CN103260407A - 节肢害虫防治组合物和用于防治节肢害虫的方法 - Google Patents
节肢害虫防治组合物和用于防治节肢害虫的方法 Download PDFInfo
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Abstract
公开了对于节肢害虫具有优异的防治效果的节肢害虫防治组合物，其包含式（I）所示的化合物∶
Description
技术领域
本申请对于日本专利申请No. 2010-289610主张优先权，其全部内容通过参考而并入本文中。
本发明涉及节肢害虫防治组合物和用于防治节肢害虫的方法。
背景技术
以往，已知有各种化合物作为节肢害虫防治组合物中的活性成分 (例如参考专利文献 1和非专利文献 1)。
引用的现有技术文献
专利文献
专利文献 1∶ WO 2009/099929
非专利文献
非专利文献 1∶ 杀虫剂手册-第15版(BCPC出版)； ISBN 978-1-901396-18-8。
发明内容
本发明的目的是提供对于节肢害虫有优良的防治效果的节肢害虫防治组合物。
本发明人等为了提供对节肢害虫有优良防治效果的节肢害虫防治组合物而进行了大量研究，结果发现包含下述式（I）所示的化合物和甲霜灵（metalaxyl）或精甲霜灵（metalaxyl M）的组合物对于节肢害虫具有优异的防治效果，由此实现本发明。
本发明提供∶
[1] 节肢害虫防治组合物，其包含下式（I）所示的化合物和甲霜灵或精甲霜灵，
其中，
Q表示CR5=CR6，S，O或NCH3，
R1表示卤素原子，氰基，硝基，任选卤代的C1-C4 烷基，任选卤代的C2-C4 烯基，任选卤代的C2-C4 炔基或任选卤代的C1-C4 烷氧基，
n表示0～3的整数，
R2表示下述R2a，R2b，R2c或R2d∶
其中，
R3a，R3b和R3c 各自独立地表示卤素原子，氰基，硝基，任选卤代的C1-C4 烷基，任选卤代的C2-C4 炔基或任选卤代的C1-C4 烷氧基，
R3d表示卤素原子，氰基，硝基，任选卤代的C1-C4 烷基或任选卤代的C1-C4 烷氧基，
Xa，Xb，Xc和Xd 各自独立地表示0，1或2，
Zb和Zc 各自独立地表示O，S或NR7，
R7表示氢原子或任选卤代的C1-C4 烷基，
其中，
当Xa表示2时，两个R3a可以相同或不同，
当Xb表示2时，两个R3b可以相同或不同，
当Xc表示2时，两个R3c可以相同或不同，和
当Xd表示2时，两个R3d可以相同或不同，
R5表示氢原子或氟原子，和
R6表示氢原子，氟原子，二氟甲基或三氟甲基，
其中，
当n表示2或3时，多个R1可以相同或不同。
[2] 根据上述[1]所述的节肢害虫防治组合物，其中式（I）所示的化合物与甲霜灵或精甲霜灵的质量比为10000∶1～0.01∶1；
[3] 用于防治节肢害虫的方法，其包括将有效量的根据上述[1]或[2]所述的节肢害虫防治组合物施用于植物或植物栽培区域；
[4] 根据上述[3]所述的用于防治节肢害虫的方法，其中，所述植物或植物栽培区域为植物的种子。
根据本发明，可防治节肢害虫。
具体实施方式
本发明的节肢害虫防治组合物包含下式(I)所示的化合物 (以下称为"中离子化合物")∶
其中，
Q表示CR5=CR6，S，O或NCH3，
R1表示卤素原子，氰基，硝基，任选卤代的C1-C4 烷基，任选卤代的C2-C4 烯基，任选卤代的C2-C4 炔基或任选卤代的C1-C4 烷氧基，
n表示0～3的整数，
R2表示下述R2a，R2b，R2c或R2d∶
其中，
R3a，R3b和R3c 各自独立地表示卤素原子，氰基，硝基，任选卤代的C1-C4 烷基，任选卤代的C2-C4 炔基或任选卤代的C1-C4 烷氧基，
R3d表示卤素原子，氰基，硝基，任选卤代的C1-C4 烷基或任选卤代的C1-C4 烷氧基，
Xa，Xb，Xc和Xd 各自独立地表示0，1或2，
Zb和Zc 各自独立地表示O，S或NR7，
R7表示氢原子或任选卤代的C1-C4 烷基，
其中，
当Xa表示2时，两个R3a可以相同或不同，
当Xb表示2时，两个R3b可以相同或不同，
当Xc表示2时，两个R3c可以相同或不同，和
当Xd表示2时，两个R3d可以相同或不同，
R5表示氢原子或氟原子，和
R6表示氢原子，氟原子，二氟甲基或三氟甲基，
其中，
当n表示2或3时，多个R1可以相同或不同；和
甲霜灵或精甲霜灵 (以下称为"活性化合物")。
式(I) 中R1，R2a，R2b，R2c，R2d，R3a，R3b，R3c，R3d和R7的例子包括如下∶
由R1，R3a，R3b，R3c或R3d 表示的“卤素”的例子包括氟原子，氯原子，溴原子和碘原子。
由R1，R3a，R3b，R3c，R3d或R7表示的“任选卤代的C1-C4 烷基”的例子包括甲基，三氟甲基，三氯甲基，氯甲基，二氯甲基，氟甲基，二氟甲基，乙基，五氟乙基，2，2，2-三氟乙基，2，2，2-三氯乙基，丙基，1-甲基乙基，1-三氟甲基四氟乙基，丁基，2-甲基丙基，1-甲基丙基和1，1-二甲基乙基。
由R1表示的“任选卤代的C2-C4 烯基”的例子包括2-丙烯基，3-氯-2-丙烯基，2-氯-2-丙烯基，3，3-二氯-2-丙烯基，2-丁烯基，3-丁烯基和2-甲基-2-丙烯基。
由R1，R3a，R3b或R3c表示的“任选卤代的C1-C4 炔基”的例子包括2-丙炔基，3-氯-2-丙炔基，3-溴-2-丙炔基，2-丁炔基和3-丁炔基。
