CN112584704A - 杀真菌活性化合物i衍生物及其混合物在种子施用和处理方法中的用途 - Google Patents
杀真菌活性化合物i衍生物及其混合物在种子施用和处理方法中的用途 Download PDFInfo
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- CN112584704A CN112584704A CN201980052905.4A CN201980052905A CN112584704A CN 112584704 A CN112584704 A CN 112584704A CN 201980052905 A CN201980052905 A CN 201980052905A CN 112584704 A CN112584704 A CN 112584704A
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- pyrazole
- methyl
- carboxamide
- ethyl
- pyridazin
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- 239000008158 vegetable oil Substances 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002578 wasp venom Substances 0.000 description 1
- 239000004562 water dispersible granule Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- FJHBOVDFOQMZRV-XQIHNALSSA-N xanthophyll Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C=C(C)C(O)CC2(C)C FJHBOVDFOQMZRV-XQIHNALSSA-N 0.000 description 1
- 235000008210 xanthophylls Nutrition 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
Abstract
本发明涉及农业方法和杀真菌活性化合物I,即4‑[[6‑[2‑(2,4‑二氟苯基)‑1,1‑二氟‑2‑羟基‑3‑(5‑硫烷基‑1,2,4‑三唑‑1‑基)丙基]‑3‑吡啶基]氧基]苯甲腈及其与杀虫剂和/或杀真菌剂的混合物在种子处理方法中的用途。
Description
描述
本发明涉及杀真菌活性化合物I:4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫烷基-1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苯甲腈或其互变异构体、对映异构体、非对映异构体或其盐在种子处理方法中用于控制和/或对抗抗性植物病原真菌的用途,其中式(I)的活性化合物通过浸湿土壤、通过滴灌施用到土壤上、通过土壤注射、通过浸渍或通过种子处理而直接和/或间接施用到植物和/或植物繁殖材料上。
本发明还涉及具有杀真菌和杀昆虫作用的杀真菌活性化合物I:4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫烷基-1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苯甲腈的用途。
此外,本发明涉及一种控制植物病原性有害生物的方法,其中用有效量的化合物I或混合物处理有害生物、其栖息地、繁殖地、其位置或需要保护以防止有害生物攻击的植物、土壤或植物繁殖材料。
术语“植物繁殖材料”应理解为是指植物的所有有生殖力的部分,如种子和有生长力的植物材料,如插条和块茎(如马铃薯),其可用于植物繁殖。这包括种子、根、果实、块茎、鳞茎、根茎、嫩枝、芽和植物的其他部分,包括幼苗和幼嫩的植物,其在发芽后或从土壤中出苗后被移植。这些幼嫩的植物也可以在移植前通过浸泡或浇灌的方式进行整体或部分处理来保护。在特别优选的实施方案中,术语繁殖材料是指种子。
化合物I和类似物及其杀虫作用以及制备它们和混合物的方法是已知的,例如来自WO 2016187201、WO2018098216、WO2018098243、WO2018098245。
化合物II及其杀虫作用和制备它们的方法是众所周知的(参考:http://www.alanwood.net/pesticides/);这些物质可在商业上购买。IUPAC命名法描述的化合物、其制剂及其杀虫活性在WO 2013/007767和Pesticide Manual V5.2(ISBN 978 1 90139685 0)(2008-2011)中也是已知的。
在有害生物防治领域出现的一个典型问题是需要降低活性成分的剂量率,以减少或避免不利的环境或毒理学作用,同时仍然提供有效的有害生物防治。
就本发明而言,术语有害生物包括有害真菌和动物害虫。
遇到的另一个问题是,需要提供对广谱的有害真菌和有害的动物害虫有效的有害生物防治剂。
此外,还需要将敲减(knock-down)活性与长期控制相结合的有害生物防治剂,即快速作用与长期作用相结合。
与杀虫剂使用有关的另一个困难是,重复和单独使用一种杀虫化合物在许多情况下会导致有害生物(即动物害虫和有害真菌)的快速选择,它们对所述活性化合物产生了天然或适应性抗性。因此,需要有助于防止或克服抗性的有害生物防治剂。
本发明潜在的另一个问题是对改良植物的组合物的需求,其是改良通常和下文中被称为“植物健康”的过程。
术语植物健康包括与有害生物防治无关的植物的各种改良。例如,可提及的有利特性是改良的作物特性,包括:出苗、作物产量、蛋白质含量、含油量、淀粉含量、更发达的根系(改良的根系生长)、改良的胁迫耐性(例如抗旱、耐热、耐盐、抗紫外线、耐水、耐寒)、乙烯减少(减少产量和/或抑制接受)、分蘖增加、株高增加、叶片变大、死的基生叶更少、分蘖更强、叶色更绿、色素含量、光合活性、所需投入(如肥料或水)减少、所需种子减少、有效分蘖增加、开花更早、籽粒成熟早、减少植物倾倒(倒伏)、增加嫩枝生长、增强植物活力、增加植物成活和提早且更好的萌芽;或本领域技术人员熟知的任何其他优点。
因此,本发明的一个目的是提供杀灭有害生物的化合物和混合物,其解决了降低剂量率和/或增强活性谱和/或将敲减活性和长期控制相结合和/或抗性管理和/或促进植物健康的问题。
我们已经发现,该目标部分或全部通过使用杀菌活性化合物I:4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫烷基-1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苯甲腈或其互变异构体、对映异构体、非对映异构体或其盐来实现,在种子处理方法中用于控制和/或对抗抗性植物病原真菌,其中式(I)的活性化合物通过浸湿土壤、通过滴灌施用到土壤上、通过土壤注射、通过浸渍或通过种子处理而直接和/或间接施用到植物和/或植物繁殖材料上。
特别地,已经发现,当应用于植物、植物部分、种子或其生长位置时,与单个化合物可能达到的控制率和/或适合于改良植物健康的控制率相比,上述定义的化合物和混合物显示出显著增强的抗有害生物的作用。
已经发现,化合物及所定义的作用远远超出混合物中存在的活性化合物单独使用时的杀真菌和/或植物健康改良作用(协同作用)。
此外,我们还发现,与单个化合物(协同混合物)可能的控制率相比,同时(即联合或分别)施用化合物I和其他化合物或连续施用化合物I和其他化合物可增强对有害真菌的控制。
此外,我们还发现,与单个化合物可能产生的植物健康效应相比,同时(即联合或分别)施用化合物I和其他化合物或连续施用化合物I和其他化合物提供了增强的植物健康效应。
二元混合物中化合物I和化合物II的重量比为10000:1至1:10000、500:1至1:500、优选100:1至1:100、更优选50:1至1:50、最优选20:1至1:20,还包括10:1至1:10、1:5至5:1或1:1的比率。
所有上述混合物在下文中称为“本发明混合物”。
本发明混合物还可包含一种或多种杀虫剂、杀真菌剂、除草剂。
本发明混合物可转化为常用类型的农药组合物,例如溶液、乳液、混悬液、粉尘、粉末、糊剂、颗粒、压片剂(pressing)、胶囊及其混合物。组合物类型的实例为混悬液(例如SC、OD、FS)、可乳化的浓缩剂(例如EC)、乳状液(例如EW、EO、ES、ME)、胶囊(例如CS、ZC)、糊剂、锭剂、可湿性粉末或粉尘(例如WP、SP、WS、DP、DS)、压片剂(例如BR、TB、DT)、颗粒(例如WG、SG、GR、FG、GG、MG)、杀虫物品(例如LN)以及用于处理植物繁殖材料(如种子)的凝胶制剂(例如GF)。这些及其他组合物类型如“Catalogue of pesticide formulation types andinternational coding system”,Technical Monograph No.2,第6版.May 2008,CropLifeInternational中所定义。
