CN102083315B - 包含取代的1-甲基吡唑-4-基甲酰苯胺的杀真菌混合物 - Google Patents
包含取代的1-甲基吡唑-4-基甲酰苯胺的杀真菌混合物 Download PDFInfo
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- CN102083315B CN102083315B CN200980125970.1A CN200980125970A CN102083315B CN 102083315 B CN102083315 B CN 102083315B CN 200980125970 A CN200980125970 A CN 200980125970A CN 102083315 B CN102083315 B CN 102083315B
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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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
- A01N57/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing acyclic or cycloaliphatic radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
-
- 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
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Abstract
杀真菌混合物,以协同增效有效量包含如下组分作为活性组分:1)至少一种式I的1-甲基吡唑-4-基甲酰苯胺,其中R1=C1-C4烷基或C1-C4卤代烷基,R2=氢或卤素,X=氢或卤素,Q=直接键、亚环丙基或稠合双环[2.2.1]庚烷环,R3=C1-C6烷基、环丙基或被2或3个卤原子或三氟甲硫基取代的苯基;和2)至少一种选自A)-K)组活性化合物的活性化合物II:A)有机(硫代)磷酸酯;B)氨基甲酸酯;C)拟除虫菊酯;D)生长调节剂;E)GABA拮抗剂化合物;F)大环内酯杀虫剂;G)METII杀螨剂;H)ME-TIII和III化合物;J)氧化磷酸化抑制剂化合物;K)各种化合物;使用至少一种化合物I和至少一种活性化合物II的混合物防治有害真菌的方法,化合物I或化合物I与活性化合物II在制备该类混合物中的用途以及包含该类混合物的组合物和种子。
Description
本发明涉及用于防治植物病原性有害真菌的混合物,其以协同增效有效量包含如下组分作为活性组分:
1)至少一种式I的1-甲基吡唑-4-基甲酰苯胺:
其中各取代基如下所定义:
R1为C1-C4烷基或C1-C4卤代烷基;
R2为氢或卤素;
X为氢或氟;
Q为直接键、亚环丙基或稠合双环[2.2.1]庚烷环;
R3为C1-C6烷基、环丙基或被2或3个卤原子或被三氟甲硫基取代的苯基;
和
2)至少一种选自A)-K)组活性化合物的活性化合物II:
A)选自如下的有机(硫代)磷酸酯:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、毒虫畏(chlorfenvinphos)、二嗪农(diazinon)、敌敌畏(dichlorvos)、百治磷(dicrotophos)、乐果(dimethoate)、乙拌磷(disulfoton)、乙硫磷(ethion)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基对硫磷(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(oxy-demeton-methyl)、对氧磷(paraoxon)、一六零五(parathion)、稻丰散(phenthoate)、伏杀硫磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、甲拌磷(phorate)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、田乐磷(sulprophos)、杀虫威(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)和敌百虫(trichlorfon);
B)选自如下的氨基甲酸酯:棉铃威(alanycarb)、涕灭威(aldicarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、双氧威(fenoxycarb)、呋线威(furathiocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)和唑蚜威(triazamate);
C)选自如下的拟除虫菊酯:丙烯除虫菊(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、(RS)氯氟氰菊酯(cyhalothrin)、苯醚氰菊酯(cyphenothrin)、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊(pyrethrin)I和II、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、氟胺氰菊酯(tau-fluvalinate)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、丙氟菊酯(profluthrin)和四氟甲醚菊酯(dimefluthrin);
D)选自如下的生长调节剂:a)几丁质合成抑制剂:苯甲酰脲类:定虫隆(chlorfluazuron)、灭蝇胺(cyramazin)、氟螨脲(flucycloxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、杀虫隆(triflumuron);噻嗪酮(buprofezin)、茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯唑(etoxazole)和四螨嗪(clofentazine);b)蜕皮激素拮抗剂:特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)和艾扎丁(azadirachtin);c)保幼激素类似物:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)和双氧威;d)类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)和螺虫乙酯(spirotetramate);
E)选自如下的GABA拮抗剂化合物:硫丹(endosulfan)、乙虫清(ethiprole)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole和式E1的苯基吡唑:
F)选自如下的大环内酯杀虫剂:齐墩螨素(abamectin)、甲氨基阿维菌素(emamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad)和spinetoram;
G)选自如下的METII杀螨剂:喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)和嘧虫胺(flufenerim);
H)选自如下的METIII和III化合物:灭螨醌(acequinocyl)、fluacyprim和灭蚁腙(hydramethylnon);
J)选自如下的氧化磷酸化抑制剂化合物:三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatin oxide)和克螨特(propargite);
K)选自如下的各种化合物:amidoflumet、benclothiaz、联苯肼酯(bifenazate)、bistrifluron、杀螟丹(cartap)、氟唑虫清(chlorfenapyr)、灭蝇胺(cryomazine)、cyazypyr(HGW86)、cyenopyrafen、丁氟螨酯(cyflumetofen)、氟啶虫酰胺(flonicamid)、氟虫酰胺(flubendiamide)、吡氟硫磷(flupyrazofos)、imicyafos、二唑虫(indoxacarb)、氰氟虫胺(metaflumizone)、增效醚(piperonyl butoxide)、拒嗪酮(pymetrozine)、啶虫丙醚(pyridalyl)、pyrifluquinazon、硫环杀(thiocyclam)和式K1的噻唑化合物:
此外,本发明涉及一种使用至少一种化合物I和至少一种活性化合物II的混合物防治有害真菌的方法,化合物I与活性化合物II在制备该类混合物中的用途以及包含该类混合物的组合物和种子。
称作组分1)的式I的1-甲基吡唑-4-基甲酰苯胺、其制备及其对有害真菌的作用由文献已知(例如参见EP-A 545 099,EP-A 589 301,WO99/09013,WO 03/010149,WO 2003/70705,WO 03/074491和WO04/035589),或者它们可以以本文所述方式制备。
然而,已知式I的1-甲基吡唑-4-基甲酰苯胺尤其在低施用率下并且在其活性谱方面并不完全令人满意。
上面作为组分2)提到的活性化合物II、其制备及其对有害真菌的作用通常是已知的(例如参见http://www.hclrss.demon.co.uk/index.html);它们可以市购。
考虑到降低化合物I的施用率并拓宽其活性谱,本发明的目的是提供在降低的活性化合物总施用量下对有害真菌,尤其是对特定适应症具有改进活性的混合物。
我们因此发现该目的由开头所定义的活性化合物I和II的混合物实现。此外,我们发现同时,即联合或分开施用至少一种化合物I和至少一种活性化合物II或依次施用化合物I和至少一种活性化合物II与单独化合物可能获得效果相比允许更好地防治有害真菌(协同增效混合物)。
通过同时,即联合或分开施用化合物I和至少一种活性化合物II,以超加和方式提高杀真菌活性。
化合物I可以生物学活性可能不同的不同晶型存在。
在式I中,卤素为氟、氯、溴或碘,优选氟或氯;
C1-C4烷基为甲基、乙基、正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基或1,1-二甲基乙基,优选甲基或乙基;
C1-C6烷基为甲基、乙基、正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、正戊基、正己基或1,3-二甲基丁基,尤其是1-甲基乙基或1,3-二甲基丁基;
C1-C4卤代烷基为部分或完全卤代的C1-C4烷基,其中卤原子尤其为氟、氯和/或溴,即例如氯甲基、溴甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、氯氟甲基、二氯一氟甲基、一氯二氟甲基、1-氯乙基、1-溴乙基、1-氟乙基、2-氟乙基、2,2-二氟乙基、2,2,2-三氟乙基、2-氯-2-氟乙基、2-氯-2,2-二氟乙基、2,2-二氯-2-氟乙基、2,2,2-三氯乙基、五氟乙基、七氟丙基或九氟丁基,尤其是卤代甲基,特别优选CH2-Cl、CH(Cl)2、CH2-F、CHF2、CF3、CHFCl、CF2Cl或CF(Cl)2,尤其是CHF2或CF3;