由R1，R3a，R3b，R3c或R3d表示的“任选卤代的C1-C4 烷氧基”的例子包括甲氧基，三氟甲氧基，乙氧基，2，2，2-三氟乙氧基，丙氧基，1-甲基乙氧基，丁氧基，2-甲基丙氧基，1-甲基丙氧基和1，1-二甲基乙氧基。
R2a 的例子包括6-氟-3-吡啶基，6-氯-3-吡啶基，6-溴-3-吡啶基，6-甲基-3-吡啶基，6-氰基-3-吡啶基，3-吡啶基，2-吡啶基，和5，6-二氯-3-吡啶基。
R2b 的例子包括2-氟-5-噻唑基，2-氯-5-噻唑基，2-溴-5-噻唑基，2-甲基-5-噻唑基，5-噻唑基，2-氟-5-噁唑基，2-氯-5-噁唑基，5-噁唑基，2-氯-1-甲基-5-咪唑基和2-氟-1-甲基-5-咪唑基。
R2c的例子包括1-甲基-4-吡唑基和3-甲基-5-异噁唑基。
R2d的例子包括四氢呋喃-2-基和四氢呋喃-3-基。
Q表示CR5=CR6的式（I）所示的化合物由下式(II-a)表示∶
其中R1，R2，R5，R6和n 与前述定义相同。
Q表示S的式（I）所示的化合物由下式(II-b)表示∶
其中R1，R2和n 与前述定义相同。
Q表示O的式（I）所示的化合物由下式(II-c)表示∶
其中R1，R2和n 与前述定义相同。
Q表示NCH3 的式（I）所示的化合物由下式(II-d)表示∶
其中R1，R2和n 与前述定义相同。
中离子化合物的例子包括下述化合物∶
由式(I)表示的那些化合物，其中n表示0或1，当n表示0时，R2表示2-氯-5-噻唑基，1-甲基-4-吡唑基，6-氯-3-吡啶基或四氢呋喃-3-基，和Q为CH=CH或S，当n表示1时，R1表示氟原子，氯原子，溴原子，甲基，甲氧基，三氟甲基或三氟甲氧基，和R2表示2-氯-5-噻唑基，6-氯-3-吡啶基，1-甲基-4-吡唑基或四氢呋喃-3-基，和Q 为CH=CH或S；
由式(I)表示的那些化合物，其中n表示0或1，当n表示1时，R1表示氟原子，氯原子，溴原子，甲基，甲氧基，三氟甲基或三氟甲氧基，和R2表示2-氯-5-噻唑基，6-氯-3-吡啶基，1-甲基-4-吡唑基或四氢呋喃-3-基，和Q 为CH=CH或S；
由式(I)表示的那些化合物，其中n表示0或1，当n表示0时，R2表示2-氯-5-噻唑基，和Q表示CH=CH，当n表示1时，R1表示氟原子，三氟甲基或三氟甲氧基，和R2表示2-氯-5-噻唑基或6-氯-3-吡啶基，和Q表示CH=CH；
由式(I)表示的那些化合物，其中n表示0或1，当n表示1时，R1表示氟原子，三氟甲基或三氟甲氧基，和R2表示2-氯-5-噻唑基或6-氯-3-吡啶基，和Q表示CH=CH。
中离子化合物的具体例子包括式(I-a)所示的这些化合物∶
其中n，R1和R2的组合表示表1和2中所示的任意组合。
表1
表2
在表1和2中，R1中的取代基"3-OCF3"，"3-Br"等中所示的"3-" 是指这样的取代基作为R1存在于上式 (I-a)中的苯环的3-位上。
由式(I-b)表示的化合物∶
其中n，R1和R2的组合表示表3中所示的任意组合。
表3
| 化合物编号 | n | R1 | R2 | |
| 40 | 0 | - | - | 6-氯-3-吡啶基 |
| 41 | 0 | - | - | 2-氯-5-噻唑基 |
| 42 | 1 | 2-F | - | 6-氯-3-吡啶基 |
| 43 | 1 | 2-F | - | 2-氯-5-噻唑基 |
| 44 | 1 | 3-OCF3 | - | 6-氯-3-吡啶基 |
| 45 | 1 | 3-OCF3 | - | 2-氯-5-噻唑基 |
| 46 | 1 | 4-F | - | 6-氯-3-吡啶基 |
| 47 | 1 | 4-F | - | 2-氯-5-噻唑基 |
| 48 | 2 | 2-F | 3-F | 6-氯-3-吡啶基 |
| 49 | 2 | 2-F | 3-F | 2-氯-5-噻唑基 |
| 50 | 2 | 2-F | 4-F | 2-氯-5-噻唑基 |
| 51 | 2 | 2-F | 4-F | 6-氯-3-吡啶基 |
| 52 | 2 | 3-OCF3 | 5-Br | 2-氯-5-噻唑基 |
| 53 | 2 | 3-OCF3 | 5-Br | 6-氯-3-吡啶基 |
在表3中，R1中的取代基"3-OCF3"，"3-F"等中所示的"3-" 是指这样的取代基作为R1存在于上式 (I-b)中的苯环的3-位上。
本发明中使用的该中离子化合物包括式(I)所示的形式和由不同于式(I)的式子表示的其离子化的形式，且可以单独以上述形式中的任一种使用，或将其两种或更多种组合使用。
该中离子化合物可以例如通过WO 2009/099929中记载的方法来制备。
本发明中使用的甲霜灵和精甲霜灵为已知的化合物，例如在"杀虫剂手册-第15版(BCPC出版)； ISBN 978-1-901396-18-8"的第737和739页中记载。这些化合物为市售品或可以由已知的方法制造。
在本发明的节肢害虫防治组合物中，活性化合物与中离子化合物的重量比不特别限定，但相对于100重量份的中离子化合物，活性化合物通常为0.001～100000重量份，优选为0.01～10000重量份，即，[式（I）所示的化合物]∶(甲霜灵或精甲霜灵) = 10000∶1～0.01∶1，更优选 [式（I）所示的化合物]∶(甲霜灵或精甲霜灵) = 1000∶1～0.1∶1。
