、氟啶草酮(fluridone)、氟咯草酮(flurochloridone)、氯氟吡氧乙酸(fluroxypyr)、氯氟吡氧乙酸丁氧异丙酯(fluroxypyr-butometyl)、氯氟吡氧乙酸异辛酯(fluroxypyr-meptyl)、呋草酮(flurtamone)、嗪草酸(fluthiacet)、嗪草酸甲酯(fluthiacet-methyl)、氟磺胺草醚(fomesafen)、氟磺胺草醚钠(fomesafen-sodium)、甲酰胺磺隆(foramsulfuron)、甲酰胺磺隆钠(foramsulfuron sodium salt)、杀木膦(fosamine)、杀木膦铵(fosamine-ammonium)、草铵膦、草铵膦铵(glufosinate-ammonium)、草铵膦钠、L-草铵膦铵、L-草铵膦钠、精草铵膦钠(glufosinate-P-sodium)、精草铵膦铵(glufosinate-P-ammonium)、草甘膦、草甘膦铵(glyphosate-ammonium)、草甘膦异丙基铵(glyphosate-isopropylammonium)、草甘膦二铵(glyphosate-diammonium)、草甘膦二甲基铵(glyphosate-dimethylammonium)、草甘膦钾(glyphosate-potassium)、草甘膦钠(glyphosate-sodium)、草甘膦倍半钠(glyphosate-sesquisodium)和草硫膦(glyphosate-trimesium)、H-9201(即O-(2,4-二甲基-6-硝基苯基)-O-乙基异丙基硫代磷酰胺酯(O-(2,4-Dimethyl-6-nitrophenyl)-O-ethyl-isopropylphosphoramidothioat))、氟氯吡啶酸(halauxifen)、氟氯吡啶酯(halauxifen-methyl)、氟硝磺酰胺(halosafen)、氯吡嘧磺隆(halosulfuron)、氯吡嘧磺隆(halosulfuron-methyl)、氟吡禾灵(haloxyfop)、精氟吡禾灵(haloxyfop-P)、氟吡禾灵乙氧基乙酯(haloxyfop-ethoxyethyl)、精氟吡禾灵乙氧基乙酯(haloxyfop-P-ethoxyethyl)、氟吡甲禾灵(haloxyfop-methyl)、精氟吡甲禾灵(haloxyfop-P-methyl)、haloxifop-sodium、环嗪酮(hexazinone)、HNPC-A8169(即(2S)-2-{3-[(5-叔丁基吡啶-2-基)氧基]苯氧基}丙酸丙-2-炔-1-基酯)、HW-02(即1-(二甲氧基磷酰基)-乙基-(2,4-二氯苯氧基)乙酸酯)、hydantocidin、咪草酸(imazamethabenz)、咪草酸甲酯(imazamethabenz-methyl)、甲氧咪草烟(imazamox)、甲氧咪草烟铵(imazamox-ammonium)、甲咪唑烟酸(imazapic)、甲咪唑烟酸铵(imazapic-ammonium)、咪唑烟酸(imazapyr)、咪唑烟酸异丙基铵(imazapyr-isopropylammonium)、咪唑喹啉酸(imazaquin)、咪唑喹啉酸铵(imazaquin-ammonium)、咪唑喹啉酸甲酯(imazaquin.methyl)、咪唑乙烟酸(imazethapyr)、咪唑乙烟酸亚铵(imazethapyr-immonium)、唑吡嘧磺隆(imazosulfuron)、茚草酮(indanofan)、茚嗪氟草胺(indaziflam)、碘甲磺隆(iodosulfuron)、碘甲磺隆(iodosulfuron-methyl)、碘甲磺隆钠(iodosulfuron-methyl-sodium)、碘苯腈(ioxynil)、碘苯腈锂(ioxynil-lithium)、辛酰碘苯腈(ioxynil-octanoate)、碘苯腈钾(ioxynil-potassium)和碘苯腈钠(ioxynil-sodium)、三唑酰草胺(ipfencarbazone)、异丙隆(isoproturon)、异噁隆(isouron)、异噁酰草胺(isoxaben)、异噁唑草酮(isoxaflutole)、特胺灵(karbutilate)、KUH-043(即3-({[5-(二氟甲基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-基]甲基}磺酰基)-5,5-二甲基-4,5-二氢-1,2-噁唑)、ketospiradox、ketospiradox-potassium、乳氟禾草灵(lactofen)、lancotrione、环草定(lenacil)、利谷隆(linuron)、MCPA、MCPA-丁氧基乙酯、MCPA-丁酯、MCPA-二甲基铵、MCPA-二乙醇胺(MCPA-diolamine)、MCPA-2-乙基己酯、MCPA-乙酯、MCPA-异丁酯、MCPA-异辛酯、MCPA-异丙酯、MCPA-异丙基铵、MCPA-甲酯、MCPA-乙醇胺(MCPA-olamine)、MCPA-钾、MCPA-钠和MCPA-三乙醇胺(MCPA-trolamine)、MCPB、MCPB-甲酯、MCPB-乙酯和MCPB-钠、2-甲-4-氯丙酸(mecoprop)、2-甲-4-氯丙酸丁氧基乙酯(mecoprop-butotyl)、2-甲-4-氯丙酸二甲基铵、2-甲-4-氯丙酸二乙醇胺(mecoprop-diolamine)、2-甲-4-氯丙酸乙基己酯(mecoprop-etexyl)、2-甲-4-氯丙酸亚乙酯(mecoprop-ethadyl)、2-甲-4-氯丙酸异辛酯、2-甲-4-氯丙酸甲酯、2-甲-4-氯丙酸钾、2-甲-4-氯丙酸钠和2-甲-4-氯丙酸三乙醇胺(mecoprop-trolamine)、精2-甲-4-氯丙酸(mecoprop-P)、精2-甲-4-氯丙酸丁氧基乙酯(mecoprop-P-butotyl)、精2-甲-4-氯丙酸-二甲基铵、精2-甲-4-氯丙酸-2-乙基己酯和精2-甲-4-氯丙酸钾、苯噻酰草胺(mefenacet)、氟磺酰草胺(mefluidide)、氟磺酰草胺二乙醇胺(mefluidide-diolamine)、氟磺酰草胺钾(mefluidide-potassium)、甲基二磺隆(mesosulfuron)、甲基二磺隆(mesosulfuron-methyl)、甲基二磺隆钠盐、甲基磺草酮(mesotrione)、甲基苯噻隆(methabenzthiazuron)、威百亩(metam)、噁唑酰草胺(metamifop)、苯嗪草酮(metamitron)、吡唑草胺(metazachlor)、嗪吡嘧磺隆(metazosulfuron)、甲基苯噻隆、甲硫嘧磺隆(methiopyrsulfuron)、甲硫唑草啉(methiozolin)、异硫氰酸甲酯、溴谷隆(metobromuron)、异丙甲草胺(metolachlor)、精异丙甲草胺(S-metolachlor)、磺草唑胺(metosulam)、甲氧隆(metoxuron)、嗪草酮(metribuzin)、甲磺隆(metsulfuron)、甲磺隆(metsulfuron-methyl)、禾草敌(molinate)、绿谷隆(monolinuron)、单嘧磺隆(monosulfuron)、单嘧磺酯(monosulfuron-methyl)、MT-5950(即N-[3-氯-4-(1-甲基乙基)-苯基]-2-甲基戊酰胺)、NGGC-011、敌草胺(napropamide)、NC-310(即4-(2,4-二氯苯甲酰基)-1-甲基-5-苄氧基吡唑)、NC-656(即3-[(异丙基磺酰基)甲基]-N-(5-甲基-1,3,4-噁二唑-2-基)-5-(三氟甲基)[1,2,4]三唑并[4,3-a]吡啶-8-甲酰胺)、草不隆(neburon)、烟嘧磺隆(nicosulfuron)、壬酸(pelargonicacid)、氟草敏(norflurazon)、油酸(脂肪酸)、坪草丹(orbencarb)、嘧苯胺磺隆(orthosulfamuron)、氨磺乐灵(oryzalin)、丙炔噁草酮(oxadiargyl)、噁草酮(oxadiazon)、环氧嘧磺隆(oxasulfuron)、噁嗪草酮(oxaziclomefon)、乙氧氟草醚(oxyfluorfen)、百草枯(paraquat)、百草枯二氯化物(paraquat dichloride)、百草枯二甲基硫酸酯(paraquat-dimethylsulfate)、克草敌(pebulate)、二甲戊灵(pendimethalin)、五氟磺草胺(penoxsulam)、五氯苯酚(pentachlorphenol)、环戊噁草酮(pentoxazone)、烯草胺(pethoxamid)、矿物油、甜菜宁(phenmedipham)、甜菜宁乙酯(phenmedipham-ethyl)、氨氯吡啶酸(picloram)、氨氯吡啶酸二甲基铵、氨氯吡啶酸乙基己酯(picloram-etexyl)、氨氯吡啶酸异辛酯、氨氯吡啶酸甲酯、氨氯吡啶酸乙醇胺(picloram-olamine)、氨氯吡啶酸钾、氨氯吡啶酸三乙基铵、氨氯吡啶酸三丙胺(picloram-tripromine)、氨氯吡啶酸三乙醇胺(picloram-trolamine)、氟吡酰草胺(picolinafen)、唑啉草酯(pinoxaden)、哌草磷(piperophos)、丙草胺(pretilachlor)、氟嘧磺隆(primisulfuron)、氟嘧磺隆(primisulfuron-methyl)、氨氟乐灵(prodiamine)、环苯草酮(profoxydim)、扑灭通(prometon)、扑草净(prometryn)、毒草胺(propachlor)、敌稗(propanil)、噁草酸(propaquizafop)、扑灭津(propazine)、苯胺灵(propham)、异丙草胺(propisochlor)、丙苯磺隆(propoxycarbazone)、丙苯磺隆钠(propoxycarbazone-sodium)、丙嗪嘧磺隆(propyrisulfuron)、炔苯酰草胺(propyzamide)、苄草丹(prosulfocarb)、氟磺隆(prosulfuron)、双唑草腈(pyraclonil)、吡草醚(pyraflufen)、吡草醚(pyraflufen-ethyl)、磺酰草吡唑(pyrasulfotole)、吡唑特(pyrazolynate(pyrazolate))、吡嘧磺隆(pyrazosulfuron)、吡嘧磺隆(pyrazosulfuron-ethyl)、苄草唑(pyrazoxyfen)、pyribambenz、异丙酯草醚(pyribambenz-isopropyl)、丙酯草醚(pyribambenz-propyl)、嘧啶肟草醚(pyribenzoxim)、稗草丹(pyributicarb)、达草止(pyridafol)、哒草特(pyridate)、环酯草醚(pyriftalid)、嘧草醚(pyriminobac)、嘧草醚(pyriminobac-methyl)、嘧氟磺草胺(pyrimisulfan)、嘧草硫醚(pyrithiobac)、嘧草硫醚(pyrithiobac-sodium)、砜吡草唑(pyroxasulfone)、甲氧磺草胺(pyroxsulam)、二氯喹啉酸(quinclorac)、二氯喹啉酸二甲基铵、二氯喹啉酸甲酯、氯甲喹啉酸(quinmerac)、灭藻醌(quinoclamine)、喹禾灵(quizalofop)、喹禾灵乙酯(quizalofop-ethyl)、精喹禾灵(quizalofop-P)、精喹禾灵乙酯(quizalofop-P-ethyl)、精喹禾糠酯(quizalofop-P-tefuryl)、QYM201(即1-{2-氯-3-[(3-环丙基-5-羟基-1-甲基-1H-吡唑-4-基)羰基]-6-(三氟甲基)苯基}哌啶-2-酮)、砜嘧磺隆(rimsulfuron)、苯嘧磺草胺(saflufenacil)、烯禾定(sethoxydim)、环草隆(siduron)、西玛津(simazine)、西草净(simetryn)、SL-261、磺草酮(sulcotrione)、甲磺草胺(sulfentrazone)、甲嘧磺隆(sulfometuron)、甲嘧磺隆(sulfometuron-methyl)、磺酰磺隆(sulfosulfuron)、SYP-249(即1-乙氧基-3-甲基-1-氧代丁-3-烯-2-基-5-[2-氯-4-(三氟甲基)苯氧基]-2-硝基苯甲酸酯)、SYP-300(即1-[7-氟-3-氧代-4-(丙-2-炔-1-基)-3,4-二氢-2H-1,4-苯并噁嗪-6-基]-3-丙基-2-硫代咪唑烷-4,5-二酮)、2,3,6-TBA、TCA(三氯乙酸)及其盐(例如TCA-铵、TCA-钙、TCA-乙酯、TCA-镁、TCA-钠)、丁噻隆(tebuthiuron)、呋喃磺草酮(tefuryltrione)、环磺酮(tembotrione)、吡喃草酮(tepraloxydim)、特草定(terbacil)、特草灵(terbucarb)、特丁通(terbumeton)、特丁津(terbuthylazine)、特丁净(terbutryn)、四氟络草胺(tetflupyrolimet)、thaxtomin、噻吩草胺(thenylchlor)、噻唑烟酸(thiazopyr)、噻酮磺隆(thiencarbazone)、噻酮磺隆(thiencarbazone-methyl)、噻吩磺隆(thifensulfuron)、噻吩磺隆(thifensulfuron-methyl)、禾草丹(thiobencarb)、氟嘧硫草酯(tiafenacil)、tolpyralate、苯吡唑草酮(topramezone)、三甲苯草酮(tralkoxydim)、氟酮磺草胺(triafamone)、野麦畏(tri-allate)、醚苯磺隆(triasulfuron)、三嗪氟草胺(triaziflam)、苯磺隆(tribenuron)、苯磺隆(tribenuron-methyl)、三氯吡氧乙酸(triclopyr)、三氯吡氧乙酸丁氧基乙酯(triclopyr-butotyl)、三氯吡氧乙酸胆碱(triclopyr-choline)、三氯吡氧乙酸乙酯、三氯吡氧乙酸三乙基铵、草达津(trietazine)、三氟啶磺隆(trifloxysulfuron)、三氟啶磺隆钠(trifloxysulfuron-sodium)、三氟草嗪(trifludimoxazin)、氟乐灵(trifluralin)、氟胺磺隆(triflusulfuron)、氟胺磺隆(triflusulfuron-methyl)、三氟甲磺隆(tritosulfuron)、硫酸脲、灭草敌(vernolate)、XDE-848、ZJ-0862(即3,4-二氯-N-{2-[(4,6-二甲氧基嘧啶-2-基)氧基]苄基}苯胺)、3-(2-氯-4-氟-5-(3-甲基-2,6-二氧代-4-三氟甲基-3,6-二氢嘧啶-1(2H)-基)苯基)-5-甲基-4,5-二氢异噁唑-5-甲酸乙酯、乙基-[(3-{2-氯-4-氟-5-[3-甲基-2,6-二氧代-4-(三氟甲基)-3,6-二氢嘧啶-1(2H)-基]苯氧基}吡啶-2-基)氧基]乙酸酯、3-氯-2-[3-(二氟甲基)异噁唑基-5-基]苯基-5-氯嘧啶-2-基醚、2-(3,4-二甲氧基苯基)-4-[(2-羟基-6-氧代环己-1-烯-1-基)羰基]-6-甲基哒嗪-3(2H)-酮、2-({2-[(2-甲氧基乙氧基)甲基]-6-甲基吡啶-3-基}羰基)环己烷-1,3-二酮、(5-羟基-1-甲基-1H-吡唑-4-基)(3,3,4-三甲基-1,1-二氧代(dioxido)-2,3-二氢-1-苯并噻吩-5-基)甲酮、1-甲基-4-[(3,3,4-三甲基-1,1-二氧代-2,3-二氢-1-苯并噻吩-5-基)羰基]-1H-吡唑-5-基丙烷-1-磺酸酯、4-{2-氯-3-[(3,5-二甲基-1H-吡唑-1-基)甲基]-4-(甲基磺酰基)苯甲酰基}-1-甲基-1H-吡唑-5-基-1,3-二甲基-1H-吡唑-4-甲酸酯、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-甲酸氰基甲酯、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-甲酸丙-2-炔-1-基酯、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-甲酸甲酯、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-甲酸、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-甲酸苄酯、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-甲酸乙酯、4-氨基-3-氯-5-氟-6-(7-氟-1-异丁酰基-1H-吲哚-6-基)吡啶-2-甲酸甲酯、6-(1-乙酰基-7-氟-1H-吲哚-6-基)-4-氨基-3-氯-5-氟吡啶-2-甲酸甲酯、4-氨基-3-氯-6-[1-(2,2-二甲基丙酰基)-7-氟-1H-吲哚-6-基]-5-氟吡啶-2-甲酸甲酯、4-氨基-3-氯-5-氟-6-[7-氟-1-(甲氧基乙酰基)-1H-吲哚-6-基]吡啶-2-甲酸甲酯、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-甲酸钾、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-甲酸钠、4-氨基-3-氯-5-氟-6-(7-氟-1H-吲哚-6-基)吡啶-2-甲酸丁酯、4-羟基-1-甲基-3-[4-(三氟甲基)吡啶-2-基]咪唑烷-2-酮、3-(5-叔丁基-1,2-噁唑-3-基)-4-羟基-1-甲基咪唑烷-2-酮、3-[5-氯-4-(三氟甲基)吡啶-2-基]-4-羟基-1-甲基咪唑烷-2-酮、4-羟基-1-甲氧基-5-甲基-3-[4-(三氟甲基)吡啶-2-基]咪唑烷-2-酮、6-[(2-羟基-6-氧代环己-1-烯-1-基)羰基]-1,5-二甲基-3-(2-甲基苯基)喹唑啉-2,4(1H,3H)-二酮、3-(2,6-二甲基苯基)-6-[(2-羟基-6-氧代环己-1-烯-1-基)羰基]-1-甲基喹唑啉-2,4(1H,3H)-二酮、2-[2-氯-4-(甲基磺酰基)-3-(吗啉-4-基甲基)苯甲酰基]-3-羟基环己-2-烯-1-酮、1-(2-羧乙基)-4-(嘧啶-2-基)哒嗪-1-鎓盐(具有阴离子,如氯离子、乙酸根或三氟乙酸根)、1-(2-羧乙基)-4-(哒嗪-3-基)哒嗪-1-鎓盐(具有阴离子,如氯离子、乙酸根或三氟乙酸根)、4-(嘧啶-2-基)-1-(2-磺乙基)哒嗪-1-鎓盐(具有阴离子,如氯离子、乙酸根或三氟乙酸根)、4-(哒嗪-3-基)-1-(2-磺乙基)哒嗪-1-鎓盐(具有阴离子,如氯离子、乙酸根或三氟乙酸根)、1-(2-羧乙基)-4-(1,3-噻唑-2-基)哒嗪-1-鎓盐(具有阴离子,如氯离子、乙酸根或三氟乙酸根)、1-(2-羧乙基)-4-(1,3-噻唑-2-基)哒嗪-1-鎓盐(具有阴离子,如氯离子、乙酸根或三氟乙酸根)。
可以与本发明的化合物和组合物混合的植物生长调节剂的实例为:
脱落酸(Abscisic acid)及相关的类似物[例如(2Z,4E)-5-[6-乙炔基-1-羟基-2,6-二甲基-4-氧代环己-2-烯-1-基]-3-甲基戊-2,4-二烯酸、甲基-(2Z,4E)-5-[6-乙炔基-1-羟基-2,6-二甲基-4-氧代环己-2-烯-1-基]-3-甲基戊-2,4-二烯酸酯(dienoate)、(2Z,4E)-3-乙基-5-(1-羟基-2,6,6-三甲基-4-氧代环己-2-烯-1-基)戊-2,4-二烯酸、(2E,4E)-5-(1-羟基-2,6,6-三甲基-4-氧代环己-2-烯-1-基)-3-(三氟甲基)戊-2,4-二烯酸、(2E,4E)-5-(1-羟基-2,6,6-三甲基-4-氧代环己-2-烯-1-基)-3-(三氟甲基)戊-2,4-二烯酸甲酯、(2Z,4E)-5-(2-羟基-1,3-二甲基-5-氧代双环[4.1.0]庚-3-烯-2-基)-3-甲基戊-2,4-二烯酸]、活化酯(acibenzolar)、苯并噻二唑(acibenzolar-S-methyl)、S-腺苷高半胱氨酸(S-adenosylhomocysteine)、尿囊素(allantoin)、2-氨基乙氧基乙烯基甘氨酸(AVG)、氨基氧基乙酸及相关的酯[例如(亚异丙基)-氨基氧基乙酸-2-(甲氧基)-2-氧代乙酯、(亚异丙基)-氨基氧基乙酸-2-(己氧基)-2-氧代乙酯、(亚环己基)-氨基氧基乙酸-2-(异丙氧基)-2-氧代乙酯]、1-氨基环丙-1-基甲酸及其衍生物(例如DE3335514、EP30287、DE2906507或US5123951中所公开的)、5-氨基乙酰丙酸、嘧啶醇(ancymidol)、6-苄基氨基嘌呤、bikinin、芸苔素内酯(brassinolide)、乙基芸苔素内酯(brassinolide-ethyl)、L-副刀豆氨酸(L-canaline)、儿茶酸(catechin)和儿茶素类(catechines)(例如(2S,3R)-2-(3,4-二羟基苯基)-3,4-二氢-2H-苯并吡喃-3,5,7-三醇((2S,3R)-2-(3,4-Dihydroxyphenyl)-3,4-dihydro-2H-chromen-3,5,7-triol))、壳寡糖(chitooligosaccharide)(CO;CO与LCO的不同之处在于其缺乏脂肪酸侧链,该脂肪酸侧链为LCO的特性。CO(有时称为N-乙酰基壳寡糖)也包含GlcNAc残基,但具有侧链修饰,使得其不同于壳多糖(chitin)分子[(C8H13NO5)n,CAS号1398-61-4]和壳聚糖(chitosan)分子[(C5H11NO4)n,CAS号9012-76-4])、壳多糖化合物、矮壮素(chlormequat chloride)、调果酸(cloprop)、环丙酰胺酸(cyclanilide)、3-(环丙-1-烯基)丙酸、1-[2-(4-氰基-3,5-二环丙基苯基)乙酰胺基]环己烷甲酸、1-[2-(4-氰基-3-环丙基苯基)乙酰胺基]环己烷甲酸、丁酰肼(daminozide)、棉隆、棉隆钠、正癸醇、敌草克(dikegulac)、敌草克钠(dikegulac-sodium)、茵多酸、茵多酸二钾、茵多酸二钠,和单(N,N-二甲基烷基铵)、乙烯利(ethephon)、氟节胺(flumetralin)、抑草丁、芴醇丁酯、芴醇甲酯、呋嘧醇(flurprimidol)、氯吡脲(forchlorfenuron)、赤霉酸(gibberellic acid)、抗倒胺(inabenfide)、吲哚-3-乙酸(IAA)、4-吲哚-3-基丁酸、稻瘟灵(isoprothiolane)、烯丙苯噻唑(probenazole)、茉莉酸(jasmonic acid)、茉莉酸或其衍生物(例如茉莉酸甲酯、茉莉酸乙酯)、脂壳寡糖(lipo-chitooligosaccharide)(LCO,有时称为共生结瘤(Nod)信号(或Nod因子)或Myc因子,由具有在非还原末端缩合的N-连接的脂肪酰基链的β-l,4-连接的N-乙酰基-D-氨基葡萄糖(“GlcNAc”)残基的寡糖主链构成。如本领域所理解的,LCO在主链中的GlcNAc残基的数量、脂肪酰基链的长度和饱和度以及还原糖和非还原糖残基的取代方面有所不同)、亚油酸或其衍生物、亚麻酸或其衍生物、马来酰肼(maleic hydrazide)、助壮素(mepiquat chloride)、助壮素五硼酸盐(mepiquat pentaborate)、1-甲基环丙烯、3-甲基环丙烯、1-乙基环丙烯、1-正丙基环丙烯、1-环丙烯基甲醇、甲氧基乙烯基甘氨酸(MVG)、3'-甲基脱落酸、1-(4-甲基苯基)-N-(2-氧代-1-丙基-1,2,3,4-四氢喹啉-6-基)甲基磺酰胺以及相关的取代的四氢喹啉-6-基)甲基磺酰胺、(3E,3aR,8bS)-3-({[(2R)-4-甲基-5-氧代-2,5-二氢呋喃-2-基]氧基}亚甲基)-3,3a,4,8b-四氢-2H-茚并[1,2-b]呋喃-2-酮和如EP2248421中概述的相关的内酯、2-(1-萘基)乙酰胺、1-萘基乙酸、2-萘基氧基乙酸、硝基酚盐混合物(nitrophenolate-mixture)、4-氧代-4[(2-苯基乙基)氨基]丁酸、多效唑(paclobutrazol)、4-苯基丁酸及其盐(例如4-苯基丁酸钠、4-苯基丁酸钾)、苯基丙氨酸(phenylalanine)、N-苯基邻苯二甲酸、调环酸(prohexadione)、调环酸钙(prohexadione-calcium)、腐胺(putrescine)、茉莉酮(prohydrojasmon)、根瘤菌素(rhizobitoxin)、水杨酸、水杨酸甲酯、肌氨酸(sarcosine)、环丙-1-烯-1-基乙酸钠、环丙-2-烯-1-基乙酸钠、3-(环丙-2-烯-1-基)丙酸钠、3-(环丙-1-烯-1-基)丙酸钠、sidefungin、亚精胺(spermidine)、精胺(spermine)、独脚金内酯(strigolactone)、四氯硝基苯(tecnazene)、噻苯隆(thidiazuron)、三十烷醇(triacontanol)、抗倒酯(trinexapac)、抗倒酯(trinexapac-ethyl)、色氨酸(tryptophan)、tsitodef、烯效唑(uniconazole)、精烯效唑(uniconazole-P)、2-氟-N-(3-甲氧基苯基)-9H-嘌呤-6-胺。
可以与本发明的化合物和组合物混合的安全剂的实例为:
S1)选自杂环羧酸衍生物类的化合物:
S1a)二氯苯基吡唑啉-3-羧酸类的化合物(S1a),优选化合物例如1-(2,4-二氯苯基)-5-(乙氧基羰基)-5-甲基-2-吡唑啉-3-甲酸、1-(2,4-二氯苯基)-5-(乙氧基羰基)-5-甲基-2-吡唑啉-3-甲酸乙酯(S1-1)(“吡唑解草酯(mefenpyr-diethyl)”),以及如在WO-A-91/07874中记载的相关化合物;
S1b)二氯苯基吡唑羧酸的衍生物(S1b),优选化合物例如1-(2,4-二氯苯基)-5-甲基吡唑-3-甲酸乙酯(S1-2)、1-(2,4-二氯苯基)-5-异丙基吡唑-3-甲酸乙酯(S1-3)、1-(2,4-二氯苯基)-5-(1,1-二甲基乙基)吡唑-3-甲酸乙酯(S1-4),以及如在EP-A-333131 131和EP-A-269806中记载的相关化合物;