C1-C4烷硫基为SCH3、SC2H5、SCH2-C2H5、SCH(CH3)2、正丁硫基、SCH(CH3)-C2H5、SCH2-CH(CH3)2或SC(CH3)3,优选SCH3或SC2H5。
优选的1-甲基吡唑-4-基甲酰苯胺I一方面为其中X为氢的那些。
另一方面,优选的化合物I为其中X为氟的那些。
对于本发明混合物,优选其中R1为甲基或卤代甲基,尤其是CH3、CHF2、CH2F、CF3、CHFCl或CF2Cl,特别优选CH3或CHF2的式I化合物。
此外还优选其中R2为氢、氟或氯,尤其是氢或氟的化合物I。
此外还优选其中R3为被2或3个卤原子取代的苯基,尤其是3,4-二氯苯基或3,4,5-三氟苯基的那些化合物I。
此外,优选N-(3’,4’,5’-三氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-[2-(1,3-二甲基丁基)苯基]-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺(通用名:Penflufen)、N-(2-双环丙-2-基苯基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺(通用名:Sedaxane)、N-(反式-2-双环丙-2-基苯基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺(通用名:Sedaxane;反式非对映体)、isopyrazam和bixafen。
非常特别优选的是N-(3’,4’,5’-三氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺和bixafen,最优选N-(3’,4’,5’-三氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺(化合物Ia)。
对于活性化合物II,优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自A)有机(硫代)磷酸酯,尤其是高灭磷、毒死蜱、二嗪农、敌敌畏、乐果、杀螟松、甲胺磷、杀扑磷、甲基对硫磷、久效磷、甲拌磷、丙溴磷或特丁磷的活性化合物II的混合物。
非常特别优选选自A)的化合物II是高灭磷、毒死蜱、乐果、甲胺磷和特丁磷。
还优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自B)氨基甲酸酯,尤其是涕灭威、甲萘威、虫螨威、丁硫克百威、灭多虫或硫双威的活性化合物的混合物。
非常特别优选选自B)的化合物II是涕灭威和虫螨威。
优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自C)拟除虫菊酯,尤其是氟氯菊酯、氟氯氰菊酯、氯氰菊酯、甲体氯氰菊酯、己体氯氰菊酯、溴氰菊酯、高氰戊菊酯、氯氟氰菊酯、氯菊酯或七氟菊酯的活性化合物的混合物。
非常特别优选选自C)的化合物II是氟氯菊酯、氯氰菊酯、甲体氯氰菊酯、溴氰菊酯、氯氟氰菊酯和七氟菊酯。
此外还优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自D)生长调节剂,尤其是氟丙氧脲或螺虫乙酯,非常特别优选螺虫乙酯的活性化合物的混合物。
此外还优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自E)GABA拮抗剂化合物,尤其是硫丹的活性化合物的混合物。
此外还优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自F)大环内酯杀虫剂,尤其是齐墩螨素、甲氨基阿维菌素、艾克敌105或spinetoram的活性化合物的混合物。
非常特别优选选自F)的化合物II是齐墩螨素、艾克敌105和spinetoram。
此外还优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自G)METII杀螨剂的活性化合物的混合物。
此外还优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自H)METIII和III化合物,尤其是灭蚁腙的活性化合物的混合物。
此外还优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自J)氧化磷酸化抑制剂化合物,尤其是杀螨锡的活性化合物的混合物。
还优选1-甲基吡唑-4-基甲酰苯胺I与至少一种选自K)各种化合物,尤其是氟唑虫清、cyazypyr(HGW86)、丁氟螨酯、氟啶虫酰胺、氟虫酰胺、二唑虫和氰氟虫胺的活性化合物的混合物。
非常特别优选选自K)的化合物II是氟唑虫清、cyazypyr(HGW86)、丁氟螨酯、氟虫酰胺和二唑虫。
还优选一种1-甲基吡唑-4-基甲酰苯胺I与两种上述活性化合物II的三组分混合物。
还优选一种式I化合物与两种上述活性化合物II或与一种活性化合物II和另一种选自活性化合物组L)-S)的其他杀真菌活性化合物III的三组分混合物:
L)嗜球果伞素类:
腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(enestroburin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、pyribencarb、肟菌酯(trifloxystrobin)、2-(2-(6-(3-氯-2-甲基苯氧基)-5-氟嘧啶-4-基氧基)苯基)-2-甲氧亚氨基-N-甲基乙酰胺、3-甲氧基-2-(2-(N-(4-甲氧基苯基)环丙烷亚胺酰硫基甲基)苯基)丙烯酸甲酯、(2-氯-5-[1-(3-甲基苄氧亚氨基)乙基]苄基)氨基甲酸甲酯和2-(2-(3-(2,6-二氯苯基)-1-甲基亚烯丙基氨基氧甲基)苯基)-2-甲氧亚氨基-N-甲基乙酰胺;
M)羧酰胺类:
-羧酰苯胺类:苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、麦锈灵(benodanil)、啶酰菌胺(boscalid)、萎锈灵(carboxin)、呋菌胺(fenfuram)、环酰菌胺(fenhexamid)、氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、isopyrazam、异噻菌胺(isotianil)、kiralaxyl、丙氧灭绣胺(mepronil)、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M(mefenoxam))、甲呋酰胺(ofurace)、霜灵(oxadixyl)、氧化萎锈灵(oxycarboxin)、吡噻菌胺(penthiopyrad)、叶枯酞(tecloftalam)、溴氟唑菌(thifluzamide)、噻酰菌胺(tiadinil);
-羧酸吗啉化物:烯酰吗啉(dimethomorph)、氟吗啉(flumorph);
-苯甲酰胺类:氟联苯菌(flumetover)、氟吡菌胺(fluopicolide)、氟吡菌酰胺(fluopyram)、苯酰菌胺(zoxamide)、N-(3-乙基-3,5,5-三甲基环己基)-3-甲酰氨基-2-羟基苯甲酰胺;
-其他羧酰胺类:氯环丙酰胺(carpropamid)、双氯氰菌胺(dicyclomet)、双炔酰菌胺(mandiproamid)、土霉素(oxytetracyclin)、硅噻菌胺(silthiofarm)和N-(6-甲氧基吡啶-3-基)环丙烷甲酰胺;
N)唑类:
-三唑类:戊环唑(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(diniconazole)、烯唑醇M(diniconazole-M)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluquinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、oxpoconazole、多效唑(paclobutrazole)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、三唑酮(triadimefon)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、烯效唑(uniconazole)、1-(4-氯苯基)-2-([1,2,4]三唑-1-基)环庚醇;
-咪唑类:氰霜唑(cyazofamid)、烯菌灵(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizol);
-苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole);
-其他:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole)和2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔基氧基乙酰胺;
P)杂环化合物
-吡啶类:氟啶胺(fluazinam)、啶斑肟(pyrifenox)、3-[5-(4-氯苯基)-2,3-二甲基异唑烷-3-基]吡啶、3-[5-(4-甲基苯基)-2,3-二甲基异唑烷-3-基]吡啶、2,3,5,6-四氯-4-甲磺酰基吡啶、3,4,5-三氯吡啶-2,6-二甲腈、N-(1-(5-溴-3-氯吡啶-2-基)乙基)-2,4-二氯烟酰胺、N-((5-溴-3-氯吡啶-2-基)甲基)-2,4-二氯烟酰胺;
-嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、二氟林(diflumetorim)、异嘧菌醇(fenarimol)、嘧菌腙(ferimzone)、嘧菌胺(mepanipyrim)、氯草定(nitrapyrin)、氟苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);
-哌嗪类:嗪氨灵(triforine);
-吡咯类:拌种咯(fenpiclonil)、氟菌(fludioxonil);
-吗啉类:4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、吗菌灵乙酸酯(dodemorph-acetate)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph);
-哌啶类:苯锈啶(fenpropidin);
-二羧酰亚胺类:氟菌安(fluoroimid)、异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);
-非芳族5员杂环:唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、异噻菌酮(octhilinone)、噻菌灵(probenazole)、5-氨基-2-异丙基-3-氧代-4-邻甲苯基-2,3-二氢吡唑-1-硫代甲酸S-烯丙基酯;
