CN101541169A - 包含n-乙烯基酰胺共聚物的农业化学配制剂 - Google Patents
包含n-乙烯基酰胺共聚物的农业化学配制剂 Download PDFInfo
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- CN101541169A CN101541169A CNA2007800436184A CN200780043618A CN101541169A CN 101541169 A CN101541169 A CN 101541169A CN A2007800436184 A CNA2007800436184 A CN A2007800436184A CN 200780043618 A CN200780043618 A CN 200780043618A CN 101541169 A CN101541169 A CN 101541169A
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及包含至少一种农药和至少一种共聚物的配制剂,该共聚物以聚合形式包含:(a)式(I)的N-乙烯基酰胺共聚单体a)其中R1和R2相互独立地为氢或C1-C4烷基,优选氢,或R1和R2一起表示-(CH2)x结构部分,其与氮和羰基结构部分一起形成5-8元环,和(b)至少一种选自乙烯基吡啶、乙烯基吡啶衍生物和N-乙烯基咪唑的共聚单体b),基于上述配制剂的对抗有害昆虫和/或植物病原性真菌的方法,一种防治不希望的植物生长的方法和改善植物健康的方法。
Description
本发明涉及包含至少一种农药和至少一种共聚物的配制剂,该共聚物以聚合形式包含:
(a)式I的N-乙烯基酰胺共聚单体a):
其中R1和R2相互独立地为氢或C1-C4烷基,优选氢,或
R1和R2一起表示-(CH2)x结构部分,其与氮和羰基结构部分一起形成5-8元环,和
(b)至少一种选自乙烯基吡啶、乙烯基吡啶衍生物和N-乙烯基咪唑的共聚单体b),
基于上述配制剂的对抗有害昆虫和/或植物病原性真菌的方法,一种防治不希望的植物生长的方法和改善植物健康的方法。
内吸的农药向农民提供了许多益处:与用非内吸农药处理的植物相比,植物吸收农药(这可通过种子处理、叶面处理或土壤处理实现,其中同时或依次施用种子和各配制剂(如颗粒配制剂))产生对害虫具有更长抗性的植物。
对于提供植物健康效果的农药,希望增加它们在植物中的吸收。术语“植物健康”例如描述了下列有利性能:改善的作物特性包括但不限于:更好萌发、作物产量增加、更有利的蛋白质和/或含量、更有利的氨基酸和/或油组成、更发达的根系(改善根的生长)、分蘖增加、植物高度增加、叶片变大、死亡的基生叶更少、更强的分蘖、叶颜色更绿、色素含量、光合作用活性、需要更少的肥料、需要更少的种子、更能生产的分蘖、较早开花、谷物更早成熟、更少的植物寄生、枝生长增加、植物活力增加、植物直立增加或早期发芽;或至少两种或更多种上述作用的组合或本领域熟练技术人员熟知的任何其它优点。
然而,许多农药不显示令人满意的内吸作用。此外,内吸的农药的内吸作用还有改进的空间。
因此,本发明的目的是改进农药的内吸作用,优选改进具有低内吸或不具有内吸的农药的内吸作用。
许多简单用作增溶剂的聚合物在本领域是已知的。然而,将这些聚合物用于上述目的在现有技术中并没有公开过。
该目的通过提供包含至少一种农药和至少一种共聚物的配制剂而实现,该共聚物以聚合形式包含:
(a)式I的N-乙烯基酰胺共聚单体a):
其中R1和R2相互独立地为氢或C1-C4烷基,优选氢,或
R1和R2一起表示-(CH2)x结构部分,其与氮和羰基结构部分一起形成5-8元环,优选5-7元环,最优选5元环,和
(b)至少一种选自乙烯基吡啶、乙烯基吡啶衍生物和N-乙烯基咪唑的共聚单体b)。
术语至少一种共聚物是指一种或多种如上所定义的共聚物可存在于上述配制剂中,即如上所定义的共聚物的混合物。优选1、2或3种,更优选1或2种,最优选1种共聚物存在于上述配制剂中。
共聚单体a以90-10重量%,优选75-25重量%,最优选50重量%存在于聚合物中。
共聚单体b以90-10重量%,优选75-25重量%,优选50重量%存在于聚合物中。
共聚物的共聚单体a)和b)的重量%数据优选总计为100重量%。
优选共聚单体(a)为其中R1和R2一起表示-(CH2)x结构部分,其与氮和羰基结构部分一起形成5-8元环,优选5-7元环,最优选5元环的那些。
优选共聚单体(b)为乙烯基吡啶共聚单体。优选乙烯基吡啶共聚单体为2-乙烯基吡啶、3-乙烯基吡啶、4-乙烯基吡啶或乙烯基-2-甲基-5-吡啶,更优选2-乙烯基吡啶、3-乙烯基吡啶或4-乙烯基吡啶,更优选2-乙烯基吡啶或4-乙烯基吡啶,其中最优选4-乙烯基吡啶。
上述共聚物可为嵌段共聚物、交替共聚物或无规嵌段共聚物,优选无规嵌段共聚物。
共聚单体(b)的吡啶基和咪唑基结构部分可被季铵化。
共聚单体(b)转化为季铵化合物可在反应中或优选在反应后进行。在随后转化的情况下,可首先将中间体聚合物分离并提纯或直接转化。可全部或部分转化。优选将所掺入共聚单体(b)的至少10%,特别优选至少20%,非常特别优选至少30%转化为相应的季铵形式。转化为季铵化合物的程度优选与共聚单体(b)在水中的溶解度成相反比例。
优选将共聚单体(b)以基本呈潜阳离子形式,即超过70mol%,优选超过90mol%,特别优选超过95mol%,非常特别优选超过99mol%为潜阳离子,即不呈季铵化或质子化形式用于聚合,并仅通过在聚合过程中或特别优选在聚合后季铵化为阳离子或质子化形式。
在本发明的一个优选实施方案中,将所得共聚物仅在聚合过程中或特别优选在聚合之后部分或完全质子化或季铵化,这是因为用于聚合的共聚单体(b)优选为仅部分(如果有的话)季铵化或质子化的共聚单体。
共聚单体(b)可以质子化或季铵化形式使用,或优选以未季铵化或未质子化形式聚合,在后者的情况下将所得共聚物在聚合过程中或优选在聚合后季铵化或质子化以用于本发明。
在共聚单体以季铵化形式使用的情况下,它们可作为干燥物质,或以在适用于共聚单体的溶剂中,如在极性溶剂如水、甲醇、乙醇或丙酮中的浓缩溶液的形式使用,或以在其它共聚单体a)中的浓缩溶液使用,条件是这些共聚单体a)适合用作溶剂。
也可将所得共聚物质子化。
适用于质子化的化合物的实例为无机酸如HCl和H2SO4,一元羧酸如甲酸和乙酸,二元羧酸和多官能羧酸,如草酸和柠檬酸,和任何能够质子化合适的氮原子的其它给质子的化合物和物质。水溶性酸特别适用于质子化。
可提及的可行的有机酸为任选取代的一元和多元脂族和芳族羧酸,任选取代的一元和多元脂族和芳族磺酸或任选取代的一元和多元脂族和芳族膦酸。
优选有机酸为羟基羧酸如羟基乙酸、乳酸、酒石酸和柠檬酸,特别优选乳酸。
可提及的优选无机酸为磷酸、亚磷酸、硫酸、亚硫酸和盐酸,特别优选磷酸。
可将聚合物或者在聚合之后直接质子化或仅在配制各农药时质子化,其中在农药配制中通常将pH调节至可生理接受的值。
质子化理解为指至少将聚合物的一些可质子化基团,优选至少20mol%,优选超过50mol%,特别优选超过70mol%,非常特别优选超过90mol%质子化,导致在聚合物上总体产生阳离子电荷。
适用于季铵化化合物a)的反应试剂的实例为在烷基中具有1-24个碳原子的烷基卤,如甲基氯、甲基溴、甲基碘、乙基氯、乙基溴、丙基氯、己基氯、十二烷基氯、月桂基氯、丙基溴、己基溴、辛基溴、癸基溴、十二烷基溴,和苄基卤,特别是苄基氯和苄基溴。用长链烷基季铵化优选用相应的烷基溴如己基溴、辛基溴、癸基溴、十二烷基溴或月桂基溴进行。
其它合适的季铵化试剂为硫酸二烷基酯,特别是硫酸二甲酯或硫酸二乙酯。
基础共聚单体b)的季铵化也可用氧化烯如氧化乙烯或氧化丙烯在酸存在下进行。
优选季铵化试剂为甲基氯、硫酸二甲酯或硫酸二乙酯,特别优选甲基氯。
用一种所述季铵化试剂将共聚单体或聚合物季铵化可通过常规已知方法进行。
制备通过已知方法如溶液聚合、沉淀聚合或通过反相悬浮聚合使用在聚合条件下形成自由基的化合物进行。聚合可在反应混合物回流下或在加压下进行。
共聚单体a):共聚单体b)的摩尔比为90∶10-10∶90,优选75∶25-25∶75,优选50∶50。
聚合温度通常为30-200℃,优选40-150℃。
合适的偶氮化合物为2,2′-偶氮二异丁腈、2,2′-偶氮二(2-甲基丁腈)、2,2′-偶氮二(2,4-二甲基戊腈)、2,2′-偶氮二(4-甲氧基-2,4-二甲基戊腈)、1,1′-偶氮二(1-环己烷甲腈)、2,2′-偶氮二(异丁酰胺)二水合物、2-苯基偶氮-2,4-二甲基-4-甲氧基戊腈、2,2′-偶氮二异丁酸二甲酯、2-(氨基甲酰基偶氮)异丁腈、2,2′-偶氮二(2,4,4-三甲基戊烷)、2,2′-偶氮二(2-甲基丙烷)、2,2′-偶氮二(N,N′-二亚甲基异丁脒)(作为游离碱或盐酸盐),2,2′-偶氮二(2-脒基丙烷)(作为游离碱或盐酸盐),2,2′-偶氮二(2-甲基-N-[1,1-二(羟基甲基)乙基]丙酰胺)或2,2′-偶氮二(2-甲基-N-[1,1-二(羟基甲基)-2-羟基乙基]丙酰胺)。
合适的过氧化物例如为乙酰基环己烷磺酰基过氧化物、过氧二碳酸二异丙基酯、过新癸酸叔戊酯、过新癸酸叔丁酯、过新戊酸叔丁酯、过新戊酸叔戊酯、过氧化二(2,4-二氯苯甲酰)、过氧化二异壬酰、过氧化二癸酰、过氧化二辛酰、过氧化二月桂酰、过氧化二(2-甲基苯甲酰)、过氧化二琥珀酰、过氧化二乙酰、过氧化二苯甲酰、过-2-乙基己酸叔丁酯、过氧二(4-氯苯甲酰)、过异丁酸叔丁酯、过马来酸叔丁酯、1,1-二(叔丁基过氧)-3,5,5-三甲基环己烷、1,1-二(叔丁基过氧)环己烷、叔丁基过氧异丙基碳酸酯、过异壬酸叔丁酯、过乙酸叔丁酯、过苯甲酸叔戊酯、过苯甲酸叔丁酯、2,2-二(叔丁基过氧)丁烷、2,2-二-10-(叔丁基过氧)丙烷、过氧二枯基、2,5-二甲基-2,5-二(叔丁基过氧)己烷、3-(叔丁基过氧)-3-苯基2-苯并呋喃酮、过氧二(叔戊基)、α,α′-二(叔丁基过氧异丙基)苯、3,5-二(叔丁基过氧)-3,5-二甲基-1,2-二氧戊环、过氧二(叔丁基)、2,5-二甲基-2,5-二(叔丁基过氧)己炔、3,3,6,6,9,9-六甲基-1,2,4,5-四氧杂环壬烷、对萜烷过氧化氢、氢过氧化蒎烷、二异丙基苯、单-α-过氧化氢、枯烯过氧化氢或氢过氧化叔丁基。
所用反应介质为其中可溶解共聚单体的任何常规溶剂。优选使用水或醇溶剂,如甲醇、乙醇、正丙醇或异丙醇或这类溶剂与水的混合物。
为了确保反应产生均相产物,有利的是向反应溶液中分开供入共聚单体和引发剂。这例如可以各反应物的分开进料的形式进行。
如果需要建立较低分子量,则聚合也可在常规链转移剂存在下进行。
所得有机溶液的固含量通常为20-60重量%,尤其是20-40重量%。
因此,用于聚合的非水性溶剂可借助蒸汽蒸馏并通过水代替而除去。
共聚物的水溶液可通过各种干燥方法如喷雾干燥、流化喷雾干燥、转鼓干燥或冷冻干燥转化为粉末形式,可通过将其再分散于水中而制备水分散体或水溶液。
