CN111955469A - 一种用于黄瓜的杀虫剂以及黄瓜害虫的防除方法 - Google Patents
一种用于黄瓜的杀虫剂以及黄瓜害虫的防除方法 Download PDFInfo
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- CN111955469A CN111955469A CN202010885210.9A CN202010885210A CN111955469A CN 111955469 A CN111955469 A CN 111955469A CN 202010885210 A CN202010885210 A CN 202010885210A CN 111955469 A CN111955469 A CN 111955469A
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- formula
- oxazoline
- compound
- cucumber
- insecticide
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
Description
技术领域
本发明涉及植物杀虫剂技术领域,具体涉及一种用于黄瓜的杀虫剂以及黄瓜害虫的防除方法。
背景技术
黄瓜原名胡瓜,肉质脆嫩,汁多味甘,生津解渴,有特殊芳香。黄瓜不仅含有粗纤维、维生素B1、核黄素、烟酸、维生素C等多种维生素,还可有生津止渴,除烦解暑,消肿利尿,治咽喉肿痛,四肢浮肿、热痢便血等功效,深受广大人们的喜爱,是现代家庭生活中比不可少的蔬菜之一。
随着黄瓜的市场需求量的增加,对黄瓜的种植过程要求越来越高。黄瓜种植过程中最常见的害虫是白粉虱、食叶虫、瓜蚜和黄守瓜。白粉虱又名小白蛾子,属同翅目粉虱科,是大棚种植黄瓜的重要害虫,白粉虱附着在黄瓜叶背面,会造成叶片变黄,从而影响植株生长。食叶虫幼虫多是附着在黄瓜的叶背,对黄瓜进行咬食,症状为叶面孔状,表面只留一层表皮。瓜蚜又名棉蚜,其危害是在瓜叶的背面吸汁液,从而导致黄瓜叶蜷缩,生长停止,影响黄瓜的产量和采收期,同时瓜蚜还能传播一些病毒病。黄守瓜是鞘翅目叶甲科害虫,它会啃食黄瓜作物的嫩叶与花朵,危害非常严重。这些害虫严重影响了黄瓜的产量,因此需要开发专门防除这些黄瓜害虫的杀虫剂。
发明内容
本发明的目的是为了提供一种用于黄瓜的杀虫剂以及黄瓜害虫的防除方法,本发明所述的杀虫剂对于黄瓜害虫具有较好杀虫活性。
优选地,所述杀虫剂的剂型为可溶液体制剂、乳油、可湿性粉剂、可溶性粉剂、水分散性粒剂、可溶性粒剂、胶悬剂、浓乳剂、悬浮乳剂、微乳剂、粉剂、颗粒剂、片剂和乳胶中的至少一种。
本发明还提供了一种黄瓜害虫的防除方法,该方法包括将主要活性成分为式(1)所示的异唑啉取代苯甲酰胺化合物的杀虫剂和或主要活性成分为式(2)所示的异唑啉连吡唑取代酰胺化合物的杀虫剂分别同时或时间接近地对黄瓜作物进行处理,
本发明还提供了一种黄瓜害虫的防除方法,该方法包括将主要活性成分为式(1)所示的异唑啉取代苯甲酰胺化合物的杀虫剂先对黄瓜作物进行处理,在1-24h后再用主要活性成分为式(2)所示的异唑啉连吡唑取代酰胺化合物的杀虫剂对黄瓜作物进行处理,
本发明所述的用于黄瓜的杀虫剂对黄瓜害虫(如白粉虱、食叶虫、瓜蚜和黄守瓜)具有较高的防除活性,而且对哺乳动物、鱼类和天敌、益虫等非目标生物的不良影响少,适合安全推广使用。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