-其他:噻二唑素(acibenzolar-S-methyl)、amisulbrom、敌菌灵(anilazin)、灭瘟素(blasticidin-S)、敌菌丹(captafol)、克菌丹(captan)、灭螨蜢(chinomethionat)、棉隆(dazomet)、咪菌威(debacarb)、哒菌清(diclomezine)、野燕枯(difenzoquat)、野燕枯甲基硫酸酯(difenzoquat-methylsulfate)、氰菌胺(fenoxanil)、灭菌丹(folpet)、恶喹酸(oxolinicacid)、粉病灵(piperalin)、丙氧喹啉(proquinazid)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、唑菌嗪(triazoxide)、三环唑(tricyclazole)、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、5-氯-1-(4,6-二甲氧基嘧啶-2-基)-2-甲基-1H-苯并咪唑、5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]三唑并[1,5-a]嘧啶、6-(3,4-二氯苯基)-5-甲基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-(4-叔丁基苯基)-5-甲基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-甲基-6-(3,5,5-三甲基己基)-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-甲基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-甲基-5-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-乙基-5-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-乙基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-乙基-6-(3,5,5-三甲基己基)-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-辛基-5-丙基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、5-甲氧基甲基-6-辛基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺、6-辛基-5-三氟甲基-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺和5-三氟甲基-6-(3,5,5-三甲基己基)-[1,2,4]三唑并[1,5-a]嘧啶-7-基胺;
Q)氨基甲酸酯
-硫代-和二硫代氨基甲酸酯:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、威百亩(metam)、磺菌威(methasulphocarb)、代森联(metiram)、甲基代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);
-氨基甲酸酯:苯噻菌胺(benthiavalicarb)、乙霉威(diethofencarb)、flubenthiavalicarb、异丙菌胺(iprovalicarb)、百维灵(propamocarb)、霜霉威盐酸盐(propamocarb hydrochlorid)、valiphenal和N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
R)其他杀真菌活性物质
-胍类:胍、多果定(dodine)、多果定游离碱、双胍盐(guazatine)、双胍辛胺(guazatine-acetate)、双胍辛醋酸盐(iminoctadine)、双胍辛胺三乙酸盐(iminoctadine triacetate)、双八胍盐(iminoctadine tris(albesilate));
-抗生素类:春雷素(kasugamycin)、水合春雷素(kasugamycinhydrochloride-hydrate)、链霉素(streptomycin)、多氧霉素(polyoxine)、井冈霉素(validamycin A);
-硝基苯基衍生物:乐杀螨(binapacryl)、敌螨通(dinobuton)、敌螨普(dinocap)、异丙消(nitrthal-isopropyl)、四氯硝基苯(tecnazen);
-有机金属化合物:三苯锡基盐,例如薯瘟锡(fentin-acetate)、三苯锡氯(fentin chloride)或毒菌锡(fentin hydroxide);
-含硫杂环化合物:二噻农(dithianon)、稻瘟灵(isoprothiolane);
-有机磷化合物:克瘟散(edifenphos)、藻菌磷(fosetyl)、乙磷铝(fosetyl-aluminum)、异稻瘟净(iprobenfos)、亚磷酸及其盐、定菌磷(pyrazophos)、甲基立枯磷(tolclofos-methyl);
-有机氯化合物:百菌清(chlorothalonil)、抑菌灵(dichlofluanid)、双氯酚(dichlorophen)、磺菌胺(flusulfamide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯酚(pentachlorphenole)及其盐、四氯苯酞(phthalide)、五氯硝基苯(quintozene)、甲基托布津(thiophanate-methyl)、对甲抑菌灵(tolylfluanid)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯磺酰胺;
-无机活性物质:波尔多液(Bordeaux混合物)、醋酸铜、氢氧化铜、王铜(copper oxychloride)、碱式硫酸铜,硫;
-其他:联苯、拌棉醇(bronopol)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、二苯胺、苯菌酮(metrafenone)、米多霉素(mildiomycin)、喹啉铜(oxin-copper)、调环酸钙(prohexadione-calcium)、螺茂胺(spiroxamine)、对甲抑菌灵、N-(环丙基甲氧亚氨基-(6-二氟甲氧基-2,3-二氟苯基)甲基)-2-苯基乙酰胺、N′-(4-(4-氯-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(4-(4-氟-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N′-(2-甲基-5-三氟甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒和N′-(5-二氟甲基-2-甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒。
S)生长调节剂
脱落酸(abscisic acid)、先甲草胺(amidochlor)、嘧啶醇(ancymidol)、苄胺基嘌呤(6-benzylaminopurine)、油菜素内酯(brassinolide)、地乐胺(butralin)、矮壮素阳离子(chlormequat)(矮壮素(chlormequatchloride))、氯化胆碱(cholin chloride)、环丙酸酰胺(cyclanilide)、丁酰肼(daminozide)、敌草克(dikegulac)、噻节因(dimethipin)、2,6-二甲基吡啶(2,6-dimethylpuridine)、乙烯利(ethephon)、抑芽敏(flumetralin)、呋嘧醇(flurprimidol)、达草氟(fluthiacet)、调吡脲(forchlorfenuron)、九二O(gibberellic acid)、抗倒胺(inabenfide)、吲哚-3-乙酸、抑芽丹(maleic hydrazide)、氟草磺(mefluidide)、助壮素阳离子(mepiquat)(助壮素(mepiquat chloride))、萘乙酸、N-6-苄基腺嘌呤、多效唑、调环酸(prohexadione)(调环酸钙)、茉莉酸丙酯(prohydrojasmon)、赛二唑素(thidiazuron)、抑芽唑(triapenthenol)、脱叶磷(tributylphosphorotrithioate)、2,3,5-三碘苯甲酸、抗倒酯(trinexapac-ethyl)和烯效唑。
上述活性化合物III、其制备及其对有害真菌的作用通常是已知的(例如参见http://www.hclrss.demon.co.uk/index.html);它们可以市购。
由IUPAC命名法描述的化合物、其制备及其杀真菌活性也时已知的(参见Can.J.Plant Sci.48(6),587-94,1968;EP-A 141 317;EP-A 152031;EP-A 226 917;EP-A 243 970;EP-A 256 503;EP-A 428 941;EP-A 532 022;EP-A 1 028 125;EP-A 1 035 122;EP-A 1 201 648;EP-A 1122 244,JP 2002316902;DE 19650197;DE 10021412;DE102005009458;US 3,296,272;US 3,325,503;WO 98/46608;WO99/14187;WO 99/24413;WO 99/27783;WO 00/29404;WO 00/46148;WO 00/65913;WO 01/54501;WO 01/56358;WO 02/22583;WO02/40431;WO 03/10149;WO 03/11853;WO 03/14103;WO 03/16286;WO 03/53145;WO 03/61388;WO 03/66609;WO 03/74491;WO04/49804;WO 04/83193;WO 05/120234;WO 05/123689;WO05/123690;WO 05/63721;WO 05/87772;WO 05/87773;WO06/15866;WO 06/87325;WO 06/87343;WO 07/82098;WO07/90624)。
还优选包含化合物I(组分1)和至少一种选自L)组嗜球果伞素类,尤其是选自腈嘧菌酯、醚菌胺、氟嘧菌酯、亚胺菌、肟醚菌胺、啶氧菌酯、唑菌胺酯和肟菌酯的活性物质II(组分2)的三组分混合物。
还优选包含化合物I(组分1)和至少一种选自M)组羧酰胺类,尤其是选自环酰菌胺、甲霜灵、精甲霜灵、甲呋酰胺、烯酰吗啉、氟吗啉、氟吡菌胺(picobenzamid)、苯酰菌胺、氯环丙酰胺和双炔酰菌胺(mandi-propamid)的活性物质II(组分2)的三组分混合物。