本发明的节肢害虫防治组合物可以通过简单地将中离子化合物与活性化合物混合来制备，但通常通过将中离子化合物、活性化合物和惰性载体、和根据需要的表面活性剂和/或其它制剂添加剂混合、然后将该混合物制成剂型、例如油溶液、可乳化浓缩物、悬浮剂、可湿性粉末、水分散颗粒剂、粉剂、或颗粒剂来制备。
由此所述制剂化的节肢害虫防治组合物可以直接用作节肢害虫防治剂，或在添加其它惰性成分后用作节肢害虫防治剂。
本发明的节肢害虫防治组合物中的中离子化合物和活性化合物的总量通常为0.1～99重量%，优选为0.2～90重量%，更优选为1～80重量%。
用于该节肢害虫防治组合物的制剂的固体载体的例子包括下述物质的细粉末或颗粒：矿物质（如高岭土、凹凸棒粘土、膨润土、蒙脱石、酸性白土、叶蜡石、滑石、硅藻土和方解石）、天然有机物质（如玉米芯粉和胡桃壳粉）、合成有机物质（如脲）、盐类（如碳酸钙和硫酸铵）、和合成无机物质（如合成水合二氧化硅）。
该液体载体的例子包括芳族烃类(例如二甲苯，烷基苯，和甲基萘)，醇类(例如2-丙醇，乙二醇，丙二醇，和乙二醇单乙醚)，酮类(例如丙酮，环己酮，和异佛尔酮)，植物油类(例如大豆油，和棉油)，石油系脂肪族烃类，酯类，二甲基亚砜，乙腈和水。
表面活性剂的例子包括阴离子表面活性剂（例如烷基硫酸酯盐，烷基芳基磺酸盐，二烷基磺基琥珀酸盐，聚氧化乙烯烷基芳基醚磷酸酯盐，木质素磺酸盐和萘磺酸盐甲醛缩聚物）；非离子型表面活性剂（例如聚氧化乙烯烷基芳基醚，聚氧化乙烯烷基聚氧化丙烯嵌段共聚物和失水山梨糖醇脂肪酸酯）；和阳离子表面活性剂（例如烷基三甲基铵盐）。
制剂添加剂的例子包括水溶性聚合物（如聚乙烯醇和聚乙烯吡咯烷酮）；多糖类（如阿拉伯胶，藻酸及其盐，CMC(羧甲基纤维素)，和苍耳烷胶（xanthane gum））；无机物质（如硅酸镁铝和氧化铝溶胶）；防腐剂，着色剂和稳定剂[（如PAP(酸式磷酸异丙基酯)），和BHT]。
本发明的节肢害虫防治组合物可以用于保护植物而使其避免受到由节肢害虫的摄食或吸汁所导致的损害。
本发明的节肢害虫组合物对其表现出防治效果的节肢害虫举例如下：
半翅目（Hemiptera）：
飞虱科如灰飞虱（Laodelphax striatellus）、褐飞虱（Nilaparvata lugens）和白背飞虱（Sogatella furcifera）； 角顶叶蝉科如黑尾叶蝉（Nephotettix cincticeps）、二点黑尾叶蝉（Nephotettix virescens），电光叶蝉（Recilia dorsalis），茶小绿叶蝉（Empoasca onukii）； 蚜科（Aphididae）例如棉蚜(Aphis gossypii)，桃蚜(Myzus persicae)，甘蓝蚜(Brevicoryne brassicae)，绣线菊蚜(Aphis spiraecola)，马铃薯蚜虫(Macrosiphum euphorbiae)，茄沟无网蚜(Aulacorthum solani)，禾谷缢管蚜(Rhopalosiphum padi)，桔蚜(Toxoptera citricidus)，桃大尾蚜(Hyalopterus pruni)，苹果绵蚜(Eriosoma lanigerum)； 蝽象科(Pentatomidae)如稻绿蝽(Nezara antennata)，赤须盲蝽(Trigonotylus caelestialium)，黑条红椿象(Graphosoma rubrolineatum)，Eysarcoris lewisi，豆蝽(Riptortus clavetus)，中华稻缘蝽(Leptocorisa chinensis)，二星蝽(Eysarcoris parvus)，茶翅蝽(Halyomorpha mista)，稻绿蝽(Nezara viridula)，和草盲蝽(Lygus lineolaris)； 粉虱科(Aleyrodidae)如温室粉虱(Trialeurodes vaporariorum)，烟粉虱(Bemisia tabaci)，通草粉虱(Dialeurodes citri)，和黑刺粉虱(Dialeurodes citri)； 蚧总科(Coccoidea)如红肾圆盾蚧(Aonidiella aurantii)，Comstockaspis perniciosa，桔矢尖盾蚧(Unaspis citri)，红蜡蚧(Ceroplastes rubens)，吹绵蚧(Icerya purchasi)，藤臀纹粉蚧(Planococcus kraunhiae)，Pseudococcus longispinis，和桑白蚧(Pseudaulacaspis pentagona)； 网蝽科(Tingidae)； 臭虫总科（Cimicoidea）例如温带臭虫（Cimex lectularius）； 木虱科（Psyllidae）例如梨木虱（Cacopsylla pyricola）； 等
鳞翅目(Lepidoptera)：