所述组合物按照已知方法制备,例如Mollet和Grubemann,Formulationtechnology,Wiley VCH,Weinheim,2001;或Knowles,New developments in cropprotection product formulation,Agrow Reports DS243,T&F Informa,London,2005中所述。
合适的辅料为溶剂、液体载体、固体载体或填充剂、表面活性剂、分散剂、乳化剂、润湿剂、佐剂、增溶剂、渗透促进剂、保护胶体、粘着剂、增稠剂、湿润剂、驱避剂、引诱剂、饲用兴奋剂、增容剂、杀菌剂、防冻剂、消泡剂、着色剂、增粘剂和粘合剂。
合适的溶剂和液体载体是水和有机溶剂,例如中到高沸点的矿物油馏分,例如煤油、柴油;植物或动物来源的油;脂肪族、环状和芳香族烃类,例如甲苯、石蜡、四氢萘、烷基化萘;醇,例如乙醇、丙醇、丁醇、苯甲醇、环己醇;二醇类;DMSO;酮,例如环己酮;酯,例如乳酸酯、碳酸酯、脂肪酸酯、γ-丁内酯;脂肪酸;膦酸酯;胺;酰胺,例如N-甲基吡咯烷酮、脂肪酸二甲基酰胺;及其混合物。
合适的固体载体或填充剂为矿物土,例如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、白垩、粘土、白云石、硅藻土、膨润土、硫酸钙、硫酸镁、氧化镁;多糖,例如纤维素、淀粉;肥料,例如硫酸铵、磷酸铵、硝酸铵、尿素;植物来源的产品,如谷类粉、树皮粉、木粉、果壳粉及其混合物。
合适的表面活性剂是表面活性化合物,如阴离子、阳离子、非离子和两性表面活性剂、嵌段聚合物、聚电解质及其混合物。这些表面活性剂可用作乳化剂、分散剂、增溶剂、润湿剂、渗透促进剂、保护胶体或辅助剂。表面活性剂的实例如McCutcheon’s,第1卷:Emulsifiers&Detergents,McCutcheon’s Directories,Glen Rock,USA,2008(国际版或北美版)中所列举。
合适的阴离子表面活性剂是磺酸、硫酸、磷酸、羧酸的碱金属、碱土金属盐或铵盐及其混合物。磺酸盐的实例有烷基芳基磺酸盐、二苯基磺酸盐、α-烯烃磺酸盐、木质素磺酸盐、脂肪酸和油类的磺酸盐、乙氧基化烷基酚磺酸盐、烷氧基化芳基酚磺酸盐、缩合萘的磺酸盐、十二烷基和十三烷基苯磺酸盐、萘和烷基萘的磺酸盐、磺基琥珀酸盐或磺基琥珀酰胺酸盐。硫酸盐的实例为下述物质的硫酸盐:脂肪酸和油类、乙氧基化烷基酚、醇、乙氧基化醇或脂肪酸酯。磷酸盐的例子是膦酸盐酯。羧酸盐的实例为烷基羧酸盐和羧化醇或烷基酚乙氧化物。
合适的非离子表面活性剂是烷氧基化物、N-取代脂肪酰胺、胺氧化物、酯、糖基表面活性剂、聚合物表面活性剂及其混合物。烷氧基化物的实例是已被1至50当量烷氧基化的化合物,例如醇、烷基酚、胺、酰胺、芳基酚、脂肪酸或脂肪酸酯。环氧乙烷和/或环氧丙烷可用于烷氧基化,优选环氧乙烷。N-取代脂肪酸酰胺的实例为脂肪酸葡糖酰胺或脂肪酸烷醇酰胺。酯的实例为脂肪酸酯、甘油酯或单甘油酯。糖基表面活性剂的实例为山梨聚糖、乙氧基化山梨聚糖、蔗糖和葡萄糖酯或烷基聚糖苷。聚合物表面活性剂的实例为乙烯基吡咯烷酮、乙烯基醇或乙酸乙烯酯的均聚物或共聚物。
合适的阳离子表面活性剂是四价表面活性剂,例如具有一个或两个疏水基团的季铵化合物,或长链伯胺的盐。合适的两性表面活性剂是烷基甜菜碱和咪唑啉类。合适的嵌段聚合物为A-B或A-B-A型嵌段聚合物,包括聚氧乙烯和聚氧丙烯的嵌段共聚物,或A-B-C型嵌段聚合物,包括烷醇、聚氧乙烯和聚氧丙烯的嵌段共聚物。合适的聚电解质是聚酸或聚碱。聚酸的实例为聚丙烯酸的碱盐或聚酸梳形聚合物。聚碱的实例为聚乙烯基胺或聚乙烯胺。
合适的辅助剂是化合物,其本身具有可忽略的或甚至没有杀灭有害生物的活性,并且其改良了本发明混合物在靶点上的生物学性能。实例有表面活性剂、矿物油或植物油以及其他辅料。其他实例如Knowles,Adjuvants and additives,Agrow Reports DS256,T&F Informa UK,2006,第5章中所列举。
合适的增稠剂是多糖(例如黄原胶、羧甲基纤维素)、无机粘土(有机改性或未改性的)、聚羧酸盐和硅酸盐。
合适的杀菌剂是溴硝丙二醇和异噻唑啉酮衍生物,如烷基异噻唑啉酮和苯并异噻唑啉酮。
合适的防冻剂是乙二醇、丙二醇、尿素和甘油。
合适的消泡剂是硅酮、长链醇和脂肪酸盐。
合适的着色剂(例如红色、蓝色或绿色)是低水溶性色素和水溶性染料。例如无机着色剂(例如氧化铁、氧化钛、六氰合铁酸铁)和有机着色剂(例如茜素-、偶氮-和酞菁着色剂)。
合适的增粘剂或粘合剂是聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇、聚丙烯酸酯、生物或合成的蜡和纤维素醚。
组合物类型及其制备实例如下:
i)水溶性浓缩剂(SL,LS)
将10-60重量%的本发明混合物和5-15重量%的润湿剂(例如醇烷氧基化物)溶解于添加到100重量%的水和/或水溶性溶剂(例如醇类)中。活性物质用水稀释后溶解。
ii)可分散的浓缩剂(DC)
将5-25重量%的本发明混合物和1-10重量%的分散剂(例如聚乙烯吡咯烷酮)溶解在添加到100重量%的有机溶剂(例如环己酮)中。用水稀释得到分散液。
iii)可乳化的浓缩剂(EC)
将15-70重量%的本发明混合物和5-10重量%的乳化剂(例如十二烷基苯磺酸钙和蓖麻油乙氧基化物)溶解在添加到100重量%的水不溶性有机溶剂(例如芳烃)中。用水稀释得到乳状液。
iv)乳状液(EW、EO、ES)
将5-40重量%的本发明混合物和1-10重量%的乳化剂(例如十二烷基苯磺酸钙和蓖麻油乙氧基化物)溶解在20-40重量%的水不溶性有机溶剂(例如芳烃)中。通过乳化机将该混合物引入添加到100重量%的水中并制成均质乳液。用水稀释形成乳状液。
v)混悬液(SC、OD、FS)
在搅拌的球磨机中,将20-60重量%的本发明混合物通过加入2-10重量%的分散剂和润湿剂(例如木质素磺酸钠和醇乙氧基化物)、0.1-2重量%的增稠剂(例如黄原胶)和添加到100重量%的水来粉碎,得到精细的活性物质混悬液。用水稀释得到活性物质的稳定混悬液。对于FS型组合物,加入至多40重量%的粘合剂(例如聚乙烯醇)。
vi)水分散性颗粒和水溶性颗粒(WG、SG)
将50-80重量%的本发明混合物通过加入添加到100重量%的分散剂和润湿剂(例如木质素磺酸钠和醇乙氧基化物)来精细研磨,并通过技术手段(例如挤出、喷雾塔、流化床)制备为水分散性或水溶性颗粒。用水稀释得到活性物质的稳定分散液或溶液。
vii)水分散性粉末和水溶性粉末(WP、SP、WS)
在转子-定子研磨机中,将50-80重量%的本发明混合物通过加入1-5重量%的分散剂(例如木质素磺酸钠)、1-3重量%的润湿剂(例如醇乙氧基化物)和添加到100重量%的固体载体(例如硅胶)来研磨。用水稀释得到活性物质的稳定分散液或溶液。
viii)凝胶(GW、GF)
在搅拌的球磨机中,将5-25重量%的本发明混合物通过加入3-10重量%的分散剂(例如木质素磺酸钠)、1-5重量%的增稠剂(例如羧甲基纤维素)和添加到100重量%的水来粉碎,得到活性物质的精细的混悬液。用水稀释得到活性物质的稳定混悬液。
ix)微乳剂(ME)
将5-20重量%的本发明混合物加入到5-30重量%的有机溶剂混合物(例如脂肪酸二甲酰胺和环己酮)、10-25重量%的表面活性剂混合物(例如醇乙氧基化物和芳基苯酚乙氧基化物)和添加到100%的水中。将该混合物搅拌1小时以自发地产生热力学稳定的微乳剂。
x)微胶囊(CS)
将包含5-50重量%本发明混合物、0-40重量%水不溶性有机溶剂(例如芳烃)、2-15重量%丙烯酸单体(例如甲基丙烯酸甲酯、甲基丙烯酸和二-或三丙烯酸酯)的油相分散到保护胶体(例如聚乙烯醇)的水溶液中。由自由基引发剂引发的自由基聚合导致形成聚(甲基)丙烯酸酯微胶囊。或者,将包含5-50重量%的根据本发明的本发明混合物、0-40重量%水不溶性有机溶剂(例如芳香烃)和异氰酸酯单体(例如二苯基亚甲基-4,4'-二异氰酸酯)的油相分散到保护胶体(例如聚乙烯醇)的水溶液中。加入聚胺(例如六亚甲基二胺)导致形成聚脲微胶囊。单体含量为1-10重量%。重量%是相对于总CS组合物而言。
xi)粉尘化的粉剂(DP、DS)
将1-10重量%的本发明混合物精细研磨,并与添加到100重量%的固体载体(例如,精细粉碎的高岭土)紧密混合。
xii)颗粒(GR、FG)
将0.5-30重量%的本发明混合物精细研磨,并与添加到100重量%的固体载体(例如硅酸盐)结合。造粒是通过挤出、喷雾干燥或流化床实现。
xiii)超低容量液体(UL)
将1-50重量%的本发明混合物溶解在添加到100重量%的有机溶剂(例如芳香烃)中。
组合物类型i)-xiii)可任选地包含其他辅料,例如0.1-1重量%杀菌剂、5-15重量%防冻剂、0.1-1重量%消泡剂及0.1-1重量%着色剂。
所得到的农药组合物通常包含0.01%-95%之间、优选0.1%-90%之间、尤其是0.5%-75%之间(按重量计)的活性物质。活性物质以90%-100%,优选95%-100%的纯度(根据NMR光谱)使用。