优选包含式I化合物(组分1)和至少一种选自N)组唑类,尤其是选自环唑醇、醚唑、氧唑菌、喹唑菌酮、氟硅唑、粉唑醇、环戊唑菌、腈菌唑、戊菌唑、丙环唑、丙硫菌唑、三唑酮、唑菌醇、戊唑醇、氟醚唑、戊叉唑菌、丙氯灵、氰霜唑、苯菌灵、多菌灵和噻唑菌胺的活性物质II(组分2)的三组分混合物。
还优选包含化合物I(组分1)和至少一种选自P)组杂环化合物,尤其是选自氟啶胺、环丙嘧啶、异嘧菌醇、嘧菌胺、二甲嘧菌胺、嗪氨灵、氟菌、吗菌灵、丁苯吗啉、克啉菌、苯锈啶、异丙定、烯菌酮、唑酮菌、咪唑菌酮、噻菌灵、丙氧喹啉、噻二唑素、敌菌丹、灭菌丹、氰菌胺和喹氧灵的活性物质II(组分2)的三组分混合物。
还优选包含化合物I(组分1)和至少一种选自Q)组氨基甲酸酯,尤其是选自代森锰锌、代森联、甲基代森锌、福美双、异丙菌胺、flubenthiavalicarb和百维灵的活性物质II(组分2)的三组分混合物。
还优选包含化合物I(组分1)和至少一种选自R)组杀真菌剂,尤其是选自二噻农、三苯锡基盐如薯瘟锡、藻菌磷、乙磷铝、H3PO3及其盐、百菌清、抑菌灵、甲基托布津、醋酸铜、氢氧化铜、王铜、硫酸铜、硫、清菌脲、苯菌酮、螺茂胺和5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)-[1,2,4]-三唑并[1,5-a]嘧啶的活性物质II(组分2)的三组分混合物。
还优选化合物I和II与两种选自上述化合物II和III的其他活性化合物的四组分混合物。
优选的活性化合物组合列于下表1-9中:
表1化合物I与A)组活性化合物II的活性化合物组合:
表2化合物I与B)组活性化合物II的活性化合物组合:
表3化合物I与C)组活性化合物II的活性化合物组合:
表4化合物I与D)组活性化合物II的活性化合物组合:
表5化合物I与E)组活性化合物II的活性化合物组合:
表6化合物I与F)组活性化合物II的活性化合物组合:
表7化合物I与H)组活性化合物II的活性化合物组合:
表8化合物I与J)组活性化合物II的活性化合物组合:
表9化合物I与K)组活性化合物II的活性化合物组合:
活性物质的混合物可以通过常规方式,例如通过对化合物I的组合物所述方式制备成除了活性化合物外还包含至少一种惰性成分的组合物。
正如式I化合物一样,本发明活性物质的混合物适合作为杀真菌剂。它们的特征在于对宽范围的植物病原性真菌,尤其选自子囊菌纲(Ascomycetes)、担子菌纲(Basidiomycetes)、半知菌纲(Deuteromycetes)和Peronosporomycetes(同义词卵菌纲(Oomycetes))的真菌具有显著有效性。此外,分别参考有关化合物和包含化合物I的组合物的杀真菌活性的解释。
化合物I与至少一种活性化合物II的混合物或同时,即联合或分开使用化合物I与至少一种活性化合物II的特征在于对宽范围的植物病原性真菌[包括尤其源于根肿菌纲(Plasmodiophoromycetes)、Peronosporomycetes(同义词卵菌纲)、壶菌纲(Chytridiomycetes)、接合菌纲(Zygomycetes)、子囊菌纲、担子菌纲和半知菌纲(同义词不完全菌纲(Fungi imperfecti))的土传真菌]具有显著的有效性。一些内吸有效并且可以作为叶面杀真菌剂、拌种用杀真菌剂和土壤杀真菌剂用于作物保护中。此外,它们适合防治尤其发生在木材或植物根部的有害真菌。
本发明化合物I和组合物对于在各种栽培植物如禾谷类,例如小麦、黑麦、大麦、小黑麦、燕麦或稻;甜菜,例如糖用甜菜或饲料甜菜;果实,如仁果、核果或浆果,例如苹果、梨、李、桃、杏仁、樱桃、草莓、悬钩子、黑莓或鹅莓;豆科植物,例如扁豆、豌豆、苜蓿或大豆;油料植物,例如油菜、芥菜、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油棕、花生或大豆;葫芦科植物,例如南瓜、黄瓜或甜瓜;纤维植物,例如棉花、亚麻、大麻或黄麻;柑桔类水果,例如橙子、柠檬、葡萄柚或橘;蔬菜,例如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、土豆、葫芦或柿子椒;月桂类植物,例如鳄梨、肉桂或樟脑;能量和原料植物,例如玉米、大豆、油菜、甘蔗或油棕;玉米;烟草;坚果;咖啡;茶;香蕉;葡萄藤(食用葡萄和葡萄汁用葡萄藤);啤酒花;草坪;天然橡胶植物或观赏和森林植物,例如花卉、灌木、阔叶树或常绿树如针叶树,以及植物繁殖材料如种子,以及这些植物的作物材料中防治大量植物病原性真菌特别重要。
优选将化合物I及其组合物分别用于在大田作物,例如土豆、糖用甜菜、烟草、小麦、黑麦、大麦、燕麦、稻、玉米、棉花、大豆、油菜、豆类、向日葵、咖啡或甘蔗;水果;葡萄藤;观赏植物或蔬菜如黄瓜、西红柿、菜豆和南瓜上防治大量真菌。
术语“植物繁殖材料”应理解为指植物的所有繁殖部分如种子,以及可以用于繁殖植物的无性植物材料如插条和块茎(例如土豆)。这包括种子、根、果实、块茎、球茎、地下茎、嫩枝、芽和其他植物部分,包括在萌发后或出苗后由土壤移植的秧苗和幼苗。这些幼苗还可以通过经由浸渍或浇灌的完全或部分处理而在移植之前保护。
优选将化合物I及其组合物分别对植物繁殖材料的处理用于在禾谷类如小麦、黑麦、大麦和燕麦;稻、玉米、棉花和大豆中防治大量真菌。
术语“栽培植物”应理解为包括已经通过育种、诱变或基因工程修饰的植物,包括但不限于上市销售或开发的农业生物技术产品(参见http://www.bio.org/speeches/pubs/er/agri_products.asp)。基因修饰植物是其基因材料通过使用在自然条件下不易通过杂交、突变或自然重组得到的重组DNA技术修饰的植物。通常将一个或多个基因整合到基因修饰植物的基因材料中以改善植物的某些性能。这类基因修饰还包括但不限于蛋白质、寡肽或多肽的靶向翻译后修饰,例如通过糖基化或聚合物加成如异戊二烯化、乙酰化或法呢基化结构部分或PEG结构部分。
例如已经通过育种、诱变或基因工程而修饰的植物已经因常规育种或基因工程方法而耐受特殊类别的除草剂施用,例如羟基苯基丙酮酸双加氧酶(HPPD)抑制剂;乙酰乳酸合成酶(ALS)抑制剂如磺酰脲类(例如见US6,222,100、WO 01/82685、WO 00/26390、WO 97/41218、WO98/02526、WO 98/02527、WO 04/106529、WO 05/20673、WO03/14357、WO 03/13225、WO 03/14356、WO 04/16073)或咪唑啉酮类(例如见US 6,222,100、WO 01/82685、WO 00/026390、WO 97/41218、WO98/002526、WO 98/02527、WO 04/106529、WO 05/20673、WO03/014357、WO 03/13225、WO 03/14356、WO 04/16073);烯醇丙酮酰莽草酸3-磷酸合成酶(EPSPS)抑制剂如草甘膦(glyphosate)(例如见WO92/00377);谷氨酰胺合成酶(GS)抑制剂如草铵膦(glufosinate)(例如见EP-A 242 236、EP-A 242 246)或oxynil除草剂(例如见US5,559,024)。几种栽培植物已经通过常规育种(诱变)方法而耐受除草剂,例如夏播油菜(Canola,德国BASF SE)耐受咪唑啉酮类如咪草啶酸(imazamox)。基因工程方法已经用于使栽培植物如大豆、棉花、玉米、甜菜和油菜耐受除草剂如草甘膦和草铵膦,它们中的一些可以以商标名(耐受草甘膦,美国Monsanto)和(耐受草铵膦,德国BayerCropScience)市购。
此外,还包括通过使用重组DNA技术而能够合成一种或多种杀虫蛋白的植物,该蛋白尤其是由芽孢杆菌属(Bacillus)细菌已知的那些,特别是由苏云金芽孢杆菌(Bacillus thuringiensis)已知的那些,例如δ-内毒素如CryIA(b)、CryIA(c)、CryIF、CryIF(a2)、CryIIA(b)、CryIIIA、CryIIIB(b1)或Cry9c;无性杀虫蛋白(VIP)如VIP1、VIP2、VIP3或VIP3A;线虫定居细菌的杀虫蛋白如发光杆菌属(Photorhabdus)或致病杆菌属(Xenorhabdus);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属(Streptomycetes)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、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)如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽蛋白、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、蜕皮甾类-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;离子通道阻断剂如钠通道或钙通道阻断剂;保幼激素酯酶;利尿激素受体(helicokinin受体);茋合成酶,联苄合成酶,壳多糖酶或葡聚糖酶。就本发明而言,这些杀虫蛋白或毒素还具体理解为前毒素、杂合蛋白、截短的或其他方面改性的蛋白。杂合蛋白的特征在于蛋白域的新型组合(例如见WO 02/015701)。该类毒素或能够合成该类毒素的基因修饰植物的其他实例公开于例如EP-A 374 753、WO93/007278、WO 95/34656、EP-A 427 529、EP-A 451 878、WO 03/18810和WO 03/52073中。生产该类基因修饰植物的方法对本领域熟练技术人员通常是已知的且例如描述于上述出版物中。这些含于基因修饰植物中的杀虫蛋白赋予产生这些蛋白的植物以对所有分类学上为节肢动物的害虫,尤其是甲虫(鞘翅目(Coeleropta))、双翅目昆虫(双翅目(Diptera))和蛾(鳞翅目(Lepidoptera))以及线虫(线虫纲(Nematoda))的耐受性。能合成一种或多种杀虫蛋白的基因修饰植物例如描述于上述出版物中,并且它们中的一些可市购,例如(产生Cry1Ab毒素的玉米栽培品种),Plus(产生Cry1Ab和Cry3Bb1毒素的玉米栽培品种),(产生Cry9c毒素的玉米栽培品种),RW(产生Cry34Ab1、Cry35Ab1和酶膦丝菌素-N-乙酰转移酶[PAT]的玉米栽培品种);33B(产生Cry1Ae毒素的棉花栽培品种),I(产生Cry1Ac毒素的棉花栽培品种),II(产生Cry1Ac和Cry2Ab2毒素的棉花栽培品种);(产生VIP毒素的棉花栽培品种);(产生Cry3A毒素的土豆栽培品种);法国Syngenta Seeds SAS的Bt11(例如CB)和Bt176(产生Cry1Ab毒素和PAT酶的玉米栽培品种),法国Syngenta Seeds SAS的MIR604(产生Cry3A毒素的修饰译本的玉米栽培品种,见WO03/018810),比利时Monsanto Europe S.A.的MON863(产生Cry3Bb1毒素的玉米栽培品种),比利时MonsantoEurope S.A.的IPC 531(产生Cry1Ac毒素的修饰译本的棉花栽培品种)和比利时Pioneer Overseas Corporation的1507(产生Cry1F毒素和PAT酶的玉米栽培品种)。