螟蛾科（Pyralidae）例如二化螟(Chilo suppressalis)，三化螟(Tryporyza incertulas)，稻纵卷叶螟(Cnaphalocrocis medinalis)，棉大卷叶螟(Notarcha derogata)，印度谷螟(Plodia interpunctella)，亚洲玉米螟(Ostrinia furnacalis)，菜心螟(Hellula undalis)，和早熟禾草暝(Pediasia teterrellus)； 夜蛾科（Noctuidae）例如斜纹夜蛾(Spodoptera litura)，甜菜夜蛾(Spodoptera exigua)，东方粘虫(Pseudaletia separata)，大螟(Sesamia inferens)，甘蓝夜蛾(Mamestra brassicae)，小地老虎(Agrotis ipsilon)，黑点银纹夜蛾(Plusia nigrisigna)，粉纹夜蛾(Trichoplusia ni)，Thoricoplusia spp.，棉花实夜蛾属害虫(Heliothis spp.)，和铃夜蛾属害虫(Helicoverpa spp.)； 粉蝶科(Pieridae)如菜粉蝶(Pieris rapae)； 卷蛾科(tortricid moths)如褐带卷蛾属害虫（Adoxophyes spp.），梨小食心虫(Grapholita molesta)，大豆食心虫(Leguminivora glycinivorella)，小豆象虫(Matsumuraeses azukivora)，苹小卷叶蛾(Adoxophyes orana fasciata)，茶小卷叶蛾(Adoxophyes honmai.)，卷叶蛾(Homona magnanima)，后黄卷叶蛾(Archips fuscocupreanus)，和苹果小卷蛾(Cydia pomonella)； 细蛾科(leafblotch miners)如 茶细蛾(Caloptilia theivora)，和金纹小潜细蛾(Phyllonorycter ringoniella)； 蛀果蛾科(Carposinidae)如桃蛀果蛾(Carposina niponensis)； 潜蛾科(Lyonetiidae)如潜蛾属(Lyonetia spp.)； 毒蛾科(Lymantriidae)如毒蛾属害虫(Lymantria spp.)，和黄毒蛾属害虫(Euproctis spp.)； 巢蛾科(Yponomeutidae)如小菜蛾(Plutella xylostella)； 麦蛾科(Gelechiidae)如棉红铃虫(Pectinophora gossypiella)，和马铃薯块茎蛾(Phthorimaea operculella)； 灯蛾科(Arctiidae)如美国白蛾(Hyphantria cunea)； 谷蛾科(Tineidae)如袋谷蛾(Tinea translucens)，和幕谷蛾(Tineola bisselliella)； 番茄斑潜蝇(Tuta absoluta)； 等
缨翅目(Thysanoptera)：
蓟马科（Thripidae）例如西花蓟马(Frankliniella occidentalis)，棕榈蓟马(Thrips palmi)，茶黄蓟马(Scirtothrips dorsalis)，葱蓟马(Thrips tabaci)，花蓟马(Frankliniella intonsa)，烟褐花蓟马(Frankliniella fusca)，稻蓟马(Stenchaetothrips biformis)，稻管蓟马(Stenchaetothrips biformis)； 等
双翅目（Diptera）∶
潜蝇科（Agromyzidae）例如葱蝇(Hylemya antiqua)，玉米种蝇(Hylemya platura)，稻黄潜蝇(Agromyza oryzae)，潜叶蝇(Hydrellia griseola)，稻秆蝇(Chlorops oryzae)，和三叶斑潜蝇(Liriomyza trifolii)； 瓜实蝇(Dacus cucurbitae)，地中海实蝇(Ceratitis capitata)； 等
鞘翅目（Coleoptera）∶
茄二十八星瓢虫（Epilachna vigintioctopunctata），黄守瓜（Aulacophora femoralis），黄曲条跳甲（Phyllotreta striolata），稻叶泥虫(Oulema oryzae)，稻鳞象甲(Echinocnemus squameus)，稻水象甲(Lissorhoptrus oryzophilus)，棉铃象甲(Anthonomus grandis)，绿豆象(Callosobruchus chinensis)，芝草害虫(Sphenophorus venatus)，日本金龟子(Popillia japonica)，铜色金龟子(Anomala cuprea)，玉米根虫(Diabrotica spp.)，马铃薯叶甲(Leptinotarsa decemlineata)，金针虫(Agriotes spp.)，烟草甲(Lasioderma serricorne)； 等
直翅目（Orthoptera）∶
非洲蝼蛄(Gryllotalpa africana)，小翅稻蝗(Oxya yezoensis)，日本稻蝗(Oxya japonica)； 等。
在上述节肢害虫中，飞虱科（Delphacidae），Deltocephalidae，蚜科（Aphididae）等适合于本发明。
本发明的节肢害虫防治组合物可以用来防治植物病害，例如在玉米，稻子，大豆，棉花，油菜籽，或小麦中由腐霉菌（Pythium spp.）引起的病害。
本发明的节肢害虫防治组合物可以用于农业用地如田地，稻田，旱地，草地，和果园中，或用于非农业用地中。本发明的节肢害虫防治组合物还可以用于防治栽培了“植物”等的农业用地等中的害虫。
可以施用本发明的节肢害虫防治组合物的植物的例子如下：
可以施用本发明的节肢害虫防治组合物的植物的例子如下：
农作物： 玉米，稻子，小麦，大麦，黑麦，燕麦，高粱，棉花，大豆，花生，荞麦，甜菜，油菜籽，向日葵，甘蔗，烟草等；
