CN101304658A - 包含啶酰菌胺和二甲嘧菌胺的杀真菌混合物 - Google Patents
包含啶酰菌胺和二甲嘧菌胺的杀真菌混合物 Download PDFInfo
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- CN101304658A CN101304658A CNA2006800417742A CN200680041774A CN101304658A CN 101304658 A CN101304658 A CN 101304658A CN A2006800417742 A CNA2006800417742 A CN A2006800417742A CN 200680041774 A CN200680041774 A CN 200680041774A CN 101304658 A CN101304658 A CN 101304658A
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- boscalid
- pyrimethanil
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-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
- A01N43/34—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
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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
- A01N2300/00—Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
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- General Health & Medical Sciences (AREA)
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- Plural Heterocyclic Compounds (AREA)
Abstract
本发明涉及以协同有效量包含如下组分的杀真菌混合物:(1)式Ⅰ的啶酰菌胺和(2)式Ⅱ的二甲嘧菌胺,一种使用啶酰菌胺(Ⅰ)与二甲嘧菌胺(Ⅱ)的混合物防治有害真菌的方法和啶酰菌胺(Ⅰ)和二甲嘧菌胺(Ⅱ)在制备这种混合物中的用途,包含这些混合物的杀真菌组合物以及包含这些混合物的种子。
Description
本发明涉及以协同有效量包含如下组分的杀真菌混合物:
(1)式I的啶酰菌胺(boscalid):
和
(2)式II的二甲嘧菌胺(pyrimethanil):
此外,本发明涉及一种使用啶酰菌胺(I)与二甲嘧菌胺(II)的混合物防治有害真菌的方法和啶酰菌胺(I)和二甲嘧菌胺(II)在制备这种混合物中的用途,包含这些混合物的杀真菌组合物以及包含这些混合物的种子。
啶酰菌胺由EP-A 545099已知。
二甲嘧菌胺由DD-A 151404已知。
就降低施用率和改善已知化合物(I)和(II)的活性谱而言,本发明的目的是提供在降低的活性化合物施用总量下,对有害真菌具有改善活性的混合物(协同增效混合物)。
因此,我们已发现开头定义的啶酰菌胺与二甲嘧菌胺的混合物。此外,我们已发现,同时,即联合或分开施用啶酰菌胺(I)和二甲嘧菌胺(II),或依次施用啶酰菌胺(I)和二甲嘧菌胺(II)使得比单独施用各个化合物更好地防治有害真菌。
啶酰菌胺可以以不同的结晶变体和水合形式存在(参看WO 03/29219和WO 2004/72039);式I包含所有变体和水合物。
化合物(I)与活性化合物(II)的混合物或同时,即联合或分开施用的化合物(I)和活性化合物(II)特征为对尤其选自子囊菌纲(Ascomycetes)、担子菌纲(Basidiomycetes)、半知菌纲(Deuteromycetes)和Peronosporomycetes(又名卵菌纲(Oomycetes))的宽范围植物病原性真菌具有极好活性。它们中一些内吸有效并可以在作物保护中用作叶面杀真菌剂,作为杀真菌剂用于拌种和用作土壤杀真菌剂。
它们对在各种作物植物如香蕉、棉花、蔬菜品种(例如黄瓜、豆类、番茄和葫芦科植物)、大麦、禾草、燕麦、咖啡、土豆、玉米、水果品种、稻、黑麦、大豆、葡萄藤、小麦、观赏植物、甘蔗以及大量种子中防治大量真菌尤其重要。
它们尤其适于防治如下植物病害:
-蔬菜、油籽油菜、糖用甜菜和水果和稻上的链格孢(Alternaria)属,
-糖用甜菜和蔬菜上的丝囊霉(Aphanomyces)属,
-玉米、禾谷类、稻和草坪中的平脐蠕孢(Bipolaris)属和内脐蠕孢(Drechslera)属,
-禾谷类上的禾白粉菌(Blumeria graminis)(白粉病),
-草莓、蔬菜、花卉和葡萄藤上的灰葡萄孢(Botrytis cinerea)(灰霉病),
-莴苣上的莴苣盘梗霉(Bremia lactucae),
-玉米、大豆、稻和糖用甜菜上的尾孢(Cercospora)属,
-玉米、禾谷类、稻上的旋孢腔菌(Cochliobolus)属(例如禾谷类上的禾旋孢腔菌(Cochliobolus sativus),稻上的宫部旋孢腔菌(Cochliobolusmiyabeanus)),
-大豆和棉花上的剌盘孢(Colletotricum)属,
-禾谷类和玉米上的内脐蠕孢(Drechslera)属,
-玉米上的突脐蠕孢(Exserohilum)属,
-黄瓜上的二孢白粉菌(Erysiphe cichoracearum)和单丝壳白粉菌(Sphaerotheca fuliginea),
-各种植物上的镰孢霉(Fusarium)属和轮枝孢(Verticillium)属,
-禾谷类上的禾顶囊壳(Gaeumanomyces graminis)属,
-禾谷类和稻上的赤霉(Gibberella)属(例如稻上的藤仓赤霉(Gibberellafujikuroi)),
-稻上的革兰氏染色配合物(Grain staining complex),
-玉米和稻上的长蠕孢(Helminthosporium)属,
-禾谷类上的Michrodochium nivale,
-禾谷类、香蕉和花生上的球腔菌(Mycosphaerella)属,
-大豆上的豆薯层锈菌(Phakopsora pachyrhizi)和山马蟥层锈菌(Phakopsara meibomiae),
-大豆和向日葵上的拟茎点霉(Phomopsis)属,
-土豆和西红柿上的致病疫霉(Phytophthora infestans),
-葡萄藤上的葡萄生单轴霉(Plasmopara viticola),
-苹果上的苹果白粉病菌(Podosphaera leucotricha),
-禾谷类上的小麦基腐病菌(Pseudocercosporella herpotrichoides),
-啤酒花和葫芦上的假霜霉(Pseudoperonospora)属,
-禾谷类和玉米上的柄锈菌(Puccinia)属,
-禾谷类上的核腔菌(Pyrenophora)属,
-稻上的稻瘟病菌(Pyricularia oryzae)、笹木伏革菌(Corticium sasakii)、帚梗柱孢属(Sarocladium oryzae)、稻叶鞘腐败病(S.attenuatum)、稻叶黑粉菌(Entyloma oryzae),
-草坪和禾谷类上的稻梨孢菌(Pyricularia grisea),
-草坪、稻、玉米、棉花、油籽油菜、向日葵、糖用甜菜、蔬菜和其他植物上的腐霉(Pythium)属,
-棉花、稻、土豆、草坪、玉米、油籽油菜、土豆、糖用甜菜、蔬菜和其他植物上的丝核菌(Rhizoctonia)属,
-油籽油菜和向日葵上的核盘菌(Sclerotinia)属,
-小麦上的小麦壳针孢(Septoria tritici)和颖枯壳多孢(Stagonosporanodorum),
-葡萄藤上的葡萄钩丝壳(Erysiphe(同义词Uncinula)necator),
-玉米和草坪上的Setospaeria属,
-玉米上的丝轴黑粉菌(Sphacelotheca reilinia),
-大豆和棉花上的根串珠霉(Thievaliopsis)属,
-禾谷类上的腥黑粉菌(Tilletia)属,
-禾谷类、玉米和糖用甜菜上的黑粉菌(Ustilago)属,
-苹果和梨上的黑星菌(Venturia)属(黑星病)。
此外,本发明混合物适用于在材料(例如木材、纸、油漆分散体、纤维或织物)保护中和储存产品保护中防治有害真菌如拟青霉(Paecilomycesvariotii)。
啶酰菌胺(I)和二甲嘧菌胺(II)可同时,即联合或分开,或依次施用,在分开施用的情况下,顺序通常对防治措施的结果不具有任何影响。
当提供混合物时,优选使用纯活性化合物(I)和(II),可向其中加入对有害真菌或其他害虫如昆虫、蜘蛛或线虫的其他活性化合物,或除草或生长调节活性化合物或肥料。
通常施用啶酰菌胺(I)与二甲嘧菌胺(II)的混合物。然而,在某种情况下也可有利地使用啶酰菌胺(I)与两种或如果合适的话多种活性组分的混合物。