目前,异唑啉系化合物在杀虫剂方面的应用得到的广泛推广和开发。本发明的发明人通过深入研究和长期实验发现,在防除黄瓜害虫方面,式(1)所示的异唑啉取代苯甲酰胺化合物和式(2)所示的异唑啉连吡唑取代酰胺化合物这两种已知的异唑啉系化合物具有较好的协同增效作用,从而完成了本发明,
在所述用于黄瓜的杀虫剂中,主要活性成分为式(1)所示的异唑啉取代苯甲酰胺化合物和式(2)所示的异唑啉连吡唑取代酰胺化合物。在具体的实施方式中,在所述杀虫剂中,式(1)所示的异唑啉取代苯甲酰胺化合物和式(2)所示的异唑啉连吡唑取代酰胺化合物的重量之比为10:1至1:10,优选为5:1至1:5,进一步优选为2:1至1:2,更进一步优选为1.2:1至1.5:1,最优选为1.3±0.05:1。
在本发明中,所述杀虫剂可以仅含有式(1)所示的异唑啉取代苯甲酰胺化合物和式(2)所示的异唑啉连吡唑取代酰胺化合物,也可以除式(1)所示的异唑啉取代苯甲酰胺化合物和式(2)所示的异唑啉连吡唑取代酰胺化合物之外还含有其他的活性成分。“主要活性成分”是指在所述杀虫剂中式(1)所示的异唑啉取代苯甲酰胺化合物和式(2)所示的异唑啉连吡唑取代酰胺化合物的总含量占所有活性组分含量的85重量%以上,优选为90重量%以上,更优选为95重量%以上,更进一步优选为98重量%以上。
在所述用于黄瓜的杀虫剂中,除了上述式(1)所示的异唑啉取代苯甲酰胺化合物和式(2)所示的异唑啉连吡唑取代酰胺化合物之外,还可以包含其他本领域常规的活性成分中的一种、两种、三种或更多种的组合,其可以选自但不仅限于选自以下组分组成的组:苯霜灵、高效苯霜灵、呋霜灵、甲霜灵、高效甲霜灵、呋酰胺、霜灵、乙嘧酚磺酸酯、乙嘧酚、苯菌灵、多菌灵、麦穗宁、噻菌灵、甲基硫菌灵、乙霉威、噻唑菌胺、苯酰菌胺、戊菌隆、氟吡菌胺、氟嘧菌胺、麦锈灵、苯并烯氟菌唑、联苯吡菌胺、烟酰胺、萎锈灵、甲呋酰胺、氟吡菌酰胺、氟酰胺、氟唑菌酰胺、呋吡菌胺、异丙噻菌胺、吡唑萘菌胺、灭锈胺、氧化萎锈灵、氟唑菌苯胺、吡噻菌胺、氟唑环菌胺、噻氟菌胺、嘧菌酯、丁香菌酯、醚菌胺、唑菌酮、咪唑菌酮、烯肟菌胺、氟菌螨酯、氟嘧菌酯、醚菌酯、苯氧菌胺、肟醚菌胺、啶氧菌酯、吡唑醚菌酯、唑胺菌酯、唑菌酯、甲基吡菌苯威、嘧螨胺、氯啶菌酯、肟菌酯、吲唑磺菌胺、氰霜唑、二硝巴豆酚酯、氟啶胺、消螨多、三苯锡、三丁基氧化锡、硅噻菌胺、唑嘧菌胺、嘧菌环胺、嘧菌胺、嘧霉胺、灰瘟素、春雷霉素、丙氧喹啉、苯氧喹啉、拌种咯、咯菌腈、乙菌利、异菌脲、腐霉利、乙烯菌核利、敌瘟磷、异稻瘟净、稻瘟灵、吡菌磷、联苯、氯苯甲醚、氯硝胺、土菌灵、五氯硝基苯、四氯硝基苯、甲基立枯磷、霜霉威盐酸盐、氧环唑、联苯三唑醇、糠菌唑、咪菌酮、环丙唑醇、苄氯三唑醇、苯醚甲环唑、烯唑醇、高效烯唑醇、氟环唑、乙环唑、氯苯嘧啶醇、腈苯唑、三氟苯唑、氟喹唑、氟硅唑、粉唑醇、呋菌唑、己唑醇、抑霉唑、亚胺唑、种菌唑、叶菌唑、腈菌唑、氟苯嘧啶醇、咪唑富马酸盐、稻瘟酯、戊菌唑、咪鲜胺、丙环唑、丙硫菌唑、啶斑肟、啶菌唑、硅氟唑、戊唑醇、四氟醚唑、三唑酮、三唑醇、氟菌唑、嗪氨灵、灭菌唑、十二环吗啉乙酸盐、苯锈啶、丁苯吗啉、病花灵、螺环菌胺、十三吗啉、环酰菌胺、胺苯吡菌酮、有效霉素、多抗霉素、多氧霉素、苯噻菌胺酯、烯酰吗啉、氟吗啉、缬霉威、双炔酰菌胺、丁吡吗啉、缬菌胺、四氯苯酞、咯喹酮、三环唑、环丙酰菌胺、双氯氰菌胺、稻瘟酰胺、活化酯、烯丙苯噻唑、异噻菌胺、噻酰菌胺、昆布多糖、波尔多液、切欣特混合液、碱式碳酸铜、氢氧化铜、环烷酸铜、油酸铜、碱式氯化铜、硫酸铜、碱式硫酸铜、羟基喹啉铜、石硫合剂、硫黄、代森铵、福美铁、代森锰锌、代森锰、代森联、代森福美锌、丙森锌、福美双、福美锌、克菌丹、灭菌丹、百菌清、苯氟磺胺、甲苯氟磺胺、双胍辛盐、双胍辛烷基苯磺酸盐、双胍辛胺乙酸盐、敌菌灵、二氰蒽醌、灭螨猛、氟氯菌核利、环氟苄