蔬菜：茄属蔬菜(茄子、西红柿、青椒、辣椒、马铃薯等)，葫芦科蔬菜(黄瓜、南瓜、西葫芦、西瓜、甜瓜等)，十字花科蔬菜 (日本萝卜、白萝卜、山葵、大头菜、大白菜、甘蓝菜、芥菜、西兰花、花椰菜、油菜等)，菊科蔬菜(牛蒡、苘蒿、洋蓟、生菜等)，百合科蔬菜（大葱、洋葱、大蒜、芦笋等)，伞形科蔬菜（胡萝卜、香菜、芹菜、欧洲防风草等)，藜科蔬菜（菠菜、唐莴苣等)，薄荷科蔬菜（日本紫苏、薄荷、罗勒等)，草莓、番薯、甘薯、天南星科植物等；
果树：仁果类水果（苹果、西洋梨、日本梨、木瓜、榅桲等)，核果类水果(stone fleshy fruit)(桃、李子、油桃、日本李子、樱桃、杏、洋李等)，柑橘类植物（温州蜜柑、橙、柠檬、来檬、葡萄柚等)，坚果类(栗、胡桃、榛子、杏仁、开心果、腰果、夏威夷果等)，浆果类(蓝莓，红莓，黑莓，树霉等)，葡萄、柿子、橄榄、李子、香蕉，咖啡，枣子、椰子、油棕等；
果树以外的树木：茶树、桑树、观花树木(杜鹃花，山茶花，绣球花，油茶，日本大茴香，樱桃，鹅掌楸，紫薇，丹桂（orange osmanthus）等)，行道树（灰树、桦树、山茱萸、桉树、银杏树、紫丁香、枫树、栎树、杨树、紫荆、中国香枫、悬铃树、光叶榉树（zelkova）、日本金钟柏（Japanese arborvitae）、冷杉树、日本铁杉树、刺柏树、松树、云杉、紫衫、云杉、榆树、七叶树等)，刺桐，罗汉松，雪松，日本柏树，巴豆，冬青卫矛（Euonymus japonicus），光叶石楠（Photinia glabra）等；
草地∶ 结缕草属（Zoysia）(结缕草（zoysiagrass），马尼拉草等)，狗牙草(狗牙根（Cynodon dactylon）等)，常绿草(小糠草，匍匐翦股颖，hiland bent等)，早熟禾 (草地早熟禾，普通早熟禾等)，牛毛草 (牛尾草，紫羊茅，匍匐紫羊茅等)，黑麦草(毒麦，黑麦草等)，果树草，猫尾草等；
其它∶ 花(玫瑰，康乃馨，菊花，桔梗，满天星，非洲菊，万寿菊，鼠尾草，矮牵牛花，马鞭草，郁金香，紫菀属植物，龙胆根，百合花，三色紫罗兰，仙客来，兰花，铃兰草，薰衣草，紫罗兰，羽衣甘蓝（ornamental cabbage），报春花，一品红，剑兰，洋兰，雏菊，兰花，秋海棠等)，生物燃料植物(麻疯树，红花，亚麻荠，柳枝稷，芒草，草芦，芦竹，洋麻，木薯，柳树等)，观赏植物等。
在上述植物中，玉米，稻子，大豆，棉花，油菜籽，小麦等适合于本发明。
这里使用的“植物”可以是具有通过基因工程技术或通过杂交方法被赋予的耐受性的那些植物。
本发明的节肢害虫防治组合物可以施用于植物或植物栽培区域，以用于防治其中的节肢害虫。这里使用的植物包括植物的茎和叶，植物的花，植物的果实，植物的种子和植物的球根（bulbs）。这里使用的球根（bulbs）包括鳞茎（scaly bulb），球茎，初生主根，块茎，块状根，和根托。
本发明的用于防治节肢害虫的方法包含将有效量的本发明的节肢害虫防治组合物施用于植物或植物栽培区域。
创造性的方法还包括将中离子化合物和活性化合物分别地或连续地施用的方案。
本文中使用的“有效量的节肢害虫防治组合物”是指可对节肢害虫发挥防治效果的、中离子化合物和活性化合物的总量。
施用方法的例子包括对植物的茎和叶的施用，例如叶面施用（foliage application）； 对植物的种子的施用；和对植物栽培区域的施用，例如土壤施用和水下施用。
在本发明中，对植物的茎和叶的施用、例如叶面施用（foliage application）的具体例子包括通过使用人工喷雾器，动力喷雾器，喷管式喷雾器或Pancle喷雾器对栽培植物的表面的施用、例如地面施用（ground application），或空中施用（aerial application）或通过使用无线电控制直升飞机喷洒等。
在本发明中，对植物的种子施用的具体例子包括将本发明的节肢害虫防治组合物施用于植物的种子或球根（bulbs），更具体地，例如在种子或球根（bulbs）的表面上的喷雾涂布处理，在植物的种子或球根（bulbs）上的敷裹处理（dressing treatment），浸渍处理，涂膜处理和包丸处理(pellet-coating treatment)。
在本发明中，对植物栽培区域的施用、例如土壤施用和水下施用的具体例子包括栽植穴处理，植物发根处理（plant foot treatment），栽植沟处理，植行处理（planting row treatment），撒施（broadcast application），侧行处理（side row treatment），秧苗箱处理（seedling box treatment），苗床处理，与栽培土壤混合，与苗床土壤混合，与糊状肥料混合，水面处理等。
当将本发明的节肢害虫防治组合物施用于植物或植物栽培区域时，该施用量根据欲保护的植物的种类，欲防治的节肢害虫的种类或群体大小，制剂形式，施用时期，天气条件等而不同，但按照中离子化合物和活性化合物的总量算，每1000 m2 的植物栽培区域通常为0.05～10000 g的范围，优选为0.5～1000 g的范围。
当将本发明的节肢害虫防治组合物施用于植物的种子时，该施用量根据欲保护的植物的种类，欲防治的节肢害虫的种类或群体大小，制剂形式，施用时期，天气条件等而不同，但按照中离子化合物和活性化合物的总量算，每1kg种子通常为0.001～100 g的范围，优选为0.05～50 g的范围。