化合物(I)和活性化合物(II)通常以100∶1-1∶100,优选20∶1-1∶20,尤其是10∶1-1∶10的重量比使用。
如果需要的话,其他活性组分与化合物(I)以20∶1-1∶20的比混合。
取决于化合物类型和所需效力,本发明混合物的施用率,尤其基于农作物面积为5-2000g/ha,优选20-900g/ha,尤其是50-750g/ha。
相应地,啶酰菌胺(I)的施周率通常为1-1000g/ha,优选10-900g/ha,尤其是20-750g/ha。
相应地,二甲嘧菌胺(II)的施用率通常为1-2000g/ha,优选10-900g/ha,尤其是40-750g/ha。
在种子处理中,混合物的施用率通常为1-1000g/100kg种子,优选1-750g/100kg种子,尤其是5-500g/100kg种子。
防治有害真菌的方法通过在植物播种之前或之后或在植物出苗之前或之后对种子、植物或土壤喷雾或撒粉分开或联合施用啶酰菌胺(I)和二甲嘧菌胺(II)或啶酰菌胺I与二甲嘧菌胺II的混合物而进行。
可将本发明混合物或啶酰菌胺(I)和二甲嘧菌胺(II)转化成常规配制剂,例如溶液、乳液、悬浮液、粉剂、粉末、糊和颗粒。使用形式取决于特定的意欲目的;在每种情况下,应确保本发明化合物精细且均匀地分布。
配制剂以已知方式制备,例如通过将活性化合物与溶剂和/或载体混合而制备,若需要的话使用乳化剂和分散剂。适于该目的的溶剂/助剂主要为:
-水、芳族溶剂(如Solvesso产品、二甲苯)、石蜡(如矿物油馏分)、醇类(如甲醇、丁醇、戊醇、苄醇)、酮类(如环己酮、γ-丁内酯)、吡咯烷酮(NMP、NOP)、乙酸酯(乙二醇二乙酸酯)、二元醇、脂肪酸二甲基酰胺、脂肪酸和脂肪酸酯。原则上还可以使用溶剂混合物,
-载体如磨碎的天然矿物(如高岭土、粘土、滑石、白垩)和磨碎的合成矿物(如高度分散的硅石、硅酸盐);乳化剂如非离子和阴离子乳化剂(如聚氧乙烯脂肪醇醚、烷基磺酸盐和芳基磺酸盐)以及分散剂如木素亚硫酸盐废液和甲基纤维素。
所用的合适表面活性剂为木素磺酸、萘磺酸、苯酚磺酸、二丁基萘磺酸的碱金属盐、碱土金属盐和铵盐,烷基芳基磺酸盐,烷基硫酸盐,烷基磺酸盐,脂肪醇硫酸盐,脂肪酸和硫酸化脂肪醇乙二醇醚,还有磺化萘和萘衍生物与甲醛的缩合物,萘或萘磺酸与苯酚和甲醛的缩合物,聚氧乙烯辛基苯基醚,乙氧基化异辛基酚,辛基酚,壬基酚,烷基苯基聚乙二醇醚,三丁基苯基聚乙二醇醚,三硬脂基苯基聚乙二醇醚,烷基芳基聚醚醇,醇和脂肪醇氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚,乙氧基化聚氧丙烯,月桂醇聚乙二醇醚缩醛,山梨醇酯,木素亚硫酸盐废液和甲基纤维素。
适于制备可直接喷雾溶液、乳液、糊或油分散体的物质为中至高沸点的矿物油馏分如煤油或柴油,还有煤焦油和植物或动物来源的油,脂族、环状和芳族烃如甲苯、二甲苯、石蜡、四氢化萘、烷基化萘或它们的衍生物,甲醇,乙醇,丙醇,丁醇,环己醇,环己酮,异佛尔酮,高度极性溶剂如二甲亚砜、N-甲基吡咯烷酮和水。
粉末、撒播用材料和可撒粉产品可以通过将活性物质与固体载体混合或一起研磨来制备。
颗粒如涂敷颗粒、浸渍颗粒和均质颗粒可以通过使活性化合物与固体载体粘附而制备。固体载体实例为矿土如硅胶、硅酸盐、滑石、高岭土、活性粘土(attaclay)、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁,磨碎的合成材料,肥料如硫酸铵、磷酸铵、硝酸铵、尿素以及植物来源的产品如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉和其它固体载体。
配制剂通常包含0.01-95重量%,优选0.1-90重量%活性化合物。活性化合物以90-100%,优选95-100%的纯度(根据NMR谱)使用。
下列为配制剂实例:
1.用水稀释的产品
A)水溶性浓缩物(SL)
将10重量份(I)、(II)或(I)与(II)的混合物溶于90重量份水或水溶性溶剂中。作为选择,加入湿润剂或其它助剂。活性化合物经水稀释溶解。这样得到具有10重量%活性化合物含量的配制剂。
B)分散性浓缩物(DC)
将20重量份(I)、(II)或(I)与(II)的混合物随着加入10重量份分散剂如聚乙烯基吡咯烷酮而溶于70重量份环己酮中。用水稀释得到分散体。活性化合物含量为20重量%。
C)可乳化浓缩物(EC)
将15重量份(I)、(II)或(I)与(II)的混合物随着加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(每种情况下5重量份)而溶于75重量份二甲苯中。用水稀释得到乳液。配制剂的活性化合物含量为15重量%。