根据本发明使用的共聚物的通过凝胶渗透色谱法(G.Odian;Principles of Polymerization(聚合原理),第4版,Wiley & son 2004,第23+24页)测量的重均分子量可为20000-100000,优选50000-100000g/mol。
上述聚合物的所有实施方案在下文中简称为“本发明聚合物”。
本发明还包括本发明聚合物在增加农药的内吸作用中的用途。这通过将农药与一定量的本发明聚合物接触,如以上述农业化学配制剂而实现。
通常而言,配制剂包含0.1-99重量%,优选1-85重量%,更优选3-70重量%,最优选5-60重量%本发明聚合物。
通常而言,配制剂包含0.1-90重量%,优选1-85重量%,更优选3-80重量%,最优选3-70重量%农药。
聚合物:农药的重量比优选为20∶1-1∶20(重量/重量),更优选10∶1-1∶10(重量/重量),最优选3∶1-1∶3(重量/重量)。
对本发明而言,术语“至少一种农药”表示可选自杀真菌剂、杀虫剂、杀线虫剂、除草剂和/或安全剂或生长调节剂,优选选自杀真菌剂、杀虫剂或杀线虫剂,最优选选自杀真菌剂的一种或多种化合物。以及两种或更多种上述类的农药的混合物也可使用。本领域熟练技术人员对这类农药是熟悉的,其例如可在Pesticide Manual,第13版,(2003),The British CropProtection Council,London中找到。
下列农药意欲阐述可能的组合,但不施加任何限制:
杀虫剂/杀线虫剂选自下组:
下列可与本发明化合物一起使用的农药意欲阐述可能的组合,但不施加任何限制:
A.1.有机(硫代)磷酸酯类: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)、异噁唑磷(Isoxathion)、马拉硫磷(Malathion)、甲胺磷(Methamidophos)、杀扑磷(Methidathion)、甲基一六零五(Methyl-Parathion)、速灭磷(Mevinphos)、久效磷(Monocrotophos)、砜吸磷(Oxydemeton-methyl)、对氧磷(Paraoxon)、一六零五(Parathion)、稻丰散(Phenthoate)、伏杀磷(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)、乙丙硫磷(Sulprophos)、杀虫畏(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(Triazophos)、敌百虫(Trichlorfon);
A.2.氨基甲酸酯:棉铃威(alanycarb)、涕灭威(aldicarb)、噁虫威(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)、唑蚜威(triazamate);
A.3.合成除虫菊酯: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)、λ-氯氟氰菊酯(Lambda-Cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊酯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)和丙氟菊酯(profluthrin)、四氟甲醚菊酯(dimefluthrin);
A.4.生长调节剂:a)几丁质合成抑制剂:苯甲酰基脲类:定虫隆(chlorfluazuron)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);噻嗪酮(Buprofezin)、噁茂醚(Diofenolan)、噻螨酮(Hexythiazox)、特苯噁唑(Etoxazole)、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)、艾扎丁(Azadirachtin);c)保幼激素类似物:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威(fenoxycarb);d)类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramat);
A.5.烟碱受体激动剂/拮抗剂化合物:噻虫胺(Clothianidin)、呋虫胺(dinotefuran)、吡虫啉(Imidacloprid)、噻虫嗪(Thiamethoxam)、硝胺烯啶(Nitenpyram)、吡虫清(acetamiprid)、噻虫啉(Thiacloprid);式(Δ1)的噻唑化合物:
A.6.GABA拮抗剂化合物:氯丹(acetoprole)、硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、式Δ2的苯基吡唑化合物:
A.7.大环内酯杀虫剂:齐墩螨素(abamectin)、甲氨基阿维菌素(cmamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad),式(Δ3)的化合物(CAS No.187166-40-1):
A.8.METI I化合物:喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、flufenerim;
A.9.METI II和III化合物:灭螨醌(acequinocyl)、fluacyprim、灭蚁腙(hydramethylnon);
A.10.分离剂化合物:氟唑虫清(chlorfenapyr);
A.11.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)、克螨特(propargite);
A.12.蜕皮干扰剂(Moulting disruptor)化合物:cryomazine;
A.13.混合功能氧化酶抑制剂化合物:增效醚(piperonyl butoxide);
A.14.钠通道阻断剂化合物:噁二唑虫(indoxacarb)、氰氟虫胺(metaflumizone);
A.15.下列各种化合物:benclothiaz、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟啶虫酰胺(flonicamid)、啶虫丙醚(pyridalyl)、拒嗪酮(pymetrozine)、硫、硫环杀(thiocyclam)、氟虫酰胺(flubendiamide)、cyenopyrafen、吡氟硫磷(flupyrazofos)、丁氟螨酯(cyflumetofen)、amidoflumet、式Δ4的氨基喹唑啉酮化合物:
N-R’-2,2-二halo-1-R”环丙烷甲酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)腙或N-R’-2,2-二(R’”)丙酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)-腙,其中R’为甲基或乙基,halo为氯或溴,R”为氢或甲基和R’”为甲基或乙基,式Δ5的邻氨基苯甲酰胺(anthranilamide)化合物:
其中A1为CH3、Cl、Br、I,X为C-H、C-Cl、C-F或N,Y′为F、Cl或Br,Y″为F、Cl、CF3,B1为氢、Cl、Br、I、CN,B2为Cl、Br、CF3、OCH2CF3、OCF2H,且RB为氢、CH3或CH(CH3)2,和如JP 2002 284608、WO 02/89579、WO 02/90320、WO 02/90321、WO 04/06677、WO 04/20399或JP 2004 99597中所述的丙二腈化合物。
组A的市售化合物可在The Pesticide Manual,第13版,British CropProtection Council(2003)和其它出版物中找到。式Δ2的硫酰胺及其制备描述于WO 98/28279中。Lepimectin由Agro Project,PJB Publications Ltd,2004年11月已知。Benclothiaz及其制备描述于EP-A1 454621中。杀扑磷和对氧磷及其制备描述于Farm Chemicals Handbook,第88卷,MeisterPublishing Company,2001中。Acetoprole及其制备描述于WO 98/28277中。氰氟虫胺及其制备描述于EP-A1 462 456中。吡氟硫磷描述于PesticideScience 54,1988,第237-243页和US 4822779中。Pyrafluprole及其制备描述于JP 2002193709和WO 01/00614中。Pyriprole及其制备描述于WO98/45274和US 6335357中。Amidoflumet及其制备描述于US 6221890和JP 21010907中。Flufenerim及其制备描述于WO 03/007717和WO 03/007718中。Cyflumetofen及其制备描述于WO 04/080180中。式Δ5的邻氨基苯甲酰胺及其制备描述于WO 01/70671;WO 02/48137;WO03/24222;WO 03/15518;WO 04/67528;WO 04/33468;和WO 05/118552中。
杀真菌剂可选自下列:
1.嗜球果伞素类(Strobilurins),如腈嘧菌酯(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)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、肟菌酯(trifloxystrobin)、肟醚菌胺(orysastrobin)、(2-氯-5-[1-(3-甲基苄氧亚氨基)乙基]苄基)氨基甲酸甲酯、(2-氯-5-[1-(6-甲基吡啶-2-基甲氧基亚氨基)乙基]苄基)氨基甲酸甲酯、2-(邻-((2,5-二甲基苯氧基亚甲基)苯基)-3-甲氧基丙烯酸甲酯;