本发明的节肢害虫防治组合物在为可乳化浓缩物、可湿性粉末或悬浮剂的形式时通常在用水稀释后施用。该情况下，该中离子化合物和该活性化合物的总浓度一般为0.00001～10重量%，优选为0.0001～5重量%。本发明的节肢害虫防治组合物为粉剂或颗粒剂的形式时，通常在不稀释的情况下施用。
实施例
以下将参考制剂实施例和试验实施例更详细地描述本发明，但是本发明不仅仅局限于此。在实施例中，除非特别说明，术语“份”是指重量份，“中离子化合物编号 X”(例如“中离子化合物编号 4”)在表1～3中表示为“化合物编号 X” (例如“化合物编号 4”)。
制剂实施例如以下所示。
制剂实施例1
将二十份中离子化合物编号1，4，5，42和44中的每一种，1份甲霜灵，和35份白炭与聚氧乙烯烷基醚硫酸铵盐(重量比1∶1)的混合物混合，用水调至总量为100份。然后将该混合物通过湿磨法磨细，以得到悬浮剂。
制剂实施例2
将二十份中离子化合物编号1，4，5，42和44中的每一种，0.5份精甲霜灵，和35份白炭与聚氧乙烯烷基醚硫酸铵盐(重量比1∶1)的混合物混合，用水调至总量为100份，然后将该混合物通过湿磨法磨细，以得到悬浮剂。
制剂实施例3
将十份中离子化合物编号1，4，5，42和44中的每一种，1份甲霜灵，1.5份脱水山梨糖醇三油酸酯，和28份含有2份聚乙烯醇的水溶液混合，然后将该混合物通过湿磨法磨细。向该混合物中，添加含有0.05份苍耳烷胶和0.1份硅酸铝镁的水溶液至总量90份，然后向其中加入10份丙二醇。将所得混合物搅拌，以得到悬浮剂。
制剂实施例4
将十份中离子化合物编号1，4，5，42和44中的每一种，0.5份精甲霜灵，1.5份脱水山梨糖醇三油酸酯，和28份含有2份聚乙烯醇的水溶液混合，然后将该混合物通过湿磨法磨细。向该混合物中，添加含有0.05份苍耳烷胶和0.1份硅酸铝镁的水溶液至总量90份，然后向其中加入10份丙二醇。将所得混合物搅拌，以得到悬浮剂。
制剂实施例5
将四十份中离子化合物编号1，4，5，42和44中的每一种，1份甲霜灵，3份木质素磺酸钙，2份十二烷基硫酸钠，和剩余份的合成水合二氧化硅充分混合，同时进行磨碎，以得到100份可湿性粉末。
制剂实施例6
将四十份中离子化合物编号1，4，5，42和44中的每一种，0.5份精甲霜灵，3份木质素磺酸钙，2份十二烷基硫酸钠，和剩余份的合成水合二氧化硅充分混合，同时进行磨碎，以得到100份可湿性粉末。
本发明的效果根据试验实施例如下所示。
试验实施例1
将中离子化合物编号 4，5，42和44，和精甲霜灵各10mg各自溶解在0.2 ml 的5%(w/v) SORGEN TW-20 (由Dai-ichi Kogyo Seiyaku Co.，Ltd.制造)的丙酮 (由Wako Pure Chemical Industries，Ltd.制造)溶液中，然后用水稀释至规定浓度。
将中离子化合物编号4，5，42和44的各水稀释液和精甲霜灵的水稀释液混合以制备试验溶液。
将稻子的种子 (Oryza sativa； 栽培品种∶ Hoshinoyume)用各试验溶液处理，然后种入充满了土壤的塑料杯中。在从各处理起9天后，该稻种发芽，并将10头褐飞虱（Nilaparvata lugens）的三龄若虫（third-instar nymphs）释放到该稻秧上。将其称为处理区。
特别地，上述处理如下述这样进行：将稻子的种子(Oryza sativa； 栽培品种∶ Hoshinoyume)放入160ml 塑料杯(直径： 50 mm，高度：80 mm)中，并以每100粒种子1ml的速率向其中加入各试验溶液。然后，将各杯子用手振摇，以将试验溶液施用于种子上（敷裹处理（dressing treatment））。在同一天，将从各杯子中取出的10粒处理后的种子种入160ml充满土壤的带有盖子的塑料杯(直径： 50 mm，高度：80 mm) 中，并在30℃和65% 相对湿度的人工气候室中，在偶尔喷洒水的情况下发芽。在从各处理起9天后，在各杯子中将10头褐飞虱（Nilaparvata lugens）的三龄若虫（third-instar nymphs）释放到发芽的稻子上，并将各杯子放入25℃和55% 相对湿度的室中。
用与处理区相同的方式，将没有用试验溶液进行任何处理的稻子的种子种下并使其生长，然后释放昆虫。将其称为未处理区。
在释放它们后经过6天，观察该供试若虫的生或死。由该观察结果，通过下述方程式1)计算昆虫死亡率并通过下述方程式2)计算修正昆虫死亡率。对于各处理，重复两次。平均值示于表4。
方程式1)； 昆虫死亡率(%) = {(供试昆虫的数量- 存活昆虫的数量)/供试昆虫的数量} x 100
方程式2)； 修正昆虫死亡率(%) = {(在处理区的昆虫死亡率- 在未处理区的昆虫死亡率)/(100 - 在未处理区的昆虫死亡率)} x 100。
表4
在表4中，术语“mg ai/种子”是指用于试验中的每一粒种子的化合物毫克数。
试验实施例2
将中离子化合物编号 1和精甲霜灵各10mg各自溶解在0.2 ml 的5%(w/v) SORGEN TW-20 (由Dai-ichi Kogyo Seiyaku Co.，Ltd.制造)的丙酮 (由Wako Pure Chemical Industries，Ltd.制造)溶液中，然后用水稀释至规定浓度。
将中离子化合物编号 1 的水稀释液与精甲霜灵的水稀释液混合以制备试验溶液。