S1c)1,5-二苯基吡唑-3-羧酸的衍生物(S1c),优选化合物例如1-(2,4-二氯苯基)-5-苯基吡唑-3-甲酸乙酯(S1-5)、1-(2-氯苯基)-5-苯基吡唑-3-甲酸甲酯(S1-6),以及如在例如EP-A-268554中记载的相关化合物;
S1d)三唑羧酸类的化合物(S1d),优选化合物例如解草唑(fenchlorazole)(乙酯),即1-(2,4-二氯苯基)-5-三氯甲基-1H-1,2,4-三唑-3-甲酸乙酯(S1-7),以及如在EP-A-174562和EP-A-346620中记载的相关化合物;
S1e)5-苄基-2-异噁唑啉-3-羧酸或5-苯基-2-异噁唑啉-3-羧酸或5,5-二苯基-2-异噁唑啉-3-羧酸类的化合物(S1e),优选化合物例如5-(2,4-二氯苄基)-2-异噁唑啉-3-甲酸乙酯(S1-8)或5-苯基-2-异噁唑啉-3-甲酸乙酯(S1-9),以及如在WO-A-91/08202中记载的相关化合物,或5,5-二苯基-2-异噁唑啉甲酸(S1-10)或5,5-二苯基-2-异噁唑啉-3-甲酸乙酯(S1-11)(“双苯噁唑酸(isoxadifen-ethyl)”)或5,5-二苯基-2-异噁唑啉-3-甲酸正丙酯(S1-12)或5-(4-氟苯基)-5-苯基-2-异噁唑啉-3-甲酸酸乙酯(S1-13),如专利申请WO-A-95/07897中所记载。
S2)选自8-喹啉氧基衍生物类的化合物(S2):
S2a)8-喹啉氧基乙酸类的化合物(S2a),优选(5-氯-8-喹啉氧基)乙酸1-甲基己酯(“解草酯(cloquintocet-mexyl)”)(S2-1)、(5-氯-8-喹啉氧基)乙酸1,3-二甲基丁-1-基酯(S2-2)、(5-氯-8-喹啉氧基)乙酸4-烯丙基氧基丁酯(S2-3)、(5-氯-8-喹啉氧基)乙酸1-烯丙基氧基丙-2-基酯(S2-4)、(5-氯-8-喹啉氧基)乙酸乙酯(S2-5)、5-氯-8-喹啉氧基乙酸甲酯(S2-6)、(5-氯-8-喹啉氧基)乙酸烯丙酯(S2-7)、(5-氯-8-喹啉氧基)乙酸2-(2-亚丙基亚氨基氧基)-1-乙酯(S2-8)、(5-氯-8-喹啉氧基)乙酸2-氧代丙-1-基酯(S2-9),以及如在EP-A-86750、EP-A-94349和EP-A-191736或EP-A-0 492 366中记载的相关化合物,以及(5-氯-8-喹啉氧基)乙酸(S2-10)、其水合物及其盐,例如其锂盐、钠盐、钾盐、钙盐、镁盐、铝盐、铁盐、铵盐、季铵盐、锍盐或鏻盐,如WO-A-2002/34048中所记载;
S2b)(5-氯-8-喹啉氧基)丙二酸类的化合物(S2b),优选化合物例如(5-氯-8-喹啉氧基)丙二酸二乙酯、(5-氯-8-喹啉氧基)丙二酸二烯丙酯、(5-氯-8-喹啉氧基)丙二酸甲基乙酯以及相关化合物,如EP-A-0 582 198中所记载。
S3)二氯乙酰胺类的活性化合物(S3),其通常用作苗前安全剂(作用于土壤的安全剂),例如“二氯丙烯胺(dichlormid)”(N,N-二烯丙基-2,2-二氯乙酰胺)(S3-1),购自Stauffer的“R-29148”(3-二氯乙酰基-2,2,5-三甲基-1,3-噁唑烷)(S3-2),购自Stauffer的“R-28725”(3-二氯乙酰基-2,2-二甲基-1,3-噁唑烷)(S3-3),“解草嗪(benoxacor)”(4-二氯乙酰基-3,4-二氢-3-甲基-2H-1,4-苯并噁嗪)(S3-4),购自PPG Industries的“PPG-1292”(N-烯丙基-N-[(1,3-二氧杂环戊烷-2-基)甲基]二氯乙酰胺)(S3-5),购自Sagro-Chem的“DKA-24”(N-烯丙基-N-[(烯丙基氨基羰基)甲基]二氯乙酰胺)(S3-6),购自Nitrokemia或Monsanto的“AD-67”或“MON 4660”(3-二氯乙酰基-1-氧杂-3-氮杂螺[4.5]癸烷)(S3-7),购自TRI-Chemical RT的“TI-35”(1-二氯乙酰基氮杂环庚烷)(S3-8),购自BASF的“Diclonon”(Dicyclonon)或“BAS145138”或“LAB145138”(S3-9)((RS)-1-二氯乙酰基-3,3,8a-三甲基全氢吡咯并[1,2-a]嘧啶-6-酮),“解草噁唑(furilazole)”或“MON 13900”((RS)-3-二氯乙酰基-5-(2-呋喃基)-2,2-二甲基噁唑烷)(S3-10),及其(R)异构体(S3-11)。
S4)选自酰基磺酰胺类的化合物(S4):
S4a)N-酰基磺酰胺及其盐,如WO-A-97/45016所记载,
S4b)4-(苯甲酰基氨磺酰基)苯甲酰胺类的化合物及其盐,如WO-A-99/16744中所记载,
S4c)苯甲酰基氨磺酰基苯基脲类的化合物,如EP-A-365484中所记载,例如1-[4-(N-2-甲氧基苯甲酰基氨磺酰基)苯基]-3-甲基脲、1-[4-(N-2-甲氧基苯甲酰基氨磺酰基)苯基]-3,3-二甲基脲以及1-[4-(N-4,5-二甲基苯甲酰基氨磺酰基)苯基]-3-甲基脲;
S4d)N-苯基磺酰基对苯二甲酰胺类的化合物及其盐,其例如由CN 101838227已知。
S5)选自羟基芳族化合物类和芳族-脂族羧酸衍生物类的活性化合物(S5),例如3,4,5-三乙酰氧基苯甲酸乙酯、3,5-二甲氧基-4-羟基苯甲酸、3,5-二羟基苯甲酸、4-羟基水杨酸、4-氟水杨酸、2-羟基肉桂酸、2,4-二氯肉桂酸,如WO-A-2004/084631、WO-A-2005/015994、WO-A-2005/016001中所记载。
S6)选自1,2-二氢喹喔啉-2-酮类的活性化合物(S6),例如1-甲基-3-(2-噻吩基)-1,2-二氢喹喔啉-2-酮、1-甲基-3-(2-噻吩基)-1,2-二氢喹喔啉-2-硫酮、1-(2-氨基乙基)-3-(2-噻吩基)-1,2-二氢喹喔啉-2-酮盐酸盐、1-(2-甲基磺酰基氨基乙基)-3-(2-噻吩基)-1,2-二氢喹喔啉-2-酮,如WO-A-2005/112630中所记载。
S7)选自二苯基甲氧基乙酸衍生物类的化合物(S7),例如二苯基甲氧基乙酸甲酯(CAS登记号41858-19-9)(S7-1)、二苯基甲氧基乙酸乙酯或二苯基甲氧基乙酸,如WO-A-98/38856中所记载。
S8)如WO-A-98/27049中所记载的2-氟丙烯酸衍生物。
S9)选自3-(5-四唑基羰基)-2-喹诺酮类的活性化合物(S9),例如1,2-二氢-4-羟基-1-乙基-3-(5-四唑基羰基)-2-喹诺酮(CAS登记号219479-18-2)、1,2-二氢-4-羟基-1-甲基-3-(5-四唑基羰基)-2-喹诺酮(CAS登记号95855-00-8),如WO-A-199/000020中所记载;
S10)如WO-A-2007/023719和WO-A-2007/023764中所记载的N-酰基磺酰胺。
S11)氧基亚氨基化合物类的活性化合物(S11),其已知为拌种剂,例如
“解草腈(oxabetrinil)”((Z)-1,3-二氧杂环戊烷-2-基甲氧基亚氨基(苯基)乙腈)(S11-1),其已知为用于黍/高粱抵抗异丙甲草胺损害的拌种安全剂,
“氟草肟(fluxofenim)”(1-(4-氯苯基)-2,2,2-三氟-1-乙酮O-(1,3-二氧杂环戊烷-2-基甲基)肟)(S11-2),其已知为用于黍/高粱抵抗异丙甲草胺损害的拌种安全剂,以及
“解草胺腈(cyometrinil)”或“CGA-43089”((Z)-氰基甲氧基亚氨基(苯基)乙腈)(S11-3),其已知为用于黍/高粱抵抗异丙甲草胺损害的拌种安全剂。
S12)选自异硫代苯并二氢吡喃酮(isothiochromanone)类的活性化合物(S12),例如[(3-氧代-1H-2-苯并噻喃-4(3H)-亚基)甲氧基]乙酸甲酯(CAS登记号205121-04-6)(S12-1),以及来自WO-A-1998/13361的相关化合物。
S13)一种或多种来自组(S13)的化合物:
“萘二甲酸酐”(1,8-萘二甲酸酐)(S13-1),其已知为用于玉米抵抗硫代氨基甲酸酯除草剂损害的拌种安全剂,
“解草啶(fenclorim)”(4,6-二氯-2-苯基嘧啶)(S13-2),其已知为用于播种的稻中的丙草胺的安全剂,
“解草胺(flurazole)”(2-氯-4-三氟甲基-1,3-噻唑-5-甲酸苄酯)(S13-3),其已知为用于黍/高粱抵抗甲草胺和异丙甲草胺损害的拌种安全剂,
购自American Cyanamid的“CL 304415”(CAS登记号31541-57-8)
(4-羧基-3,4-二氢-2H-1-苯并吡喃-4-乙酸)(S13-4),其已知为用于玉米抵抗咪唑啉酮损害的安全剂,
购自Nitrokemia的“MG 191”(CAS登记号96420-72-3)(2-二氯甲基-2-甲基-1,3-二氧杂环戊烷)(S13-5),其已知为用于玉米的安全剂,
来自Nitrokemia的“MG 838”(CAS登记号133993-74-5)(1-氧杂-4-氮杂螺[4.5]癸烷-4-二硫代甲酸2-丙烯酯)(S13-6),
“乙拌磷(disulfoton)”(S-2-乙硫基乙基二硫代磷酸O,O-二乙酯)(S13-7),
“增效磷(dietholate)”(O-苯基硫代磷酸O,O-二乙酯)(S13-8),
“mephenate”(甲基氨基甲酸4-氯苯酯)(S13-9)。
S14)除了对杂草具有除草作用以外,还对作物植物(如稻)具有安全剂作用的活性化合物,例如
“哌草丹”或“MY-93”(1-苯基乙基哌啶-1-硫代甲酸S-1-甲酯),其已知为用于稻抵抗除草剂禾草敌损害的安全剂,
“杀草隆”或“SK 23”(1-(1-甲基-1-苯基乙基)-3-对甲苯基脲),其已知为用于稻抵抗唑吡嘧磺隆除草剂损害的安全剂,
“苄草隆”=“JC-940”(3-(2-氯苯基甲基)-1-(1-甲基-1-苯基乙基)脲,参见JP-A-60087254),其已知为用于稻抵抗一些除草剂损害的安全剂,
“苯草酮(methoxyphenone)”或“NK 049”(3,3'-二甲基-4-甲氧基二苯甲酮),其已知为用于稻抵抗一些除草剂损害的安全剂,
购自Kumiai的“CSB”(1-溴-4-(氯甲基磺酰基)苯),(CAS登记号54091-06-4),其已知为用于在稻中抵抗一些除草剂损害的安全剂。
S15)如WO-A-2008/131861和WO-A-2008/131860中所记载的吡啶-2-氧基-苯甲酰胺。
S16)主要用作除草剂但还对作物植物具有安全剂作用的活性化合物,例如(2,4-二氯苯氧基)乙酸(2,4-D)、(4-氯苯氧基)乙酸、(R,S)-2-(4-氯-邻甲苯氧基)丙酸(2-甲-4-氯丙酸)、4-(2,4-二氯苯氧基)丁酸(2,4-DB)、(4-氯-邻甲苯氧基)乙酸(MCPA)、4-(4-氯-邻甲苯氧基)丁酸、4-(4-氯苯氧基)丁酸、3,6-二氯-2-甲氧基苯甲酸(麦草畏)、3,6-二氯-2-甲氧基苯甲酸1-(乙氧基羰基)乙酯(lactidichlor-ethyl)。
可以与本发明的化合物和组合物混合的硝化抑制剂的实例选自:2-(3,4-二甲基-1H-吡唑-1-基)琥珀酸、2-(4,5-二甲基-1H-吡唑-1-基)琥珀酸、吡唑鎓乙醇酸3,4-二甲基酯、吡唑鎓柠檬酸3,4-二甲基酯、吡唑鎓乳酸3,4-二甲基酯、吡唑鎓扁桃酸3,4-二甲基酯、1,2,4-三唑、4-氯-3-甲基吡唑、N-((3(5)-甲基-1H-吡唑-1-基)甲基)乙酰胺、N-((3(5)-甲基-1H-吡唑-1-基)甲基)甲酰胺、N-((3(5),4-二甲基吡唑-1-基)甲基)甲酰胺、N-((4-氯-3(5)-甲基-吡唑-1-基)甲基)甲酰胺;双氰胺、脲和甲醛的反应加成物,三唑基-甲醛-双氰胺加成物,2-氰基-1-((4-氧代-1,3,5-三嗪烷(azinan)-1-基)甲基)胍,1-((2-氰基胍基)甲基)脲,2-氰基-1-((2-氰基胍基)甲基)胍,2-氯-6-(三氯甲基)-吡啶(nitrapyrin或N-serve),双氰胺,3,4-二甲基吡唑磷酸酯,4,5-二甲基吡唑磷酸酯,3,4-二甲基吡唑,4,5-二甲基吡唑,硫代硫酸铵,印度楝,基于印度楝、亚油酸、α-亚麻酸成分的产品,p-香豆酸甲酯,阿魏酸甲酯,3-(4-羟基苯基)丙酸甲酯,水黄皮次素,brachialacton,p-苯醌高粱酮(sorgoleone),4-氨基-1,2,4-三唑盐酸盐,1-氨基-2-硫脲,2-氨基-4-氯-6-甲基嘧啶,2-巯基-苯并噻唑,5-乙氧基-3-三氯甲基-1,2,4-噻二唑(氯唑灵(terrazole),土菌灵(etridiazole)),2-对氨基苯磺酰胺噻唑(sulfanilamidothiazole),3-甲基吡唑,1,2,4-三唑硫脲,氰胺,三聚氰胺,沸石粉,邻苯二酚,苯醌,四硼酸钠,烯丙基硫脲,氯酸盐和硫酸锌。
本发明的化合物和组合物可以与一种或多种农业上有益的试剂结合。