种子处理溶液(LS)、混悬液(SE)、可流动浓缩液(FS)、用于干处理的粉末(DS)、用于浆体处理的水分散性粉末(WS)、水溶性粉末(SS)、乳液(ES)、可乳化的浓缩剂(EC)和凝胶(GF)通常用于处理植物繁殖材料(特别是种子)的目的。所述组合物在稀释2至10倍后,在可立即使用的(ready-to-use)制剂中提供0.01-60重量%,优选0.1-40重量%的活性物质浓度。可在播种前或播种期间进行施用。将本发明混合物及其组合物分别应用于植物繁殖材料(特别是种子)的方法包括繁殖材料的敷裹、包衣、造粒、撒粉(dusting)、浸泡和沟内施用方法。优选地,本发明混合物或其组合物分别通过例如通过种子敷裹、造粒、包衣和撒粉等不诱导发芽的方法施加到植物繁殖材料上。
当用于植物保护时,所施用的活性物质的量根据所期望效果的种类,从0.001到2kg/ha,优选从0.005到2kg/ha,更优选从0.01到1.0kg/ha,特别是从0.05到0.75kg/ha。
在植物繁殖材料例如种子的处理中,例如通过对种子进行撒粉、包衣或浸种,通常每100kg植物繁殖材料(优选种子)需要0.01-10kg、优选0.1-1000g、更优选1-100g的活性物质的量。
当用于保护材料或储存产品时,活性物质的用量取决于施用区域的种类和预期效果。通常用于保护材料的量为每立方米的处理材料使用0.001g至2kg,优选0.005g至1kg活性物质。
各种类型的油、湿润剂、佐剂、肥料或微量营养素以及其他杀虫剂(如除草剂、杀虫剂、杀真菌剂、生长调节剂、安全剂)可添加到活性物质中或包含其作为预混料的组合物中,或在适宜的情况下直到使用前才加入(罐式混合)。这些试剂可与根据本发明的组合物以1:100到100:1、优选1:10到10:1的重量比混合。
使用者通常从预投料装置、背负式喷雾器、喷雾罐、喷雾飞机或灌溉系统中施用本发明的组合物。通常情况下,农药组合物由水、缓冲剂和/或其他辅料配制成所需的施用浓度,从而获得本发明的可立即使用的喷雾液或农药组合物。通常,每公顷农业用地施用20-2000升,优选50-400升可立即使用的喷雾液。
根据一个实施方案,本发明的组合物的单个组分(例如试剂盒的一部分或二元混合物的一部分)可由用户自己在喷雾罐或用于施用的任何其他种类的容器(例如种子处理器滚筒、种子造粒机、背负式喷雾器)中混合,并且在合适时可加入其他辅料。
因此,本发明的一个实施方案是用于制备可用杀虫组合物的试剂盒,该试剂盒包括:a)包含如本文所定义的组分1)和至少一种辅料的组合物;和b)包含如本文所定义的组分2)和至少一种辅料的组合物;以及任选的c)包含至少一种辅料和任选的如本文所定义的其他活性组分3)的组合物。
如上所述,本发明包括所述混合物用于控制植物病原性有害真菌的用途以及控制植物病原性有害生物的方法,其中所述有害生物、其栖息地、繁殖地、其位置或被保护以免受有害生物攻击的植物、土壤或植物繁殖材料用有效量的所述混合物处理。
有利地,本发明混合物适合于控制以下真菌植物病害:
观赏植物、蔬菜(例如白锈菌(A.candida))和向日葵(例如婆罗门参白锈菌(A.tragopogonis))上的白锈菌属(Albugo)(白锈病);蔬菜(如胡萝卜链格孢(A.dauci)或葱链格孢(A.porri)、油菜(芸苔生链格孢(A.brassicicola)或芸苔链格孢(A.brassicae))、糖用甜菜(A.tenuis)、水果(如巨链格孢(A.grandis))、稻、大豆、马铃薯和番茄(例如早疫链格孢(A.solani)、巨链格孢(A.grandis)或链格孢(A.alternata))、番茄(例如早疫链格孢或链格孢)和小麦(如小麦链格孢(A.triticina))上的链格孢属(Alternaria)(链格孢叶斑病);糖用甜菜和蔬菜上的丝囊霉属(Aphanomyces);禾谷类和蔬菜上的壳二孢属(Ascochyta),例如小麦上的A.tritici(炭疽病)和大麦上的大麦壳二孢(A.hordei);玉米上的玉蜀黍出芽短梗霉(Aureobasidium zeae)(同义词:Kapatiellazeae);平脐蠕孢属(Bipolaris)和内脐蠕孢属(Drechslera)(有性型:旋孢腔菌属(Cochliobolus)),例如玉米上的叶斑病(玉蜀黍平脐蠕孢(D.maydis)或玉米生离蠕孢(B.zeicola)),例如禾谷类上的斑枯病(麦根腐平脐蠕孢(B.sorokiniana)以及例如稻和草坪上的稻平脐蠕孢(B.oryzae);禾谷类(例如小麦或大麦)上的小麦白粉菌(Blumeria(旧名:Erysiphe)graminis)(白粉病);水果和浆果(例如草莓)、蔬菜(例如莴苣、胡萝卜、根芹菜和卷心菜)上的灰葡萄孢(Botrytis cinerea)(有性型:灰葡萄孢霉(Botryotiniafuckeliana):灰霉病);洋葱科、油菜、观赏植物(例如百合灰霉病菌(B eliptica))、藤本植物、森林植物和小麦上的葱鳞葡萄孢菌(B.squamosa)或B.allii);莴苣上的莴苣盘梗霉(Bremia lactucae)(霜霉病);阔叶树和常绿树上的长喙壳属(Ceratocystis)(同义词线嘴壳属(Ophiostoma))(腐烂病或枯萎病),例如榆树上的榆枯萎病菌(C.ulmi)(荷兰榆病);玉米(例如灰叶斑病:玉米尾孢菌(C.zeae-maydis))、稻、糖用甜菜(例如甜菜生尾孢(C.beticola))、甘蔗、蔬菜、咖啡、大豆(例如大豆灰斑病菌(C.sojina)或大豆紫斑病菌(C.kikuchii))和稻上的尾孢属(Cercospora)(尾孢叶斑病);蘑菇上的Cladobotryum(同义词:轮指孢霉属(Dactylium))(例如C.mycophilum(旧名为Dactylium dendroides,有性型:Nectria albertinii、Nectria rosella同义词:Hypomyces rosellus);番茄(例如番茄叶霉菌(C.fulvum):叶霉病)和禾谷类(例如小麦上的草芽枝孢(C.herbarum)(穗腐病))上的枝孢属(Cladosporium);禾谷类上的麦角菌(Claviceps purpurea)(麦角病);玉米(灰色长蠕孢(C.carbonum))、禾谷类(例如禾旋孢腔菌(C.sativus),无性型:麦根腐平脐蠕孢)和稻(例如宫部旋孢腔菌(C.miyabeanus),无性型:水稻长蠕孢(H.oryzae))上的旋孢腔菌属(无性型:长蠕孢属(Helminthosporium)或平脐蠕孢属)(叶斑病);棉花(例如棉炭疽病菌(C.gossypii))、玉米(例如禾生炭疽病菌(C.graminicola):炭疽茎腐病)、浆果、马铃薯(例如西瓜炭疽病菌(C.coccodes):黑点病)、菜豆(例如菜豆炭疽病菌(C.lindemuthianum))、大豆(例如大豆炭疽病菌(C.truncatum)或毛豆炭疽病菌(C.gloeosporioides))、蔬菜(例如黄瓜炭疽病菌(C.lagenarium)或辣椒炭疽菌(C.capsici))、水果(例如多犯性植物炭疽病菌(C.acutatum))、咖啡(例如咖啡刺盘孢菌(C.coffeanum)或卡哈瓦刺盘孢(C.kahawae))上的剌盘孢属(Colletotrichum)(有性型:围小丛壳菌属(Glomerella))(炭疽病)和多种作物上的胶孢炭疽菌(C.gloeosporioides);伏革菌属(Corticium),例如稻上的笹木伏革菌(C.sasakii)(纹枯病);大豆和观赏植物上的黄瓜褐斑病菌(Corynesporacassiicola)(叶斑病);锈斑病菌属(Cycloconium),例如橄榄树上的C.oleaginum;果树、藤本植物(例如C.liriodendri,有性型:Neonectria liriodendri:乌脚病)和观赏树上的人参生柱隔孢属(Cylindrocarpon)(例如果树腐烂病或葡萄藤乌脚病,有性型:丛赤壳属(Nectria)或杓兰菌根菌属(Neonectria));大豆上的白纹羽菌(Dematophora(有性型:Rosellinia)necatrix)(根腐病/茎腐病);北茎溃疡菌属(Diaporthe),例如大豆上的大豆北茎溃疡病菌(D.phaseolorum)(立枯疡);玉米、禾谷类如大麦(例如大麦网斑内脐蠕孢(D.teres),网斑病)和小麦(例如D.tritici-repentis:褐斑病)、稻和草坪上的内脐蠕孢属(同义词长蠕孢属,有性型:核腔菌属(Pyrenophora));由斑褐孔菌(Formitiporia(同义词Phellinus)punctata)、F.mediterranea、Phaeomoniella chlamydospora(旧名为Phaeoacremonium chlamydosporum)、Phaeoacremonium aleophilum和/或葡萄座腔菌(Botryosphaeria obtusa)引起的葡萄藤上的埃斯卡(Esca)(葡萄藤枯萎病,干枯病);仁果(E.pyri)、浆果(覆盆子痂囊腔菌(E.veneta):炭疽病)和葡萄藤(葡萄痂囊腔菌(E.ampelina):炭疽病)上的痂囊腔菌属(Elsinoe);稻上的稻叶黑粉菌(Entyloma