将稻子的种子 (Oryza sativa； 栽培品种∶ Hoshinoyume)用各试验溶液处理，然后种入充满了土壤的塑料杯中。在从各处理起10天后，该稻种发芽，并将10头褐飞虱（Nilaparvata lugens）的三龄若虫（third-instar nymphs）释放到该稻秧上。将其称为处理区。
特别地，上述处理如下述这样进行：将稻子的种子(Oryza sativa；栽培品种∶ Hoshinoyume)放入160ml 塑料杯(直径：50 mm，高度：80 mm)中，并以每100粒种子1ml的速率向其中加入各试验溶液。然后，将各杯子用手振摇，以将试验溶液施用于种子上（敷裹处理（dressing treatment））。在同一天，将从各杯子中取出的10粒处理后的种子种入160ml充满土壤的带有盖子的塑料杯(直径： 50 mm，高度：80 mm) 中，并在30℃和65% 相对湿度的人工气候室中，在偶尔喷洒水的情况下发芽。在从各处理起10天后，在各杯子中将10头褐飞虱（Nilaparvata lugens）的三龄若虫（third-instar nymphs）释放到发芽的稻子上，并将各杯子放入25℃和55% 相对湿度的室中。
用与处理区相同的方式，将没有用试验溶液进行任何处理的稻子的种子种下并使其生长，然后释放昆虫。将其称为未处理区。
在释放它们后经过6天，观察供试若虫的生或死。由该观察结果，通过下述方程式1)计算昆虫死亡率并通过下述方程式2)计算修正昆虫死亡率。对于各处理，重复两次。平均值示于表5。
方程式1)； 昆虫死亡率(%) = {(供试昆虫的数量- 存活昆虫的数量)/供试昆虫的数量} x 100
方程式2)； 修正昆虫死亡率(%) = {(在处理区的昆虫死亡率- 在未处理区的昆虫死亡率)/(100 - 在未处理区的昆虫死亡率)} x 100。
表5
在表5中，术语“mg ai/种子”是指用于试验中的每一粒种子的化合物毫克数。
Claims (4)
1.节肢害虫防治组合物，其包含下式（I）所示的化合物和甲霜灵或精甲霜灵，
上式（I）中，
Q表示CR5=CR6、S、O或NCH3，
R1表示卤素原子、氰基、硝基、任选卤代的C1-C4 烷基、任选卤代的C2-C4 烯基、任选卤代的C2-C4 炔基或任选卤代的C1-C4 烷氧基，
n表示0～3的整数，
R2表示下述R2a、R2b、R2c或R2d∶
其中，
R3a、R3b和R3c 各自独立地表示卤素原子、氰基、硝基、任选卤代的C1-C4 烷基、任选卤代的C2-C4 炔基或任选卤代的C1-C4 烷氧基，
R3d表示卤素原子、氰基、硝基、任选卤代的C1-C4 烷基或任选卤代的C1-C4 烷氧基，
Xa、Xb、Xc和Xd 各自独立地表示0、1或2，
Zb和Zc 各自独立地表示O、S或NR7，
R7表示氢原子或任选卤代的C1-C4 烷基，
其中，
当Xa表示2时，两个R3a可以相同或不同，
当Xb表示2时，两个R3b可以相同或不同，
当Xc表示2时，两个R3c可以相同或不同，和
当Xd表示2时，两个R3d可以相同或不同，
R5表示氢原子或氟原子，和
R6表示氢原子、氟原子、二氟甲基或三氟甲基，
其中，
当n表示2或3时，多个R1可以相同或不同。
2.根据权利要求1所述的节肢害虫防治组合物，其中式（I）所示的化合物与甲霜灵或精甲霜灵的重量比为10000∶1～0.01∶1。
3.用于防治节肢害虫的方法，其包括将有效量的权利要求1或2所述的节肢害虫防治组合物施用于植物或植物栽培区域。
4.根据权利要求3所述的用于防治节肢害虫的方法，其中，所述植物或植物栽培区域为植物的种子。
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| PCT/JP2011/054204 WO2012090514A1 (en) | 2010-12-27 | 2011-02-18 | Arthropod pest control composition and method for controlling arthropod pests |
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| WO2017109795A1 (en) * | 2015-12-21 | 2017-06-29 | Council Of Scientific & Industrial Research | Novel compounds useful as potential insect antifeedant and a process for the preparation thereof |
| ES2929076T3 (es) * | 2019-03-26 | 2022-11-24 | Basf Agro Trademarks Gmbh | Rociador de control de plagas basado en cámara |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993023398A1 (en) * | 1992-05-13 | 1993-11-25 | E.I. Du Pont De Nemours And Company | Substituted pyrido[1,2-a]pyrimidinone derivatives as fungicides |
| WO2009099929A1 (en) * | 2008-02-06 | 2009-08-13 | E. I. Du Pont De Nemours And Company | Mesoionic pesticides |