农业上有益的试剂的实例包括:生物刺激剂、植物生长调节剂、植物信号分子、生长促进剂、微生物刺激分子、生物分子、土壤改良剂、营养素、植物营养增强剂等,例如脂-壳低聚糖(LCO)、壳低聚糖(CO)、几丁质化合物、类黄酮、茉莉酸或其衍生物(例如茉莉酸盐)、细胞分裂素、植物生长激素、赤霉素、脱落酸、乙烯、油菜素内酯、水杨酸盐、宏观和微观营养素、亚油酸或其衍生物、亚麻酸或其衍生物、karrikins和有益微生物(例如根瘤菌属、慢生根瘤菌属、中华根瘤菌属(Sinorhizobium spp.)、固氮根瘤菌属(Azorhizobium spp.)、球囊霉属、巨孢囊霉属、Hymenoscyphous spp.、树粉孢属(Oidiodendron spp.)、蜡蘑属、豆马勃属(Pisolithus spp.)、须腹菌属、硬皮马勃属、丝核菌属(Rhizoctonia spp.)、不动菌属(Acinetobacter spp.)、节杆菌属(Arthrobacter spp.)、线虫捕捉菌属(Arthrobotrysspp.)、曲霉属(Aspergillus spp.)、固氮螺菌属、杆状菌属(Bacillus spp.)、伯克霍尔德菌属、念珠菌属(Candida spp.)、金色单胞菌属(Chryseomonas spp.)、肠杆菌属(Enterobacter spp.)、正青霉属(Eupenicillium spp.)、微小杆菌属(Exiguobacteriumspp.)、克雷白氏菌属(Klebsiella spp.)、克吕沃尔氏菌属(Kluyvera spp.)、微杆菌属(Microbacterium spp.)、毛霉属(Mucor spp.)、拟青霉属(Paecilomyces spp.)、类芽孢杆菌属(Paenibacillus spp.)、青霉菌属(Penicillium spp.)、假单胞菌属、沙雷氏菌属(Serratia spp.)、寡养单胞菌属(Stenotrophomonas spp.)、链霉菌属、(Streptosporangium spp.)、Swaminathania spp.、硫杆菌属(Thiobacillus spp.)、Torulospora spp.、弧菌属(Vibrio spp.)、黄色杆菌属(Xanthobacter spp.)、黄单胞菌属(Xanthomonas spp.)等),及其结合。
根据某些实施方案,本发明的化合物和组合物可与一种或多种生物刺激剂结合使用。生物刺激剂可增强新陈代谢或生理过程,如呼吸、光合作用、核酸吸收、离子吸收、营养输送或其结合。本发明组合物中可包括或使用的生物刺激剂的非限制性实例可包括海藻提取物(例如,ascophyllum nodosum;BAYFOLAN ALGAE,Aglukon gmbH,Germany)、细菌提取物(例如,一种或多种固氮细菌的提取物、溶磷微生物和/或生物农药)、真菌提取物、腐殖酸(例如,腐殖酸钾)、富里酸、肌醇和/或甘氨酸、来自动物的蛋白质水解物和氨基酸、如腐植酸钾)、富里酸、肌醇和/或甘氨酸、水解蛋白和氨基酸(包括动物源BAYFOLAN AMBITION&BAYFOLAN cobre,SICIT,Italy)和植物源、无机化合物(如二氧化硅)以及它们的任何组合。根据某些实施方案,生物刺激剂可包括一种或多种固氮螺菌属提取物(例如,包含巴西固氮螺菌INTA Az-39的培养基提取物)、一种或多种慢生根瘤菌属种提取物(例如,介质的提取物包括埃尔坎慢生根瘤菌(B.elkanii)SEMIA 501,埃尔坎慢生根瘤菌SEMIA 587,埃尔坎慢生根瘤菌SEMIA 5019,B.japonicum NRRL B-50586(也作为NRRL B-59565),B.japonicumNRRL B-50587(也作为NRRL B-59566),B.japonicum NRRL B-50588(也作为NRRL B-59567),B.japonicum NRRL B-50589(也作为NRRL B-59568),B.japonicum NRRL B-50590(也作为NRRL B-59569),B.japonicum NRRL B-50591(也作为NRRL B-59570),B.japonicumNRRL B-50592(也作为NRRL B-59571),B.japonicum NRRL B-50593(也作为NRRL B-59572),B.japonicum NRRL B-50594(也作为NRRL B-50493),B.japonicum NRRL B-50608,B.japonicum NRRL B-50609,B.japonicum NRRL B-50610,B.japonicum NRRL B-50611,B.japonicum NRRL B-50612,B.japonicum NRRL B-50726,B.japonicum NRRL B-50727,B.japonicum NRRL B-50728,B.japonicum NRRL B-50729,B.japonicum NRRL B-50730,B.japonicum SEMIA 566,B.japonicum SEMIA 5079,B.japonicum SEMIA 5080,B.japonicum USDA 6,B.japonicum USDA 110,B.japonicum USDA 122,B.japonicum USDA123,B.japonicum USDA 127,B.japonicum USDA129和/或B.japonicum USDA 532C),一种或多种根瘤菌提取物(例如,介质的提取物包括R.leguminosarum SO12A-2),一种或多种苜蓿中华根瘤菌提取物(例如,介质的提取物包括S.fredii CCBAU114和/或S.fredii USDA205),一种或多种青霉菌提取物(例如,介质的提取物包括P.bilaiae ATCC 18309,P.bilaiae ATCC 20851,P.bilaiae ATCC 22348,P.bilaiae NRRL 50162,P.bilaiae NRRL50169,P.bilaiae NRRL 50776,P.bilaiae NRRL 50777,P.bilaiae NRRL 50778,P.bilaiae NRRL 50777,P.bilaiae NRRL 50778,P.bilaiae NRRL 50779,P.bilaiae NRRL50780,P.bilaiae NRRL 50781,P.bilaiae NRRL 50782,P.bilaiae NRRL 50783,P.bilaiae NRRL 50784,P.bilaiae NRRL 50785,P.bilaiae NRRL 50786,P.bilaiae NRRL50787,P.bilaiae NRRL 50788,P.bilaiae RS7B-SD1,P.brevicompactum AgRF18,P.canescens ATCC 10419,P.expansum ATCC 24692,P.expansum YT02,P.fellatanumATCC 48694,P.gaestrivorus NRRL 50170,P.glabrum DAOM 239074,P.glabrumCBS229.28,P.janthinellum ATCC 10455,P.lanosocoeruleum ATCC 48919,P.radicumATCC 201836,P.radicum FRR 4717,P.radicum FRR 4719,P.radicum N93/47267和/或P.raistrickii ATCC 10490),一种或多种假单胞菌提取物(例如,介质的提取物包括P.jessenii PS06),一种或多种杀螨的、杀昆虫的和/或杀线虫的提取物(例如,介质的提取物包括坚强芽孢杆菌I-1582,蕈状芽孢杆菌AQ726,NRRL B-21664;球孢白僵菌ATCC-74040,球孢白僵菌ATCC-74250,Burkholderia sp.A396 sp.nov.rinojensis,NRRL B-50319,色素杆菌属亚种NRRL B-30655,Chromobacterium vaccinii NRRL B-50880,黄杆菌(Flavobacterium)H492,NRRL B-50584,金龟子绿僵菌F52(也被称为金龟子绿僵菌菌株52,金龟子绿僵菌菌株7,金龟子绿僵菌菌株43and金龟子绿僵菌BIO-1020,TAE-001;作为DSM3884,DSM 3885,ATCC 90448,SD 170和ARSEF 7711)和/或玫烟色拟青霉FE991),和/或一种或多种真菌的提取物(例如,介质的提取物包括白粉寄生孢AQ(Intrachem Bio GmbH&Co.KG,Germany),黄曲霉(Syngenta Crop Protection,Inc.,CH),出芽短梗霉菌(bio ferm GmbH,Germany),短小芽孢杆菌AQ717(NRRL B21662),短小芽孢杆菌NRRL B-30087,芽孢杆菌AQ175(ATCC 55608),芽孢杆菌AQ177(ATCC55609),枯草芽孢杆菌AQ713(NRRL B-21661),枯草芽孢杆AQ743(NRRL B-21665),枯草芽孢杆菌解淀粉变种FZB24,枯草芽孢杆菌解淀粉变种NRRL B 50349,枯草芽孢杆菌解淀粉变种TJ1000(也被称为1BE,isolate ATCC BAA-390),苏云金芽孢杆菌AQ52(NRRL B-21619),假丝酵母(Candida oleophila)I 82(例如,购自Ecogen Inc.,USA),Candidasaitoana(与溶菌酶混合;BASF,USA)和(ArystaLifeScience,Ltd.,Cary,NC),链孢粘帚霉J1446(Verdera,Finland),盾壳霉(Prophyta,Germany),板栗疫病菌(Cryphonectria parasitica)(CNICM,France),浅白隐球菌(Cryptococcus albidus)YIELD(Anchor BioTechnologies,South Africa),尖孢镰刀菌(购自S.I.A.P.A.,Italy)和(Natural Plant Protection,France),核果梅奇酵母(Agrogreen,Israel),Microdochium dimerum(Agrauxine,France),Muscodor albus NRRL 30547,粉红产气霉NRRL 30548,大伏革菌(Verdera,Finland),酵母絮绒假酶菌(Plant Products Co.Ltd.,Canada),寡雄腐霉DV74(Remeslo SSRO,Biopreparaty,Czech Rep.),Reynoutriasachlinensis(例如,购自Marrone BioInnovations,USA),利迪链霉菌NRRLB-30145,利迪链霉菌M1064,鲜黄链霉菌(Streptomyces galbus)NRRL 30232,利迪链霉菌WYEC 108(ATCC 55445),Streptomyces violaceusniger YCED 9(ATCC 55660;和THATCHIdaho ResearchFoundation,USA),链霉菌WYE 53(ATCC 55750;和THATCHIdaho Research Foundation,USA),黄蓝状菌V117b(Prophyta,Germany),棘孢木霉SKT-1(Kumiai ChemicalIndustry Co.,Ltd.,Japan),深绿木霉LC52(Agrimm Technologies Ltd,NZ),哈茨木霉T 22(der Firma BioWorks Inc.,USA),哈茨木霉TH-35(ROOT购自Mycontrol Ltd.,Israel),哈茨木霉T 39(Mycontrol Ltd.,Israel;TRICHODERMAMakhteshim Ltd.,Israel),哈茨木霉ICC012和绿色木霉TRICHOPEL(Agrimm Technologies Ltd,NZ),哈茨木霉ICC012和绿色木霉ICC080(WP,Isagro Ricerca,Italy),多孢木霉和哈茨木霉(BINAB Bio Innovation AB,Sweden),子座木霉(C.E.P.L.A.C.,Brazil),绿木霉GL 21(Certis LLC,USA),哈茨木霉G1-3,ATCC 57678,哈茨木霉G1-21(Thermo Trilogy Corporation,Wasco,CA),哈茨木霉G1-3和枯草芽孢杆菌解淀粉变种FZB2,哈茨木霉G1-3和枯草芽孢杆菌解淀粉变种NRRL B50349,哈茨木霉G1-3和枯草芽孢杆菌解淀粉变种TJ1000,哈茨木霉G1-21和枯草芽孢杆菌解淀粉变种FZB24,哈茨木霉G1-21和枯草芽孢杆菌解淀粉变种NRRL B 50349,哈茨木霉G1-21和枯草芽孢杆菌解淀粉变种TJ1000,绿色木霉(Ecosense Labs.(India)Pvt.Ltd.,Indien,F购自T.Stanes&Co.Ltd.,Indien),绿色木霉TV1(Agribiotec srl,Italy),绿色木霉ICC080,和/或奥德曼细基格孢HRU3(BOTRYBotry Zen Ltd,NZ)),及其结合。
根据某些实施方案,本发明的化合物和组合物可以与一种或多种脂壳寡糖(LCO)、壳寡糖(CO)和/或壳基化合物结合使用。LCO,有时也称为共生结瘤(Nod)信号(或Nod因子)或Myc因子,由β-l,4-连接的N乙酰D葡糖胺(“GlcNAc”)残基寡糖骨架和在非还原端缩合的N连接脂肪酰基链组成。正如本领域所理解的,LCO在骨架中GlcNAc残基的数量、脂肪酰基链的长度和饱和度以及还原性和非还原性糖残基的取代方面有所不同。参见例如Denarie等人,Ann.Rev.Biochem.65:503(1996);Diaz等人,Mol.Plant Microbe Interactions 13:268(2000);Hungria等,Soil Biol.Biochem.29:819(1997);Hamel等人,Planta 232:787(2010);以及Prome等人,Pure&Appl.70(1):55(1998)。