oryzae)(叶黑粉病);小麦上的附球菌属(Epicoccum)(黑穗病);糖用甜菜(甜菜白粉菌(E.betae))、蔬菜(例如豌豆白粉菌(E.pisi))如葫芦科植物(例如二孢白粉菌(E.cichoracearum))、卷心菜、油菜(例如E.cruciferarum)上的白粉菌属(Erysiphe)(白粉病);果树、葡萄藤和观赏树上的侧弯孢菌(Eutypa lata)(Eutypa溃疡病或枯萎病,无性型:Cytosporina lata,同义词Libertella blepharis);玉米(例如玉米大斑病菌(E.turcicum))上的突脐蠕孢属(Exserohilum)(同义词长蠕孢属);各种植物上的镰孢霉属(Fusarium)(有性型:赤霉属(Gibberella))(枯萎病,根腐病或茎腐病),例如禾谷类(例如小麦或大麦)上的禾本科镰孢(F.graminearum)或大刀镰孢(F.culmorum)(根腐病、黑星病或银尖病),番茄上的尖镰孢(F.oxysporum),大豆上的茄镰孢(F.solani)(f.sp.glycines,现在的同义词为北美大豆猝死综合症病菌(F.virguliforme)及各自引起猝死综合症的南美大豆猝死综合症病菌(F.tucumaniae)和F.brasiliense以及玉米上的轮枝镰孢(F.verticillioides);禾谷类(例如小麦或大麦)和玉米上的禾顶囊壳(Gaeumannomyces graminis)(全蚀病);禾谷类(例如玉蜀黍赤霉(G.zeae))和稻(例如藤仓赤霉(G.fujikuroi):恶苗病)上的赤霉属;藤本植物、仁果和其他植物上的苹果炭疽病菌(Glomerella cingulata)以及棉花上的棉炭疽病菌(G.gossypii);稻上的Grainstaining complex;葡萄藤上的葡萄黑腐病菌(Guignardiabidwellii)(黑腐病);蔷薇科植物和刺柏上的锈菌属(Gymnosporangium),例如梨上的G.sabinae(锈病);玉米、禾谷类、马铃薯和稻上的长蠕孢属(同义词内脐蠕孢属,有性型:旋孢腔菌属);驼孢锈菌属(Hemileia),例如咖啡上的咖啡驼孢锈菌(H.vastatrix)(咖啡叶锈病);藤本植物上的褐斑拟棒束孢(Isariopsis clavispora)(同义词Cladosporiumvitis);大豆和棉花上的菜豆壳球孢(Macrophomina phaseolina(同义词phaseoli))(根腐病/茎腐病);禾谷类(例如小麦或大麦)上的雪霉叶枯菌(Microdochium(同义词Fusarium)nivale(雪霉病);大豆上的扩散叉丝壳(Microsphaera diffusa)(白粉病);丛梗孢属(Monilinia),例如核果和其他蔷薇科植物上的核果链核盘菌(M.laxa)、桃褐腐菌(M.fructicola)和果生链核盘菌(M.fructigena)(同义词:丛梗孢属物种(Monilia spp.):花腐病和枝腐病,褐腐病);禾谷类、香蕉、浆果和花生上的球腔菌属(Mycosphaerella),例如小麦上的禾生球腔菌(M.graminicola)(无性型:Zymoseptoria tritici,以前为小麦壳针孢(Septoria tritici),壳针孢叶斑病)或香蕉上的斐济球腔菌(M.fijiensis)(同义词:Pseudocercospora fijiensis:Sigatoka黑斑病)和香蕉褐条斑小球壳菌(M.musicola);花生上的落花生球腔菌(M.arachidicola)(同义词:落花生球腔菌(M.arachidis)或Cercospora arachidis)、伯克利球腔菌(M.berkeleyi),豌豆上的M.pisi和芸苔属(brassicas)上的芸苔生球腔菌(M.brassiciola);卷心菜(例如芸苔霜霉(P.brassicae))、油菜(例如寄生霜霉(P.parasitica))、洋葱(例如大葱霜霉(P.destructor))、烟草(烟草霜霉(P.tabacina))和大豆(例如大豆霜霉病菌(P.manshurica))上的霜霉属(Peronospora)(霜霉病);大豆上的豆薯层锈菌(Phakopsora pachyrhizi)和山马蟥层锈菌(P.Meibomiae)(大豆锈病);例如藤本植物(例如P.Tracheiphila和P.tetraspora)和大豆(例如大豆茎褐腐病菌(P.gregata):茎病害)上的瓶霉菌属(Phialophora);油菜和卷心菜上的黑胫茎点霉(Phoma lingam)(同义词:油菜黑胫病菌(Leptosphaeria biglobosa)和油菜茎基溃疡病菌(L.maculans):根腐病和茎腐病)以及糖用甜菜上的甜菜茎点霉(P.betae)(根腐病、叶斑病和立枯疡)和玉米上的P.zeae-maydis(同义词:Phyllostica zeae);向日葵、葡萄藤(例如葡萄黑腐病菌(P.viticola):蔓割病和叶斑病)和大豆(例如茎腐病:P.phaseoli,有性型:大豆北茎溃疡病菌(Diaporthe phaseolorum))上的拟茎点霉属(Phomopsis);玉米上的玉米褐斑病菌(Physoderma maydis)(褐斑病);各种植物如柿子椒和葫芦科植物(例如辣椒疫霉(P.capsici))、大豆(例如大豆疫霉(P.megasperma),同义词P.sojae)、马铃薯和番茄(例如致病疫霉(P.infestans):晚疫病)和阔叶树(例如栎树猝死病菌(P.ramorum):橡树急死病)上的疫霉属(Phytophthora)(枯萎病,根腐病,叶腐病,茎腐病和果树腐烂病);卷心菜、油菜、小萝卜和其他植物上的芸苔根肿菌(Plasmodiophora brassicae)(根肿病);霜霉属(Plasmopara),例如葡萄藤上的葡萄生单轴霉(P.viticola)(葡萄藤霜霉病)和向日葵上的霍尔斯单轴霉(P.halstedii);蔷薇科植物、啤酒花、仁果和浆果上的叉丝单囊壳属(Podosphaera)(白粉病)(例如苹果上的苹果白粉病菌(P.leucotricha))和葫芦(苍耳单囊白粉菌(P.xanthii);例如禾谷类如大麦和小麦(禾谷多粘菌(P.graminis))以及糖用甜菜(甜菜多粘菌(P.betae))上的多粘菌属(Polymyxa)以及由此传播的病毒病害;禾谷类如小麦或大麦上的小麦基腐病菌(Pseudocercosporella herpotrichoides)(同义词:Oculimacula yallundae,O.acuformis:眼斑病,有性型:Tapesia yallundae);各种植物上的假霜霉属(Pseudoperonospora)(霜霉病),例如葫芦科植物上的古巴假霜霉(P.cubensis)或啤酒花上的葎草假霜(P.humili);葡萄藤上的Pseudopeziculatracheiphila(葡萄角斑叶焦病菌或‘rotbrenner’,无性型:瓶霉属(Phialophora));各种植物上的柄锈菌属(Puccinia)(锈病),例如禾谷类如小麦、大麦或黑麦上的小麦柄锈菌(P.triticina)(褐锈病或叶锈病),条形柄锈病(P.striiformis)(条纹病或黄锈病),大麦柄锈病(P.hordei)(大麦黄矮叶锈病),禾柄锈菌(P.graminis)(茎腐病或黑锈病)或小麦叶锈菌(P.recondita)(褐锈病或叶锈病),甘蔗上的P.kuehnii(橙锈病)和芦笋上的天门冬属柄锈病(P.asparagi);埋核盘菌属(Pyrenopeziza),例如油菜上的芸苔叶斑病菌(P.brassicae);小麦上的小麦黄斑叶枯病菌(Pyrenophora(无性型:Drechslera)tritici-repentis)(黄斑病)或大麦上的圆核腔菌(P.teres)(网斑病);梨孢属(Pyricularia),例如稻上的稻瘟病菌(P.oryzae)(有性型:Magnaporthe grisea,稻瘟病)以及草坪和禾谷类上的稻梨孢菌(P.grisea);草坪、稻、玉米、小麦、棉花、油菜、向日葵、大豆、糖用甜菜、蔬菜和各种其他植物(例如终极腐霉菌(P.ultimum)或瓜果腐霉(P.aphanidermatum))上的腐霉属(Pythium)(立枯病)和蘑菇上的寡雄腐霉(P.oligandrum);柱隔孢属(Ramularia),例如大麦上的R.collo-cygni(柱隔孢叶斑病,生理叶斑病)和糖用甜菜上的甜菜叶斑病菌(R.Beticola);棉花、稻、马铃薯、草坪、玉米、油菜、马铃薯、糖用甜菜、蔬菜和各种其他植物上的丝核菌属(Rhizoctonia),例如大豆上的立枯丝核菌(R.solani)(根腐病/茎腐病),稻上的R.solani(纹枯病)或小麦或大麦上的禾谷丝核菌(R.Cerealis)(小麦纹枯病);草莓、胡萝卜、卷心菜、藤本植物和番茄上的葡枝根霉(Rhizopus stolonifer)(黑霉病,软腐病);大麦、黑麦和小黑麦上的黑麦喙孢(Rhynchosporium secalis)和R.commune(叶斑病);稻上的稻帚枝霉(Sarocladium oryzae)和S.attenuatum(叶鞘腐败病);蔬菜(小核盘菌(S.minor)和核盘菌(S.sclerotiorum))和大田作物如油菜、向日葵(例如核盘菌(S.sclerotiorum))和大豆(S.rolfsii(同义词:罗耳阿太菌(Athelia rolfsii))、花生、蔬菜、玉米、谷物和观赏植物上上的核盘菌属(Sclerotinia)(茎腐病或白绢病);各种植物上的壳针孢属(Septoria),例如大豆上的大豆壳针孢(S.glycines)(褐斑病),小麦上的小麦壳针孢(S.tritici)(同义词:Zymoseptoria tritici,壳针孢叶斑病)和禾谷类上的颖枯壳多孢(S.