| WO2011017334A2 (en) * | 2009-08-05 | 2011-02-10 | E. I. Du Pont De Nemours And Company | Mesoionic pesticides |
| WO2011017347A2 (en) * | 2009-08-05 | 2011-02-10 | E. I. Du Pont De Nemours And Company | Mesoionic pesticides |
| WO2011017351A2 (en) * | 2009-08-05 | 2011-02-10 | E. I. Du Pont De Nemours And Company | Mixtures of mesoionic pesticides |
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2011
- 2011-02-18 WO PCT/JP2011/054204 patent/WO2012090514A1/en active Application Filing
- 2011-02-18 US US13/997,472 patent/US20130289052A1/en not_active Abandoned
- 2011-02-18 BR BR112013016517A patent/BR112013016517A2/pt not_active IP Right Cessation
- 2011-02-18 KR KR1020137019844A patent/KR20140003512A/ko not_active Application Discontinuation
- 2011-02-18 MX MX2013006933A patent/MX2013006933A/es unknown
- 2011-02-18 CA CA2819637A patent/CA2819637A1/en not_active Abandoned
- 2011-02-18 CN CN2011800630547A patent/CN103260407A/zh active Pending
- 2011-02-18 EP EP11854226.5A patent/EP2658380A4/en not_active Withdrawn
- 2011-12-15 JP JP2011274035A patent/JP2012149037A/ja active Pending
- 2011-12-23 AR ARP110104930A patent/AR084590A1/es unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993023398A1 (en) * | 1992-05-13 | 1993-11-25 | E.I. Du Pont De Nemours And Company | Substituted pyrido[1,2-a]pyrimidinone derivatives as fungicides |
| WO2009099929A1 (en) * | 2008-02-06 | 2009-08-13 | E. I. Du Pont De Nemours And Company | Mesoionic pesticides |
| WO2011017334A2 (en) * | 2009-08-05 | 2011-02-10 | E. I. Du Pont De Nemours And Company | Mesoionic pesticides |
| WO2011017347A2 (en) * | 2009-08-05 | 2011-02-10 | E. I. Du Pont De Nemours And Company | Mesoionic pesticides |
| WO2011017351A2 (en) * | 2009-08-05 | 2011-02-10 | E. I. Du Pont De Nemours And Company | Mixtures of mesoionic pesticides |
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| KR20140003512A (ko) | 2014-01-09 |
| JP2012149037A (ja) | 2012-08-09 |
| CA2819637A1 (en) | 2012-07-05 |
| MX2013006933A (es) | 2013-07-22 |
| BR112013016517A2 (pt) | 2016-07-12 |
| AR084590A1 (es) | 2013-05-29 |
| WO2012090514A1 (en) | 2012-07-05 |
| EP2658380A1 (en) | 2013-11-06 |
| US20130289052A1 (en) | 2013-10-31 |
| EP2658380A4 (en) | 2014-05-28 |
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