LCO(及其衍生物)可以各种形式的纯度被包含或被使用,并且可以单独使用,也可以以产生LCO的细菌或真菌的培养物形式使用。例如,(可从拜耳公司购入)含有一种能产生LCO的慢生型大豆根瘤菌培养物。提供基本上纯的LCO的方法包括:从LCO和微生物的混合物中去除微生物细胞,或继续通过LCO溶剂相分离法分离和纯化LCO分子,然后进行HPLC色谱分析,如美国专利第5,549,718号所述。可通过重复高效液相色谱法提高纯化效果,纯化的LCO分子可冷冻干燥,以便长期储存。本公开的组合物和方法可包括LCO的类似物、衍生物、水合物、异构体、盐和/或溶剂化物。根据本发明,LCO可以以任何合适的量/浓度加入到组合物中。例如,根据本发明的组合物包含约1x10-20M至约1x10-1M LCO。LCO的量/浓度可以为能够有效赋予植物积极特质或益处的量,例如促进施用组合物的植物的生长和/或提升产量。根据某些实施方案,如果没有组合物中一种或多种其它成分(如CO和/或一种或多种农药)的有益贡献,LCO的用量/浓度不能有效提高植物的产量。
本发明的化合物和组合物可以与任何合适的CO结合使用,也可以与一种或多种LCO结合使用。CO与LCO的不同之处在于它们缺少LCO所特有的悬垂脂肪酸链。CO,有时被称为N-乙酰壳寡糖,也由GlcNAc残基组成,但其侧链修饰使其不同于甲壳素分子[(C8-H13NO5)n,CAS编号1398-61-4]和壳聚糖分子[(C5H11NO4)n,CAS编号9012-76-4]。参见D'Haeze等人,Glycobiol.12(6):79R(2002);Demont Caulet等人,《Plant physiol》120(1):83(1999);Hanel等人,《Planta》232:787(2010);Muller等人,《Plant physiol》124:733(2000);Robina等人,《Tetrahedron》58:521 530(2002);Rouge等人,Docking of ChitinOligomers and Nod Factors on LysM-RLK Receptors in the Medicago-RhizobiumSymbiosis,in The Molecular Immunology of Complex Carbohydrates-3(SpringerScience,2011);Van der Holst等人,Curr.Opin.Struc.Biol.11:608(2001);以及Wan等人,《Plant cell》21:1053(2009)。CO可以从任何合适的来源获得。例如,CO可以衍生自LCO。例如,在一个方面,根据本发明的组合物包含一种或多种衍生自LCO的CO,可以从下列菌株获得(分离和/或纯化):固氮根瘤菌、慢生根瘤菌(如B.japonicum)、文新中慢生根瘤菌、根瘤菌(如豌豆根瘤菌)、中华根瘤菌(如苜蓿中华根瘤菌)或霉菌(如Glomus intraradicus)。或者,CO也可以是合成的。重组CO的制备方法是本领域已知的。例如,参见Cottaz等人,Meth.Eng.7(4):311(2005);Samain等人,Carbohydrate Res.302:35(1997);以及Samain等人,J.Biotechnol.72:33(1999),其中的内容和公开内容通过引用并入本文。
CO(及其衍生物)可以各种形式的纯度被包含或被使用,并且可以单独使用,也可以以产生CO的细菌或真菌的培养物形式使用。应理解,根据本发明的化合物和组合物可与CO的水合物、异构体、盐和/或溶剂化物结合使用。CO可以任何合适的量/浓度使用。例如,根据本发明的组合物可包含约1x10-20M至约1x10-1M的CO。CO的量/浓度可以为能够有效地赋予植物积极特质或益处的量,例如增强土壤微生物环境、养分吸收或促进施用组合物的植物的生长和/或提升产量。根据某些实施方案,如果没有组合物中一种或多种其它成分(如LCO和/或一种或多种接种剂、生物大分子、营养素或农药)的有益贡献,CO的用量/浓度可能无法有效促进植物的生长。
本发明的化合物和组合物可与一种或多种合适的几丁质化合物结合,例如甲壳素、壳聚糖及其异构体、盐和溶胶。甲壳素和壳聚糖是真菌细胞壁以及昆虫和甲壳类动物外骨骼的主要成分,由GlcNAc残基组成。甲壳素和壳聚糖可以通过商业途径获得,也可以从昆虫、甲壳类动物外壳或真菌细胞壁中制备。甲壳素和壳聚糖的制备方法在本领域是众所周知的。例如,参见美国专利第4,536,207号(从甲壳类动物壳中制备)和第5,965,545号(从蟹壳中制备和水解商用壳聚糖);以及Pochanavanich等人,Lett.Appl.35:17(2002)(从真菌细胞壁中制备)。脱乙酰化的甲壳素和壳聚糖的脱乙酰化程度可从小于35%到大于90%不等,并涵盖广泛的分子量范围,例如,分子量小于15kD的低分子量壳聚糖低聚物和0.5至2kD的甲壳素低聚物;分子量约为15kD的"实用级"壳聚糖;以及分子量最高达70kD的高分子量壳聚糖。用于种子处理的甲壳素和壳聚糖组合物可通过商业途径获得。商用产品包括(Plant Defense Boosters,Inc.)和BEYONDTM(Agrihouse,Inc.)。
本发明的化合物和组合物可与一种或多种合适的类黄酮结合,包括但不限于花青素、花黄素、查耳酮、香豆素、黄烷酮、黄烷醇、黄烷和异黄酮,以及它们的类似物、衍生物、水合物、异构体、聚合物、盐和溶剂化物。类黄酮是酚类化合物,其一般结构是由三个碳桥连接的两个芳香环。类黄酮是本领域已知的化合物。例如,参见Jain等人,J.Plant Biochem.11:1(2002);以及Shaw等人,Environ.Microbiol.11:1867(2006),其中的内容和公开内容通过引用并入本文。市面上有多种类黄酮化合物。类黄酮化合物可从植物或种子中分离出来,如美国专利5,702,752、5,990,291和6,146,668中所述。类黄酮化合物也可由基因工程生物生产,如酵母。参见Ralston等人,《Plant physiol》137:1375(2005)。
根据一些实施方案,本发明的化合物和组合物可以与一种或多种黄烷酮结合使用,例如紫铆素(butin)、圣草酚(eriodictyol)、橙皮素(hesperetin)、橘皮苷(hesperidin)、高圣草素(homoeriodictyol)、异野樱素(isosakuranetin)、柚皮素(naringenin)、柚皮苷(naringin)、乔松素(pinocembrin)、枳属甙(poncirin)、樱花素(sakuranetin)、樱花苷(sakuranin)和/或sterubin中的一种或多种;与一种或多种黄烷醇结合使用,如二氢山柰酚(dihydrokaempferol)和/或花旗松素(taxifolin);与一种或多种黄烷结合使用,例如一种或多种黄烷-3-醇(例如儿茶素(C)、儿茶素3-没食子酸酯(Cg)、表儿茶素(EC)、表没食子儿茶素(EGC)表儿茶素3-没食子酸酯(ECg)、表没食子儿茶素3-没食子酸酯(EGCg)、表非儿茶素(epiafzelechin)、非瑟酮醇(fisetinidol)、没食子儿茶素(GC)、没食子儿茶素3-没食子酸酯(GCg)、guibourtinidol,mesquitol,robinetinidol,茶黄素-3-没食子酸盐、茶黄素-3'-没食子酸盐、黄素-3,3'-没食子酸盐、大黄素)、黄烷-4-醇(例如芹菜醇和/或芦荟醇)和/或黄烷-3,4-二醇(例如无色花青素、leucodelphinidin、白漆苷配基(leucofisetinidin)、leucomalvidin、luecopelargonidin、leucopeonidin、无色刺槐亭定(leucorobinetinidin)、黑木金合欢素(melacacidin)和/或teracacidin)和/或其二聚体、三聚体、低聚物和/或聚合物(如一种或多种原花青素);与一种或多种异黄酮结合使用,例如一种或多种异黄酮或黄酮衍生物(例如鸡豆黄素(biochanin A)、大豆黄酮(daidzein)、7-羟-4-甲氧异黄酮(formononetin)、染料森黄酮(genistein和/或glycitein)、异黄烷(例如雌马酚(equol)、ionchocarpane和/或laxifloorane)、异黄烷二醇、异黄素(例如甘草素(glabrene、haginin D和/或2-methoxyjudaicin)、香豆雌酚(coumestans)(例如拟雌内酯(coumestrol)、plicadin和/或蟛蜞菊内酯(wedelolactone))、紫檀素(pterocarpans)、roetonoids、newoflavonoids(例如海棠果内酯;红厚壳烯酮内酯(calophyllolide)、coutareagenin、黄檀色烯(Dalbergichromene)、黄檀内酯(Dalbergin)、nivetin),和/或紫檀素(例如bitucarpin A、bitucarpin B、erybraedin A、erybraedin B、阿比西尼亚桐素-Ⅱ(erythrabyssin-Ⅱ)、阿比西尼亚桐素-1(erythrabyssin-1)、erycristagallin、glycinol、glyceollidins、大豆抗毒素(glyceollins)、glycyrrhizol、高丽槐素(maackiain)、美迪紫檀素(medicarpin)、morisianine、orientanol、菜豆蛋白(phaseolin)、豌豆素(pisatin)、striatine、三叶豆紫檀苷(trifolirhizin)),及其结合。类黄酮化合物及其衍生物可以任何合适的形式包含在本发明的组合物中,包括但不限于多晶型和晶型。根据本发明,类黄酮化合物可以任何合适的量或浓度加入组合物中。类黄酮的用量/浓度可以是对植物有益的有效用量,这可以通过对土壤微生物的活性或其他方式间接实现,例如提高植物营养和/或产量。根据某些实施方案,如果没有组合物中一种或多种其他成分(如LCO、CO和/或一种或多种农药)的有益贡献,类黄酮化合物的用量/浓度可能无法有效提高植物的营养或产量。
本发明的化合物和组合物可以与一种或多种合适的非黄酮类结瘤基因诱导剂结合使用,包括但不限于茉莉酸([1R-[1α,2β(Z)]]-3-氧代-2-(戊烯基)环戊烷乙酸;JA)、亚油酸((Z,Z)-9,12-十八碳二烯酸)和/或亚麻酸((Z,Z,Z)-9,12,15-十八碳三烯酸),以及它们的类似物、衍生物、水合物、异构体、聚合物、盐和溶剂化物。茉莉酸及其茉莉酸甲酯(MeJA)统称为茉莉酸盐,是一种十八烷基化合物,天然存在于某些植物(如小麦)、真菌(如可可球二孢菌(Botryodiplodia theobromae)、Gibbrella fujikuroi)、酵母(如酿酒酵母)和细菌(如大肠杆菌)中。亚油酸和亚麻酸可能在茉莉酸的生物合成过程中产生。据报道,茉莉酸、亚油酸和亚麻酸(及其衍生物)是根瘤菌表达结瘤基因或产生LCO的诱导物。例如,参见Mabood等人,Plant Physiol.Biochem 44(11):759(2006);Mabood等人,Agr.J.98(2):289(2006);Mabood等人,Field Crops Res.95(2-3):412(2006);以及Mabood和Smith,Linoleic and linolenic acid induce the expression of nod genes inBradyrhizobium japonicum USDA 3,Plant Biol.(2001)。
可包括或与本发明的化合物和组合物结合使用的茉莉酸、亚油酸和亚麻酸的衍生物包括酯类、酰胺类、苷类及其盐类。代表性的酯类是亚油酸、亚麻酸或茉莉酸的羧基被-COR基团替代的那些,其中R是-OR1基团,其中R1为:烷基,如C1-C8无支链或支链烷基,如甲基、乙基或丙基;烯基,如C2-C8无支链或支链烯基;炔基、例如C2-C8无支链或支链炔基;例如具有6至10个碳原子的芳基;或例如具有4至9个碳原子的杂芳基,其中杂芳基中的杂原子可以是例如N、O、P或S。代表性的酰胺是亚油酸、亚麻酸或茉莉酸的羧基被-COR基团替代的那些,其中R是NR2R3基团,其中R2和R3各自独立地为:氢;烷基,如C1-C8无支链或支链烷基,例如,甲基、乙基或丙基;烯基,如C2-C8非支链或支链烯基;炔基,如C2-C8非支链或支链炔基;芳基,例如,具有6至10个碳原子;或杂芳基,例如,具有4至9个碳原子,其中杂芳基中的杂原子可以是例如N、O、P或S。酯可以通过已知的方法制备,例如酸催化亲核加成法,其中羧酸与醇在催化量的矿物酸存在下发生反应。酰胺也可以通过已知的方法制备,例如在中性条件下,在偶联剂(如二环己基碳二亚胺(DCC))的存在下,使羧酸与适当的胺发生反应。亚油酸、亚麻酸和茉莉酸的合适盐包括例如碱加成盐等。可用作制备这些化合物的代谢上可接受的碱式盐的碱试剂包括:从碱金属阳离子(如钾和钠)和碱土金属阳离子(如钙和镁)等阳离子衍生而来的那些。将亚油酸、亚麻酸或茉莉酸的溶液与碱的溶液混合,可以容易地制备出这些盐。这些盐可以从溶液中析出并通过过滤收集,也可以通过其他方法来回收,比如蒸发溶剂法。