2.羧酰胺类,如羧酰苯胺类:苯霜灵(benalaxyl)、麦锈灵(benodanil)、啶酰菌胺(boscalid)、萎锈灵(carboxin)、丙氧灭绣胺(mepronil)、呋菌胺(fenfuram)、环酰菌胺(fenhexamide)、氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、甲霜灵(metalaxyl)、甲呋酰胺(ofurace)、噁霜灵(oxadixyl)、氧化萎锈灵(oxycarboxin)、吡噻菌胺(penthiopyrad)、溴氟唑菌(thifluzamide)、噻酰菌胺(tiadinil)、N-(4’-溴联苯-2-基)-4-二氟甲基-2-甲基噻唑-5-甲酰胺、N-(4’-三氟甲基联苯-2-基)-4-二氟甲基-2-甲基噻唑-5-甲酰胺、N-(4’-氯-3’-氟联苯-2-基)-4-二氟甲基-2-甲基噻唑-5-甲酰胺、N-(3’,4’-二氯-4-氟联苯-2-基)-3-二氟甲基-1-甲基吡唑-4-甲酰胺、N-(2-氰基苯基)-3,4-二氯异噻唑-5-甲酰胺;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)、fluopicolide(氟吡菌胺(picobenzamid))、苯酰菌胺(zoxamide);其他羧酰胺:氯环丙酰胺(carpropamid)、双氯氰菌胺(diclocymet)、双炔酰菌胺(mandipropamid)、N-(2-(4-[3-(4-氯苯基)丙-2-炔氧基]-3-甲氧基苯基)乙基)-2-甲基磺酰基氨基-3-甲基丁酰胺、N-(2-(4-[3-(4-氯苯基)丙-2-炔氧基]-3-甲氧基苯基)乙基)-2-乙基磺酰基氨基-3-甲基丁酰胺;N-(3′,4′-二氯-5-氟联苯-2-基)-3-二氟甲基-1-甲基吡唑-4-甲酰胺和3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(2-双环丙基-2-基-苯基)-酰胺
3.唑类,如三唑类:双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、噁醚唑(difenoconazole)、烯唑醇(diniconazole)、烯菌灵(enilconazole)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、氟硅唑(flusilazole)、喹唑菌酮(fluquinconazole)、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)、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)、唑菌醇(triadimenol)、三唑酮(triadimefon)、戊叉唑菌(triticonazole);咪唑类:氰霜唑(cyazofamid)、烯菌灵(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizole);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);
4.含氮杂环基化合物如吡啶类:氟啶胺(fluazinam)、啶斑肟(pyrifenox)、3-[5-(4-氯苯基)-2,3-二甲基异噁唑烷-3-基]吡啶;嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、嘧菌腙(ferimzone)、异嘧菌醇(fenarimol)、嘧菌胺(mepanipyrim)、氟苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);哌嗪类:嗪氨灵(triforine);吡咯类:氟噁菌(fludioxonil)、拌种咯(fenpiclonil);吗啉类:4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph);二羧酰亚胺类:异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);其他:噻二唑素(acibenzolar-S-methyl)、敌菌灵(anilazine)、克菌丹(captan)、敌菌丹(captafol)、棉隆(dazomet)、哒菌清(diclomezine)、氰菌胺(fenoxanil)、灭菌丹(folpet)、苯锈啶(fenpropidin)、噁唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、异噻菌酮(octhilinone)、噻菌灵(probenazole)、丙氧喹啉(proquinazid)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、三环唑(tricyclazole)、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、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、N,N-二甲基-3-(3-溴-6-氟-2-甲基吲哚-1-磺酰基)-[1,2,4]三唑-1-磺酰胺;
5.氨基甲酸盐和二硫代氨基甲酸盐如二硫代氨基甲酸盐:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、代森联(metiram)、威百亩(metam)、甲基代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);氨基甲酸盐类:乙霉威(diethofencarb)、flubenthiavalicarb、异丙菌胺(iprovalicarb)、百维灵(propamocarb)、3-(4-氯苯基)-3-(2-异丙氧羰基氨基-3-甲基丁酰氨基)丙酸甲酯、N-(1-(1-(4-氰基苯基)乙基磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
6.其他杀真菌剂,如胍类:多果定(dodine)、双胍辛醋酸盐(iminoctadine)、双胍盐(guazatine);抗菌素类:春雷素(kasugamycin)、多氧霉素(polyoxins)、链霉素(streptomycin)、井冈霉素(validamycin A);有机金属化合物类:三苯锡基盐;含硫的杂环基化合物:稻瘟灵(isoprothiolane)、二噻农(dithianon);有机磷化合物:克瘟散(edifenphos)、藻菌磷(fosetyl)、乙膦铝(fosetyl-aluminum)、异稻瘟净(iprobenfos)、定菌磷(pyrazophos)、甲基立枯磷(tolclofos-methyl)、亚磷酸及其盐;有机氯化合物:甲基托布津(thiophanate-methyl)、百菌清(chlorothalonil)、抑菌灵(dichlofluanid)、对甲抑菌灵(tolylfluanid)、磺菌胺(flusulfamide)、四氯苯酞(phthalide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯硝基苯(quintozene);硝基苯基衍生物:乐杀螨(binapacryl)、敌螨普(dinocap)、敌螨通(dinobuton);无机活性化合物:波尔多液(Bordeaux Mixture)、醋酸铜、氢氧化铜、王铜(copper oxychloride)、碱式硫酸铜、硫;其他:螺噁茂胺(spiroxamine)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、苯菌酮(metrafenone)。
除草剂选自下列:
b1)类脂生物合成抑制剂,如炔禾灵(chlorazifop)、炔草酯(clodinafop)、氯丁草(clofop)、氰氟草酯(cyhalofop)、氯甲草(diclofop)、噁唑禾草灵(fenoxaprop)、高噁唑禾草灵(fenoxaprop-p)、噻唑禾草灵(fenthiaprop)、吡氟禾草灵(fluazifop)、精吡氟禾草灵(fluazifop-P)、吡氟氯禾灵(haloxyfop)、精吡氟氯禾灵(haloxyfop-P)、恶草醚(isoxapyrifop)、噁唑酰草胺(metamifop),喔草酯(propaquizafop)、喹禾灵(quizalofop)、精喹禾灵(quizalofop-P)、三氟苯氧丙酸(trifop)、枯杀达(alloxydim)、丁氧环酮(butroxydim)、烯草酮(clethodim)、环己烯草酮(cloproxydim)、噻草酮(cycloxydim)、环苯草酮(profoxydim)、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim)、苏达灭(butylate)、草灭特(cycloate)、燕麦敌(di-allate)、哌草丹(dimepiperate)、扑草灭(EPTC)、禾草畏(esprocarb)、抑草威(ethiolate)、氮草(isopolinate)、甲硫苯威(methiobencarb)、草达灭(molinate)、坪草丹(orbencarb)、克草猛(pebulate)、苄草丹(prosulfocarb)、草克死(sulfallate)、杀草丹(thiobencarb)、丁草成(tiocarbazil)、野麦畏(triallate)、灭草猛(vernolate)、呋草黄(benfuresate)、乙呋草黄(ethofumesate)和地散磷(bensulide);
b2)ALS抑制剂,如磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、氯嘧黄隆(chlorimuron)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、胺苯黄隆(ethametsulfuron)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟定黄隆(flupyrsulfuron)、甲酰氨磺隆(foramsulfuron)、吡氯黄隆(halosulfuron)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、甲基二磺隆(mesosulfuron)、甲黄隆(metsulfuron)、烟嘧黄隆(nicosulfuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、三氟啶磺隆(trifloxysulfuron)、氟胺磺隆(triflusulfuron)、三氟甲磺隆(tritosulfuron)、咪草酯(imazamethabenz)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr)、唑嘧磺胺盐(cloransulam)、唑嘧磺胺(diclosulam)、双氟磺草胺(florasulam)、氟唑啶草(flumetsulam)、唑草磺胺(metosulam)、五氟磺草胺(penoxsulam)、双嘧苯甲酸(bispyribac)、肟啶草(pyriminobac)、丙苯磺隆(propoxycarbazone)、氟酮磺隆(flucarbazone)、嘧苯草肟(pyribenzoxim)、环酯草醚(pyriftalid)和嘧硫苯甲酸(pyrithiobac);