(同义词Stagonospora)nodorum)(斑枯病);葡萄藤上的葡萄钩丝壳(Uncinula(同义词Erysiphe)necator)(白粉病,无性型:Oidium tuckeri);玉米(例如玉米大斑病菌(S.turcicum),同义词大斑凸脐蠕孢(Helminthosporium turcicum))和草坪上的大斑病菌属(Setospaeria)(叶枯病);玉米(例如丝轴黑粉菌(S.reiliana),同义词:Ustilagoreiliana:丝黑穗病)、小米和甘蔗上的轴黑粉菌属(Sphacelotheca)(黑穗病);葫芦科植物上的单丝壳白粉菌(Sphaerotheca fuliginea)(同义词:苍耳单囊壳白粉菌(Podosphaeraxanthii):白粉病);马铃薯上的粉痂菌(Spongospora subterranea)(粉痂病)以及由此传播的病毒病害;禾谷类上的壳多孢属(Stagonospora),例如小麦上的颖枯壳多孢(S.nodorum)(斑枯病,有性型:颖枯球腔菌(Leptosphaeria[同义词Phaeosphaeria]nodorum),同义词:Septoria nodorum);马铃薯上的马铃薯癌肿病菌(Synchytriumendobioticum)(马铃薯癌肿病);外囊菌属(Taphrina),例如桃上的畸形外囊菌(T.Deformans)(缩叶病)和李上的李外囊菌(T.pruni)(囊果李);烟草、仁果、蔬菜、大豆和棉花上的根串珠霉属(Thielaviopsis)(黑色根腐病),例如黑色根腐病菌(T.basicola)(同义词Chalara elegans);禾谷类上的腥黑粉菌属(Tilletia)(腥黑穗病或光腥黑穗病),例如小麦上的T.tritici(同义词T.caries,小麦腥黑穗病)和T.controversa(矮腥黑穗病);蘑菇上的哈茨木霉(Trichoderma harzianum);大麦或小麦上的肉孢核瑚菌(Typhulaincarnata)(灰雪腐病);黑粉菌属(Urocystis),例如黑麦上的隐条黑粉菌(U.occulta)(条黑粉病);蔬菜如菜豆(例如疣顶单胞锈菌(U.appendiculatus),同义词U.phaseoli)和糖用甜菜(例如甜菜锈病菌(U.betae或U.beticola))上的单孢锈属(Uromyces)(锈病)和pulses上的(例如豇豆属单胞锈菌(U.vignae)、豌豆单孢锈菌(U.pisi)、蚕豆单胞锈菌(U.viciae-fabae)和蚕豆锈菌(U.fabae));禾谷类(例如麦散黑粉菌(U.nuda)和U.avaenae)、玉米(例如玉蜀黍黑粉菌(U.maydis):玉米黑穗病)和甘蔗上的黑粉菌属(Ustilago)(黑穗病);苹果(例如苹果黑星病(V.inaequalis))和梨上的黑星菌属(Venturia)(黑星病);以及各种植物如果树和观赏植物、藤本植物、浆果、蔬菜和大田作物上的轮生菌属(Verticillium)(枯萎病),例如油菜上的油菜黄萎菌(V.longisporum),草莓、油菜、马铃薯和番茄上的茄黄萎病菌(V.dahliae),和蘑菇上的V.fungicola;在谷物上的Zymoseptoria tritici;Phaeosphaeria maydis和Puccinia polysora.Microsphaera diffusa。
一般而言,“杀虫有效量”是指本发明混合物或包含该混合物的组合物实现对生长的可观察到的作用所需的量,所述作用包括目标生物体的坏死、死亡、阻滞、预防和去除、破坏或以其他方式减少目标生物体的产生和活性的作用。对于本发明中使用的各种混合物/组合物,杀虫有效量可以不同。所述混合物/组合物的杀虫有效量也将根据例如所需杀虫效果和持续时间、天气、目标物种、位置、施用方式等的占优势的条件而变化。
如上所述,本发明包括用于改善植物健康的方法,其中用植物健康有效量的本发明混合物处理植物、植物正在生长或预期生长的位置或植物繁殖材料。
术语“植物有效量”表示本发明混合物的量,其足以实现下文所定义的植物健康效应。下文给出了关于用量、施用方式和所使用的适当比率的更多示例性信息。无论如何,本领域技术人员清楚地知道这样一个事实,即这样的量可以在广泛的范围内变化并且取决于各种因素,例如所处理的栽培植物或材料以及气候条件。
在制备混合物时,优选使用纯的活性化合物,其中可根据需要加入其他抗有害生物的活性化合物例如杀虫剂、除草剂、杀真菌剂或其他除草或生长调节活性化合物或肥料等作为其他活性组分。
通过用杀虫有效量的活性化合物处理真菌或植物、植物繁殖材料(优选种子)、需要保护免受真菌侵袭的材料或土壤来使用本发明的混合物。施用可以在有害生物侵染材料、植物或植物繁殖材料(优选种子)之前和之后进行。
在本发明的上下文中,术语植物是指整个植物、植物的一部分或植物的繁殖材料。
本发明混合物及其组合物在控制各种栽培植物上的多种植物病原真菌方面尤其重要,所述植物例如谷物,如小麦、黑麦、大麦、黑小麦、燕麦或大米;甜菜,如糖用甜菜或饲用甜菜;水果,例如梨果、核果或浆果,如苹果、梨、李子、桃子、杏仁、樱桃、草莓、覆盆子、黑莓或醋栗;豆科植物,例如扁豆、豌豆、苜蓿或大豆;油料作物,如油菜、芥、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油椰、花生或大豆;葫芦类,如南瓜、黄瓜或甜瓜;纤维植物,如棉花、亚麻、大麻或黄麻;柑橘类水果,如橘子、柠檬、葡萄柚或柑桔;蔬菜,如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、番茄、马铃薯、葫芦或红辣椒;月桂科植物,如鳄梨、肉桂或樟脑;能量和原料植物,如玉米、大豆、油菜、甘蔗或油椰;玉米;烟草;坚果;咖啡;茶;香蕉;藤本植物(食用葡萄和葡萄汁葡萄藤);啤酒花;草皮;甜叶(也称甜叶菊(Stevia));天然橡胶植物或观赏和林业植物,如花卉、灌木、阔叶树或常绿植物,如针叶树;以及植物繁殖材料例如种子,和这些植物的作物材料。
优选地,本发明混合物及其组合物分别用于控制田间作物上的多种真菌,例如马铃薯、糖用甜菜、烟草、小麦、黑麦、大麦、燕麦、水稻、玉米、棉花、大豆、油菜、豆类、向日葵、咖啡或甘蔗;水果;藤本植物;观赏植物;或蔬菜,例如黄瓜、番茄、豆类或南瓜。
优选地,分别用本发明混合物及其组合物处理植物繁殖材料,用于控制谷物上的多种真菌,例如小麦、黑麦、大麦和燕麦;马铃薯、番茄、藤本植物、水稻、玉米、棉花和大豆。
术语“栽培植物”应理解为包括通过育种、诱变或基因工程改良的植物,包括但不限于市场上或开发中的农业生物技术产品(参考http://cera-gmc.org/,参见其中的GM农作物数据库)。基因修饰的植物是指通过使用重组DNA技术对遗传物质进行修饰的植物,其在自然条件下不能通过杂交育种、突变或自然重组轻易获得。通常,一个或多个基因已整合到基因修饰植物的遗传物质中,以改善植物的某些特性。此类基因修饰还包括但不限于蛋白质、寡肽或多肽的靶向的翻译后修饰,例如通过糖基化或添加聚合物,例如异戊二烯化、乙酰化或法尼基化部分或PEG部分。
通过育种、诱变或基因工程改良的植物,例如,对特定种类的除草剂具有耐受性,例如生长素除草剂,如麦草畏或2,4-D;漂白剂除草剂,如羟基苯丙酮酸双加氧酶(HPPD)抑制剂或八氢番茄红素脱饱和酶(PDS)抑制剂;乙酰乳酸合酶(ALS)抑制剂,如磺酰脲或咪唑啉酮;烯醇丙酮莽草酸-3-磷酸合酶(EPSPS)抑制剂,如草甘膦;谷氨酰胺合成酶(GS)抑制剂,如草铵膦(glufosinate);原卟啉原IX氧化酶抑制剂;脂质生物合成抑制剂,如乙酰辅酶A羧化酶(ACCase)抑制剂;或传统育种或基因工程方法产生的oxynil(即溴苯腈(bromoxynil)或碘苯腈(ioxynil))除草剂。此外,植物已通过多种基因修饰对多种类型的除草剂产生抗性,例如对草甘膦和草铵膦二者或对草甘膦和另一类除草剂(如ALS抑制剂、HPPD抑制剂、生长素除草剂或ACCase抑制剂)两者均产生抗性。这些除草剂抗性技术例如Pest Management Sci.61,2005,246;61,2005,258;61,2005,277;61,2005,269;61,2005,286;64,2008,326;64,2008,332;Weed Sci.57,2009,108;Austral.J.Agricult.Res.58,2007,708;Science 316,2007,1185;以及其中所引用的参考文献中所述。通过传统的育种方法(诱变),一些栽培植物已对除草剂具有耐受性,例如夏油菜(Canola,BASFSE,德国)对咪唑啉酮类例如咪草啶酸(imazamox)具有耐受性,或者向日葵(DuPont,USA)对磺酰脲类例如苯磺隆具有耐受性。基因工程方法已被用于使栽培植物如大豆、棉花、玉米、甜菜和油菜等对草甘膦和草铵膦等除草剂具有耐受性,其中一些按商品名在市场出售:(耐受草甘膦,Monsanto,美国)、(耐受咪唑啉酮,BASF SE,德国)和(耐受草铵膦,Bayer CropScience,德国)。