非黄酮类结瘤基因诱导剂可与本发明的化合物和组合物结合使用并以任何合适的量/浓度使用。例如,非黄酮类结瘤基因诱导剂的剂量/浓度可以为能够有效地赋予植物积极特质或益处的量,例如促进施用组合物的植物的生长和/或提高产量。根据某些实施方案,如果没有组合物中一种或多种其它成分(如LCO、CO和/或一种或多种农药)的有益贡献,非黄酮类结瘤基因诱导剂的用量/浓度可能无法有效促进植物的生长。
本发明的化合物和组合物可与卡拉激素(karrakins)结合,包括但不限于2H-呋喃并[2,3-c]吡喃-2-酮,以及其类似物、衍生物、水合物、异构体、聚合物、盐和溶剂化物。卡拉激素的生物可接受盐的例子包括与生物可接受的酸形成的酸加成盐,其例子包括盐酸盐、氢溴酸盐、硫酸盐或硫酸氢盐、磷酸或磷酸氢盐、醋酸盐、苯甲酸盐、琥珀酸盐、富马酸盐、马来酸盐、乳酸盐、柠檬酸盐、酒石酸盐、葡萄糖酸盐;甲磺酸盐、苯磺酸盐和对甲苯磺酸。其他生物可接受的金属盐可包括与碱的碱金属盐,例如钠盐和钾盐。卡拉激素可以任何合适的量/浓度使用并加入到根据本发明的化合物中。例如,卡拉激素的剂量/浓度可以为能够有效地赋予植物积极特质或益处的量,促进施用组合物的植物的生长和/或提高产量。一方面,如果没有组合物中一种或多种其它成分(如LCO、CO和/或一种或多种农药)的有益贡献,卡拉激素的用量/浓度可能无法有效促进植物的生长。
本发明的化合物和组合物可与一种或多种花青素类和/或花黄素结合使用,例如一种或多种矢车菊色素(cyanidin)、飞燕草色素(delphinidin)、二甲花翠素(malvidin)、花葵素(pelargonidin)、甲基花青素(peonidin)、甲基花青素(petunidin)、黄酮(例如芹黄素(apigenin)、黄芩黄素(baicalein)、白杨素(chrysin)、7,8-二羟基黄酮、香叶木甙(diosmin)、黄酮哌酯(flavoxate)、6-羟基黄酮、毛地黄黄酮(luteolin)、野黄芩素(scutellarein)、柑橘黄酮(tangeritin和/或汉黄芩素(Wogonin)和/或黄酮醇(例如黄柏苷(amurensin)、黄芪甙(astragalin)、杜鹃黄素(azaleatin)、杜鹃黄甙(azalein)、非瑟酮(fisetin)、呋喃黄酮醇类高良姜素(furanoflavonols galangin)、棉黄素(gossypetin)、3-羟基黄酮、金丝桃苷(hyperoside)、淫羊藿苷(icariin)、异槲皮素(isoquercetin)、山柰素(kaempferide)、小叶丁香素(kaempferitrin)、山柰酚(kaempferol)、异鼠李素(isorhamnetin)、桑色素(morin)、杨梅酮(myricetin)、杨梅苷(myricitrin)、natsudaidain、藿香黄酮醇(pachypodol)、pyranoflavonols quercetin、quericitin、鼠李精醚(rhamnazin)、鼠李黄素(rhamnetin)、刺槐苷(robinin)、芸香苷(rutin)、绣线菊甙(spiraeoside)、曲克芦丁(troxerutin)和/或黄檗苷(zanthorhamnin),及其结合。
本发明的化合物和组合物可与葡萄糖酸内酯和/或其类似物、衍生物、水合物、异构体、聚合物、盐和/或溶剂化物结合使用。葡萄糖酸内酯可以任何合适的量/浓度加入到根据本发明的组合物中。例如,葡糖酸内酯的用量/浓度可以是向植物传递或赋予积极特质或益处的有效用量,如促进施用组合物的植物的生长和/或提高产量。在一个方面,如果没有组合物中一种或多种其他成分(如LCO、CO和/或一种或多种农药)的有益贡献,葡萄糖酸内酯的用量/浓度可能无法有效提高植物的生长和/或产量。
本发明的化合物和组合物可与一种或多种合适的营养素和/或肥料结合使用,如有机酸(如醋酸、柠檬酸、乳酸、苹果酸、牛磺酸等)、宏量矿物质(如磷、钙、镁、钾、钠、铁等)、微量矿物质(如硼、钴、氯、铬、铜、氟、碘、铁、锰、钼、硒、锌等)、维生素(例如,维生素A、维生素B群(即维生素B1、维生素B2、维生素B3、维生素B5、维生素B6、维生素B7、维生素B8、维生素B9、维生素B12、胆碱)、维生素C、维生素D、维生素E、维生素K)和/或类胡萝卜素(α-胡萝卜素、β-胡萝卜素、隐黄素、叶黄素、番茄红素、玉米黄质等),及其结合。在一个方面,根据本发明的化合物和组合物可以与植物或微生物的宏量和微量营养素相结合,包括磷、硼、氯、铜、铁、锰、钼和/或锌。根据某些实施方案,根据本发明的化合物和组合物可与一种或多种有益的微量营养素结合使用。用于本文所述组合物的微量营养素的非限制性实例可包括维生素(例如,维生素A、维生素B群(即、维生素B5、维生素B6、维生素B7、维生素B8、维生素B9、维生素B12、胆碱)、维生素C、维生素D、维生素E、维生素K、类胡萝卜素(α-胡萝卜素、β-胡萝卜素、隐黄素、叶黄素、番茄红素、玉米黄质等)、宏量矿物质(如磷、钙、镁、钾、钠、铁等)、微量矿物质(如硼、钴、氯化物、铬、铜、氟化物、碘、铁、锰、钼、硒、锌等)、有机酸(如醋酸、柠檬酸、乳酸、苹果酸、牛磺酸等),及其结合(德国Aglukon公司的BAYFOLAN secure、BAYFOLAN complete、BAYFOLAN energy、BAYFOLAN power)。在一个特别的方面,组合物可以包括磷、硼、氯、铜、铁、锰、钼和/或锌,及其结合。对于包含磷的组合物,设想可以使用任何合适的磷源。例如,磷可以来自磷酸盐岩源,如磷酸一铵、磷酸二铵、磷酸一钙、过磷酸钙、三重过磷酸钙和/或聚磷酸铵、有机磷源或能被一种或多种微生物(如比莱青霉(Penicillum bilaiae))溶解的磷源。
制剂
在另一个实施方案中,本发明涉及含有式(I)的(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型B的常规制剂形式的植物保护剂。
在本发明的一个优选实施方案中,植物保护剂含有大于90重量%且优选大于95重量%的式(I)化合物的多晶型B,基于组合物中存在的式(I)化合物的所有形式的总量计。
在一个更优选的实施方案中,本发明涉及悬浮浓缩剂(SC)制剂,其包含式(I)化合物的多晶型B、一种或多种分散剂、一种或多种消泡剂、一种或多种杀生物剂、一种或多种流变添加剂、一种或多种防冻剂和/或一种或多种载体。
在另一个实施方案中,本发明涉及包含式(I)化合物的多晶型B的农用化学制剂,其用于叶面施用的用途;其在低喷雾量下的用途;其通过无人机系统(UAS)、无人导引车(UGV)和安装有配备常规喷嘴以及脉宽调制喷嘴(pulse width modulation spraynozzle)的喷杆式喷雾器或转盘式液滴施用器(rotating disc droplet applicator)的牵引车的用途;以及其用于防治农业病害的应用,特别是在蜡质叶上的应用,并且特别地,本发明涉及具有降低的漂移的农业化学品组合物,特别是在喷雾施用中。
在一个方面,本发明涉及一种制剂,其包含:
a)式(I)化合物的多晶型B和一种或多种其它活性成分如杀真菌剂、杀细菌剂、杀螨剂、杀线虫剂、杀昆虫剂、生物防治剂或除草剂,
b)一种或多种漂移减少剂,
c)一种或多种铺展剂,
d)一种或多种吸收促进剂,
e)一种或多种耐雨添加剂,
f)其他助剂,
g)每体积(1L或1kg)一个或多个载体。
在一个优选的实施方案中,b)是植物油或植物油酯或二酯,并且在另一个实施方案中,组分b)是聚合物漂移减少剂。
漂移减少剂b)
合适的漂移减少剂是聚环氧乙烷,其中聚合物的平均分子量优选为50万至1200万g/mol,更优选为75万至1000万g/mol,最优选为100万至800万g/mol;羟丙基瓜尔胶,以及植物油、植物油酯和植物油二酯(包括与丙三醇和丙二醇的酯)。
特别优选的为甲酯、乙酯、异丙酯、异丁酯、丁酯、己酯和乙基己酯。
更优选的植物油和植物油酯选自油酸甲酯、棕榈酸甲酯、油菜籽油甲酯、肉豆蔻酸异丙酯、棕榈酸异丙酯、棕榈酸乙基己酯、油酸乙基己酯、肉豆蔻酸/月桂酸乙基己酯的混合物、月桂酸乙基己酯、辛酸/癸酸乙基己酯的混合物、己二酸二异丙酯、椰子油丙二醇二酯、葵花油、油菜籽油、玉米油、大豆油、米糠油、橄榄油、花生油、混合的辛酸和癸酸甘油三酯(mixed caprylic and capric triglycerides),以及混合的癸酰基和辛酰基甘油酯(mixed decanoyl and octanoyl glycerides)。
矿物油也适合作为漂移减少剂。
铺展剂c)
合适的铺展剂选自磺基琥珀酸金属盐与包含1-10个碳原子的支链醇或直链醇的单酯和二酯,特别是碱金属盐,更特别是钠盐,最特别是二辛基磺基琥珀酸酯钠;以及有机硅乙氧基化物,例如具有以下CAS号的有机改性聚硅氧烷/三硅氧烷烷氧基化物:27306-78-1、67674-67-3、134180-76-0,例如L77、408、806、S240、S278。
其他合适的铺展剂是具有1至6个EO的乙氧基化二乙炔二醇,例如420和440,以及乙氧基化丙氧基化的3,5,5-三甲基-1-己醇,(CAS-No 204336-40-3),例如Vibrant。
优选的是聚醚改性七甲基三硅氧烷,更优选选自包含硅氧烷基团的组:聚(氧-1,2-乙二基)、α-甲基-ω-[3-[1,3,3,3-四甲基-1-[(三甲基硅基)氧基]二硅氧烷基]丙氧基](CAS号27306-78-1)、聚(氧基-1,2-乙二基)、α-[3-[1,3,3,3-四甲基-1-[(三甲基硅基)氧基]二硅氧烷基]丙基]-ω-羟基(CAS号67674-67-3),以及甲基环氧乙烷与环氧乙烷单3-1,3,3,3-四甲基-1-(三甲基硅基)氧基二硅氧烷基丙基醚的聚合物(Cas号134180-76-0)。
优选地,铺展剂选自二辛基磺基琥珀酸酯钠、聚醚改性七甲基三硅氧烷和乙氧基化的二乙炔二醇。
吸收促进剂(d)
吸收促进剂也可以选自以下化合物:
其他合适的吸收促进剂为醇的乙氧基化物,优选地选自乙氧基化的醇类、丙氧基-乙氧基化的醇类、乙氧基化的羧酸类、丙氧基-乙氧基化的羧酸类,或乙氧基化的丙三醇单酯、二酯或三酯,其包含具有8-18个碳原子的脂肪酸和平均5-40个EO单元。所述乙氧基化或丙氧基-乙氧基化的醇类或羧酸类任选地通过向剩余的醇的官能团加入甲基基团而进一步改性(参见“甲基封端的”)。根据d)的术语“醇类”是指可具有6-22个碳原子且任选地带有额外的取代基(例如OH基团)的饱和或不饱和的支链或直链的醇。根据d)的术语“羧酸类”是指可具有6-22个碳原子且任选地带有额外的取代基(例如OH基团)的饱和或不饱和的支链或直链的羧酸。
例如,合适的d)组分为:
-乙氧基化的直链和/或支链脂肪醇(例如Clariant的X-型),其具有2-20个EO单元;
-甲基封端的乙氧基化的直链和/或支链脂肪醇(例如Clariant的XM型),其包含2-20个EO单元;
-乙氧基化的椰子醇(例如Clariant的C型),其包含2-20个EO单元;
-乙氧基化的C12/15醇(例如Croda的A型),其包含2-20个EO单元;
-支链或直链的丙氧基-乙氧基化的醇,例如Solvay的B/848、Croda的G5000、Levaco的HOT 5902;
-甲基封端的丙氧基-乙氧基化的脂肪酸,例如Lion的OC0503M;
-烷基醚柠檬酸盐表面活性剂(例如Adsee CE系列,Akzo Nobel);
-烷基多糖(例如BASF的PG8107、PG8105;Croda的438、AL-2559、AL-2575);
-乙氧基化的丙三醇单酯或二酯,其包含具有8-18个碳原子的脂肪酸和平均10-40个EO单元(例如Croda的产品系列);
-蓖麻油乙氧基化物,其包含平均5-40个EO单元(例如Nouryon的系列、Clariant的EL系列);
-乙氧基化的油酸(例如A和AP),其包含2-20个EO单元;
-乙氧基化的脱水山梨糖醇脂肪酸酯,其包含具有8-18个碳原子的脂肪酸和平均10-50个EO单元(例如T,Tween系列)。
耐雨添加剂(e):
合适的耐雨添加剂是基于丙烯酸的乳液聚合物或聚合物分散体和基于苯乙烯的乳液聚合物或聚合物分散体,d)为聚合物水分散体,其Tg为-100℃至30℃,优选-60℃至20℃,更优选-50℃至10℃,最优选-45℃至5℃,例如Acronal V215、Acronal 3612、LicomerADH 205和Atplus FA。特别优选的是Licomer ADH205和Atplus FA。
优选地,所述聚合物选自丙烯酸聚合物、苯乙烯聚合物、乙烯基聚合物及其衍生物、聚烯烃、聚氨酯和天然聚合物及其衍生物。
更优选地,该聚合物选自丙烯酸聚合物、苯乙烯-丁二烯共聚物、苯乙烯-马来酸酐共聚物、聚乙烯醇、聚乙酸乙烯酯、部分水解的聚乙酸乙烯酯、甲基乙烯基醚-马来酸酐共聚物、羧基改性的聚乙烯醇、乙酰乙酰基改性的聚乙烯醇、双丙酮改性的聚乙烯醇和有机硅改性的聚乙烯醇、异丙烯-马来酸酐共聚物、聚氨酯、纤维素、明胶、酪蛋白(caesin)、氧化淀粉、淀粉-乙酸乙烯酯接枝共聚物、羟乙基纤维素、甲基纤维素、乙基纤维素、羧甲基纤维素和乙酰纤维素。