b3)光合成抑制剂,如莠去通(atraton)、莠去津(atrazine)、莠灭净(ametryn)、叠氮津(aziprotryn)、草净津(cyanazine)、硫草净津(cyanatryn)、可乐津(chlorazine)、环草津(cyprazine)、敌草净(desmetryn)、戊草津(dimethametryn)、杀草净(dipropetryn)、草止津(eglinazine)、抑草津(ipazine)、麦苏百津(mesoprazine)、醚草通(methometon)、盖草津(methoprotryne)、环氰津(procyazine)、丙草止津(proglinazine)、扑灭通(prometon)、扑草净(prometryn)、扑灭津(propazine)、另丁津(sebuthylazine)、密草通(secbumeton)、西玛津(simazine)、西玛通(simeton)、西草净(simetryn)、甲氧去草净(terbumeton)、特丁津(terbuthylazine)、去草净(terbutryn)、草达津(trietazine)、特津酮(ametridione)、特草嗪酮(amibuzin)、六嗪同(hexazinone)、嗪丁草(isomethiozin)、苯嗪草(metamitron)、赛克津(metribuzin)、除草定(bromacil)、异草定(isocil)、环草定(lenacil)、特草定(terbacil)、溴杀草敏(brompyrazon)、杀草敏(chloridazon)、敌米达松(dimidazon)、异苯敌草(desmedipham)、敌克草(phenisopham)、苯敌草(phenmedipham)、乙苯敌草(phenmedipham-ethyl)、噻草隆(benzthiazuron)、丁噻隆(buthiuron)、噻二唑隆(ethidimuron)、异恶隆(isouron)、噻唑隆(methabenzthiazuron)、单异恶隆(monoisouron)、丁唑隆(tebuthiuron)、赛唑隆(thiazafluron)、疏草隆(anisuron)、播土隆(buturon)、氯溴隆(chlorbromuron)、乙氧苯隆(chloreturon)、绿麦隆(chlorotoluron)、枯草隆(chloroxuron)、枯莠隆(difenoxuron)、丁噁隆(dimefuron)、敌草隆(diuron)、非草隆(fenuron)、伏草隆(fluometuron)、氟苯隆(fluothiuron)、异丙隆(isoproturon)、利谷隆(linuron)、灭草恒(methiuron)、色满隆(metobenzuron)、秀谷隆(metobromuron)、甲氧隆(metoxuron)、绿谷隆(monolinuron)、灭草隆(monuron)、草不隆(neburon)、对伏隆(parafluron)、稀草隆(phenobenzuron)、环草隆(siduron)、氟氧隆(tetrafluron)、赛二唑素(thidiazuron)、莎草快(cyperquat)、二乙除草双(diethamquat)、苯敌快(difenzoquat)、敌草快(diquat)、伐草快(morfamquat)、对草快(paraquat)、糠草腈(bromobonil)、溴苯腈(bromoxynil)、羟敌草腈(chloroxynil)、碘草腈(iodobonil)、碘苯腈(ioxynil)、氨唑草酮(amicarbazone)、杀草全(bromofenoxim)、三氟噁嗪(flumezin)、灭草定(methazole)、噻草平(bentazone)、敌稗(propanil)、蔬草灭(pentanochlor)、达草止(pyridate)和6-氯-3-苯基-4-哒嗪醇(pyridafol);
b4)原卟啉原-IX氧化酶抑制剂,如氟锁草醚(acifluorfen)、治草醚(bifenox)、氯硝醚(chlomethoxyfen)、草枯醚(chlornitrofen)、氯氟草醚(ethoxyfen)、消草醚(fluorodifen)、乙羧氟草醚(fluoroglycofen)、氯草醚(fluoronitrofen)、氟黄胺草醚(fomesafen)、氟呋草醚(furyloxyfen)、氟硝磺酰胺(halosafen)、乳氟禾草灵(lactofen)、除草醚(nitrofen)、硝氟草醚(nitrofluorfen)、氟硝草醚(oxyfluorfen)、异丙吡草酯(fluazolate)、氟唑草酯(pyraflufen)、吲哚酮草酯(cinidon-ethyl)、酰亚胺苯氧乙酸(flumiclorac)、氟噁嗪酮(flumioxazin)、炔草胺(flumipropyn)、达草氟(fluthiacet)、噻二唑胺(thidiazimin)、恶草灵(oxadiazon)、炔丙噁唑草(oxadiargyl)、唑啶炔草(azafenidin)、氟酮唑草(carfentrazone)、磺胺草唑(sulfentrazone)、戊噁唑草(pentoxazone)、双苯嘧草酮(benzfendizone)、氟丙嘧草酯(butafenacil)、双唑草腈(pyraclonil)、氟唑草胺(profluazol)、氟哒嗪草酯(flufenpyr)、flupropacil、吡氯草胺(nipyraclofen)和乙胺草醚(etnipromid);
b5)漂白剂除草剂,如氟哒草(metflurazon)、达草灭(norflurazon)、氟苯啶草(flufenican)、吡氟草胺(diflufenican)、氟吡酰草胺(picolinafen)、氟丁酰草胺(beflubutamid)、氟草同(fluridone)、氟咯草酮(flurochloridone)、呋草酮(flurtamone)、甲基磺草酮(mesotrione)、磺草酮(sulcotrione)、异恶氯草酮(isoxachlortole)、异噁氟草(isoxaflutole)、吡草酮(benzofenap)、吡唑特(pyrazolynate)、苄草唑(pyrazoxyfen)、苯并双环酮(benzobicyclon)、杀草强(amitrole)、异恶草酮(clomazone)、苯草醚(aclonifen)、4-(3-三氟甲基苯氧基)-2-(4-三氟甲基苯基)嘧啶以及下式II的3-杂环基取代的苯甲酰基衍生物(参见WO 96/26202、WO 97/41116、WO 97/41117和WO 97/41118):
其中变量R8-R13如下所定义:
R8、R10为氢、卤素、C1-C6烷基、C1-C6卤代烷基、C1-C6烷氧基、C1-C6卤代烷氧基、C1-C6烷硫基、C1-C6烷基亚磺酰基或C1-C6烷基磺酰基;
R9为选自如下的杂环基:噻唑-2-基、噻唑-4-基、噻唑-5-基、异噁唑-3-基、异噁唑-4-基、异噁唑-5-基、4,5-二氢异噁唑-3-基、4,5-二氢异噁唑-4-基和4,5-二氢异噁唑-5-基,其中上述9个基团可未被取代或被单取代或多取代,例如被卤素、C1-C4烷基、C1-C4烷氧基、C1-C4卤代烷基、C1-C4卤代烷氧基或C1-C4烷硫基单-、二-、三-或四取代;
R11为氢、卤素或C1-C6烷基;
R12为C1-C6烷基;
R13为氢或C1-C6烷基。
b6)EPSP合成酶抑制剂,如草甘膦(glyphosate);
b7)谷氨酰胺合成酶抑制剂,如草铵膦(glufosinate)和双丙氨酰磷(bilanaphos);
b8)DHP合成酶抑制剂,如黄草灵(asulam);
b9)有丝分裂抑制剂,如氟草胺(benfluralin)、地乐胺(butralin)、敌乐胺(dinitramine)、丁氟消草(ethalfluralin)、氟消草(fluchloralin)、异乐灵(isopropalin)、氟烯硝草(methalpropalin)、磺乐灵(nitralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、卡乐施(profluralin)、氟乐灵(trifluralin)、甲基胺草磷(amiprofos-methyl)、草胺磷(butamifos)、氟硫草定(dithiopyr)、噻氟啶草(thiazopyr)、拿草特(propyzamide)、丙戊草胺(tebutam)、敌草索(chlorthal)、长杀草(carbetamide)、氯草灵(chlorbufam)、氯苯胺灵(chlorpropham)和苯胺灵(propham);
b10)VLCFA抑制剂,如乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、丁烯草胺(butenachlor)、敌草乐(delachlor)、安塔(diethatyl)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、精噻吩草胺(dimethenamid-P)、吡草胺(metazachlor)、异丙甲草胺(metolachlor)、S-异丙甲草胺(S-metolachlor)、丙草胺(pretilachlor)、扑草胺(propachlor)、异丙草胺(propisochlor)、广草胺(prynachlor)、猛杀草(terbuchlor)、噻醚草胺(thenylchlor)、二甲苯草胺(xylachlor)、草毒死(allidochlor)、草立死(CDEA)、磺唑草(epronaz)、草乃敌(diphenamid)、草萘胺(napropamide)、萘丙胺(naproanilide)、烯草胺(pethoxamid)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、四唑酰草胺(fentrazamide)、莎稗磷(anilofos)、哌草磷(piperophos)、胺草唑(cafenstrole)、茚草酮(indanofan)和灭草环(tridiphane);
b11)纤维素生物合成抑制剂,如敌草腈(dichlobenil)、草克乐(chlorthiamid)、异恶草胺(isoxaben)和胺草唑(flupoxam);
b12)去偶(decoupler)除草剂,如消草酯(dinofenate)、硝丙酚(dinoprop)、戊硝酚(dinosam)、地乐酚(dinoseb)、地乐消酚(dinoterb)、二硝甲酚(DNOC)、硝草酚(etinofen)和丁硝酚(medinoterb);
b13)植物生长素除草剂,如稗草胺(clomeprop)、2,4-滴(2,4-D)、2,4,5-涕(2,4,5-T)、2甲4氯(MCPA)、酚硫杀(MCPA-thioethyl)、2,4-滴丙酸(dichlorprop)、高2,4-滴丙酸(dichlorprop-P)、2甲4氯丙酸(mecoprop)、高2甲4氯丙酸盐(mecoprop-P)、2,4-滴丁酸(2,4-DB)、2甲4氯丁酸(MCPB)、草灭平(chloramben)、麦草畏(dicamba)、草芽平(2,3,6-TBA)、杀草畏(tricamba)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、二氯皮考啉酸(clopyralid)、氟草烟(fluroxypyr)、毒莠定(picloram)、定草酯(triclopyr)和草除灵(benazolin);