酰胺、霜脲氰、哒菌酮、多果定、嘧菌腙、磺菌胺、氟噻菌净、三乙膦酸铝、苯菌酮、氟噻唑吡乙酮、异丁乙氧喹啉、咪唑嗪、阿维菌素、乙酰甲胺磷、啶虫脒、棉铃威、涕灭威、烯丙菊酯、甲基吡磷、益棉磷、保棉磷、苏云金杆菌、虫威、四氟苯菊酯、丙硫克百威、杀虫磺、联苯菊酯、生物烯丙菊酯、生物苄呋菊酯、双三氟虫脲、噻嗪酮、丁酮威、甲萘威、克百威、丁硫克百威、杀螟丹、氯虫酰胺、氯氧磷、虫螨腈、毒虫畏、氟啶脲、氯甲硫磷、毒死蜱、甲基毒死蜱、环虫酰肼、噻虫胺、杀螟腈、氰虫酰胺、环溴虫酰胺、乙氰菊酯、氟氯氰菊酯、高效氟氯氰菊酯、氯氟氰菊酯、精高效氯氟氰菊酯、高效氯氟氰菊酯、氯氰菊酯、顺式氯氰菊酯、高效氯氰菊酯、zeta-氯氰菊酯、苯醚氰菊酯、灭蝇胺、溴氰菊酯、丁醚脲、二嗪磷、敌敌畏、除虫脲、乐果、甲基毒虫畏、呋虫胺、苯虫醚、乙拌磷、甲氨基阿维菌素苯甲酸盐、右旋烯炔菊酯、硫丹、α-硫丹、苯硫膦、S-氰戊菊酯、乙硫苯威、乙虫腈、醚菊酯、乙嘧硫磷、杀螟硫磷、仲丁威、苯氧威、倍硫磷、氰戊菊酯、氟虫腈、氟啶虫酰胺、啶蜱脲、氟虫酰胺、氟环脲、氟氰戊菊酯、嘧虫胺、氟虫脲、丁烯氟虫腈、氟氯苯菊酯、氟吡呋喃酮、氟胺氰菊酯、τ-氟胺氰菊酯、地虫硫磷、呋线威、氯虫酰肼、氟铃脲、氟蚁腙、吡虫啉、炔咪菊酯、茚虫威、茚虫威MP、异丙威、唑磷、雷皮菌素、虱螨脲、马拉硫磷、氯氟醚菊酯、氰氟虫腙、四聚乙醛、虫螨畏、甲胺磷、杀扑磷、灭多威、烯虫酯、甲氧滴滴涕、甲氧虫酰肼、甲氧苄氟菊酯、诱虫烯、烯啶虫胺、氟酰脲、多氟脲、氧乐果、亚砜磷、甲基对硫磷、氯菊酯、苯醚菊酯、稻丰散、甲拌磷、伏杀硫磷、亚胺硫磷、辛硫磷、抗蚜威、甲基嘧啶磷、丙溴磷、丙硫磷、吡蚜酮、吡唑硫磷、除虫菊素、啶虫醚、吡氟喹虫唑、吡啶氟虫腈、吡丙醚、苄呋菊酯、鱼藤酮、氟硅菊酯、乙基多杀菌素、多杀霉素、螺虫乙酯、治螟磷、氟啶虫胺腈、虫酰肼、氟苯脲、七氟菊酯、特丁硫磷、杀虫畏、胺菊酯、右旋胺菊酯、四氟醚菊酯、氟氰虫酰胺、噻虫啉、噻虫嗪、杀虫环、硫双威、久效威、甲基乙拌磷、唑虫酰胺、四溴菊酯、四氟苯菊酯、唑蚜威、敌百虫、三氟苯嘧啶、杀铃脲、灭螨醌、氟丙菊酯、磺胺螨酯、双甲脒、三唑锡、苯螨特、联苯肼酯、溴螨酯、四螨嗪、腈吡螨酯、丁氟螨酯、三氯杀螨醇、遍地克、乙螨唑、喹螨醚、苯丁锡、苯硫威、甲氰菊酯、唑螨酯、嘧螨酯、伐虫脒、苄螨醚、噻螨酮、弥拜菌素、快螨特、哒螨灵、嘧螨醚、螺螨酯、螺虫酯、吡螨胺、硫线磷、除线磷、灭线磷、苯线磷、联氟砜、噻唑膦、丁硫环磷、新烟磷、氯唑磷、溴甲烷、敌线酯、杀线威、叠氮化钠、吖啶黄、丙硫多菌灵、阿托伐醌、阿奇霉素、硫氯酚、溴酚磷、坎苯达唑、卡硝唑、氯喹、克拉珠利、克林霉素、氯舒隆、氯生太尔、蝇毒磷、双氯酚、乙胺嗪、二脒那秦、二碘硝酚、碘二噻宁、多西环素、多拉克丁、依立诺克丁、非班太尔、芬苯达唑、氟苯达唑、呋喃唑酮、咪唑双酰胺、咪多卡、伊维菌素、左旋咪唑、甲苯达唑、甲氟喹、美拉索明二盐酸盐、甲硝唑、美替立啶、米尔贝肟、莫奈太尔、酒石酸莫仑太尔、莫昔克丁、尼卡巴嗪、氯硝柳胺、硝硫氰酯、硝碘酚腈、环十二缩肽、双羟萘酸奥克太尔、酒石酸奥克太尔、奥芬达唑、奥苯达唑、羟氯扎胺、帕马喹、吩噻嗪、己二酸哌嗪、柠檬酸哌嗪、磷酸哌嗪、吡喹酮、伯氨喹、胺丙畏、残杀威、双羟萘酸噻嘧啶、乙胺嘧啶、司拉克丁、磺胺地索辛、磺胺多辛、磺胺甲嘧啶、磺胺间甲氧嘧啶、噻菌灵、替硝唑、托曲珠利、三溴沙仑、三氯苯达唑、酮康唑、咪康唑硝酸盐、阿莫西林、氨苄西林、硫氯酚、溴硝醇、头孢匹林、头孢唑林、头孢喹肟、头孢噻呋、金霉素、克拉维酸、达氟沙星、二氟沙星、二硝托胺、恩氟沙星、氟苯尼考、林可霉素、洛美沙星、马波沙星、米洛沙星、米罗米星、三氯甲基吡啶、诺氟沙星、辛噻酮、氧氟沙星、奥比沙星、奥索利酸、土霉素、青霉素、链霉素、甲砜霉素、富马酸硫姆林、磷酸替米考星、乙酸异戊酸泰乐菌素、磷酸泰乐菌素、妥拉霉素、伐奈莫林、贝壳烧成钙(氧化钙)、踝节菌属菌、木霉属菌和盾壳霉属菌。