此外,植物还包括通过使用重组DNA技术能够合成一种或多种杀虫蛋白质的植物,特别是从细菌属芽孢杆菌(Bacillus),尤其是苏云金芽孢杆菌(Bacillus thuringiensis)中已知的那些蛋白质,例如δ-内毒素,如CryIA(b)、CryIA(c)、CryIF、CryIF(a2)、CryIIA(b)、CryIIIA、CryIIIB(b1)或Cry9c;植物杀虫蛋白(VIP),如VIP1、VIP2、VIP3或VIP3A;寄生于线虫的细菌的杀虫蛋白,如发光杆菌属(Photorhabdus)或致病杆菌属(Xenorhabdus)物种;动物产生的毒素,如蝎毒素、蜘蛛毒素、黄蜂毒素或其他昆虫特异性神经毒素;真菌产生的毒素,如链霉菌毒素、植物凝集素如豌豆或大麦凝集素;凝集素;蛋白酶抑制剂,如胰蛋白酶抑制剂、丝氨酸蛋白酶抑制剂、马铃薯块茎储藏蛋白(patatin)、半胱氨酸蛋白酶抑制剂或木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),如蓖麻毒蛋白、玉米RIP、相思豆毒蛋白、丝瓜素、皂草素或异株腹泻毒蛋白(bryodin);类固醇代谢酶,如3-羟基类固醇氧化酶、蜕皮激素-IDP-糖基转移酶、胆固醇氧化酶、蜕皮激素抑制剂或HMG-CoA还原酶;离子通道阻滞剂,如钠或钙通道阻滞剂;保幼激素酯酶;利尿激素受体(利尿多肽受体);茋合酶、联苄基合酶、壳多糖酶或葡聚糖酶。在本发明的上下文中,这些杀虫蛋白质或毒素也被明确地理解为前毒素、杂合蛋白质、截短的或以其他方式修饰的蛋白质。杂合蛋白质的特征是蛋白质结构域的新组合(参见例如WO 02/015701)。这类毒素或者能够合成这类毒素的基因修饰植物的其他实例在例如EP-A 374 753、WO 93/007278、WO 95/34656、EP-A 427 529、EP-A 451 878、WO 03/18810和WO 03/52073中描述。生产这种基因修饰植物的方法为本领域技术人员所熟知,并且例如在上述出版物中描述。基因修饰植物中所含的这些杀虫蛋白赋予产生这些蛋白的植物对某些分类学上为节肢动物昆虫的有害生物,尤其是甲虫(鞘翅目(Coleoptera))、双翅目昆虫(Diptera)、蛾(鳞翅目(Lepidoptera))以及线虫(线虫纲(Nematoda))的耐受性。能够合成一种或多种杀虫蛋白的基因修饰植物例如上述出版物中所述,其中一些可商购,例如(生产Cry1Ab毒素的玉米品种)、Plus(生产Cry1Ab和Cry3Bb1毒素的玉米品种)、(产生Cry9c毒素的玉米品种)、RW(生产Cry34Ab1、Cry35Ab1和草胺膦-N-乙酰转移酶[PAT]);33B(生产Cry1Ac毒素的棉花品种)、(生产Cry1Ac毒素的棉花品种)、II(生产Cry1Ac和Cry2Ab2毒素的棉花品种);(生产VIP-毒素的棉花品种);(产生Cry3A毒素的马铃薯品种);Bt11(如CB)和来自法国Syngenta Seeds SAS的Bt176(产生Cry1Ab毒素和PAT酶的玉米品种)、来自法国Syngenta Seeds SAS的MIR604(产生Cry3A毒素修饰版本的玉米品种,参考WO 03/018810)、来自比利时Monsanto Europe S.A.的MON 863(生产Cry3Bb1毒素的玉米品种)、来自比利时Monsanto Europe S.A.的IPC 531(生产Cry1Ac毒素修饰版本的棉花品种)和来自比利时Pioneer Overseas Corporation的1507(生产Cry1F毒素和PAT酶的玉米品种)。
此外,植物还包括通过使用重组DNA技术而能够合成一种或多种蛋白以增加其对细菌、病毒或真菌病原体的抗性或耐受性的植物。这类蛋白的实例是所谓的“与发病机理相关的蛋白”(PR蛋白,例如见EP-A 392 225),植物病害抗性基因(例如表达针对来自墨西哥野生马铃薯Solanum bulbocastanum的致病疫霉(Phytophthora infestans)的抗性基因的马铃薯栽培品种)或T4溶菌酶(例如能够合成对细菌如Erwinia amylvora具有增强抗性的这些蛋白的马铃薯栽培品种)。生产该类基因修饰植物的方法对本领域技术人员通常是已知的且例如描述于上述出版物中。
此外,植物还包括通过使用重组DNA技术而能够合成一种或多种蛋白以提高产量(例如生物质产量、谷粒产量、淀粉含量、油含量或蛋白含量),提高对干旱、盐或其他限制生长的环境因素的耐受性或对有害生物以及真菌、细菌或其病毒病原体的耐受性的植物。
此外,植物还包括通过使用重组DNA技术而含有改变量的物质含量或新物质含量以便尤其改善人类或动物营养的植物,例如产生促进健康的长链ω-3脂肪酸或不饱和ω-9脂肪酸的油料作物(例如油菜,DOW Agro Sciences,加拿大)。
本发明混合物的化合物的分别或联合施用是通过在植物播种之前或之后或植物出苗之前或之后对种子、幼苗、植物或土壤进行喷洒或撒粉来实施。
本发明混合物和包含它们的组合物可用于保护例如树木、木板栅栏、枕木等木质材料和例如房屋、库房、工厂等建筑物,也可用于保护建筑材料、家具、皮革、纤维、乙烯基制品、电线和电缆等免受蚂蚁和/或白蚁的侵害,以及控制蚂蚁和白蚁对农作物或人类的危害(例如,当害虫侵入房屋和公共设施时)。
材料保护中的惯常施用率例如为每m2的所处理材料0.01g-1000g活性化合物,期望为每m2施用0.1g-50g。
对于喷雾组合物中使用时,活性成分混合物的含量为0.001-80重量%,优选0.01-50重量%且最优选0.01-15重量%。
微试验
将活性化合物单独配制成在二甲基亚砜中浓度为10000ppm的储备溶液。
产品氟噻唑吡乙酮(oxathiapiroline)用作商业的成品配方,并用水稀释至活性化合物的所述浓度。
实施例1:在微量滴定试验中对晚疫病的病原体致病疫霉(Phytophthorainfestans)的活性
储备溶液按比例混合,用移液管移到微量滴定板(MTP)上,用水稀释至所述浓度。然后加入含有豌豆汁基质的水营养培养基或DDC培养基的致病疫霉(Phytophtorainfestans)孢子混悬液。将培养板置于温度为18℃的水蒸气饱和室中。使用吸收光度计,在接种7天后在405nm处测量MTP。
实施例2:在微量滴定板试验中对灰霉菌灰葡萄孢(Botrytis cinerea)的活性
储备溶液按比例混合,用移液管移到微量滴定板(MTP)上,用水稀释至所述浓度。然后加入生物麦芽水溶液或酵母-细菌蛋白胨-乙酸钠溶液中的灰葡萄孢(Botrytiscinerea)孢子混悬液。将培养板置于温度为18℃的水蒸气饱和室中。使用吸收光度计,在接种7天后在405nm处测量MTP。
实施例3:对颖枯壳小球腔菌(Leptosphaeria nodorum)引发的小麦叶斑病的活性
储备溶液按比例混合,用移液管移到微量滴定板(MTP)上,用水稀释至所述浓度。然后加入生物麦芽水溶液或酵母-细菌蛋白胨-甘油或DOB溶液中的颖枯壳小球腔菌(Leptosphaeria nodorum)孢子混悬液。将培养板置于温度为18℃的水蒸气饱和室中。使用吸收光度计,在接种7天后在405nm处测量MTP。
实施例4:在微量滴定板试验中对稻瘟病稻瘟病菌(Pyricularia oryzae)的活性
储备溶液按比例混合,用移液管移到微量滴定板(MTP)上,用水稀释至所述浓度。然后加入生物麦芽水溶液或酵母-细菌蛋白胨-甘油溶液中的稻瘟病菌(Pyriculariaoryzae)孢子混悬液。将培养板置于温度为18℃的水蒸气饱和室中。使用吸收光度计,在接种7天后在405nm处测量MTP。
实施例5:对圆核腔菌(Pyrenophora teres)的活性研究
储备溶液按比例混合,用移液管移到微量滴定板(MTP)上,用水稀释至所述浓度。然后加入生物麦芽水溶液或酵母-细菌蛋白胨-甘油或DOB溶液中的圆核腔菌(Pyrenophorateres)的QoI抗性分离物的孢子混悬液。将培养板置于温度为18℃的水蒸气饱和室中。使用吸收光度计,在接种7天后在405nm处测量MTP。
将测量参数与不含活性化合物的对照变体的生长(100%)以及不含真菌和不含活性化合物的空白值进行比较,以确定各活性化合物中病原体的相对生长百分比(%)。
这些百分比被转换成功效。
功效为0表示病原体的生长水平与未经处理的对照相当;功效为100表示病原体没有生长。