b14)植物生长素输送抑制剂,如抑草生(naptalam)、二氟吡隆(diflufenzopyr);
b15)新燕灵(benzoylprop)、氟燕灵(flamprop)、麦草伏M(flamprop-M)、溴丁酰草胺(bromobutide)、氯甲丹(chlorflurenol)、环庚草醚(cinmethylin)、苯丙隆(methyldymuron)、乙苯酰草(etobenzanid)、膦铵素(fosamine)、威百亩(metam)、稗草畏(pyributicarb)、氯噁嗪草(oxaziclomefone)、棉隆(dazomet)、苯氧丙胺津(triaziflam)和溴甲烷(methyl bromide)。
合适的安全剂可选自下列:解草酮(benoxacor)、喹氧乙酸(cloquintocet)、抑害腈(cyometrinil)、抑害胺(dichlormid)、dicyclonon、dietholate、解草唑(fenchlorazole)、解草啶(fenclorim)、解草胺(flurazole)、肟草安(fluxofenim)、解草呋(furilazole)、双苯恶唑酸(isoxadifen)、吡咯二酸(mefenpyr)、mephenate、萘二甲酸酐(naphthalic anhydride)、2,2,5-三甲基-3-(二氯乙酰基)-1,3-噁唑烷(R-29148)、4-(二氯乙酰基)-1-氧杂-4-氮杂螺[4.5]癸烷(AD-67;MON 4660)和解草腈(oxabetrinil)。
通常优选杀真菌剂和杀虫剂。
优选杀虫剂为谷硫磷、毒死蜱、甲基毒死蜱、毒虫畏、二嗪农、乙拌磷、乙硫磷、杀螟松、倍硫磷、异噁唑磷、马拉硫磷、杀扑磷、甲基一六零五、一六零五、稻丰散、伏杀磷、亚胺硫磷、甲拌磷、辛硫磷、虫螨磷、丙溴磷、丙硫磷、乙丙硫磷、杀虫畏、特丁磷、棉铃威、丙硫克百威、丁硫克百威、双氧威、呋线威、灭虫威、唑蚜威;定虫隆、氟脲杀、氟螨脲、氟虫脲、氟铃脲、氟丙氧脲、双苯氟脲、伏虫隆、杀虫隆;甲氧苯酰肼、双苯酰肼、艾扎丁、蚊蝇醚、蒙五一五、双氧威;螺螨酯、螺甲螨酯、螺虫乙酯;噻虫胺、呋虫胺、吡虫啉、噻虫嗪、硝胺烯啶、吡虫清、噻虫啉;氯丹、硫丹、乙虫清、锐劲特、氟吡唑虫、pyrafluprole、pyriprole,式Δ2的苯基吡唑化合物:
齐墩螨素、甲氨基阿维菌素、米尔螨素、lepimectin、喹螨醚、哒螨酮、吡螨胺、灭螨醌、fluacyprim、灭蚁腙、氟唑虫清、三环锡、杀螨硫隆、杀螨锡、克螨特;增效醚;噁二唑虫、氰氟虫胺、联苯肼酯、拒嗪酮、N-R’-2,2-二halo-1-R”环丙烷甲酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)腙或N-R’-2,2-二(R’”)丙酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)-腙,其中R’为甲基或乙基,halo为氯或溴,R”为氢或甲基和R”’为甲基或乙基。
更优选杀虫剂为氟氯氰菊酯、λ-氯氟氰菊酯、氯氰菊酯、甲体氯氰菊酯、乙体氯氰菊酯、溴氰菊酯、高氰戊菊酯、杀灭菊酯、氯菊酯、七氟菊酯、胺菊酯、四氟菊酯、氟虫脲、伏虫隆、噻虫胺、噻虫嗪、吡虫清、乙虫清、锐劲特,式Δ2的苯基吡唑化合物:
氟唑虫清;增效醚;噁二唑虫、氰氟虫胺、拒嗪酮、N-R’-2,2-二halo-1-R”环丙烷甲酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)腙或N-R’-2,2-二(R’”)丙酰胺-2-(2,6-二氯-α,α,α-三氟对甲苯基)-腙,其中R’为甲基或乙基,halo为氯或溴,R”为氢或甲基和R’”为甲基或乙基。
优选杀真菌剂为:腈嘧菌酯、醚菌胺、氟嘧菌酯、亚胺菌、啶氧菌酯、唑菌胺酯、肟菌酯、肟醚菌胺、2-(邻-((2,5-二甲基苯氧基亚甲基)苯基)-3-甲氧基丙烯酸甲酯;啶酰菌胺、甲霜灵、吡噻菌胺、N-(3’,4’-二氯-4-氟联苯-2-基)-3-二氟甲基-1-甲基吡唑-4-甲酰胺、烯酰吗啉、氟吡菌胺、苯酰菌胺;双炔酰菌胺、N-(3′,4′-二氯-5-氟联苯-2-基)-3-二氟甲基-1-甲基吡唑-4-甲酰胺、3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(2-双环丙基-2-基-苯基)-酰胺、环唑醇、噁醚唑、氧唑菌、喹唑菌酮、环戊唑菌、丙环唑、丙硫菌唑、戊唑醇、戊叉唑菌;氰霜唑、丙氯灵、噻唑菌胺、氟啶胺、环丙嘧啶、二甲嘧菌胺;嗪氨灵;氟噁菌、吗菌灵、丁苯吗啉、克啉菌、烯菌酮、棉隆、氰菌胺、苯锈啶、丙氧喹啉;flubenthiavalicarb、异丙菌胺、多果定、二噻农、藻菌磷、藻菌磷、百菌清、螺噁茂胺、环氟菌胺、清菌脲、苯菌酮。
更优选杀真菌剂为腈嘧菌酯、醚菌胺、嘧菌酯、亚胺菌、啶氧菌酯、唑菌胺酯、肟菌酯、肟醚菌胺、啶酰菌胺、甲霜灵、N-(3’,4’-二氯-4-氟联苯-2-基)-3-二氟甲基-1-甲基吡唑-4-甲酰胺、烯酰吗啉、氟吡菌胺、苯酰菌胺;双炔酰菌胺、N-(3′,4′-二氯-5-氟联苯-2-基)-3-二氟甲基-1-甲基吡唑-4-甲酰胺、3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(2-双环丙基-2-基-苯基)-酰胺、环唑醇、噁醚唑、氧唑菌、环戊唑菌、丙环唑、丙硫菌唑、戊唑醇、氰霜唑、丙氯灵、环丙嘧啶、嗪氨灵;氟噁菌、吗菌灵、丁苯吗啉、克啉菌、烯菌酮、棉隆、氰菌胺、异丙菌胺、多果定、二噻农、藻菌磷、藻菌磷、百菌清、螺噁茂胺、苯菌酮。
最优选杀真菌剂为:腈嘧菌酯、嘧菌酯、啶氧菌酯、唑菌胺酯、肟菌酯、肟醚菌胺、啶酰菌胺、甲霜灵、N-(3’,4’-二氯-4-氟联苯-2-基)-3-二氟甲基-1-甲基吡唑-4-甲酰胺、烯酰吗啉、氟吡菌胺、苯酰菌胺;双炔酰菌胺、3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(2-双环丙基-2-基-苯基)-酰胺、环唑醇、噁醚唑、氧唑菌、丙环唑、丙硫菌唑、戊唑醇、丙氯灵、环丙嘧啶、氟噁菌、异丙菌胺、藻菌磷、藻菌磷、百菌清、螺噁茂胺、苯菌酮。
如上所述,在本发明的一个实施方案中,也可使用赋予植物健康效果的农药。这类农药在本领域是已知的。适用于此的例如是:
在b/c1复合物水平上抑制线粒体呼吸链的活性化合物;
选自下列的羧酰胺类:苯霜灵、麦锈灵、啶酰菌胺、萎锈灵、丙氧灭绣胺、呋菌胺、环酰菌胺、氟酰胺、呋吡唑灵、甲霜灵、甲呋酰胺、噁霜灵、氧化萎锈灵、吡噻菌胺、溴氟唑菌、噻酰菌胺、4-二氟甲基-2-甲基-噻唑-5-甲酸-(4’-溴-联苯-2-基)-酰胺、4-二氟甲基-2-甲基-噻唑-5-甲酸-(4’-三氟甲基-联苯-2-基)-酰胺、4-二氟甲基-2-甲基-噻唑-5-甲酸-(4’-氯-3’-氟-联苯-2-基)-酰胺、3-二氟甲基-1-甲基-吡唑-4-甲酸-(3’,4’-二氯-4-氟-联苯-2-基)-酰胺、3,4-二氯-异噻唑-5-甲酸-(2-氰基-苯基)-酰胺、烯酰吗啉、氟吗啉、氟联苯菌、氟吡菌胺、苯酰菌胺、氯环丙酰胺、双氯氰菌胺、双炔酰菌胺、N-(2-(4-[3-(4-氯-苯基)-丙-2-炔氧基]-3-甲氧基-苯基)-乙基)-2-甲烷磺酰基氨基-3-甲基-丁酰胺和N-(2-(4-[3-(4-氯-苯基)-丙-2-炔氧基]-3-甲氧基-苯基)-乙基)-2-乙烷磺酰基氨基-3-甲基-丁酰胺;
选自下列的唑类:双苯三唑醇、糠菌唑、环唑醇、噁醚唑、烯唑醇、烯菌灵、氧唑菌、腈苯唑、氟硅唑、喹唑菌酮、粉唑醇、己唑醇、酰胺唑、环戊唑醇、环戊唑菌、腈菌唑、戊菌唑、丙环唑、丙硫菌唑、硅氟唑、戊唑醇、氟醚唑、唑菌醇、三唑酮、戊叉唑菌、氰霜唑、烯菌灵、稻瘟酯、丙氯灵、氟菌唑、苯菌灵、多菌灵、麦穗宁、涕必灵、噻唑菌胺、氯唑灵和土菌消;
选自下列的含氮杂环化合物:氟啶胺、啶斑肟、3-[5-(4-氯苯基)-2,3-二甲基异噁唑烷-3-基]吡啶、磺嘧菌灵、环丙嘧啶、嘧菌腙、异嘧菌醇、嘧菌胺、氟苯嘧啶醇、二甲嘧菌胺、嗪氨灵、氟噁菌、拌种咯、4-十二烷基-2,6-二甲基吗啉、吗菌灵、丁苯吗啉、克啉菌、异丙定、杀菌利、烯菌酮、噻二唑素、敌菌灵、克菌丹、敌菌丹、棉隆、哒菌清、氰菌胺、灭菌丹、苯锈啶、噁唑酮菌、咪唑菌酮、异噻菌酮、噻菌灵、丙氧喹啉、咯喹酮、喹氧灵、三环唑、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、3-(3-溴-6-氟-2-甲基吲哚-1-磺酰基)-[1,2,4]三唑-1-磺酸二甲基酰胺;
选自下列的氨基甲酸盐和二硫代氨基甲酸盐:福美铁、代森锰锌、代森联、威百亩、甲基代森锌、福美双、代森锌、福美锌、乙霉威、flubenthiavalicarb、异丙菌胺、百维灵、3-(4-氯苯基)-3-(2-异丙氧羰基氨基-3-甲基丁酰氨基)丙酸甲酯和N-(1-(1-(4-氰基苯基)乙基磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
选自下列的胍类:多果定、双胍辛醋酸盐和双胍盐;
选自下列的抗菌素类:春雷素、多氧霉素、链霉素和井冈霉素;
三苯锡基盐;
选自下列的含硫的杂环基化合物:稻瘟灵和二噻农;
选自下列的有机磷化合物:克瘟散、藻菌磷、乙膦铝、异稻瘟净、定菌磷、甲基立枯磷和亚磷酸及其盐;
选自下列的有机氯化合物:甲基托布津、百菌清、抑菌灵、对甲抑菌灵、磺菌胺、四氯苯酞、六氯苯、戊菌隆、五氯硝基苯;
选自下列的硝基苯基衍生物:乐杀螨、敌螨普和敌螨通;
选自下列的无机活性化合物:波尔多液、醋酸铜、氢氧化铜、王铜、碱式硫酸铜和硫;
螺噁茂胺;环氟菌胺;清菌脲;苯菌酮;
选自下列的有机(硫代)磷酸酯类:高灭磷、唑啶磷、谷硫磷、毒死蜱、甲基毒死蜱、毒虫畏、二嗪农、敌敌畏、百治磷、乐果、乙拌磷、乙硫磷、杀螟松、倍硫磷、异噁唑磷、马拉硫磷、甲胺磷、杀扑磷、甲基一六零五、速灭磷、久效磷、砜吸磷、对氧磷、一六零五、稻丰散、伏杀磷、亚胺硫磷、磷胺、甲拌磷、辛硫磷、虫螨磷、丙溴磷、丙硫磷、乙丙硫磷、杀虫畏、特丁磷、三唑磷和敌百虫;
选自下列的氨基甲酸酯:棉铃威、涕灭威、噁虫威、丙硫克百威、甲萘威、虫螨威、丁硫克百威、双氧威、呋线威、灭虫威、灭多虫、甲氨叉威、抗蚜威、残杀威、硫双威和唑蚜威;
选自下列的合成除虫菊酯: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、λ-氯氟氰菊酯、氯菊酯、炔酮菊酯、除虫菊酯I和II、灭虫菊、灭虫硅醚、氟胺氰菊酯、七氟菊酯、胺菊酯、四溴菊酯、四氟菊酯和丙氟菊酯、四氟甲醚菊酯;
选自下列的生长调节剂:a)选自下列的几丁质合成抑制剂:苯甲酰基脲类:定虫隆、氟脲杀、氟螨脲、氟虫脲、氟铃脲、氟丙氧脲、双苯氟脲、伏虫隆、杀虫隆;噻嗪酮、噁茂醚、噻螨酮、特苯噁唑和四螨嗪;b)选自下列的蜕皮激素拮抗剂:特丁苯酰肼、甲氧苯酰肼、双苯酰肼和艾扎丁;c)选自下列的保幼激素类似物:蚊蝇醚、蒙五一五和双氧威;d)选自下列的类脂生物合成抑制剂:螺螨酯、螺甲螨酯和螺虫乙酯;