本发明所述的用于黄瓜的杀虫剂可以与适当的固体载体或液体载体混合,进一步根据需要添加表面活性剂、渗透剂、展开剂、增稠剂、防冻剂、粘合剂、固结防止剂、崩解剂、消泡剂、防腐剂和防分解剂等。
本发明所述的用于黄瓜的杀虫剂可以根据需要制成可溶液体制剂、乳油、可湿性粉剂、可溶性粉剂、水分散性粒剂、可溶性粒剂、胶悬剂、浓乳剂、悬浮乳剂、微乳剂、粉剂、颗粒剂、片剂、乳胶等任意剂型的制剂而供于使用。在优选的实施方式中,为了提高使用安全性,还可以将上述任意剂型的制剂封入水溶性胶囊和水溶性膜的袋等水溶性包装体中来提供。
在本发明中,作为固体载体,其可以选自但不仅限于:石英、方解石、海泡石、白云石、白垩、高岭石、叶蜡石、绢云母、埃洛石、准埃洛石、有机碳粘土、蛙目粘土、陶石、水铝英石、白砂、云母、滑石、膨润土、活性白土、酸性白土、浮石、硅镁土、沸石和硅藻土等天然矿物质、例如煅烧粘土、珍珠岩、白砂球、蛭石、煅烧硅藻土等天然矿物质的煅烧品、例如碳酸镁、碳酸钙、碳酸钠、碳酸氢钠、硫酸铵、硫酸钠、硫酸镁、磷酸氢二铵、磷酸二氢铵和氯化钾等无机盐类、例如葡萄糖、果糖、蔗糖和乳糖等糖类、例如淀粉、粉末纤维素和糊精等多糖类、例如脲、脲衍生物、苯甲酸和苯甲酸的盐等有机物、例如木粉、软木屑、玉米穗轴、核桃壳和烟草茎等植物类、粉煤灰、白炭墨(例如,含水合成二氧化硅、无水合成二氧化硅和含水合成硅酸盐等)以及肥料等。
在本发明中,作为液体载体,其可以选自但不仅限于:二甲苯、烷基(C9或C10等)苯、苯基二甲苯基乙烷和烷基(C1或C3等)萘等芳香族烃类、机械油、正链烷、异链烷和环烷等脂肪族烃类、煤油等芳香族烃与脂肪族烃的混合物、乙醇、异丙醇、环己醇、苯氧基乙醇和苄醇等醇、乙二醇、丙二醇、二甘醇、己二醇、聚乙二醇和聚丙二醇等多元醇、丙基溶纤剂、丁基溶纤剂、苯基溶纤剂、丙二醇单甲基醚、丙二醇单乙基醚、丙二醇单丙基醚、丙二醇单丁基醚和丙二醇单苯基醚等醚、苯乙酮、环己酮和γ-丁内酯等酮、脂肪酸甲基酯、琥珀酸二烷基酯、谷氨酸二烷基酯、己二酸二烷基酯和邻苯二甲酸二烷基酯等酯、N-烷基(C1、C8或C12等)吡咯烷酮等酸酰胺、豆油、亚麻子油、菜籽油、椰子油、棉籽油和蓖麻油等油脂、二甲亚砜以及水。
这些固体和液体载体可以单独使用,也可以两种、三种或更多种混合并用。
在本发明中,作为表面活性剂,其可以选自但不仅限于:聚氧乙烯烷基醚、聚氧乙烯烷基(单或二)苯基醚、聚氧乙烯(单、二或三)苯乙烯基苯基醚、聚氧乙烯聚氧丙烯嵌段共聚物、聚氧乙烯脂肪酸(单或二)酯、失水山梨糖醇脂肪酸酯、聚氧乙烯失水山梨糖醇脂肪酸酯、蓖麻油氧化乙烯加成物、炔属烃邻二醇、炔属醇、炔属烃邻二醇的氧化乙烯加成物、炔属醇的氧化乙烯加成物和烷基糖苷等非离子性表面活性剂、烷基硫酸酯盐、烷基苯磺酸盐、木质素磺酸盐、烷基磺基琥珀酸盐、萘磺酸盐、烷基萘磺酸盐、萘磺酸的甲醛缩合物的盐、烷基萘磺酸的甲醛缩合物的盐、聚氧乙烯烷基醚硫酸或磷酸酯盐、聚氧乙烯(单或二)烷基苯基醚硫酸或磷酸酯盐、聚氧乙烯(单、二或三)苯乙烯基苯基醚硫酸或磷酸酯盐、多元羧酸盐(例如,聚丙烯酸盐、聚马来酸盐和马来酸与烯烃的共聚物等)和聚苯乙烯磺酸盐等阴离子性表面活性剂、烷基胺盐和烷基季铵盐等阳离子性表面活性剂、氨基酸型和甜菜碱型等两性表面活性剂、有机硅系表面活性剂以及氟系表面活性剂。
在本发明中,所述增稠剂可以选自黄原胶、聚乙烯醇、膨润土、羧甲基纤维素和硅酸镁铝中的一种或多种,最优选为硅酸镁铝,其粒径优选为1000-1200目。