最优选地,所述聚合物选自丙烯酸酯和苯乙烯的共聚物,其中,所述丙烯酸酯选自丙烯酸2-乙基己酯、丙烯酸丁酯、丙烯酸仲丁酯、丙烯酸乙酯、丙烯酸甲酯、丙烯酸、丙烯酰胺、丙烯酸异丁酯、甲基丙烯酸甲酯或其结合。所述苯乙烯选自苯乙烯、叔丁基苯乙烯、对甲基苯乙烯或其结合。
在一个优选的实施方案中,如上所述,聚合物的分子量不超过40000,优选不超过10000。
在一个优选的实施方案中,聚合物D是如WO 2017/202684中所记载的乳液聚合物。
就许多聚合物而言,玻璃化转变温度(Tg)是已知的,如果没有另行定义,则在本发明中根据ASTM E1356-08(2014)“差示扫描量热法确定玻璃化转变温度的标准试验方法(Standard Test Method for Assignment of the Glass Transition Temperatures byDifferential Scanning Calorimetry)”进行测定,其中样品在DSC之前在110℃干燥1小时,以消除水和/或溶剂的影响,DSC样品大小为10-15mg,在N2下以20℃/min从-100℃测量至100℃,其中Tg定义为转变区的中点。
其他助剂(f)
f1合适的非离子表面活性剂或分散助剂f1)是通常可用于农业化学试剂的所有此类物质。优选地,聚环氧乙烷-聚环氧丙烷嵌段共聚物,优选具有大于6,000g/mol的分子量或大于45%的聚环氧乙烷含量,更优选具有大于6,000g/mol的分子量和大于45%的聚环氧乙烷含量,聚氧亚烷基胺衍生物、聚乙烯吡咯烷酮、聚乙烯醇和聚乙烯吡咯烷酮的共聚物,以及(甲基)丙烯酸和(甲基)丙烯酸酯的共聚物。在上文提到的实例中,可以任选地将所选种类磷酸化、磺化或硫酸化并用碱中和。
可能的阴离子表面活性剂f1)是通常可用于农业化学试剂的所有此类物质。优选烷基磺酸或烷基磷酸以及烷基芳基磺酸或烷基芳基磷酸的碱金属盐、碱土金属盐和铵盐。另一组优选的阴离子表面活性剂或分散助剂是聚苯乙烯磺酸的碱金属盐、碱土金属盐和铵盐、聚乙烯磺酸的盐、烷基萘磺酸的盐、萘-磺酸-甲醛缩合产物的盐,萘磺酸、苯酚磺酸和甲醛的缩合产物的盐,以及木质素磺酸的盐。
f2流变改性剂是一种添加剂,当以减少储存期间分散的活性成分重力分离的浓度添加到配方中时,导致在低剪切速率下的粘度显著增加。出于本发明的目的,低剪切速率被定义为0.1s-1及以下,并且显著增加为大于x2。粘度可通过旋转剪切流变仪测量。
合适的流变改性剂E2)例如是:
-多糖,其包括黄原胶和羟乙基纤维素。实例为G和23、CX911和250系列。
-粘土,其包括蒙脱石、膨润土、海泡石、绿坡缕石、合成锂皂石、锂皂石。实例为R、VanB、34、38、CT、HC、EW、M100、M200、M300、S、M、W、50、RD。
-热解法二氧化硅和沉淀二氧化硅,实例为200、22。
优选的是黄原胶、蒙脱石粘土、膨润土和热解法二氧化硅。
f3合适的消泡物质e3)是通常可为此目的用于农业化学试剂中的所有物质。优选硅油、硅油制剂。实例为来自Bluestar Silicones的426和432、来自Wacker的SRE和SC132、来自Silchem的来自Basildon ChemicalCompany Ltd的Foam-Clear来自Momentive[二甲基硅氧烷和有机硅,CAS号63148-62-9]的1572和30。优选的是1572。
f4合适的防冻剂是通常可为此目的用于农业化学试剂的所有物质。合适的实例为丙二醇、乙二醇、脲和丙三醇。
f5合适的其他助剂e5)选自杀生物剂、着色剂、pH调节剂、缓冲剂、稳定剂、抗氧化剂、惰性填充材料、湿润剂、晶体生长抑制剂、微量营养素,例如为:
可能的防腐剂是通常可为此目的用于农业化学试剂中的所有物质。防腐剂的合适实例是含有5-氯-2-甲基-4-异噻唑啉-3-酮[CAS号26172-55-4]、2-甲基-4-异噻唑啉-3-酮[CAS号2682-20-4]或1.2-苯并异噻唑-3(2H)-酮[CAS号2634-33-5]的制剂。可提及的实例是D7(Lanxess)、CG/ICP(Dow)、SPX(Thor GmbH)和GXL(Arch Chemicals)。
可能的着色剂是通常可为此目的用于农业化学试剂中的所有物质。例如可提及二氧化钛、炭黑、氧化锌、蓝色颜料、亮蓝FCF、红色颜料和永久红FGR。
可能的pH调节剂和缓冲剂是通常可为此目的用于农业化学试剂中的所有物质。例如可提及柠檬酸、硫酸、盐酸、氢氧化钠、磷酸氢钠(Na2HPO4)、磷酸二氢钠(NaH2PO4)、磷酸二氢钾(KH2PO4)、磷酸氢钾(K2HPO4)。
合适的稳定剂和抗氧化剂是通常可为此目的用于农业化学试剂中的所有物质。优选丁基羟基甲苯[3,5-二叔丁基-4-羟基甲苯,CAS号128-37-0]。
载体(g)是通常可为此目的用于农业化学制剂中的那些。
载体是固体或液体、天然的或合成的、有机或无机物质,其通常是惰性的并且可用作溶剂。载体通常改善化合物对例如植物、植物部位或种子的施用。合适的固体载体的实例包括但不限于铵盐,特别是硫酸铵、磷酸铵和硝酸铵,天然岩粉,例如高岭土、粘土、滑石、白垩、石英、绿坡缕石、蒙脱石和硅藻土、硅胶和合成岩粉,例如细碎的二氧化硅、氧化铝和硅酸盐。
通常可用于制备颗粒剂的固体载体的实例包括但不限于粉碎并分级的天然岩石,例如方解石、大理石、浮石、海泡石和白云石,无机粉和有机粉的合成颗粒以及有机材料(例如纸张、锯屑、椰壳、玉米穗轴和烟草茎)的颗粒。
优选的固体载体选自粘土、滑石和二氧化硅。
合适的液体载体的实例包括但不限于水、有机溶剂及其结合。合适的溶剂的实例包括极性和非极性有机化学液体,例如来自以下种类:
-醇和多元醇(其也可任选地被取代、醚化和/或酯化,例如乙醇、丙醇、丁醇、苯甲醇、环己醇或乙二醇、2-乙基己醇),
-醚类,例如二辛基醚、四氢呋喃、异山梨醇二甲基醚、丙酮缩甘油(solketal)、环戊基甲基醚、Dow提供的Dowanol产品系列的溶剂,例如Dowanol DPM,苯甲醚、苯乙醚、不同分子量等级的二甲基聚乙二醇、不同分子量等级的二甲基聚丙二醇、二苄基醚
-酮类(例如丙酮、甲乙酮、甲基异丁基酮、环戊酮、环己酮、环庚酮、苯乙酮、苯丙酮),
-乳酸酯类,例如乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、乳酸2-乙基己酯,
-(聚)醚类,例如不同分子量等级的聚乙二醇、不同分子量等级的聚丙二醇,
-未取代和取代的胺类,
-酰胺类(例如二甲基甲酰胺,或N,N-二甲基乳酰胺,或N-甲酰基吗啉,或脂肪酸酰胺类,如N,N-二甲基癸酰胺或N,N-二甲基十二-9-烯酰胺)及其酯类,
-内酰胺类(例如2-吡咯烷酮,或N-烷基吡咯烷酮,例如N-甲基吡咯烷酮,或N-丁基吡咯烷酮,或N-辛基吡咯烷酮,或N-十二烷基吡咯烷酮或N-甲基己内酰胺,N-烷基己内酰胺),
-内酯类(例如γ-丁内酯、γ-戊内酯、δ-戊内酯或α-甲基γ-丁内酯),
-砜类和亚砜类(例如二甲基亚砜),
-腈类,例如直链或环状烷基腈,特别是乙腈、环己烷腈、辛腈、十二腈,
-直链和环状碳酸酯类,例如碳酸二乙酯、碳酸二丙酯、碳酸二丁酯、碳酸二辛酯或碳酸亚乙酯、碳酸亚丙酯、碳酸亚丁酯、碳酸丙三醇酯,
最优选的载体是水。
这些喷雾液通过常规方法施用,即例如通过喷雾、倾倒或注射,特别是通过喷雾,最特别是通过UAV喷雾。
A.方法和缩写
A-1.方法
除非另有说明,否则作为本申请一部分的所有数据均已根据下述方法准备。用于测量的样品直接使用,不进行任何进一步的样品制备。
LogP值的测定
本文所提供的LogP值的测量根据EEC directive 79/831Annex V.A8,通过反相柱上的HPLC(高效液相色谱法),用通过在酸性范围内使用0.1%甲酸水溶液和乙腈作为洗脱液(线性梯度为10%乙腈至95%乙腈)进行LC-UV测量而确定的方法进行。
校准使用具有已知LogP值的直链烷-2-酮(具有3至16个碳原子)进行(LogP值的测量使用保留时间,通过在相邻烷酮之间的线性插值进行)。λmax值使用200nm至400nm的UV光谱和色谱信号的峰值确定。
1H-NMR数据
本文提供的所选实施例的1H-NMR数据以1H-NMR峰列表的形式示出。对于各信号峰,列出了以ppm计的d值,并且在圆括号内列出了信号强度。在d值-信号强度数对之间以分号分隔列出。
因此,一个实例的峰值列表采用以下形式:
d1(强度1);d2(强度2);……;di(强度i);……;dn(强度n)
锐锋信号的强度与打印出的以厘米计的NMR光谱实例中的信号的高度相关,并显示信号强度的实际关系。由宽峰信号可以展示多个峰或信号中部以及其与光谱中最强信号相比的相对强度。
为校准1H谱的化学位移,我们利用四甲基硅烷和/或所用溶剂的化学位移,尤其是在DMSO中测量的光谱的情况下。因此,在NMR峰列表中,四甲基硅烷峰可以但不是必需出现。
1H-NMR峰的列表类似于传统1H-NMR打印件,因此,其通常含有在传统NMR解析中列出的所有峰。
另外,如同传统1H-NMR打印件,其可显示出溶剂、目标化合物的立体异构体(其也是本发明的主题)和/或杂质峰的信号。
为了示出在溶剂和/或水的δ范围内的化合物信号,通常的溶剂峰,例如在DMSO-D6中的DMSO的峰和水的峰示于我们的1H-NMR峰列表中,并且通常具有平均的高强度。
目标化合物的立体异构体的峰和/或杂质的峰通常具有比目标化合物(例如具有>90%的纯度)的峰平均更低的强度。
这些立体异构体和/或杂质对于特定制备方法可以是典型的。因此,它们的峰可借助“副产品指纹图谱”帮助识别制备方法的再现性。
通过已知方法(MestreC,ACD模拟,以及利用凭经验评估的预期值)的计算目标化合物峰的专家可以任选地使用附加的强度滤波器按照需要分离出目标化合物的峰。这种分离类似于传统1H-NMR解析下相关峰的拾取。
带有峰列表的NMR数据说明的进一步细节可在研究公开数据库第564025号(Research Disclosure Database Number 564025)的出版物“Citation of NMR PeaklistData within Patent Applications”中找到。
对映异构体的分离
外消旋体的对映体分离通过制备型超临界流体色谱,使用超临界二氧化碳作为流动相和低级醇作为改性剂,更优选甲醇、乙醇或异丙醇,比例为15至30体积%而进行。总流速在70-100mL/min的范围内,并且在30℃至50℃范围内的温度下和70巴至130巴范围内的背压下在以下可商购且已知的恒温手性固定相之一中进行色谱分离:
-ChiralPakIA,250x20mm,Daicel Chemical Industries公司。
-LuxAmylose-1,250x21.2mm 5μm,Phenomenex公司Axia装填。
-LuxCellulose-1,250x21.2mm 5μm,Phenomenex公司Axia装填。
-Luxi-Cellulose-5,250x21.2mm 5μm,Phenomenex公司Axia装填。
XRPD
X射线衍射图使用XRD衍射仪X`Pert PRO(PANalytical)和STOE STADI-P(Cu Kα1辐射,波长1.5406)在室温下记录。所有X射线反射均引用为°2θ(θ)值(峰最大值),分辨率为±0.2°。
拉曼
拉曼光谱使用Bruker的FT-拉曼分光光度计(型号MultiRam)在室温下记录。分辨率为2cm-1。测量在玻璃瓶或铝盘中进行。
IR
IR-ATR-光谱使用Bruker的带通用金刚石ATR装置的FT-IR-分光光度计Tensor 37或Alpha在室温下记录。分辨率为2cm-1。
TGA
TGA热谱图使用Perkin-Elmer的热天平(型号TGA 8000)和Mettler Toledo的热天平(型号TGA/DSC3+)记录。测量使用开放的铂金盘(Perkin Elmer)和有孔的铝盘(Mettler)以10Kmin-1的加热速率进行。流动气体为氮气。
B.实施例
B-1.合成制备
制备实施例1:(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪(I)[2446130-20-5]
步骤1:N-[(2RS)-1-氯-3-(2-氯-4-甲苯基)丙-2-基]-3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-甲酰胺[2446133-45-3]的制备
在氩气下,将3-(3-氯-2-氟-苯氧基)-6-甲基-哒嗪-4-甲酸[2435607-79-5](175g,619mmol)和(2RS)-1-氯-3-(2-氯-4-甲苯基)丙-2-胺盐酸盐(1:1)[2446132-78-9](262g,928mmol)悬浮于3L二氯甲烷中,然后在10分钟内缓慢加入丙烷膦酸酐(682mL,2290mmol),滴加N,N-二异丙基乙胺(393mL,2250mmol),反应在室温下搅拌18小时。然后将反应混合物倒入1.5L饱和碳酸氢钠水溶液中,加入1L水。用500mL二氯甲烷萃取混合物两次。将合并的有机层用硫酸钠干燥、过滤并蒸发。产物通过柱色谱法使用3kg硅胶柱(固体沉积物)纯化,洗脱梯度为庚烷/乙酸乙酯100/0至0/100。蒸发溶剂后,回收250g(100%纯度,83%产率)为固体的标题化合物。