此外,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 392225),植物病害抗性基因(例如表达针对来自野生墨西哥土豆Solanumbulbocastanum的致病疫霉(Phytophthora infestans)的抗性基因的土豆栽培品种)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土豆栽培品种)。生产这类基因修饰植物的方法通常为本领域熟练技术人员所已知且例如描述于上述出版物中。
此外,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),对干旱、盐或其他限制生长的环境因素的耐受性或对害虫以及真菌、细菌或其病毒病原体的耐受性的植物。
此外,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,加拿大DOW Agro Sciences)。
此外,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尤其改善原料生产的植物,例如通过产生增加量的支链淀粉的土豆(例如土豆,德国BASF SE)。
化合物I及其组合物分别特别适合防治下列植物病害: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、油菜(芸苔生链格孢(A.brassicola)或芸苔链格孢(A.brassicae))、糖用甜菜(A.tenuis)、水果、稻、大豆、土豆(例如早疫链格孢(A.solani)或链格孢(A.alternata))、西红柿(例如早疫链格孢或链格孢)和小麦上的链格孢属(Alternaria)(链格孢叶斑病);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(例如玉蜀黍平脐蠕孢(D.maydis))、禾谷类(例如麦根腐平脐蠕孢(B.sorokiniana):斑枯病)稻(稻平脐蠕孢(B.oryzae))和草坪上的平脐蠕孢属(Bipolaris)和内脐蠕孢属(Drechslera)(有性型:旋孢腔菌属(Cochliobolus));禾谷类(例如小麦或大麦)上的小麦白粉菌(Blumeria(以前:Erysiphe)graminis)(白粉病);水果和浆果(例如草莓)、蔬菜(例如莴苣、胡萝卜、根芹菜和卷心菜)、油菜、花卉、葡萄藤、森林植物和小麦上的灰葡萄孢(Botrytis cinerea)(有性型:灰葡萄孢霉(Botryotiniafuckeliana):灰霉病);莴苣上的莴苣盘梗霉(Bremia lactucae)(霜霉病);阔叶树和常绿树上的长喙壳属(Ceratocystis)(同义词线嘴壳属(Ophiostoma))(腐烂或枯萎),例如榆树上的榆枯萎病菌(C.ulmi)(荷兰榆病);玉米、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);西红柿(例如番茄叶霉菌(C.fulvum):叶霉病)和禾谷类(例如小麦上的草芽枝孢(C.herbarum)(黑穗病))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)、浆果、土豆(例如西瓜炭疽病菌(C.coccodes):黑点病)、菜豆(例如菜豆炭疽病菌(C.lindemuthianum))和大豆(例如大豆炭疽病菌(C.truncatum)或荔枝炭疽病菌(C.gloeosporioides))上的剌盘孢属(Colletotrichum)(有性型:围小丛壳菌属(Glomerella)(炭疽病);伏革菌属(Corticium),例如稻上的笹木伏革菌(C.sasakii)(纹枯病);大豆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、葡萄藤(例如C.liriodendri,有性型:Neonectrialiriodendri:乌脚病)和观赏植物上的人参生柱隔孢属(Cylindrocarpon)(例如果树腐烂病或葡萄藤幼苗衰弱病,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:黄斑病)、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(以前为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)(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)(黑霉病);糖用甜菜(例如甜菜白粉菌(E.betae))、蔬菜(例如豌豆白粉菌(E.pisi))如葫芦(例如二孢白粉菌(E.cichoracearum))、卷心菜、油菜(例如E.cruciferarum)上的白粉菌属(Erysiphe)(白粉病);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、黑星病或穗霉病),西红柿上的尖镰孢(F.oxysporum),大豆上的茄镰孢(F.solani)和玉米上的轮枝镰孢(F.verticillioides);禾谷类(例如小麦或大麦)和玉米上的禾顶囊壳(Gaeumannomyces graminis)(全蚀病);禾谷类(例如玉蜀黍赤霉(G.zeae))和稻(例如藤仓赤霉(G.fujikuroi):恶苗病)上的赤霉属;葡萄藤、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(Guignardia bidwellii)(黑腐病);蔷薇科植物和刺柏上的锈菌属(Gymnosporangium),例如梨上的G.sabinae(锈病);玉米、禾谷类和稻上的长蠕孢属(同义词内脐蠕孢属,有性型:旋孢腔菌属);驼孢锈菌属(Hemileia),例如咖啡上的咖啡驼孢锈菌(H.vastatrix)(咖啡叶锈病);葡萄藤上的褐斑拟棒束孢(Isariopsis clavispora)(同义词Cladosporium vitis);大豆和棉花上的菜豆壳球孢(Macrophomina phaseolina(同义词phaseoli))(根腐病和茎腐病);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M.fructigena(花腐病和枝腐病,褐腐病);禾谷类、香蕉、浆果和花生上的球腔菌属(Mycosphaerella),例如小麦上的禾生球腔菌(M.graminicola)(无性型:小麦壳针孢(Septoria tritici),壳针孢叶斑病)或香蕉上的斐济球腔菌(M.fijiensis)(Sigatoka黑斑病);卷心菜(例如芸苔霜霉(P.brassicae))、油菜(例如寄生霜霉(P.parasitica))、洋葱(例如大葱霜霉(P.destructor))、烟草(烟草霜霉(P.tabacina))和大豆(例如大豆霜霉病菌(P.manshurica))上的霜霉属(Peronospora)(霜霉病);大豆上的豆薯层锈菌(Phakopsorapachyrhizi)和山马蟥层锈菌(P.Meibomiae)(大豆锈病);例如葡萄藤(例如P.Tracheiphila和P.tetraspora)和大豆(例如大豆茎褐腐病菌(P.gregata):茎病害)上的瓶霉菌属(Phialophora);油菜和卷心菜上的黑胫茎点霉(Phoma lingam)(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,叶斑病和立枯病);向日葵、葡萄藤(例如葡萄黑腐病菌(P.viticola):茎斑病和叶斑病)和大豆(例如茎枯病: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(例如辣椒疫霉(P.capsici))、大豆(例如大豆疫霉(P.megasperma),同义词P.sojae)、土豆和西红柿(例如致病疫霉(P.infestans):晚疫病)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(Plasmodiophorabrassicae)(根肿病);霜霉属(Plasmopara),例如葡萄藤上的葡萄生单轴霉(P.viticola)(葡萄藤霜霉病)和向日葵上的霍尔斯单轴霉(P.halstedii);蔷薇科植物、啤酒花、仁果和浆果上的叉丝单囊壳属(Podosphaera)(白粉病),例如苹果上的苹果白粉病菌(P.leucotricha);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)(眼斑病,有性型:Tapesiayallundae);各种植物上的假霜霉属(Pseudoperonospora)(霜霉病),例如葫芦上的古巴假霜霉(P.cubensis)或啤酒花上的葎草假霜(P.humili);葡萄藤上的Pseudopezicula tracheiphila(葡萄角斑叶焦病菌或‘rotbrenner’,无性型:瓶霉属(Phialophora));各种植物上的柄锈菌属(Puccinia)(锈病),例如禾谷类如小麦、大麦或黑麦上的小麦柄锈菌(P.triticina)(褐锈病或叶锈病),条形柄锈病(P.striiformis)(条锈病或黄锈病),大麦柄锈病(P.hordei)(黄矮叶锈病),禾柄锈菌(P.graminis)(茎锈病或黑锈病)或小麦叶锈菌(P.recondita)(褐锈病或叶锈病),以及芦笋上的柄锈菌属(例如天门冬属柄锈病(P.asparagi));小麦上的小麦黄斑叶枯病菌(Pyrenophora(无性型:Drechslera)tritici-repentis)(黄斑病)或大麦上的大麦网斑内脐蠕孢(P.teres)(网斑病);梨孢属(Pyricularia),例如稻上的稻瘟病菌(P.oryzae)(有性型:Magnaporthe grisea,稻瘟病)以及草坪和禾谷类上的稻梨孢菌(P.grisea);草坪、稻、玉米、小麦、棉花、油菜、向日葵、大豆、糖用甜菜、蔬菜和各种其他植物(例如终极腐霉菌(P.ultimum)或瓜果腐霉(P.aphanidermatum))上的腐霉属(Pythium)(立枯病);柱隔孢属(Ramularia),例如大麦上的R.collo-cygni(Ramularia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、土豆、草坪、玉米、油菜、糖用甜菜、蔬菜和各种其他植物上的丝核菌属(Rhizoctonia),例如大豆上的立枯丝核菌(R.solani)(根腐病和茎腐病),稻上的R.solani(纹枯病)或小麦或大麦上的禾谷丝核菌(R.Cerealis)(Rhizoctonia纹枯病);草莓、胡萝卜、卷心菜、葡萄藤和西红柿上的葡枝根霉(Rhizopus stolonifer)(黑霉病,软腐病);大麦、黑麦和小黑麦上的黑麦喙孢(Rhynchosporium secalis)(褐斑病);稻上的稻帚枝霉(Sarocladium oryzae)和S.attenuatum(叶鞘腐败病);蔬菜和大田作物如油菜、向日葵(例如核盘菌(S.sclerotiorum))和大豆(例如S.rolfsii或核盘菌S.sclerotiorum)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)(壳针孢叶斑病)和禾谷类上的颖枯壳多孢(S.