在本发明中,所述防腐剂可以选自苯甲酸钠、山梨酸钾、乳酸钠、丙酸钙和对羟苯甲酸中的一种或多种,最优选为苯甲酸钠。
在本发明中,所述防冻剂可以选自乙二醇、丙二醇、丙三醇和尿素中的一种或多种,最优选为乙二醇。
在本发明中,所述消泡剂可以选自硅油、硅酮类化合物、C10-C20饱和脂肪酸类化合物或C8-C10脂肪醇类化合物中的一种或多种,最优选为硅油。
(1)可湿性粉剂
该其他组分为固结防止剂、防分解剂等。
(2)乳油
该其他组分为展开剂、防分解剂等。
(3)胶悬剂
该其他组分为防冻剂、增稠剂等。
(4)水分散性粒剂
该其他组分为粘合剂、防分解剂等。
(5)可溶液体制剂
活性成分 0.01-70重量份
液体载体 20-99.99重量份
其他组分 0-10重量份
该其他组分为防冻剂、展开剂等。
(6)颗粒剂
活性成分 0.01-80重量份
固体载体 10-99.99重量份
其他组分 0-10重量份
该其他组分为粘合剂、防分解剂等。
(7)粉剂
活性成分 0.01-30重量份
固体载体 65-99.99重量份
其他组分 0-5重量份
该其他组分为防漂移剂、防分解剂等。
配方制剂1:可湿性粉剂
将以上组分均匀混合粉碎以制成可湿性粉剂。
配方制剂2:乳油
将以上组分均匀混合以制成乳油。
配方制剂3:胶悬剂
将以上组分均匀混合后,进行湿式粉碎以制成胶悬剂。
配方制剂4:水分散性粒剂
将以上组分均匀混合粉碎后,添加少量的水并搅拌混合,利用挤出造粒机进行造粒,干燥,以制成水分散性粒剂。
配方制剂5:颗粒剂
将以上组分均匀混合粉碎后,添加少量的水并搅拌混合,利用挤出造粒机进行造粒,干燥,以制成颗粒剂。
配方制剂6:粉剂
将以上组分均匀混合粉碎以制成粉剂。
使用时,上述可湿性粉剂、乳油、胶悬剂、水分散性粒剂用水稀释至50~20000倍,使活性成分为每1公顷(ha)为0.005~50kg的方式进行撒布。
在本发明的另一种实施方式中,所述黄瓜害虫的防除方法包括将主要活性成分为式(1)所示的异唑啉取代苯甲酰胺化合物的杀虫剂和或主要活性成分为式(2)所示的异唑啉连吡唑取代酰胺化合物的杀虫剂分别同时或时间接近地对黄瓜作物进行处理。
在本发明的另一种实施方式中,所述黄瓜害虫的防除方法包括将主要活性成分为式(1)所示的异唑啉取代苯甲酰胺化合物的杀虫剂先对黄瓜作物进行处理,在1-24h后再用主要活性成分为式(2)所示的异唑啉连吡唑取代酰胺化合物的杀虫剂对黄瓜作物进行处理。
以下将通过实施例对本发明进行详细描述。以下制备例、实施例和对比例中,如果没有特别说明,所用原料都是市售商品。
制备例1
制备式(1)所示的化合物:
(1)制备4-甲酰基-N-(2,2,2-三氟乙基)苯甲酰胺
在1.00g 4-甲酰基苯甲酸的苯15ml悬浊液中,加入0.87g亚硫酰氯及2滴N,N-二甲基甲酰胺,在加热回流下搅拌2小时。反应完成后,将反应混合物放冷至室温,减压蒸馏除去溶剂、得到白色结晶状的粗制4-甲酰基苯甲酰氯1.14g。
在0.66g 2,2,2-三氟乙胺及0.81g三乙胺的6ml氯仿的溶液中,在冰水搅拌下,滴加1.14g上述粗制4-甲酰基苯甲酰氯的6ml氯仿的溶液,滴加结束后,在室温下继续搅拌18小时。反应完成后,将反应混合物投入30ml水中,氯仿萃取(20ml×3),用水洗涤有机层,然后使用无水硫酸钠进行干燥,减压蒸馏除去溶剂。使用己烷洗涤残留固体,得到白色结晶状的目标产物1.32g。
(2)制备4-羟基亚氨基甲基-N-(2,2,2-三氟乙基)苯甲酰胺
在4.11g 4-甲酰基-N-(2,2,2-三氟乙基)苯甲酰胺的30ml乙醇及10ml水的溶液中,加入1.99g羟胺盐酸盐及2.51g无水乙酸钠,在室温下搅拌3.5小时。反应完成后,将反应混合物注入100ml水中,使用乙酸乙酯萃取(30ml×3)、使用50ml饱和碳酸氢钠水溶液洗涤有机层,然后依次使用饱和食盐水、无水硫酸钠进行脱水干燥,减压蒸馏除去溶剂。使用己烷洗涤残留固体,得到白色结晶状的目标产物3.92g。