选自下列的烟碱受体激动剂/拮抗剂化合物:噻虫胺、呋虫胺、(EZ)-1-(6-氯-3-吡啶基甲基)-N-硝基咪唑烷-2-亚基胺(吡虫啉)、(EZ)-3-(2-氯-1,3-噻唑-5-基甲基)-5-甲基-1,3,5-噁二嗪-4-亚基(硝基)胺(噻虫嗪)、硝胺烯啶、吡虫清、噻虫啉;式(Γ1)的噻唑化合物:
选自下列的GABA拮抗剂化合物:氯丹、硫丹、乙虫清、5-氨基-1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-三氟甲基亚磺酰基吡唑-3-甲腈(锐劲特)、氟吡唑虫、pyrafluprole、pyriprole和式Γ2的苯基吡唑化合物:
选自下列的METI I化合物:喹螨醚、哒螨酮、吡螨胺、唑虫酰胺和flufenerim;
选自下列的METI II和III化合物:灭螨醌、fluacyprim和灭蚁腙;氟唑虫清;
选择下列的氧化磷酸化抑制剂化合物:三环锡、杀螨硫隆、杀螨锡和克螨特;
cryomazine;增效醚;噁二唑虫;benclothiaz、联苯肼酯、杀螟丹、氟啶虫酰胺、啶虫丙醚、拒嗪酮、硫、硫环杀、氟虫酰胺、cyenopyrafen、吡氟硫磷、丁氟螨酯、amidoflumet、式Γ4的氨基喹唑啉酮化合物:
和式Γ5的邻氨基苯甲酰胺化合物:
其中A1为CH3、Cl、Br、I,X为C-H、C-Cl、C-F或N,Y′为F、Cl或Br,Y″为F、Cl、CF3,B1为氢、Cl、Br、I、CN,B2为Cl、Br、CF3、OCH2CF3、OCF2H,且RB为氢、CH3或CH(CH3)2。
其中优选唑菌胺酯、腈嘧菌酯、亚胺菌、肟菌酯、啶氧菌酯、醚菌胺、嘧菌酯、肟醚菌胺、戊唑醇、噁醚唑、氧唑菌、环唑醇、丙硫菌唑、丙环唑、锐劲特、吡虫啉和噻虫嗪。
如上所述,本发明聚合物可用于制备包含至少一种农药和本发明聚合物的配制剂。包含至少一种农药和至少一种本发明聚合物的配制剂可任选包含其它配制助剂。
通常而言,配制剂包含0-90重量%,优选1-85重量%,更优选5-80重量%,最优选5-65重量%的配制助剂。
对本发明而言,术语“配制助剂”为适用于配制农药的助剂,如其它溶剂和/或载体和/或表面活性剂(离子或非离子表面活性剂、辅助剂、分散剂)和/或防腐剂和/或消泡剂和/或防冻剂和任选用于种子处理配制剂的着色剂和/或粘合剂和/或胶凝剂和/或增稠剂。
合适的溶剂的实例为水,芳族溶剂(例如Solvesso产品,二甲苯),石蜡(例如石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、烷基化萘或其衍生物,醇类(如甲醇,丁醇,戊醇,苄醇,环己醇),酮类(例如环己酮、γ-丁内酯)、吡咯烷酮(NMP、NEP、NOP)、乙酸酯(乙二醇二乙酸酯),二醇类,脂肪酸的二甲基酰胺,脂肪酸和脂肪酸酯、异佛尔酮和二甲亚砜。原则上还可以使用溶剂混合物。
合适的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,聚氧乙烯辛基酚醚,乙氧基化异辛基酚、辛基酚和壬基酚,烷基酚聚乙二醇醚,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。
合适的载体的实例矿土如硅胶、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;植物来源的产品如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉、聚乙烯基吡咯烷酮和其它固体载体。
防冻剂如甘油、乙二醇、己二醇、丙二醇以及杀菌剂也可加入配制剂。
合适的消泡剂例如为基于聚硅氧烷或硬脂酸镁的消泡剂。
合适的防腐剂例如为1,2-苯并异噻唑啉-3-酮和/或2-甲基-2H-异噻唑-3-酮或苯甲酸钠或苯甲酸。
增稠剂的实例(即赋予配制剂假塑性流动行为如静止状态下高粘度和运动状态下低粘度的化合物)例如为多糖或有机或无机层状矿物,如黄原胶(Kelco的Kelzan),Rhodopol23(Rhone Poulenc)或Veegum(R.T.Vanderbilt)或Attaclay(Engelhardt)。
种子处理配制剂可额外包含粘合剂和任选着色剂。
配制剂也可任选包括着色剂。适用于种子处理的着色剂或染料为若丹明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。
粘合剂可改进活性材料在处理后对于种子的粘附。合适粘合剂为聚乙烯吡咯烷酮、聚乙烯基乙酸酯、聚乙烯醇和纤基乙酸钠。
配制剂的使用形式(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)完全取决于意欲的目的;它们意欲在每种情况下确保农药和本发明聚合物的最佳可能分布。
其中可使用本发明聚合物的合适的配制剂类型的实例为:
1.液体配制剂,如EC(乳油)配制剂;SL或LS(可溶性浓缩物)配制剂、EW(乳液,水包油)配制剂、ME(微乳液)配制剂、MEC(微乳化浓缩物)配制剂、CS(胶囊悬浮液)配制剂、TK(工业浓缩物)配制剂、OD(基于油的悬浮液浓缩物)配制剂、SC(悬浮液浓缩物)配制剂;SE(悬浮乳液)配制剂;ULV(超低体积液体)配制剂;SO(撒播油)配制剂;AL(任何其它液体)配制剂;LA(Lacquer)配制剂;DC(可分散性浓缩物)配制剂;
2.固体配制剂,如WG(水分散性颗粒)配制剂;TB(片)配制剂;FG(细颗粒)配制剂;MG(微颗粒)配制剂;SG(可溶性颗粒)。
优选配制剂类型例如为EC(乳油)配制剂;SL或LS(可溶性浓缩物)配制剂;EW(乳液,水包油)配制剂、ME(微乳液)配制剂、CS(胶囊悬浮液)配制剂、OD(基于油的悬浮液浓缩物)配制剂;SC(悬浮液浓缩物)配制剂;SE(悬浮乳液)配制剂;DC(分散性浓缩物)配制剂、WG(水分散性颗粒)配制剂;TB(片)配制剂;FG(细颗粒)配制剂和SG(可溶性颗粒)。
本发明还包括一种制备本发明配制剂的方法。用于此的方法通常对本领域熟练技术人员是熟知的且例如以各种配制剂类型描述于文献中(例如参见综述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页及随后各页。WO 91/13546、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(杂草防治科学),JohnWiley and Sons,Inc.,New York,1961,Hance等,Weed ControlHandbook(杂草防治手册),第8版,Blackwell Scientific Publications,Oxford,1989和Mollet,H.,Grubemann,A.,Formulation technology(配制技术),Wiley VCH Verlag GmbH,Weinheim(德国),2001,2.D.A.Knowles,Chemistry and Technology of Agrochemical Formulations(农业化学配制剂化学和技术),Kluwer Academic Publishers,Dordrecht,1998(ISBN 0-7514-0443-8)。
液体配制剂可通过将本发明聚合物与至少一种农药或其它配制助剂混合或结合而制备。
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化合物与固体载体粘附而制备。
上述配制剂可以直接或由其制备的使用形式,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、撤播用材料或颗粒,借助喷雾、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农药和聚合物的最佳可能分布。
含水使用形式可通过加入合适的溶剂如水由乳液浓缩物、糊或可湿性粉末(可喷雾粉末、油分散体)制备。
通常而言,可将本发明聚合物加入已经制备的配制剂中或包括在包含至少一种农药和至少一种本发明聚合物的配制剂中。将聚合物加入配制剂可在用水稀释配制剂之前或之后进行;如在含有本发明聚合物之前制备上述配制剂或在用合适的溶剂如水稀释农药配制剂之后加入聚合物(如所谓的桶混合)。
上述施用的所有实施方案在下文中称作“本发明配制剂”。
本发明进一步包括一种对抗有害昆虫和/或植物病原性真菌的方法,其包括使有害昆虫和/或植物病原性真菌在其中或其上生长或会生长的植物、种子、土壤或植物生长地,需防止所述有害昆虫和/或植物病原性真菌侵袭或侵染的植物、种子或土壤与有效量的本发明农业化学配制剂接触。
因此,本发明配制剂可用于防治各种栽培植物以及这些植物的种子上的大量植物病原性真菌或昆虫,或杂草,所述植物例如为小麦、黑麦、大麦、燕麦、稻、玉米、禾草、香蕉、棉花、大豆、咖啡、甘蔗、葡萄藤、水果和观赏植物以及蔬菜植物如黄瓜、豆类、西红柿、土豆和葫芦科植物。
本发明进一步涉及一种改善植物健康的方法,其包括向植物、植物部分或植物生长的场所施加其中农药为赋予植物健康效果的农药的本发明配制剂。
本发明进一步包括一种防治不希望的植物生长的方法,其包括使除草有效量的本发明农业化学配制剂作用于植物、其生长地或所述植物的种子。
因此,本发明配制剂,本发明组合物适用于防治有用植物,尤其是作物中的常规有害植物,所述作物例如为燕麦、大麦、小米、玉米、稻、小麦、甘蔗、棉花、油菜、亚麻、扁豆、糖用甜菜、烟草、向日葵和大豆或多年生作物。
术语植物病原性真菌包括但不限于下种类:
蔬菜、油籽油菜、糖用甜菜、水果和稻上的链格孢属(Alternaria)(例如土豆和其它植物上的早疫链格孢(A.solani)或链格孢(A.alternata);糖用甜菜和蔬菜上的丝囊霉属(Aphanomyces);玉米、禾谷类、稻和草坪中的平脐蠕孢属(Bipolaris)和内脐蠕孢属(Drechslera),(例如大麦上的大麦网斑内脐蠕孢(D.teres),小麦上的D.tritci-repentis;禾谷类上的禾白粉菌(Blumeriagraminis)(白粉病);草莓、蔬菜、花卉和葡萄藤上的灰葡萄孢(Botrytiscinerea)(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属(Cercospora)(例如糖用甜菜上的C.Beticula);玉米、禾谷类、稻上的旋孢腔菌属(Cochliobolus)(例如禾谷类上的禾旋孢腔菌(Cochliobolus sativus),稻上的宫部旋孢腔菌(Cochliobolus miyabeanus));大豆、棉花和其它植物上的剌盘孢属(Colletotricum)(例如各种植物上的C.acutatum);由Phaeoacremonium chlamydosporium、Ph.Aleophilum和Formitipora punctata(同义词斑孔木层孔菌(Phellinus punctatus))引起的葡萄藤上的埃斯卡(Esca);玉米上的突脐蠕孢属(Exserohilum);葫芦上的二孢白粉菌(Erysiphe cichoracearum)和单丝壳白粉菌(Sphaerothecafuliginea),各种植物上的镰孢霉属(Fusarium)和轮枝孢属(Verticillium)(例如例如大丽轮枝菌(V.Dahliae))(例如小麦上的禾本科镰孢(F.graminearum));禾谷类上的禾顶囊壳(Gaeumanomyces graminis);禾谷类和稻上的赤霉属(Gibberella)(例如稻上的藤仓赤霉(Gibberella fuiikuroi));稻上的Grainstaining complex;玉米和稻上的长蠕孢属(Helminthosporium)(例如H.graminicola);禾谷类上的Michrodochiumnivale;禾谷类、香蕉和花生上的球腔菌属(Mycosphaerella)(小麦上的禾生球腔菌(M.graminicola)或香蕉上的斐济球腔菌(M.fijiensis));大豆上的豆薯层锈菌(Phakopsora pachyrhizi)和山马蟥层锈菌(Phakopsarameibomiae);大豆、向日葵和葡萄藤上的拟茎点霉属(Phomopsis)(葡萄藤上的葡萄拟茎点霉(P.viticola),向日葵上的P.helianthii);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(例如黄瓜上的古巴假霜霉(P.cubenis));禾谷类、玉米和芦笋上的柄锈菌属(Puccinia)(小麦上的小麦柄锈菌(P.triticina)和条锈病菌(P.striformis),芦笋上的天门冬属柄锈病(P.asparagi));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、蔬菜和其它植物上的腐霉属(Pythium);棉花、稻、土豆、草坪、玉米、油籽油菜、糖用甜菜、蔬菜和各种植物上的丝核菌属(Rhizoctonia)(如立枯丝核病菌(R.solani));例如黑麦和大麦上的黑麦喙孢(Rhynchosporium secalis);油籽油菜、向日葵和其它植物上的核盘菌属(Sclerotinia)(例如核盘菌(Sclerotiniasclerotiorum));小麦上的小麦壳针孢(Septoria tritici)和颖枯壳多孢(Stagonospora nodorum);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属(Thievaliopsis);禾谷类上的腥黑粉菌属(Tilletia);禾谷类、玉米和糖用甜菜上的黑粉菌属(Ustilago);苹果和梨上的黑星菌属(Venturia)(黑星病)(例如苹果上的苹果黑星病(V.inaequalis))。它们特别适合防治选自卵菌纲的有害真菌如霜霉属、疫霉属、葡萄生单轴霉和假霜霉属。
本发明配制剂还适于防治有害真菌以保护材料如木材。真菌的实例为子囊菌纲真菌,如线嘴壳属(Ophiostoma spp.),长喙壳属(Ceratocystisspp.),出芽短梗霉(Aureobasidium pullulans),Sclerophoma spp.,毛壳属(Chaetomium spp.),腐质霉属(Humicola spp.),彼得壳属(Petriella spp.),毛束霉属(Trichurus spp.);担子菌纲真菌,如粉孢革菌属(Coniophoraspp.),革盖菌属(Coriolus spp.),粘褶菌属(Gloeophyllum spp.),香菇属(Lentinus spp.),侧耳属(Pleurotus spp.),卧孔属(Poria spp.),干朽菌属(Serpula spp.)和干酪菌属(Tyromyces spp.),半知菌纲真菌,如曲霉属(Aspergillus spp.),枝孢属(Cladosporium spp.),青霉属(Penicillium spp.),木霉属(Trichoderma spp.),链格孢属(Alternaria spp.),拟青霉属(Paecilomyces spp.)和接合菌纲(Zygomycetes)真菌,如毛霉属(Mucor spp.)。
本发明进一步涉及一种防治作物中的不希望的植物生长的方法(所述作物尤其为燕麦、大麦、小米、玉米、稻、小麦、甘蔗、棉花、油菜、亚麻、扁豆、糖用甜菜、烟草、向日葵和大豆或多年生作物),该方法包括使有效量的本发明农业化学配制剂作用于植物、其生长地或所述植物的种子。
本发明进一步涉及一种防治通过基因工程或通过育种而耐受一种或多种除草剂和/或杀真菌剂和/或耐受昆虫侵袭的作物中的不希望植物生长的方法,该方法包括使有效量的本发明农业化学配制剂作用于植物、其生长地或所述植物的种子。
防治不希望的植物生长理解为指破坏杂草。在最宽的意义上,杂草应理解为指那些生长在其中不希望它们生产的场所的所有植物,例如:
如下类型的双子叶杂草:白芥属(Smapis)、独行菜属(Lepidium)、猪殃殃属(Galium)、繁缕属(Stellaria)、母菊属(Matricaria)、春黄菊属(Anthemis)、牛膝菊属(Galinsoga)、藜属(Chenopodium)、荨麻属(Urtica)、千里光属(Senecio)、苋属(Amaranthus)、马齿苋属(Portulaca)、苍耳属(Xanthium)、旋花属(Convolvulus)、番薯属(Ipomoea)、蓼属(Polygonum)、田菁属(Sesbania)、豚草属(Ambrosia)、蓟属(Cirsium)、飞廉属(Carduus)、苦苣菜属(Sonchus)、茄属(Solanum)、蔊菜属(Rorippa)、节节菜属(Rotala)、母草属(Lindernia)、野芝麻属(Lamium)、婆婆纳属(Veronica)、苘麻属(Abutilon)、刺酸模属(Emex)、曼陀罗属(Datura)、堇菜属(Viola)、鼬瓣花属(Galeopsis)、罂粟属(Papaver)、矢车菊属(Centaurea)、车轴草属(Trifoliu m)、毛莨属(Ranunculus)、蒲公英属(Taraxacum)。
如下类型的单子叶植物:稗属(Echinochloa)、狗尾草属(Setaria)、黍属(Panicum)、马唐属(Digitaria)、梯牧草属(Phleum)、早熟禾属(Poa)、羊茅属(Festuca)、椮属(Eleusine)、臂形草属(Brachiaria)、黑麦草属(Lolium)、雀麦属(Bromus)、燕麦属(Avena)、莎草属(Cyperus)、高梁属(Sorghum)、冰草属(Agropyron)、狗牙根属(Cynodon)、雨久花属(Monochoria)、飘拂草属(Fimbristyslis)、慈姑属(Sagittaria)、荸荠属(Eleocharis)、藨草属(Scirpus)、雀稗属(Paspalum)、鸭嘴草属(Ischaemum)、尖瓣花属(Sphenoclea)、龙爪茅属(Dactyloctenium)、剪股颖属(Agrostis)、看麦娘属(Alopecurus)、阿披拉草属(Apera)。
因此,如上所述,本发明配制剂可经由各种方法施用。
在本发明的一个实施方案中,本发明配制剂的叶面施用例如通过喷雾或撒粉或其它施用而向种子、秧苗、植物施加混合物来进行。
本发明的另一实施方案包括在植物播种之前(如土壤浸润)或播种后或植物出苗前或出苗后例如通过喷雾或撒粉或其它施用向土壤施加混合物而进行土壤处理。
根据土壤施用的一个变型,本发明的另一目的是一种通过特别施加入种子条播机中而处理土壤的方法。
根据本发明土壤施用的一个变型,本发明另一主题是犁沟处理,其包括将固体或液体配制剂加入其中播种了种子的敞开犁沟中,或者将种子和配制剂同时施加入敞开犁沟中。
本发明的另一实施方案包括处理植物的种子或秧苗。
术语种子处理包括本领域已知的合适的所有种子处理技术,如拌种、种子包衣、种子撒粉、种子浸泡和种子造粒。
因此,本发明配制剂的施用通过喷雾或撒粉或其它施用而向种子或秧苗施加本发明配制剂来进行。
本发明还包括用本发明配制剂涂覆的种子。
术语种子包括种子和各种植物繁殖体,包括但不限于真正种子、种子块、根出条、球茎、鳞茎、果实、块茎、谷粒、插条、伐条等且在优选实施方案中意指真正种子。
合适的种子为禾谷类、根用作物、油料作物、蔬菜、香料、观赏植物的种子,例如以下植物的种子:硬粒小麦及其它小麦、大麦、燕麦、黑麦、玉米(饲料玉米和甜玉米/甜玉米和大田玉米)、大豆、油料作物、十字花科植物、棉花、向日葵、香蕉、水稻、油菜、球茎甘蓝、糖用甜菜、饲料甜菜、茄子、土豆、草、草坪、草皮、牧草、西红柿、韮菜、南瓜、卷心菜、卷心莴苣、胡椒、黄瓜、甜瓜、芸苔(Brassica)属、甜瓜、菜豆、豌豆、大蒜、洋葱、胡萝卜、块茎类植物(如土豆)、糖用甘蔗、烟草、葡萄、矮牵牛、天竺葵、三色堇和凤仙花。
另外,本发明配制剂也可处理由于包括基因工程方法在内的育种而对除草剂或杀真菌剂或杀虫剂具有耐受性的植物种子,例如转基因作物的种子,该转基因作物耐受选自磺酰脲类(EP-A-0257993、美国专利号5,013,659)、咪唑啉酮类(例如参见US 6,222,100、WO 01/82685、WO00/26390、WO 97/41218、WO 98/02526、WO 98/02527、WO 04/106529、WO 05/20673、WO 03/14357、WO 03/13225、WO 03/14356、WO 04/16073)、草铵膦类(例如参见EP-A-0242236、EP-A-242246)或草甘膦类(例如参见WO 92/00377)的除草剂,或可用于耐受选自环己二烯酮/芳氧基苯氧基丙酸除草剂的除草剂的植物的种子(US 5,162,602、US 5,290,696、US 5,498,544、US 5,428,001、US 6,069,298、US 6,268,550、US 6,146,867、US 6,222,099、US 6,414,222)或可用于能够产生使植物抵抗某些害虫的芽孢杆菌(Bacillusthuringiensis)毒素(Bt毒素)的转基因作物植物如棉花的种子(EP-A-0142924、EP-A-0193259)。
本发明配制剂的种子处理施用通过在植物播种之前和植物出苗之前通过本领域熟练技术人员已知的方法对种子喷雾或撒粉而进行。
在处理种子中,通过用有效量的本发明配制剂处理种子来施用相应配制剂。本文中,农药的施用率通常为每100kg种子0.1g至10kg,优选每100kg种子1g至5kg,尤其是每100kg种子1g至2.5kg。对于诸如莴苣和洋葱的特定作物而言,施用率可更高。
对本发明而言,优选种子处理和土壤(或植物生长地)处理。
本发明通过如下非限制性实施例进一步阐述。
实施例
为制备聚合物使用如下装置。
具有控制工艺的水浴、锚式搅拌器和温度计的2L开口装置。该装置具有用于3股进料的接头、回流冷凝器和用于引入氮气或蒸汽的入口管。或者使用不具有回流冷凝器的6L密闭装置。该装置用于在高于溶剂沸点的温度下合成聚合物。