使用Colby公式[R.S.Colby,“Calculating synergistic and antagonisticresponses of herbicide combinations",Weeds 15,20-22(1967)]确定活性化合物混合物的预期功效,并与观察到的功效进行比较。
Claims (10)
1.杀真菌活性化合物I:4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫烷基-1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苯甲腈或其互变异构体、对映异构体、非对映异构体或其盐在种子处理方法中用于控制和/或对抗抗性植物病原真菌的用途,其中式(I)的活性化合物通过浸湿土壤、通过滴灌施用到土壤上、通过土壤注射、通过浸渍或通过种子处理而直接和/或间接施用到植物和/或植物繁殖材料上。
2.如权利要求1所述的用途,其用于控制谷物上的植物病原性有害真菌。
3.如权利要求1或2所述的用途,其中活性化合物I 4-[[6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(5-硫烷基-1,2,4-三唑-1-基)丙基]-3-吡啶基]氧基]苯甲腈是与选自杀虫剂和/或杀真菌剂的至少一种其他具有农业活性的化合物组合和/或一起施用。
4.如权利要求1-3中任一项所述的用途,其中所述其他活性化合物是选自以下的杀虫剂:
齐墩螨素(abamectin)、高灭膦、吡虫清(acetamiprid)、双丙环虫酯(afidopyropen)、α-氯氰菊酯(alphacypermethrin)、氟氯菊酯(bifenthrin)、溴虫氟苯双酰胺(broflanilide)、氟唑虫清(chlorfenapyr)、毒死蜱(chlorpyriphos)、噻虫胺(clothianidin)、氰虫酰胺(cyazypyr)、环溴虫酰胺(cyclaniliprole)、氯氰菊酯、dicloromezotiaz、呋虫胺、氟虫腈(fipronil)、三氟咪啶酰胺(fluazaindolizine)、氟吡菌酰胺(fluopyram)、氟吡呋喃酮(flupyradifurone)、fluxametamide、吡虫啉、氰氟虫胺(metaflumizone)、灭虫威(methiocarb)、灭虫威、氯虫苯甲酰胺(rynaxapyr)、乙基多杀菌素、艾克敌105(spinosad)、氟啶虫胺腈、七氟菊酯、四唑虫酰胺(tetraniliprole)、噻虫啉、噻虫嗪、硫双威、tioxazafen、三氟苯嘧啶(triflumezopyrim)、tyclopyrazoflor、N-[4-氯-2-[(二乙基-λ-4-亚硫烷基)氨甲酰基]-6-甲基-苯基]-2-(3-氯-2-吡啶基)-5-(三氟甲基)吡唑-3-甲酰胺、1-异丙基-N,5-二甲基-N-哒嗪-4-基-吡唑-4-甲酰胺、N,5-二甲基-N-哒嗪-4-基-1-(2,2,2-三氟-1-甲基-乙基)吡唑-4-甲酰胺;1-[1-(1-氰基环丙基)乙基]-N-乙基-5-甲基-N-哒嗪-4-基-吡唑-4-甲酰胺;N-乙基-1-(2-氟-1-甲基-丙基)-5-甲基-N-哒嗪-4-基-吡唑-4-甲酰胺。
5.如权利要求4所述的用途,其中其他活性化合物是选自以下的杀虫剂:
吡虫清、双丙环虫酯、α-氯氰菊酯、溴虫氟苯双酰胺、噻虫胺、氰虫酰胺、氯氰菊酯、dicloromezotiaz、呋虫胺、氟虫腈(fipronil)、三氟咪啶酰胺、氟吡菌酰胺、氟吡呋喃酮、fluxametamide、吡虫啉、氰氟虫胺(metaflumizone)、氯虫苯甲酰胺、乙基多杀菌素、艾克敌105(spinosad)、氟啶虫胺腈、噻虫啉、噻虫嗪、硫双威、三氟苯嘧啶、tyclopyrazoflor、N-[4-氯-2-[(二乙基-λ-4-亚硫烷基)氨甲酰基]-6-甲基-苯基]-2-(3-氯-2-吡啶基)-5-(三氟甲基)吡唑-3-甲酰胺、1-异丙基-N,5-二甲基-N-哒嗪-4-基-吡唑-4-甲酰胺、N,5-二甲基-N-哒嗪-4-基-1-(2,2,2-三氟-1-甲基-乙基)吡唑-4-甲酰胺;1-[1-(1-氰基环丙基)乙基]-N-乙基-5-甲基-N-哒嗪-4-基-吡唑-4-甲酰胺;N-乙基-1-(2-氟-1-甲基-丙基)-5-甲基-N-哒嗪-4-基-吡唑-4-甲酰胺。
6.如权利要求4或5所述的用途,其中其他活性化合物是选自以下的杀昆虫剂:
α-氯氰菊酯、溴虫氟苯双酰胺、噻虫胺、氰虫酰胺、dicloromezotiaz、呋虫胺、氟虫腈、三氟咪啶酰胺、fluxametamide、氰氟虫胺、氯虫苯甲酰胺、乙基多杀菌素、艾克敌105(spinosad)、氟啶虫胺腈、噻虫嗪、硫双威、三氟苯嘧啶、tyclopyrazoflor、N-[4-氯-2-[(二乙基-λ-4-亚硫烷基)氨甲酰基]-6-甲基-苯基]-2-(3-氯-2-吡啶基)-5-(三氟甲基)吡唑-3-甲酰胺、1-异丙基-N,5-二甲基-N-哒嗪-4-基-吡唑-4-甲酰胺、N,5-二甲基-N-哒嗪-4-基-1-(2,2,2-三氟-1-甲基-乙基)吡唑-4-甲酰胺;1-[1-(1-氰基环丙基)乙基]-N-乙基-5-甲基-N-哒嗪-4-基-吡唑-4-甲酰胺;N-乙基-1-(2-氟-1-甲基-丙基)-5-甲基-N-哒嗪-4-基-吡唑-4-甲酰胺。
7.如权利要求1-3中任一项所述的用途,其中其他活性化合物是选自以下的杀真菌剂:
腈嘧菌酯(azoxystrobin)、啶酰菌胺(boscalid)、多菌灵、萎锈灵、环丙唑醇(cyproconazole)、恶醚唑(difenoconazole)、烯酰吗啉、噻唑菌胺(ethaboxam)、fenpicoxamid、florylpicoxamid、氟噁菌(fludioxinil)、氟茚唑菌胺(fluindapyr)、氟吡菌酰胺、喹唑菌酮(fluquinconazole)、粉唑醇、氟唑菌酰胺、inpyrfluxam、环戊唑醇、isoflucypram、精甲霜灵、氯氟醚菌唑(mefentrifluconazole)、甲霜灵、甲霜灵-M、氟噻唑吡乙酮(oxathiapiprolin)、氟唑菌苯胺(penflufen)、吡噻菌胺、四唑吡氨酯(picarbutrazox)、啶氧菌酯(picoxystrobin)、丙氯灵(prochloraz)、丙硫菌唑(prothioconazole)、氟唑菌酰羟胺(pydiflumetofen)、唑菌胺酯(pyraclostrobin)、氟唑环菌胺(sedaxane)、硅噻菌胺(silthiofarm)、戊唑醇、四唑虫酰胺(tetraniliprole)、涕必灵(thiabendazole)、甲基硫菌灵(thiophanate-methyl)、福美双、唑菌醇(triadimenol)、肟菌酯(trifloxistrobin)、戊叉唑菌(triticonazole)、缬菌胺(valifenalate)、福美锌。
8.如权利要求7所述的用途,其中其他活性化合物是选自以下的杀真菌剂:
腈嘧菌酯、啶酰菌胺、恶醚唑(difenoconazole)、烯酰吗啉、噻唑菌胺、fenpicoxamid、florylpicoxamid、氟噁菌(fludioxinil)、氟吡菌酰胺、喹唑菌酮(fluquinconazole)、氟唑菌酰胺、inpyrfluxam、isoflucypram、氯氟醚菌唑、甲霜灵、氟噻唑吡乙酮、氟唑菌苯胺、吡噻菌胺、四唑吡氨酯、啶氧菌酯、丙氯灵(prochloraz)、丙硫菌唑、氟唑菌酰羟胺、唑菌胺酯、氟唑环菌胺、戊唑醇、四唑虫酰胺、涕必灵、甲基硫菌灵、肟菌酯、戊叉唑菌(triticonazole)。
9.如权利要求7或8所述的用途,其中其他活性化合物是选自以下的杀真菌剂:
腈嘧菌酯、啶酰菌胺、噻唑菌胺、fenpicoxamid、florylpicoxamid、氟噁菌(fludioxinil)、喹唑菌酮、氟唑菌酰胺、氯氟醚菌唑、氟噻唑吡乙酮、吡噻菌胺、啶氧菌酯、丙氯灵、丙硫菌唑、氟唑菌酰羟胺、唑菌胺酯、涕必灵、甲基硫菌灵、肟菌酯、戊叉唑菌(triticonazole)。
10.一种控制植物病原性有害生物的方法,其中使用有效量的如权利要求3-9中任一项所定义的化合物I或混合物处理有害生物、其栖息地、繁殖地、其位置或者需要保护以防止有害生物攻击的植物、土壤或植物繁殖材料。
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PCT/EP2019/070298 WO2020030454A1 (en) | 2018-08-08 | 2019-07-29 | Use of fungicidal active compound i derivative and mixtures thereof in seed application and treatment methods |
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EP (1) | EP3833187A1 (zh) |
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CN114668012B (zh) * | 2022-03-29 | 2023-10-24 | 山东云农智德检验检测有限公司 | 含吡啶菌酰胺和戊唑醇的杀菌组合物及其应用 |