(3)制备4-氯羟基亚氨基甲基-N-(2,2,2-三氟乙基)苯甲酰胺
在3.80g 4-羟基亚氨基甲基-N-(2,2,2-三氟乙基)苯甲酰胺的50ml四氢呋喃溶液加入3N盐酸20ml,在冰水搅拌下,在10分钟时间内滴加8%次氯酸钠水溶液14ml,滴加结束后,在相同温度下进一步继续搅拌15分钟。反应完成后,将反应混合物注入200ml水中,使用乙酸乙酯萃取(30ml×3)、依次使用饱和食盐水、无水硫酸钠对有机层进行脱水干燥,减压蒸馏除去溶剂。使用己烷洗涤残留固体,得到白色结晶状的目标产物4.15g。
在0.21g 4-氟-3-甲基苯基硼酸及0.23g 2-溴-3,3,3-三氟丙烷的6ml 1,2-二甲氧基乙烷及2ml水的溶液中加入0.24g碳酸钠及0.05g二氯双(三苯基膦)钯(II),在75下搅拌3小时。接着将反应混合物放冷至室温,然后加入0.25g4-氯羟基亚氨基甲基-N-(2,2,2-三氟乙基)苯甲酰胺的4ml 1,2-二甲氧基乙烷的溶液,在相同温度下进一步继续搅拌18小时。反应完成后,将反应混合物注入到50ml水中,使用乙酸乙酯萃取(10ml×3),依次使用饱和食盐水、无水硫酸钠对有机层进行脱水干燥,减压蒸馏除去溶剂。使用以氯仿进行洗脱的硅胶柱色谱精制残留固体,得到白色结晶状的目标产物0.24g。
其熔点为151.0~152.0;
其核磁数据为:
1H NMR(CDCl3、Me4Si,400MHz)δ7.86(d,J=8.4Hz,2H),7.76(d,J=8.4Hz,2H),7.35-7.5(m,2H),7.0-7.15(m,1H),6.39(t,J=6.3Hz,1H),4.05-4.25(m,2H),4.09(d,J=17.3Hz,1H),3.74(d,J=17.3Hz,1H),2.32(d,J=1.7Hz,3H)。
制备例2
制备式(2)所示的化合物:
(1)制备中间体(I)
将3.13g盐酸羟胺和2.46g乙酸钠混合,加入15mL水,室温下搅拌制备羟胺水溶液。将5.1g(30mmol)3-甲酰基-1-甲基-1H-吡唑-5-羧酸乙酯溶于20mL的THF中,室温下滴入制备的羟胺水溶液,滴完后继续搅拌2小时。完全反应后,脱溶除去THF,加水后,过滤,水洗晾干得白色固体4.95g。
(2)制备中间体(II)
在250mL的圆底烧瓶中加入所述中间体(I)8.0g,加入100ml N,N-二甲基甲酰胺(DMF)作溶剂将其溶解,加入7.5gN-氯代丁二酰亚胺(NCS),加热到60℃搅拌3小时,冷却至室温,加入5.1g 4-氟-苯乙烯,再滴入5.7g三乙胺,滴完后室温搅拌4小时,将体系倒入250ml冰水中,乙酸乙酯萃取(3次,每次50ml),将有机相浓缩后柱层析分离(展开剂石油醚:乙酸乙酯=5:1)得粘稠液体,产率为74%。
(3)制备中间体(III)
将1.0g所述中间体(II)溶于10mL四氢呋喃(THF)和5mL水的混合液中,加入0.15g氢氧化钠,加热回流2h,冷却,浓缩去掉THF,加入20mL水,盐酸调pH值成酸性,白色固体出现。过滤水洗晾干得白色固体0.95g。
(4)制备中间体(IV)
将0.91g(3.28mmol)所述中间体(III)加到50mL的二氯甲烷中,加入2滴DMF,将4.0mmol草酰氯滴入到反应液中,加热回流反应1小时,蒸出溶剂,隔膜泵将溶剂抽干。残液无需后处理直接用于下一步合成化合物。
(5)制备式(2)所示的化合物