所用缩写
VP 乙烯基吡咯烷酮
4-Vpyr 4-乙烯基吡啶
V59 2,2’-偶氮二(2-甲基丁腈)
IT 内部温度
t 进料引入时间
VI 乙烯基咪唑
iP 异丙醇
tBHP 氢过氧化叔丁基
NaBS 亚硫酸氢钠
实施例1:制备聚合物A
制备VP/4-Vpyr(75/25mol%)共聚物,其中装置具有回流冷凝器。
向起始装料(65g进料1、15g进料2、27g乙醇)中通入氮气并加热至80℃的反应器内部温度。然后启动进料1(166.65g VP、52.7g 4-Vpyr、215g乙醇)和2(2.19g V59、100g乙醇)。进料1在4小时内引入,进料2在5小时内引入。然后,将反应混合物在80℃下再保持2小时。然后在30分钟内引入进料3(4.39g V59、50g乙醇)。又将反应混合物在80℃下再保持2小时。如果对聚合物进行季铵化,则用200g乙醇稀释反应混合物。如果聚合物以未季铵化形式使用,则蒸除乙醇并对反应混合物进行蒸汽蒸馏。
实施例2:制备聚合物B-F,其中装置具有回流冷凝器
聚合物B通过季铵化聚合物A而制备
向起始装料(200g聚合物A)中通入氮气并加热至30℃的反应器内部温度。然后将进料1(21.7g硫酸二乙酯)在1小时内引入。在引入进料1之后,将反应容器在30℃下再保持1小时,然后加热至溶剂回流。在回流下再保持2小时。蒸除乙醇,并对反应混合物进行蒸汽蒸馏。在蒸馏之后,用200g水稀释聚合物溶液。
类似于实施例1进行聚合物C-F的聚合。如果将聚合物季铵化,则类似于实施例2进行季铵化。用于起始装料的量和物质、进料1、2和3如表1所设定。
表1
起始装料 | 进料1t=4h | 进料2t=9h | 进料3 | ||
聚合物CIT=120℃ | 聚合,密闭装置 | 180g乙醇252g进料160g进料2 | 444.4g VP421.6g 4-Vpyr860g乙醇 | 33.2g V59450g乙醇 |
起始装料 | 进料1t=4h | 进料2t=9h | 进料3 | ||
聚合物DIT=120℃ | 聚合,密闭装置 | 180g乙醇252g进料160g进料2 | 222.2g VP632.4g 4-Vpyr860g乙醇 | 33.2g V59450g乙醇 | |
起始装料 | 进料1t=3h | 进料2分批 | 进料3t=30分钟 | ||
聚合物EIT=85℃ | 聚合,敞开装置 | 50g VI450g VP1200g水 | 5g V59100g iP | 3.6g tBHP | 2.5g NaBS100g水 |
起始装料 | 进料1t=1h | 进料2 | 进料3 | ||
聚合物F | 季铵化,敞开装置 | 100g聚合物E400g乙醇 | 26.4g十二烷基溴 |
实施例3-根吸收
为测试本发明聚合物的根内吸作用,使用辐射活性标记的啶酰菌胺(类似于EP 0545099基于14C标记的吡啶而制备)。对于测试,用啶酰菌胺/聚合物在水/丙酮混合物中的溶液浸润蛭石中的小麦植物。作为参比,使用不含聚合物的啶酰菌胺在水/丙酮混合物中的溶液[将25μl冷的活性溶液(10000ppm的在丙酮中的储备溶液),20μl热活性溶液(0.1ppm,在丙酮中,1μl对应于~22000Bcq),25μl丙酮和25μl聚合物溶液(在水中的10000ppm储备溶液)混合并再充入水至10ml]。在48和120小时之后,从植物上切下叶并溶于Soluene 350(60-80%甲苯,20-40%氢氧化十二烷基(二甲基)(十四烷基)铵,2.5-10%甲醇)中。然后测量植物材料中的辐射活性。植物材料中的高辐射活性对应于高的活性成分吸收。结果示于表2。
表2
测量时的时间[h] | 吸收[Bcq] | |
不含聚合物的参比 | 120 | 228 |
聚合物A | 120 | 735 |
聚合物B | 120 | 393 |
聚合物C | 120 | 413 |
聚合物D | 120 | 520 |
结果显示,聚合物A-D实现了根吸收的显著改进。
实施例4-叶吸收
为了测量具有聚合物的叶吸收,将辐射标记的噻草平的水/DMF溶液(类似于现有技术已知的方法制备,基于14C标记的苯)(1μl冷的活性溶液(10000ppm,在DMF中的溶液),10μl热的活性溶液(0.1ppm,在DMF中,~2000000计数/μl),9μl聚合物溶液(1000ppm水溶液)和80μl DMF)滴加至小麦植物的叶(每片叶10滴)。分别在48和168小时之后,在各自的时间之后切下叶,通过用醋酸纤维素膜刮叶片而除去叶表面的过量活性物质。然后用Soluene 350溶解叶,以测定被植物吸收的活性成分的绝对量。作为参比,施加不含聚合物的在水/DMF中的活性物质。结果示于表3。
表3
结果显示聚合物B、E和F实现了显著改进的叶吸收。
实施例5-根吸收
为了测试具有聚合物的锐劲特的根内吸作用,用hoagland溶液/丙酮混合物(0.6体积%丙酮)中的20ml锐劲特/聚合物(1∶1重量比)浸润蛭石中的小麦植物。使用两种锐劲特和聚合物浓度(3ppm和6ppm)。作为参比,使用不含聚合物的在Hoagland溶液/丙酮混合物中的锐劲特溶液。Hoagland溶液由如下成分组成:
0.25体积%1M KNO3水溶液,0.1体积%1M MgSO4水溶液,0.05体积%1M KH2PO4水溶液,0.25体积%1M Ca(NO3)2)水溶液,0.05体积%由2.86g/l H3BO3,1.81g/l MnCl2*4H2O,0.22g/l ZnSO4*7H2O,0.08g/lCuSO4*5H2O,0.016g/lMoO3组成的微量元素水溶液,0.075体积%乙二胺四乙酸钠138Fe(由30g/l钠铁乙二胺二-(邻羟基苯基乙酸盐)水溶液组成),99.225体积%灭菌水并用NaOH将pH调节至6-6.5。
然后用蚜虫侵染植物。在4天后,计算小麦植物上的蚜虫数量。锐劲特和具有聚合物的锐劲特的结果基于未用锐劲特处理的植物上的蚜虫数量。结果示于表4。
表4
结果显示聚合物A和C对两种浓度均实现了显著改进的害虫防治。
实施例6-种子处理
为了测试聚合物,将100μL COSMOS50FS(购自BASFAktiengesellschaft的用于种子处理的市售含水悬浮液浓缩物,包含500g/L锐劲特)与1100μL 4.5重量%的聚合物水溶液混合。作为参比,使用(“不含聚合物的COSMOS50FS”),在1100μL水中的100μL COSMOS50FS混合物。然后用300μl聚合物/COSMOS50FS混合物(对应于25g锐劲特/100kg种子和25g聚合物/100kg种子)处理100粒糖用甜菜的种子两次,用300μl参比(“不含聚合物的COSMOS50FS”)处理另外的100粒种子两次。
将糖用甜菜的种子在温室条件下播种在含有土壤的styropor箱中。在约10-15cm的植物高度时取样。在取样后,将植物(两种处理组)分为两部分(植物的胚轴和剩余部分)。将样品在取样之后立即冷冻并保持冷冻直至分析。在分析之前,使用Stephans磨机在干冰存在下将样品材料均化导致非常小的样品颗粒。
使用甲醇和水的混合物从植物基质中萃取锐劲特。为了提纯,使用相对于二氯甲烷的液/液分配。最后,通过HPLC-MS/MS进行锐劲特含量的测定。结果示于表4。
表4
结果显示,在种子处理实验中,聚合物C实现了显著改进的根吸收。
Claims (14)
1.一种包含至少一种农药和至少一种共聚物的配制剂,该共聚物以聚合形式包含:
(a)式I的N-乙烯基酰胺共聚单体a):
其中R1和R2相互独立地为氢或C1-C4烷基,优选氢,或
R1和R2一起表示-(CH2)x结构部分,其与氮和羰基结构部分一起形成5-8元环,和
(b)至少一种选自乙烯基吡啶、乙烯基吡啶衍生物和N-乙烯基咪唑的共聚单体b)。
2.根据权利要求1的配制剂,其中所述共聚物包含90-10重量%共聚单体a)和10-90重量%共聚单体b)。
3.根据权利要求2的配制剂,其中所述共聚物的各组分的重量%数据总计为100重量%。
4.根据权利要求1-3中任一项的配制剂,其中所述共聚物包含2-乙烯基吡啶、3乙烯基吡啶、4-乙烯基吡啶或乙烯基-2-甲基-5-吡啶作为共聚单体b)。
5.根据权利要求1-4中任一项的配制剂,其中所述共聚物包含1-乙烯基-2-吡咯烷酮作为共聚单体a)。
6.根据权利要求1-5中任一项的配制剂,其中所述共聚物包含1-乙烯基-2-吡咯烷酮作为共聚单体a)和4-乙烯基吡啶作为共聚单体b)。
7.根据权利要求1-6中任一项的配制剂,其进一步包含配制助剂。
8.根据权利要求1-7中任一项的配制剂,其中所述农药为赋予植物健康效果的农药。
11.一种对抗有害昆虫和/或植物病原性真菌的方法,其包括使有害昆虫和/或植物病原性真菌在其中或其上生长或会生长的植物、种子、土壤或植物生长地,需防止所述有害昆虫和/或植物病原性真菌侵袭或侵染的植物、种子或土壤与有效量的根据权利要求1-7中任一项的农业化学配制剂接触。
12.一种防治不希望的植物生长的方法,其包括使除草有效量的根据权利要求1-7中任一项的农业化学配制剂作用于植物、其生长地或所述植物的种子。
13.一种改善植物健康的方法,其包括向植物、植物部分或植物生长的场所施加根据权利要求8的配制剂。
14.用根据权利要求1-8中任一项的配制剂处理的种子。
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BRPI0719399A2 (pt) | 2014-02-18 |
BRPI0719399B8 (pt) | 2016-06-28 |
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US20100075850A1 (en) | 2010-03-25 |
IL198300A0 (en) | 2010-02-17 |
CA2668564A1 (en) | 2008-06-05 |
EP2099292A1 (en) | 2009-09-16 |
BRPI0719399B1 (pt) | 2016-03-08 |
US8097562B2 (en) | 2012-01-17 |
EA016925B1 (ru) | 2012-08-30 |
EP2099292B1 (en) | 2010-05-26 |
ATE468748T1 (de) | 2010-06-15 |
WO2008064987A1 (en) | 2008-06-05 |
JP5323714B2 (ja) | 2013-10-23 |
ZA200904512B (en) | 2010-09-29 |
EA200900642A1 (ru) | 2009-12-30 |
DE602007006842D1 (de) | 2010-07-08 |
ES2346263T3 (es) | 2010-10-13 |
CN101541169B (zh) | 2013-05-15 |
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