D)乳液(EW、EO)
将25重量份(I)、(II)或(I)与(II)的混合物随着加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(每种情况下5重量份)而溶于35重量份二甲苯中。通过乳化机(例如Ultraturrax)将该混合物引入30重量份水中并制成均匀乳液。用水稀释得到乳液。配制剂的活性化合物含量为25重量%。
E)悬浮液(SC、OD)
在搅拌球磨机中,将20重量份(I)、(II)或(I)与(II)的混合物随着加入10重量份分散剂和润湿剂和70重量份水或有机溶剂而粉碎以得到细活性化合物悬浮液。用水稀释得到活性化合物的稳定悬浮液。配制剂中活性化合物含量为20重量%。
F)水分散性颗粒和水溶性颗粒(WG、SG)
将50重量份(I)、(II)或(I)与(II)的混合物随着加入50重量份分散剂和润湿剂而精细磨碎并通过技术应用(例如挤出机、喷雾塔、流化床)而制得水分散性或水溶性颗粒。用水稀释得到活性化合物的稳定分散体或溶液。配制剂的活性化合物含量为50重量%。
G)水分散性和水溶性粉末(WP、SP)
将75重量份(I)、(II)或(I)与(II)的混合物在转子-定子研磨机中随着加入25重量份分散剂、润湿剂和硅胶而磨碎。用水稀释得到活性化合物的稳定分散体或溶液。配制剂的活性化合物含量为75重量%。
2.不经稀释而施用的产品
H)可撒粉粉末(DP)
将5重量份(I)、(II)或(I)与(II)的混合物细碎研磨并与95%的细碎高岭土充分混合。这得到活性化合物含量为5重量%的可撒粉产品。
J)颗粒(GR、FG、GG、MG)
将0.5重量份(I)、(II)或(I)与(II)的混合物细碎研磨并结合99.5重量份载体。现行方法是挤出、喷雾干燥或流化床方法。这得到活性化合物含量为0.5重量%的不经稀释而施用的颗粒。
K)ULV溶液(UL)
将10重量份(I)、(II)或(I)与(II)的混合物溶于90重量份有机溶剂如二甲苯中。这得到活性化合物含量为10重量%的不经稀释而施用的产物。
活性化合物可以直接、以其配制剂形式或由其制备的使用形式,例如可直接喷雾溶液、粉末、悬浮液或分散体、乳液、油分散体、糊、可撒粉产品、撒播用材料或颗粒形式,借助喷雾、雾化、撒粉、撒播或浇灌而使用。使用形式完全取决于意欲的目的;它们意欲在每种情况下确保本发明活性化合物的最佳可能分布。
含水使用形式可通过加入水由乳液浓缩物、糊或可湿性粉末(可喷雾粉末、油分散体)制备。为制备乳液、糊或油分散体,可借助湿润剂、增粘剂、分散剂或乳化剂将该物质直接或溶于油或溶剂中后在水中均化。然而,也可制备由活性物质、湿润剂、增粘剂、分散剂或乳化剂和如果合适的话溶剂或油组成的浓缩物且该浓缩物适于用水稀释。
即用制剂中的活性化合物浓度可在相对宽范围内变化。通常为0.0001-10%,优选0.01-1%。
活性化合物也可成功用于超低容量法(ULV),其中可以施用包含超过95重量%活性化合物的配制剂,或甚至施用不含添加剂的活性化合物。
可将各种类型的油、湿润剂、辅助剂加入活性化合物中,甚至如果合适的话,恰在紧邻使用前加入(桶混合)。这些试剂通常与本发明组合物以1∶100-100∶1,优选1∶10-10∶1的重量比混合。
化合物I和II或混合物或对应的配制剂通过用杀真菌有效量的混合物,或在分开施用的情况下化合物I和II处理有害真菌或待保护以防它们的植物、种子、土壤、区域、材料或空间而施用。施用可以在有害真菌侵染之前或之后进行。
本发明各个化合物和混合物的杀真菌作用可以通过下列试验证实。
将活性化合物分开或联合制备成含有25mg活性化合物的储液,将其以99∶1的溶剂/乳化剂体积比使用丙酮和/或二甲亚砜和乳化剂EL(基于乙氧基化烷基酚具有乳化和分散作用的润湿剂)的混合物补充至10ml。然后将混合物用水补充至100ml。将储液用所述溶剂/乳化剂/水混合物稀释以得到以下指定的活性化合物浓度。
将目测的侵染叶面积百分数转化成以未处理对照的%表示的效力。
使用Abbot公式按如下计算效力(E):
E=(1-α/β)·100
α对应于%表示的处理植物的真菌侵染百分数,和
β对应于%表示的未处理(对照)植物的真菌侵染百分数。
效力为0,处理植物的侵染水平相当于未处理对照植物的;效力为100,处理植物未受侵染。
活性化合物混合物的预期效力使用Colby公式(S.R.Colby,“Calculating synergistic and antagonistic responses of herbicidecombinations”,Weeds(杂草),15,20-22,1967)确定并与观察到的效力比较。
Colby公式:
E=x+y-x·y/100