(同义词Stagonospora)nodorum)(叶花斑枯病);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):丝黑穗病)、高粱和甘蔗上的轴黑粉菌属(Sphacelotheca)(黑穗病);葫芦上的单丝壳白粉菌(Sphaerothecafuliginea)(白粉病);土豆上的粉痂菌(Spongospora subterranea)(粉痂病)以及由此传播的病毒病害;禾谷类上的壳多孢属(Stagonospora),例如小麦上的颖枯壳多孢(S.nodorum)(叶花斑枯病,有性型:颖枯球腔菌(Leptosphaeria[同义词Phaeosphaeria]nodorum));土豆上的马铃薯癌肿病菌(Synchytrium endobioticum)(土豆癌肿病);外囊菌属(Taphrina),例如桃上的畸形外囊菌(T.Deformans)(缩叶病)和李上的李外囊菌(T.pruni)(囊果李);烟草、仁果、蔬菜、大豆和棉花上的根串珠霉属(Thielaviopsis)(黑色根腐病),例如黑色根腐病菌(T.basicola)(同义词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);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))上的单孢锈属(Uromyces)(锈病);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、葡萄藤、浆果、蔬菜和大田作物上的轮生菌属(Verticillium)(枯萎病),例如草莓、油菜、土豆和西红柿上的茄黄萎病菌(V.dahliae)。
化合物I及其组合物分别还适合防治有害真菌以保护材料(例如木材、纸张、漆分散体、纤维或织物)和保护储藏的产品。对于木材和建筑材料的保护,特别应注意下列有害真菌:子囊菌纲真菌,例如线嘴壳属,长喙壳属,出芽短梗霉(Aureobasidium pullulans),Sclerophoma spp.,毛壳属(Chaetomium),腐质霉属(Humicola),彼得壳属(Petriella),毛束霉属(Trichurus);担子菌纲真菌,例如粉孢革菌属(Coniophora),革盖菌属(Coriolus),粘褶菌属(Gloeophyllum),香菇属(Lentinus),侧耳属(Pleurotus),卧孔属(Poria),干朽菌属(Serpula)和干酪菌属(Tyromyces),半知菌纲真菌,例如曲霉属(Aspergillus),枝孢属,青霉属(Penicillium),木霉属(Trichorma),链格孢属,拟青霉属(Paecilomyces)和接合菌纲(Zygomycetes)真菌,例如毛霉属(Mucor),此外在储藏产品保护中应注意下列酵母真菌:假丝酵母属(Candida)和酿酒酵母(Saccharomyces cerevisae)。
本发明组合对有用植物的施用还可能导致作物产量的提高。
式I化合物可以以其生物学活性可能不同的不同晶型存在。它们同样为本发明主题。
化合物I直接或以组合物形式通过用杀真菌有效量的活性物质处理真菌或需要防止真菌侵袭的植物、植物繁殖材料如种子、土壤、表面、材料或空间而使用。施用可以在植物、植物繁殖材料如种子、土壤、表面、材料或空间被真菌侵染之前和之后进行。
植物繁殖材料可以在播种或移栽时或在播种或移栽之前用包含至少一种化合物I的组合物预防性地处理。
本发明还涉及包含溶剂或固体载体以及至少一种化合物I的农化组合物以及在防治有害真菌中的用途。
农化组合物包含杀真菌有效量的化合物I。术语“有效量”指足以在栽培植物上或在材料保护中防治有害真菌且不对被处理植物引起显著损害的量的组合物或化合物I。该量可以在宽范围内变化且取决于许多因素如待防治的真菌、被处理的各种栽培植物或材料、气候条件和所用具体化合物I。
化合物I、II和任选的III可以转化成农化组合物常用的类型,例如溶液、乳液、悬浮液、粉剂、粉末、糊和颗粒。组合物的类型取决于特定的意欲目的;在每种情况下应确保本发明化合物精细和均匀分布。
组合物类型的实例是悬浮液(SC、OD、FS),糊,锭剂,可湿性粉末或粉剂(WP、SP、SS、WS、DP、DS)或可以是水溶性的或可湿性的颗粒(GR、FG、GG、MG),还有处理植物繁殖材料如种子的凝胶配制剂(GF)。
组合物类型(例如SC、OD、FS、WG、SG、WP、SP、SS、WS、GF)通常稀释后使用。组合物类型如DP、DS、GR、FG、GG和MG通常不经稀释使用。
组合物以已知方式制备(参见US 3,060,084,EP-A 707 445(对于液体浓缩物),Browning:“Agglomeration”,Chemical Engineering,1967年12月4日,147-48,Perry’s Chemical Engineer’s Handbook,第4版,McGraw-Hill,New York,1963,第8-57及后续页,WO91/13546,US 4,172,714,US 4,144,050,US 3,920,442,US 5,180,587,US 5,232,701,US 5,208,030,GB 2,095,558,US 3,299,566,Klingman:Weed Control as a Science(John Wiley &Sons,New York,1961),Hance等:Weed Control Handbook(第8版,Blackwell Scientific,Oxford,1989)以及Mollet,H.和Grubemann,A.:FormulationTechnology(Wiley VCH Verlag,Weinheim,2001)。
农化组合物还可以包含常用于农化组合物的助剂。所用助剂分别取决于特定的施用形式和活性物质。
合适助剂的实例是溶剂,固体载体,分散剂或乳化剂(例如其他加溶剂、保护性胶体、表面活性剂和粘附剂),有机和无机增稠剂、杀菌剂、防冻剂、消泡剂,合适的话还有着色剂和增粘剂或粘合剂(例如用于种子处理配制剂)。
合适的溶剂是水,有机溶剂,例如中至高沸点的矿物油馏分如煤油或柴油,此外还有煤焦油,以及植物或动物来源的油,脂族、环状和芳族烃类,例如甲苯、二甲苯、石蜡、四氢化萘、烷基化萘或其衍生物,醇类如甲醇、乙醇、丙醇、丁醇和环己醇,二元醇,酮类如环己酮和γ-丁内酯,脂肪酸二甲基酰胺,脂肪酸和脂肪酸酯以及强极性溶剂,例如胺类如N-甲基吡咯烷酮。
固体载体为矿土如硅酸盐、硅胶、滑石、高岭土、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、脲类;以及植物来源的产品如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉和其他固体载体。
合适的表面活性剂(助剂、润湿剂、增粘剂、分散剂或乳化剂)是芳族磺酸如木素磺酸(类型,挪威Borregaard)、苯酚磺酸、萘磺酸(类型,Akzo Nobel,USA)、二丁基萘磺酸(类型,德国BASF)以及脂肪酸的碱金属、碱土金属和铵盐,烷基磺酸盐,烷基芳基磺酸盐,烷基硫酸盐,月桂基醚硫酸盐,脂肪醇硫酸盐,以及硫酸化十六-、十七-和十八烷醇的盐,硫酸化脂肪醇乙二醇醚的盐,此外还有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,以及蛋白质,变性蛋白,多糖(例如甲基纤维素),疏水改性淀粉,聚乙烯醇(类型,瑞士Clariant),聚羧酸盐(类型,德国BASF),聚烷氧基化物,聚乙烯胺(类型,德国BASF),聚乙烯吡咯烷酮及其共聚物。
增稠剂(即赋予组合物以改性的流动性能,即静止状态下的高粘度和搅动过程中的低粘度的化合物)的实例是多糖以及有机和无机粘土如黄原胶(CP Kelco,USA),23(法国Rhodia)、(R.T.Vanderbilt,USA)或(Engelhard Corp.,NJ,USA)。
可以加入杀菌剂来保存和稳定该组合物。合适杀菌剂的实例是基于双氯酚和苄醇半缩甲醛的那些(ICI的或Thor Chemie的RS和Rohm&Haas的MK),以及异噻唑啉酮衍生物如烷基异噻唑啉酮类和苯并异噻唑啉酮类(Thor Chemie的MBS)。
合适防冻剂的实例是乙二醇、丙二醇、尿素和甘油。
消泡剂实例是聚硅氧烷乳液(例如SRE,德国Wacker或法国Rhodia),长链醇,脂肪酸,脂肪酸盐,有机氟化合物及其混合物。
合适的着色剂是低水溶性颜料和水溶性染料。可以提到的实例是以下列名称已知的染料和颜料:若丹明B、C.I.颜料红112、C.I.溶剂红1、颜料蓝15:4、颜料蓝15:3、颜料蓝15:2、颜料蓝15:1、颜料蓝80、颜料黄1、颜料黄13、颜料红112、颜料红48:2、颜料红48:1、颜料红57:1、颜料红53:1、颜料橙43、颜料橙34、颜料橙5、颜料绿36、颜料绿7、颜料白6、颜料棕25、碱性紫10、碱性紫49、酸性红51、酸性红52、酸性红14、酸性蓝9、酸性黄23、碱性红10、碱性红108。
增粘剂或粘合剂的实例是聚乙烯吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇和纤维素醚(日本Shin-Etsu)。
粉末、撒播用材料和粉剂可以通过将化合物I以及合适的话其他活性物质与至少一种固体载体混合或同时研磨而制备。
颗粒如涂覆颗粒、浸渍颗粒和均质颗粒可以通过将活性物质与固体载体粘附而制备。固体载体的实例是矿土如硅胶、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、脲;以及植物来源的产品如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉和其他固体载体。
组合物类型的实例是:
1.用水稀释的组合物类型
i)水溶性浓缩物(SL,LS)
将10重量份本发明活性化合物溶于90重量份水或水溶性溶剂中。作为替换,加入润湿剂或其他助剂。活性物质在用水稀释时溶解。以此方式得到活性物质含量为10重量%的组合物。
ii)分散性浓缩物(DC)
将20重量份本发明活性化合物溶于70重量份环己酮中并加入10重量份分散剂如聚乙烯吡咯烷酮。用水稀释得到分散体。活性物质含量为20重量%。
iii)可乳化浓缩物(EC)
将15重量份本发明活性化合物溶于75重量份二甲苯中并加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(在每种情况下5重量份)。用水稀释得到乳液。该组合物的活性物质含量为15重量%。
iv)乳液(EW,EO,ES)
将25重量份本发明活性化合物溶于35重量份二甲苯中并加入十二烷基苯磺酸钙和蓖麻油乙氧基化物(在每种情况下5重量份)。借助乳化机(Ultraturrax)将该混合物引入30重量份水中并制成均相乳液。用水稀释得到乳液。该组合物的活性物质含量为25重量%。
v)悬浮液(SC,OD,FS)
在搅拌的球磨机中将20重量份本发明活性化合物粉碎并加入10重量份分散剂和润湿剂以及70重量份水或有机溶剂,得到细碎活性物质悬浮液。用水稀释得到稳定的活性物质悬浮液。该组合物的活性物质含量为20重量%。
vi)水分散性颗粒和水溶性颗粒(WG,SG)