将1.0mmol所述中间体(IV)溶于5mL的THF中,加入1.1mmol三乙胺,室温下加入1.1mmol N-甲基苯胺,室温搅拌2小时,层析分离(展开剂石油醚:乙酸乙酯=3:1),得到白色固体,产率为84%。
其核磁数据为:
1H NMR(CDCl3/TMS,600MHz):δ3.26(q,1H,J=8.4Hz,-CH2),3.47(s,3H,Ph-CH3),3.69(q,1H,J=10.8Hz,-CH2),4.09(s,3H,Ar-CH3),5.58(q,1H,J=8.4Hz,-CH),7.02(t,2H,J=9.0Hz,Ph-H),7.11(d,2H,J=7.8Hz,Ar-H),7.25-7.38(m,6H,Ph-H);
13C NMR(CDCl3,150MHz):δ38.2,39.5,43.0,81.5,107.5,115.5,115.6,126.7,127.8,128.1,129.8,136.5,137.0,140.3,143.5,151.6,160.7。
实施例1
提供活性成分为式(1)所示化合物和式(2)所示化合物的杀虫剂,其中,式(1)所示化合物和式(2)所示化合物的重量比为1.3:1。
实施例2
提供活性成分为式(1)所示化合物和式(2)所示化合物的杀虫剂,其中,式(1)所示化合物和式(2)所示化合物的重量比为1.2:1。
实施例3
提供活性成分为式(1)所示化合物和式(2)所示化合物的杀虫剂,其中,式(1)所示化合物和式(2)所示化合物的重量比为1.5:1。
实施例4
提供活性成分为式(1)所示化合物和式(2)所示化合物的杀虫剂,其中,式(1)所示化合物和式(2)所示化合物的重量比为1:1。
实施例5
提供活性成分为式(1)所示化合物和式(2)所示化合物的杀虫剂,其中,式(1)所示化合物和式(2)所示化合物的重量比为1:2。
实施例6
提供活性成分为式(1)所示化合物和式(2)所示化合物的杀虫剂,其中,式(1)所示化合物和式(2)所示化合物的重量比为2:1。
对比例1
提供活性成分仅为式(1)所示化合物的杀虫剂。
对比例2
提供活性成分仅为式(2)所示化合物的杀虫剂。
测试例1
毒力测试:
试验依据:农业部NY/T1154.6-2006《农药室内生物测定试验准则杀虫剂第6部分:浸虫法》、NY/T1154.7-2006《农药室内生物测定试验准则杀虫剂第7部分:混配的联合作用测定》。评价标准:共毒系数(CTC)≥120表现为增效作用;共毒系数(CTC)≤80表现为拮抗作用;80<共毒系数(CTC)<120表现为相加作用。
实测毒力指数(ATI)=(标准药剂LC50/供试药剂LC50)×100。
理论毒力指数(TTI)=A药剂毒力指数×混剂中A的百分含量+B药剂毒力指数×混剂中B的百分含量。
共毒系数(CTC)=[混剂实测毒力指数(ATI)/混剂理论毒力指数(TTI)]×100。
试验方法:采用浸渍法进行室内毒力测定,将实施例1-6和对比例1-2的杀虫剂分别用0.1%的吐温80水溶解稀释制成等比质量浓度,各置于250ml烧杯中。
选择室内培养、龄期一致的黄守瓜若虫,将若虫至于冷藏冰箱4℃中10分钟,待其不活动时拿出,将若虫浸入药液中10s中后取出,用吸水纸吸去多余的药液,分别标记,然后放入26℃,相对湿度为70%的物候箱中,用新鲜干净的黄瓜叶饲喂。每一浓度处理若虫30头,重复4次,以浸含相应量吐温80水为对照,药后48小时检查结果,对照死亡率高于20%为无效试验,试虫死亡的标准是,用小毛笔轻触试虫,5s后无反应者视为死亡,否则视为活虫。根据统计结果计算出共毒系数(CTC值),结果如表1所示。
表1
式(1)化合物:式(2)化合物 | LC<sub>50</sub>(mg/L) | 共毒系数(CTC值) | 作用类型 | |