E使用浓度为a和b的活性化合物A和B的混合物时的预期效力,以未
处理对照的%表示;
x使用浓度为a的活性化合物A时的效力,以未处理对照的%表示;
y使用浓度为b的活性化合物B时的效力,以未处理对照的%表示。
应用实施例1-对小麦上柄锈菌属(Puccinia recondita)(小麦褐锈病)(Puccrt
P1)的保护活性
将栽培品种“Kanzler”的盆栽小麦秧苗的叶子用具有以下指定的活性化合物浓度的含水悬浮液喷雾至滴流点。第二天将处理的植物接种小麦褐锈病(柄锈菌属)的孢子悬浮液。然后将盆放在20-22℃下的具有高大气湿度(90-95%)的室中24小时。在此期间,孢子发芽并且芽管渗入叶组织中。第二天,将测试植物返回至温室中并在20-22℃和65-70%相对大气湿度下培育另外7天。然后目测叶子上锈菌发展的程度。
活性化合物/活性化合物组合 | 浓度(ppm) | 比 | 观察的活性(%) | 根据Colby计算的活性(%) | 协同增效 | 协同增效水平(%) |
二甲嘧菌胺 | 24 | 00 | ||||
啶酰菌胺 | 8 | 22 | ||||
啶酰菌胺二甲嘧菌胺 | 82 | 4∶1 | 56 | 22 | 是 | 34 |
啶酰菌胺二甲嘧菌胺 | 84 | 2∶1 | 67 | 22 | 是 | 45 |
未处理 | 90%侵染 |
Claims (9)
2.根据权利要求1的杀真菌混合物,其中啶酰菌胺(I)与二甲嘧菌胺(II)的重量比为100∶1-1∶100。
3.一种防治植物病原性有害真菌的方法,其中用有效量的根据权利要求1的混合物处理有害真菌、它们的栖息地或待保护以防真菌侵袭的植物、土壤或种子。
4.根据权利要求3的方法,其中根据权利要求1的啶酰菌胺(I)和二甲嘧菌胺(II)同时,即联合或分开,或依次施用。
5.根据权利要求3或4的方法,其中根据权利要求1的啶酰菌胺(I)和二甲嘧菌胺(II)或根据权利要求1的杀真菌混合物以5-2000g/ha的量施用。
6.根据权利要求3或4的方法,其中根据权利要求1的啶酰菌胺(I)和二甲嘧菌胺(II)或根据权利要求1的杀真菌混合物以每100kg种子1-1000g的量施用。
7.以1-1000g每100kg的量包含根据权利要求1的混合物的种子。
8.根据权利要求1的化合物I和II在制备适于防治有害真菌的组合物中的用途。
9.一种包含根据权利要求1的杀真菌混合物和固体或液体载体的杀真菌组合物。
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PL2575477T3 (pl) | 2010-05-05 | 2020-09-21 | Stockton (Israel) Ltd. | Kombinacje związków przeciwgrzybiczych i olejku z drzewa herbacianego |
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CN103338642A (zh) * | 2010-09-09 | 2013-10-02 | 桑科能源股份有限公司 | 协同作用的石蜡油和啶酰菌胺杀真菌剂 |
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IL190851A0 (en) | 2008-11-03 |
JP2009515848A (ja) | 2009-04-16 |
AR057167A1 (es) | 2007-11-21 |
ATE429147T1 (de) | 2009-05-15 |
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ZA200804949B (en) | 2010-03-31 |
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CA2627955A1 (en) | 2007-05-18 |
WO2007054473A1 (de) | 2007-05-18 |
PL1947941T3 (pl) | 2009-09-30 |
BRPI0618351A2 (pt) | 2012-02-22 |
EA013817B1 (ru) | 2010-08-30 |
EA200801351A1 (ru) | 2008-10-30 |
UA90035C2 (ru) | 2010-03-25 |
PE20070873A1 (es) | 2007-09-14 |
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