将50重量份本发明活性化合物细碎研磨并加入50重量份分散剂和润湿剂,借助工业装置(例如挤出机、喷雾塔、流化床)将其制成水分散性或水溶性颗粒。用水稀释得到稳定的活性物质分散体或溶液。该组合物的活性物质含量为50重量%。
vii)水分散性粉末和水溶性粉末(WP,SP,SS,WS)
将75重量份本发明活性化合物在转子-定子磨机中研磨并加入25重量份分散剂、润湿剂和硅胶。用水稀释得到稳定的活性物质分散体或溶液。该组合物的活性物质含量为75重量%。
viii)凝胶(GF)
在搅拌的球磨机中研磨20重量份本发明活性化合物并加入10重量份分散剂、1重量份胶凝剂润湿剂和70重量份水或有机溶剂而得到活性物质的精细悬浮液。用水稀释得到活性物质的稳定悬浮液,由此得到含20重量%活性物质的组合物。
2.不经稀释施用的组合物类型
ix)可撒粉粉末(DP,DS)
将5重量份本发明活性化合物细碎研磨并与95重量份细碎高岭土充分混合。这得到活性物质含量为5重量%的可撒粉组合物。
x)颗粒(GR,FG,GG,MG)
将0.5重量份本发明活性化合物细碎研磨并结合99.5重量份载体。常见方法是挤出、喷雾干燥或流化床方法。这得到活性物质含量为0.5重量%的不经稀释而施用的颗粒。
xi)ULV溶液(UL)
将10重量份本发明活性化合物溶于90重量份有机溶剂如二甲苯中。这得到活性物质含量为10重量%的不经稀释而施用的组合物。
农化组合物通常包含0.01-95重量%,优选0.1-90重量%,最优选0.5-90重量%的活性物质。活性物质以90-100%,优选95-100%的纯度(根据NMR光谱)使用。
为了处理植物繁殖材料,尤其是种子,通常使用水溶性浓缩物(LS),流动性浓缩物(FS),干处理用粉末(DS),淤浆处理用水分散性粉末(WS),水溶性粉末(SS),乳液(ES),可乳化浓缩物(EC)和凝胶(GF)。这些组合物可以经稀释或不经稀释施用于繁殖材料,尤其是种子上。所述组合物在稀释2-10倍后使即用制剂中的活性物质浓度为0.01-60重量%,优选0.1-40重量%。施用可以在播种之前进行。分别将农化化合物及其组合物施用于植物繁殖材料,尤其是种子上或在其上处理的方法由本领域已知且包括繁殖材料的拌种、包衣、造粒、撒粉和浸泡施用方法。在优选实施方案中,化合物或其组合物分别通过不诱发萌发的方法,例如通过拌种、造粒、包衣和撒粉施用于植物繁殖材料上。
在优选实施方案中,将悬浮液类型(FS)的组合物用于种子处理。FS组合物通常可以包含1-800g/l活性物质,1-200g/l表面活性剂,0-200g/l防冻剂,0-400g/l粘合剂,0-200g/l颜料和至多1升溶剂,优选水。
活性物质可以直接或以其组合物形式(例如以可直接喷雾溶液、粉末、悬浮液、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)通过喷雾、雾化、撒粉、撒播、刷涂、浸渍或浇灌来施用。施用形式完全取决于意欲的目的;意欲在每种情况下确保本发明活性物质的最佳可能分布。
含水施用形式可通过加入水由乳液浓缩物、糊或可湿性粉末(可喷雾粉末、油分散体)制备。为制备乳液、糊或油分散体,可借助润湿剂、增粘剂、分散剂或乳化剂将该物质直接或溶于油或溶剂中后在水中均化。或者,可以制备由活性物质、润湿剂、增粘剂、分散剂或乳化剂以及合适的话溶剂或油组成的浓缩物且该类浓缩物适于用水稀释。
即用制剂中的活性物质浓度可以在较宽范围内变化。它们通常为0.0001-10重量%,优选0.001-1重量%的活性物质。
活性物质也可成功用于超低容量法(ULV),其中可以施用包含超过95重量%活性物质的组合物,或甚至施用不含添加剂的活性物质。
当用于植物保护中时,活性物质的施用量取决于所需效果的种类为0.01-2.0kg/ha。
在例如通过撒粉、包衣或浸透种子而进行的植物繁殖材料如种子的处理中,活性物质的用量通常为1-1000g/100kg,优选5-100g/100kg种子。
当用于保护材料或储存产品中时,活性物质的施用量取决于施用区域的种类和所需效果。在材料保护中常用的施用量例如为0.001g-2kg,优选0.005g-1kg活性物质/立方米被处理材料。
可以向活性物质或包含它们的组合物中加入各种类型的油、润湿剂、辅助剂、除草剂、杀菌剂、其他杀真菌剂和/或杀虫剂,合适的话在紧临使用前加入(桶混合)。这些试剂可以以1∶100-100∶1,优选1∶10-10∶1的重量比与本发明组合物混合。
可以使用的助剂尤其是有机改性的聚硅氧烷,例如Break Thru S醇烷氧基化物,例如AtplusAtplus MBAPlurafacLF和Lutensol ONEO/PO嵌段聚合物,例如Pluronic RPE和Genapol醇乙氧基化物,例如Lutensol XP以及磺基琥珀酸二辛酯钠,例如Leophen
呈杀真菌剂使用形式的本发明组合物还可以与其他活性物质(例如除草剂、杀虫剂、生长调节剂、杀真菌剂或肥料)一起作为预混物存在或合适的话在紧临施用前混合(桶混合)。
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(例如以可直接喷雾溶液、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)通过喷雾、雾化、撒粉、撒播或浇灌来使用。使用形式完全取决于意欲的目的;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,可借助润湿剂、增粘剂、分散剂或乳化剂将该物质直接或溶于油或溶剂中后在水中均化。然而,还可以制备由活性物质、润湿剂、增粘剂、分散剂或乳化剂以及合适的话溶剂或油组成的浓缩物且该类浓缩物适于用水稀释。
即用制剂中的活性化合物浓度可以在较宽范围内变化。它们通常为0.0001-10重量%,优选0.01-1重量%。
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%活性化合物的组合物,或甚至施用不含添加剂的活性化合物。
可以向活性化合物中加入各种类型的油、润湿剂或辅助剂,合适的话甚至在紧临使用前加入(桶混合)。这些试剂通常以1∶100-100∶1,优选1∶10-10∶1的重量比与本发明组合物混合。
就此而言助剂尤其是有机改性的聚硅氧烷,例如Break Thru S醇烷氧基化物,例如AtplusAtplus MBAPlurafacLF和Lutensol ONEO/PO嵌段聚合物,例如Pluronic RPE和Genapol醇乙氧基化物,例如Lutensol XP以及磺基琥珀酸二辛酯钠,例如Leophen
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用化合物I和II处理有害真菌,需要防止有害真菌的植物、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。
本发明单个化合物和协同增效活性混合物的杀真菌作用由下列试验证实。
A)微滴定试验
在二甲亚砜中将活性化合物单独配制成浓度为10000ppm的储备溶液。将产品乐果、溴氰菊酯、氯氟氰菊酯、齐墩螨素、灭蚁腙、杀螨锡和二唑虫以市售成品配制剂使用并用水稀释至所述活性化合物浓度。将测量的参数与不含活性化合物的对照方案的生长(100%)和不含真菌且不含活性化合物的空白值比较以确定病原体在各活性化合物中的相对生长百分数。
将这些百分数转化成效力。
效力为0表示病原体的生长水平对应于未处理对照的水平;效力为100表示病原体不生长。
活性化合物混合物的预期效力使用Colby公式(Colby,S.R.“计算除草剂组合的协同增效和拮抗响应”,Weeds,15,第20-22页,1967)确定并与观察到的效力比较。
Colby公式:E=x+y-x×y/100
E以浓度a和b使用活性化合物A和B的混合物时的预期效力,以未处理对照的%表示
x以浓度a使用活性化合物A时的效力,以未处理对照的%表示
y以浓度b使用活性化合物B时的效力,以未处理对照的%表示
应用实施例1:对晚疫病病原体致病疫霉的活性
根据配比将储备溶液混合,用移液管将其移到微滴定板(MTP)上并用水稀释至所示浓度。然后加入致病疫霉在豌豆汁水溶液中的游动孢子悬浮液。将各板置于温度为18℃的水蒸气饱和室中。接种7天后使用吸收光度计在405nm下测量MTP。将测量的参数与不含活性物质的对照方案的生长(=100%)以及不含真菌和活性物质的空白值相比较,以确定病原体在各活性物质中的相对生长百分数。
应用实施例2:对稻瘟病病原体稻瘟病菌的活性
根据配比将储备溶液混合,用移液管将其移到微滴定板(MTP)上并用水稀释至所示浓度。然后加入稻瘟病菌在生物麦芽水溶液中的孢子悬浮液。将各板置于温度为18℃的水蒸气饱和室中。接种7天后使用吸收光度计在405nm下测量MTP。将测量的参数与不含活性物质的对照方案的生长(=100%)以及不含真菌和活性物质的空白值相比较,以确定病原体在各活性物质中的相对生长百分数。
表10
应用实施例3:对小麦壳针孢在小麦上引起的叶斑病的活性
根据配比将储备溶液混合,用移液管将其移到微滴定板(MTP)上并用水稀释至所示浓度。然后加入小麦壳针孢在生物麦芽水溶液中的孢子悬浮液。将各板置于温度为18℃的水蒸气饱和室中。接种7天后使用吸收光度计在405nm下测量MTP。将测量的参数与不含活性物质的对照方案的生长(=100%)以及不含真菌和活性物质的空白值相比较,以确定病原体在各活性物质中的相对生长百分数。
表11
应用实施例4:对早疫链格孢的活性
根据配比将储备溶液混合,用移液管将其移到微滴定板(MTP)上并用水稀释至所示浓度。然后加入早疫链格孢在生物麦芽水溶液中的孢子悬浮液。将各板置于温度为18℃的水蒸气饱和室中。接种7天后使用吸收光度计在405nm下测量MTP。
表12
应用实施例5:对大豆炭疽病菌的活性
根据配比将储备溶液混合,用移液管将其移到微滴定板(MTP)上并用水稀释至所示浓度。然后加入大豆炭疽病菌在生物麦芽水溶液中的孢子悬浮液。将各板置于温度为18℃的水蒸气饱和室中。接种7天后使用吸收光度计在405nm下测量MTP。
表13
应用实施例6:对颖枯球腔菌(Leptospharium nodorum)的活性
根据配比将储备溶液混合,用移液管将其移到微滴定板(MTP)上并用水稀释至所示浓度。然后加入颖枯球腔菌在生物麦芽水溶液中的孢子悬浮液。将各板置于温度为18℃的水蒸气饱和室中。接种7天后使用吸收光度计在405nm下测量MTP。
表14
应用实施例7:对大刀镰孢的活性
根据配比将储备溶液混合,用移液管将其移到微滴定板(MTP)上并用水稀释至所示浓度。然后加入大刀镰孢在生物麦芽水溶液中的孢子悬浮液。将各板置于温度为18℃的水蒸气饱和室中。接种7天后使用吸收光度计在405nm下测量MTP。
表15
B)温室测试
使用溶剂/乳化剂体积比为99∶1的丙酮和/或二甲亚砜(DMSO)与乳化剂Wettol EM 31(基于乙氧基化烷基酚的具有乳化和分散作用的润湿剂)的混合物将活性物质分开或一起配制成包含25mg活性物质并配成10ml的储备溶液。用水将该溶液配成100ml。用所述溶剂/乳化剂/水混合物将该储备溶液稀释至下面所给活性物质浓度。
应用实施例8:对西红柿上由致病疫霉引起的早疫病的活性,保护性施用
使西红柿植物的幼苗盆中生长。用活性物质浓度如下所述的含水悬浮液喷雾植物至滴流。第二天将处理过的植物用致病疫霉的孢子囊含水悬浮液接种。接种之后将试验植物立即转移到潮湿室中。在18-20℃和接近100%的相对湿度下6天之后,以患病叶面积百分数肉眼评价叶子上的真菌侵袭程度。
应用实施例9:在小麦上对小麦叶锈菌(小麦褐锈病)的治疗作用