实施例1 | 1.3:1 | 1.97 | 162.82 | 增效作用 |
实施例2 | 1.2:1 | 2.87 | 147.51 | 增效作用 |
实施例3 | 1.5:1 | 2.32 | 143.95 | 增效作用 |
实施例4 | 1:1 | 3.52 | 130.26 | 增效作用 |
实施例5 | 1:2 | 3.95 | 125.33 | 增效作用 |
实施例6 | 2:1 | 3.17 | 132.47 | 增效作用 |
对比例1 | 1:0 | 4.49 | / | / |
对比例2 | 0:1 | 9.25 | / | / |
由表1的数据可以看出,本发明所述的杀虫剂中式(1)所示的异唑啉取代苯甲酰胺化合物和式(2)所示的异唑啉连吡唑取代酰胺化合物的复配组合对黄瓜害虫防治的共毒系数均在120以上,表现为协同增效作用。尤其是当式(1)所示的异唑啉取代苯甲酰胺化合物和式(2)所示的异唑啉连吡唑取代酰胺化合物的配比为1.2-1.5:1时,对黄瓜害虫防治的共毒系数均在140以上,协同增效作用更明显。
实施例7
按照如下配方均匀混合后,进行湿式粉碎,制得胶悬剂A1。
组分 | 用量(重量%) |
式(1)所示化合物 | 13.00 |
式(2)所示化合物 | 10.00 |
十二烷基苯磺酸钙 | 1.00 |
黄原胶 | 0.50 |
去离子水 | 85.50 |
实施例8
按照实施例1配制胶悬剂,所不同的是,式(1)所示化合物与式(2)所示化合物的重量比为1.2:1,二者总量仍为23重量%,得到胶悬剂A2。
实施例9
按照实施例1配制胶悬剂,所不同的是,式(1)所示化合物与式(2)所示化合物的重量比为1.5:1,二者总量仍为23重量%,得到胶悬剂A3。
实施例10
按照实施例1配制胶悬剂,所不同的是,式(1)所示化合物与式(2)所示化合物的重量比为1:1,二者总量仍为23重量%,得到胶悬剂A4。
实施例11
按照实施例1配制胶悬剂,所不同的是,式(1)所示化合物与式(2)所示化合物的重量比为1:2,二者总量仍为23重量%,得到胶悬剂A5。
实施例12
按照实施例1配制胶悬剂,所不同的是,式(1)所示化合物与式(2)所示化合物的重量比为2:1,二者总量仍为23重量%,得到胶悬剂A6。
对比例3
按照实施例1配制胶悬剂,所不同的是,不加入式(2)所示化合物,且式(1)所示化合物的用量为23重量%,得到胶悬剂D1。
对比例4
按照实施例1配制胶悬剂,所不同的是,不加入式(1)所示化合物,且式(2)所示化合物的用量为23重量%,得到胶悬剂D2。
测试例2
使用制剂:实施例7-12制备的胶悬剂A1-A6和对比例3-4制备的胶悬剂D1-D2。
试验方法:称取一定质量制剂,加蒸馏水稀释配制成浓度为100mg/L的药液,药剂处理药液量10mL。实验对象为白粉虱、食叶虫、瓜蚜和黄守瓜。
将黄瓜叶在药液中充分浸润后自然阴干,放入培养皿中,接3龄中期幼虫,加盖标记后置于观察室内。试验重复4次。72h后检查结果。以毛笔轻触虫体,无反应视为死虫。
试验统计:统计各个处理的死虫数和活虫数,计算死亡率。死亡率计算公式如下:
计算结果如表2所示。
表2
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
Claims (10)
7.根据权利要求1-6中任意一项所述的用于黄瓜的杀虫剂,其特征在于,所述杀虫剂的剂型为可溶液体制剂、乳油、可湿性粉剂、可溶性粉剂、水分散性粒剂、可溶性粒剂、胶悬剂、浓乳剂、悬浮乳剂、微乳剂、粉剂、颗粒剂、片剂和乳胶中的至少一种。
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