步骤2:N-[(2RS)-1-氯-3-(2-氯-4-甲苯基)丙-2-基]-3-(3-氯-2-氟苯氧基)-N'-羟基-6-甲基哒嗪-4-甲脒[2446133-13-5]的制备
向N-[(2RS)-1-氯-3-(2-氯-4-甲苯基)丙-2-基]-3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-甲酰胺[2446133-45-3](249g,515mmol)于甲苯(3L)的溶液中添加五氯化磷(215g,1030mmol)。将反应混合物在75℃下搅拌1h,然后减压浓缩。将残余物溶解在1,4-二噁烷(1.2L)中,并在30分钟内向反应混合物中加入在15℃下羟胺(681g,10.3mol,50%水溶液)稀释于1,4-二噁烷(2.8L)中的溶液。在室温下搅拌16h后,将反应混合物用水(6L)稀释,然后缓慢加入1.6L盐酸6M。用乙酸乙酯(4×750mL)萃取水相。用盐水(1L)洗涤有机萃取物,经硫酸钠干燥、过滤并减压浓缩。蒸发溶剂,得到309g(80%纯度,96%产率)为黄色油状物的标题产物。
步骤3:(5RS)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪[2446129-82-2]的制备
向N-[(2RS)-1-氯-3-(2-氯-4-甲苯基)丙-2-基]-3-(3-氯-2-氟苯氧基)-N'-羟基-6-甲基哒嗪-4-甲脒[2446133-13-5](278g,474mmol)于乙腈(5L)和水(50mL)中的溶液中添加叔丁醇钾(173g,830mmol)。将反应混合物在45℃下搅拌45min。反应混合物用水(1L)稀释,在真空下蒸发乙腈。将所得混合物用水(8L)稀释并用乙酸乙酯(3×1.5L)萃取。将合并的有机层用盐水(2×1L)洗涤,经硫酸镁干燥、过滤并浓缩。将残余物首先通过柱色谱法使用3kg硅胶柱(固体沉积物)纯化,洗脱梯度为二氯甲烷100至二氯甲烷/乙酸乙酯70/30,然后通过柱色谱法使用1.5kg硅胶柱固体沉积物进行二次纯化,梯度为庚烷100至乙酸乙酯100。将收集到的级分进行浓缩,得到橙色粘性固体。将固体在500mL庚烷中在50℃下研磨2小时,然后过滤,得到115g(99%纯度,50%产率)标题化合物。
对映异构体的分离
制备级的分离在Pic Solution的装置SFC-PICLAB Hybrid 10-150上进行,UV检测范围在210nm和280nm之间,优选220nm和254nm之间。
将(5RS)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪(非对映异构体的混合物)(17g,99%纯度)通过制备型超临界流体色谱法分离,得到(5R)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪(8.71g,100%纯度)和(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪(8.77g,100%纯度)。
色谱柱:ChiralPakIA,250x20mm;洗脱液A:CO2;洗脱液B:甲醇;等度25%
分析手性HPLC。色谱柱ChiralPakIB N-5 150x2,1 5μm;洗脱液A:水+0.1%HCOOH;洗脱液B:乙腈+0.1%HCOOH;等度45:55A/B;流量:0.175ml/min;UV:220nm;烘箱:25℃
(5R)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪:Rt=12.33min;旋光度:+79.7°(c=1.21,CDCl3,25℃),浓度c以g/100mL表示
(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)-5,6-二氢-4H-1,2,4-噁二嗪(I):Rt=13.09min;旋光度:-81.4°(c=1.16,CDCl3,25℃),浓度c以g/100mL表示
LogP:3.88
1H-NMR(600.2MHz,CDCl3):
δ=7.9188(5.3);7.3551(0.6);7.3490(0.7);7.3445(1.1);7.3389(1.2);7.3333(0.7);7.3280(0.7);7.2619(5.8);7.1515(3.6);7.1452(2.0);7.1397(2.8);7.1100(2.3);7.1090(2.3);7.0607(2.1);7.0479(2.3);6.7461(1.2);6.7449(1.2);6.7334(1.1);6.7322(1.1);6.0010(1.2);4.2055(1.0);4.1999(1.1);4.1873(1.2);4.1817(1.2);4.0168(0.4);4.0118(0.5);4.0075(0.6);4.0045(0.6);4.0016(0.6);3.9973(0.6);3.9923(0.4);3.8732(1.3);3.8641(1.2);3.8550(1.2);3.8459(1.1);3.1400(0.9);3.1316(0.9);3.1175(1.0);3.1091(1.0);2.8832(1.1);2.8676(1.1);2.8608(1.0);2.8452(0.9);2.6415(16.0);2.1863(11.5);1.5862(2.0);0.0000(7.7)
B-2.(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)- 5,6-二氢-4H-1,2,4-噁二嗪的多晶型B
B-2-1.多晶型B的制备
将式(I)化合物在各自的沸腾温度下溶解于各溶剂(在表5中给出)中。将溶液过滤,分成四份、三份或两份(取决于所用溶剂,如果有的话)。
将各份分别存放于
a)室温下
b)冷藏箱中(4℃至7℃)
c)冷冻箱中(-20℃至-18℃)
直至干燥,
d)任选地,添加抗溶剂。
表5:用于晶型B的溶剂
表5中的实施例4至16得到多晶型B。将所得到的多晶型B的晶体分离,并通过X射线粉末衍射(XRPD)、拉曼光谱和红外光谱进行分析。
B-3.(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基苄基)- 5,6-二氢-4H-1,2,4-噁二嗪的多晶型A
B-3-1.多晶型A的制备
制备多晶型A的方法
为了获得多晶型A的晶体,进行温度依赖型X射线粉末衍射(XRPD)实验,其中允许在不同温度下重结晶。加热时在60℃以及冷却时在40℃观察到相变。多晶型A的X射线衍射图在75℃观察。
将所得到的多晶型A的晶体分离,并通过X射线粉末衍射(XRPD)进行分析。
C.式(I)的(5S)-3-[3-(3-氯-2-氟苯氧基)-6-甲基哒嗪-4-基]-5-(2-氯-4-甲基 苄基)-5,6-二氢-4H-1,2,4-噁二嗪的多晶型B的性质
C-1.制剂实施例
根据表6中的配方将多晶型B的式(I)化合物的制剂制备为悬浮浓缩剂(SC)制剂。该制剂通过以下方法制备:首先在含有杀生物剂的水中制备2%Rhodopol 23的凝胶。在搅拌下按以下顺序混合余下组分:水、防冻剂、消泡剂和分散剂,直至溶解,然后加入式(I)化合物的多晶型B的粉末,通过混合进行分散,并在珠磨机中研磨,得到1至10微米的粒度(Dv50)。在低剪切混合下向经研磨的分散体中加入2% Rhodopol 23凝胶以得到SC制剂。然后通过在70℃和80℃下储存样品对制剂进行稳定性测试。
表6:SC制剂配方1
物理特性通过目视检查样品确定,微观形态通过将SC制剂稀释至约1%并观察本发明的式(I)化合物的多晶型B的晶体的聚集状态和尺寸来确定。稀释稳定性(也称为悬浮性)通过以下方法测定:在底部有一个特殊窄端的刻度量筒中通过在CIPAC C水(硬度500ppm)(www.cipac.org MT18.1)中混合制备100毫升1%v/v分散体,以使得1小时后任何沉淀物的体积可视化。测量在室温下进行。
表7:制剂配方1的稳定性
试验 | 初始 | 1周@70℃ | 5天@80℃ |
微观 | 分散颗粒 | 分散颗粒 | 分散颗粒 |
外观 | 流体悬浮液 | 流体悬浮液 | 流体悬浮液 |
悬浮性(1%,1h) | 痕量# | 痕量# | 痕量# |
痕量#指可以在100mL的样品体积中观察到小于0.1mL的颗粒
表7中施加的温度远高于其中样品经受54℃的温度2周的标准程序中使用的温度。
表7中的结果显示,在70℃下一周后和在80℃下5天后,就外观和悬浮性方面在显微镜下探针中没有差异。特别地,关于悬浮性,即使在使探针经受70℃(持续一周)和80℃(持续5天)的温度之后,包含式(I)化合物的多晶型B的SC制剂也仅显示痕量(小于0.1mL)的颗粒。这些温度高于49℃至66℃的转变温度范围。未观察到向多晶型物A的转变。
这些结果表明,即使经受高于多晶型物B到多晶型物A的转变温度范围的温度持续数天,多晶型物B也表现出令人惊讶的高稳定性。因此,包含式(I)化合物的多晶型B的SC制剂令人惊讶地具有高稳定性,优选具有高稀释稳定性,更优选具有高悬浮性,这是显著相关的,因为多晶转变预期会导致SC制剂的不稳定性。
C-2.浆液实验
如表8所示,将式(I)化合物悬浮于相应溶剂中并在0℃、40℃(Mya4搅拌器站,250U/min)和80℃(Reacti-Therm III,搅拌等级6)下搅拌。三至八天后,向悬浮液中加入额外量的溶剂。在两个实验中,四天后加入其他物质。八天后,将悬浮液在环境条件下干燥。将所得到的晶体分离,并通过X射线粉末衍射(XRPD)光谱、DSC和TGA进行分析。图3a显示了浆液实验3之后的XRPD。
表8:
*4天后加入83mg
**4天后加入272mg
Claims (18)
1.式(I)化合物的晶型B
其在25℃和Cu-Kα1辐射下的X射线粉末衍射图中显示至少以下反射,引用为2θ值±0.2°:20.2、23.3和25.1。
2.权利要求1的化合物的型B,其在25℃和Cu-Ka1辐射下的X射线粉末衍射图中显示至少以下反射,引用为2θ值±0.2°:20.2、23.3、25.1、14.5和19.4。
3.权利要求1的化合物的型B,其在25℃和Cu-Kα1辐射下的X射线粉末衍射图中显示至少以下反射,引用为2θ值±0.2°:20.2、23.3、25.1、14.5、19.4、23.4和10.6。
4.权利要求1的式(I)化合物的型B,其在拉曼光谱中显示至少以下谱带(峰最大值,单位为cm-1):98、112和1585。
5.权利要求1的式(I)化合物的型B,其在拉曼光谱中显示至少以下谱带(峰最大值,单位为cm-1):98、112、1585、1279和2925。
6.权利要求1的式(I)化合物的型B,其在拉曼光谱中显示至少以下谱带(峰最大值,单位为cm-1):98、112、1585、1279、2925、688和1609。
7.制备权利要求1至6中任一项的晶型B的方法,包括以下步骤:
a)在合适的溶剂或溶剂混合物中稀释式(I)化合物,
b)将步骤a)的组合物加热至至少70℃的温度,以及
c)将来自步骤b)的溶液冷却至低于20℃的温度。
8.包含权利要求1至6中任一项的多晶型B的组合物。
9.权利要求8的组合物,其中所述组合物包括至少a)一种或多种漂移减少成分,b)一种或多种铺展剂,c)一种或多种吸收促进剂,d)一种或多种耐雨添加剂,e)任选的其它助剂和/或f)一种或多种载体增容。
10.权利要求8或9的组合物,其中所述组合物是悬浮浓缩剂制剂。
11.一种植物保护剂,包括权利要求1至6中任一项的式(I)的晶型B或权利要求8至10中任一项的组合物。
12.权利要求11所述的植物保护剂,其还包括一种或多种选自以下的其他活性物质:除草剂、杀昆虫剂、杀螨剂、杀真菌剂、安全剂和/或植物生长调节剂。
13.权利要求1至6中任一项的多晶型B在制备组合物或植物保护剂中的用途,所述组合物或植物保护剂优选具有高稳定性,更优选在高于转变温度的温度下具有高稳定性。
14.权利要求1至6中任一项的多晶型B、或权利要求8至10中任一项的制剂或权利要求11或12的植物保护剂用于防治不想要的微生物的用途。
15.用于防治不想要的微生物的方法,其中将权利要求1至6中任一项的多晶型B、权利要求8至10中任一项的制剂或权利要求11或12的植物保护剂施用于有用植物。
16.式(I)化合物的晶型A
其在25℃和Cu-Kα1辐射下的X射线粉末衍射图中显示至少以下反射,引用为2θ值±0.2°:16.9、19.8和24.5。
17.权利要求16的化合物的型A,其在25℃和Cu-Kα1辐射下的X射线粉末衍射图中显示至少以下反射,引用为2θ值±0.2°:16.9、19.8、24.5、14.2和24.7。
18.权利要求16的化合物的型A,其在25℃和Cu-Kα1辐射下的X射线粉末衍射图中显示至少以下反射,引用为2θ值±0.2°:16.9、19.8、24.5、14.2、24.7、20.8和21.8。
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CN (1) | CN119522219A (zh) |
AR (1) | AR129211A1 (zh) |
AU (1) | AU2023263693A1 (zh) |
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