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BR8600161A (pt) | 1985-01-18 | 1986-09-23 | Plant Genetic Systems Nv | Gene quimerico,vetores de plasmidio hibrido,intermediario,processo para controlar insetos em agricultura ou horticultura,composicao inseticida,processo para transformar celulas de plantas para expressar uma toxina de polipeptideo produzida por bacillus thuringiensis,planta,semente de planta,cultura de celulas e plasmidio |
NZ231804A (en) | 1988-12-19 | 1993-03-26 | Ciba Geigy Ag | Insecticidal toxin from leiurus quinquestriatus hebraeus |
ATE241699T1 (de) | 1989-03-24 | 2003-06-15 | Syngenta Participations Ag | Krankheitsresistente transgene pflanze |
ES2074547T3 (es) | 1989-11-07 | 1995-09-16 | Pioneer Hi Bred Int | Lectinas larvicidas, y resistencia inducida de las plantas a los insectos. |
UA48104C2 (uk) | 1991-10-04 | 2002-08-15 | Новартіс Аг | Фрагмент днк, який містить послідовність,що кодує інсектицидний протеїн, оптимізовану для кукурудзи,фрагмент днк, який забезпечує направлену бажану для серцевини стебла експресію зв'язаного з нею структурного гена в рослині, фрагмент днк, який забезпечує специфічну для пилку експресію зв`язаного з нею структурного гена в рослині, рекомбінантна молекула днк, спосіб одержання оптимізованої для кукурудзи кодуючої послідовності інсектицидного протеїну, спосіб захисту рослин кукурудзи щонайменше від однієї комахи-шкідника |
US5530195A (en) | 1994-06-10 | 1996-06-25 | Ciba-Geigy Corporation | Bacillus thuringiensis gene encoding a toxin active against insects |
EP1311162B1 (en) | 2000-08-25 | 2005-06-01 | Syngenta Participations AG | Bacillus thurigiensis crystal protein hybrids |
US7230167B2 (en) | 2001-08-31 | 2007-06-12 | Syngenta Participations Ag | Modified Cry3A toxins and nucleic acid sequences coding therefor |
AR037856A1 (es) | 2001-12-17 | 2004-12-09 | Syngenta Participations Ag | Evento de maiz |
CA2840286C (en) | 2011-07-13 | 2016-04-12 | Basf Se | Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds |
CA2986041C (en) | 2015-05-18 | 2021-06-29 | Viamet Pharmaceuticals, Inc. | 4-((6-(2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1h-1,2,4-triazol-1-yl)propyl)pyridin-3-yl)oxy)benzonitrile and 4-((6-(2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4,5-dihydro-1h-1,2,4-triazol-1-yl)propyl)pyridin-3-yl)oxy)benzonitrile compounds as antifungal agents |
AR110208A1 (es) * | 2016-11-22 | 2019-03-06 | Viamet Pharmaceuticals Inc | Uso de un compuesto de difluoro-(2-hidroxipropil)piridina como fungicida para el control de hongos fitopatógenos en arroz |
EP3544429A4 (en) * | 2016-11-22 | 2020-04-29 | Dow Agrosciences Llc | USE OF A DIFLUOR (2-HYDROXYPROPYL) PYRIDINE COMPOUND AS A FUNGICIDE FOR COMBATING PHYTOPATHOGENIC MUSHROOMS OF WHEAT |
CA3044386A1 (en) | 2016-11-22 | 2018-05-31 | Dow Agrosciences Llc | Use of a difluoro-(2-hydroxypropyl)pyridine compound as a fungicide for control of phytopathogenic fungi of corn |
WO2018098222A1 (en) * | 2016-11-22 | 2018-05-31 | Vps-3, Inc. | Fungicidal compounds and mixtures for fungal control in cereals |
WO2018098236A1 (en) * | 2016-11-22 | 2018-05-31 | Vps-3, Inc. | Fungicidal compounds and mixtures for fungal control in cereals |
BR112019010147A2 (pt) * | 2016-11-22 | 2019-09-17 | Dow Agrosciences Llc | compostos fungicidas e misturas para controle de fungos em cereais |
JP2020500201A (ja) | 2016-11-22 | 2020-01-09 | ダウ アグロサイエンシィズ エルエルシー | オオムギの植物病原性真菌の防除のための殺真菌剤としてのジフルオロ−(2−ヒドロキシプロピル)ピリジン化合物の使用 |
BR112019010087A2 (pt) * | 2016-11-22 | 2019-10-01 | Dow Agrosciences Llc | compostos fungicidas e misturas para controle de fungos em cereais |
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- 2019-07-29 US US17/261,905 patent/US20210251232A1/en not_active Abandoned
- 2019-07-29 BR BR112021001650-3A patent/BR112021001650A2/pt not_active IP Right Cessation
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