用小麦褐锈病病菌(小麦叶锈菌)的孢子悬浮液对栽培品种为“Kanzler”的盆栽小麦秧苗的叶子撒粉。然后使植物在高大气湿度(90-95%)的室中于20-22℃下放置24小时。在此期间,孢子萌发并且芽管穿透到叶组织中。第二天将侵染的植物用活性物质浓度如下所述的含水悬浮液喷雾至滴流点。在喷雾悬浮液干燥之后,将试验植物送回温室中并在20-22℃的温度和65-70%相对大气湿度下再栽培7天。然后肉眼测定叶子上的锈病发展程度。
应用实施例10:在小麦上对小麦叶锈菌(小麦褐锈病)的保护作用
将栽培品种为“Kanzler”的盆栽小麦秧苗的叶子用活性物质浓度如下所述的含水悬浮液喷雾至滴流点。第二天将处理过的植物用小麦褐锈病病菌(小麦叶锈菌)的孢子悬浮液撒粉。然后将植物在高大气湿度(90-95%)的室中于20-22℃下放置24小时。在此期间,孢子萌发并且芽管穿透到叶组织中。第二天将试验植物送回温室中并在20-22℃的温度和65-70%的相对大气湿度下再栽培7天。然后肉眼测定叶子上的锈病发展程度。
应用实施例11:在小麦上对小麦白粉菌(Blumeria graminis tritici)(小麦白粉病菌)的保护作用
将栽培品种为“Kanzler”的盆栽小麦秧苗的叶子用活性物质浓度如下所述的含水悬浮液喷雾至滴流点。第二天将处理过的植物用小麦白粉菌的孢子悬浮液撒粉。然后将植物送回温室中并在20-24℃的温度和60-90%的相对大气湿度下再栽培7天。然后肉眼测定叶子上的白粉病发展程度。
应用实施例12:在黄瓜上对单丝壳白粉菌(黄瓜白粉病菌)的保护作用
将盆栽黄瓜秧苗(处于胚叶阶段)的叶子用活性物质浓度如下所述的含水悬浮液喷雾至滴流点。第二天将处理过的植物用黄瓜白粉病菌的孢子悬浮液撒粉。然后将植物送回温室中并在20-24℃的温度和60-80%的相对大气湿度下再栽培7天。然后肉眼测定叶子上的白粉病发展程度。
Claims (16)
1.一种防治植物病原性有害真菌的混合物,以协同增效有效量包含如下组分作为活性组分:
1)至少一种式I的1-甲基吡唑-4-基甲酰苯胺:
其中各取代基如下所定义:
R1为C1-C4烷基或C1-C4卤代烷基;
R2为氢或卤素;
X为氢或氟;
Q为直接键、亚环丙基或稠合双环[2.2.1]庚烷环;
R3为C1-C6烷基、环丙基或被2或3个卤原子取代的苯基;
和
2)至少一种选自如下的活性化合物II:
选自如下的拟除虫菊酯:丙烯除虫菊、氟氯菊酯、氟氯氰菊酯、(RS)氯氟氰菊酯、苯醚氰菊酯、氯氰菊酯、甲体氯氰菊酯、乙体氯氰菊酯、己体氯氰菊酯、溴氰菊酯、高氰戊菊酯、醚菊酯、甲氰菊酯、杀灭菊酯、咪炔菊酯、氯氟氰菊酯、氯菊酯、炔酮菊酯、除虫菊酯I和酯II、灭虫菊、灭虫硅醚、氟胺氰菊酯、七氟菊酯、胺菊酯、四溴菊酯、四氟菊酯、丙氟菊酯和四氟甲醚菊酯。
2.根据权利要求1的混合物,包含其中R1为C1-C4卤代烷基,R2为氢,Q为直接键且R3为被2或3个卤原子取代的苯基的式I的1-甲基吡唑-4-基甲酰苯胺作为组分1)。
3.根据权利要求1的混合物,包含其中R1为C1-C4卤代烷基,R2为氢,X为氢,Q为稠合双环[2.2.1]庚烷环且R3为C1-C4烷基的式I的1-甲基吡唑-4-基甲酰苯胺作为组分1)。
4.根据权利要求1的混合物,包含其中R1为C1-C4卤代烷基,R2为氢,X为氢,Q为亚环丙基且R3为环丙基的式I的1-甲基吡唑-4-基甲酰苯胺作为组分1)。
5.根据权利要求1的混合物,包含其中R1为C1-C4烷基,R2为卤素,X为氢,Q为直接键且R3为C1-C6烷基的式I的1-甲基吡唑-4-基甲酰苯胺作为组分1)。
6.根据权利要求1的混合物,其中R1为甲基或卤代甲基。
7.根据权利要求1-6中任一项的混合物,包含额外的活性化合物。
8.根据权利要求1-6中任一项的混合物,以100∶1-1∶100的重量比包含组分1)和2)。
9.一种组合物,包含至少一种液体或固体载体和根据权利要求1-6中任一项的混合物。
10.一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1-6中任一项的至少一种组分1)和至少一种组分2)处理真菌,其栖息地,需要防止真菌侵袭的植物,土壤,种子,区域,材料或空间。
11.根据权利要求10的方法,其中同时,即联合或分开,或依次施用根据权利要求1-6中任一项的组分1)和2)。
12.根据权利要求10或11的方法,其中根据权利要求1-6中任一项的组分1)和2)以5-2000g/ha的量施用。
13.根据权利要求10或11的方法,其中根据权利要求1-6中任一项的组分1)和2)以1-1000g/100kg种子的量施用。
14.一种通过将根据权利要求1-6中任一项的混合物以1-1000g/100kg种子的量施用于种子而处理种子的方法。
15.根据权利要求1-6中任一项的组分1)和2)在制备适合防治有害真菌的组合物中的用途。
16.根据权利要求1-6中任一项的组分1)和2)在处理转基因植物或其种子中的用途。
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- 2009-07-02 AU AU2009265697A patent/AU2009265697B2/en not_active Ceased
- 2009-07-02 KR KR1020117002742A patent/KR20110026018A/ko not_active Application Discontinuation
- 2009-07-02 JP JP2011515457A patent/JP5530428B2/ja not_active Expired - Fee Related
- 2009-07-02 CA CA2728887A patent/CA2728887A1/en not_active Abandoned
- 2009-07-02 US US13/002,127 patent/US8871679B2/en active Active
- 2009-07-02 CN CN201310153909.6A patent/CN103250712A/zh active Pending
- 2009-07-02 CN CN200980125970.1A patent/CN102083315B/zh active Active
- 2009-07-02 EA EA201100127A patent/EA018990B1/ru not_active IP Right Cessation
- 2009-07-02 MX MX2011000077A patent/MX2011000077A/es not_active Application Discontinuation
- 2009-07-02 EP EP09772490.0A patent/EP2306834B1/en active Active
- 2009-07-02 BR BRPI0914606-7A patent/BRPI0914606B1/pt active IP Right Grant
- 2009-07-02 WO PCT/EP2009/058298 patent/WO2010000790A1/en active Application Filing
- 2009-07-02 UA UAA201101138A patent/UA101382C2/ru unknown
- 2009-07-03 AR ARP090102517A patent/AR072549A1/es active IP Right Grant
- 2009-07-03 UY UY0001031961A patent/UY31961A/es unknown
- 2009-07-03 TW TW098122669A patent/TW201006384A/zh unknown
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- 2010-12-21 IL IL210140A patent/IL210140A/en not_active IP Right Cessation
- 2010-12-30 CL CL2010001648A patent/CL2010001648A1/es unknown
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- 2011-01-24 MA MA33553A patent/MA32500B1/fr unknown
- 2011-01-24 CR CR20110043A patent/CR20110043A/es not_active Application Discontinuation
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Also Published As
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AR072549A1 (es) | 2010-09-08 |
BRPI0914606B1 (pt) | 2023-11-21 |
IL210140A (en) | 2014-08-31 |
JP5530428B2 (ja) | 2014-06-25 |
AU2009265697A1 (en) | 2010-01-07 |
MX2011000077A (es) | 2011-02-24 |
UA101382C2 (ru) | 2013-03-25 |
EP2306834B1 (en) | 2018-09-12 |
US20150087510A1 (en) | 2015-03-26 |
CN102083315A (zh) | 2011-06-01 |
UY31961A (es) | 2010-01-29 |
EA018990B1 (ru) | 2013-12-30 |
CR20110043A (es) | 2011-02-16 |
CL2010001648A1 (es) | 2011-06-17 |
US20110098176A1 (en) | 2011-04-28 |
MA32500B1 (fr) | 2011-07-03 |
EA020599B1 (ru) | 2014-12-30 |
EP2306834A1 (en) | 2011-04-13 |
IL210140A0 (en) | 2011-03-31 |
TW201006384A (en) | 2010-02-16 |
AU2009265697B2 (en) | 2015-02-05 |
EA201201162A1 (ru) | 2013-02-28 |
CA2728887A1 (en) | 2010-01-07 |
BRPI0914606A2 (pt) | 2015-08-04 |
WO2010000790A1 (en) | 2010-01-07 |
US8871679B2 (en) | 2014-10-28 |
JP2011526599A (ja) | 2011-10-13 |
CN103250712A (zh) | 2013-08-21 |
KR20110026018A (ko) | 2011-03-14 |
EA201100127A1 (ru) | 2011-08-30 |
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