CN106386815A - 邻氨基苯甲酰胺衍生物的多种用途 - Google Patents
邻氨基苯甲酰胺衍生物的多种用途 Download PDFInfo
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- CN106386815A CN106386815A CN201610591292.XA CN201610591292A CN106386815A CN 106386815 A CN106386815 A CN 106386815A CN 201610591292 A CN201610591292 A CN 201610591292A CN 106386815 A CN106386815 A CN 106386815A
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Classifications
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- A—HUMAN NECESSITIES
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- 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
- A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Cultivation Of Plants (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
本发明涉及通式(I)的邻氨基苯甲酰胺衍生物通过灌注、土混、浇灌处理、滴注施用、注射至土壤、茎杆或花、在水培体系中通过处理栽植穴或浸渍施用、漂浮或种子箱施用或通过处理种子来防治昆虫和蛛螨的用途,以及增加植物对非生物胁迫的胁迫耐受性的用途,其中R1、R2、R3、R4、R5、A、X、Qx、Qy和n具有说明书中给出的宽泛含义。
Description
本申请是申请日为2011年7月15日、申请号为“201180044865.2”、发明名称为“邻氨基苯甲酰胺衍生物通过灌注、土混、浇灌处理、滴注施用、注射至土壤、茎杆或花、在水培体系中通过处理栽植穴或浸渍施用、漂浮或种子箱施用或通过处理种子来防治昆虫和蛛螨的用途,以及增加植物对非生物胁迫的胁迫耐受性的用途”的发明专利申请的分案申请。
本发明涉及邻氨基苯甲酰胺(anthranilamide)衍生物通过灌注、土混、犁沟处理、滴注施用、在水培体系中通过栽植穴处理、土壤、茎杆或花注射、浸渍施用、漂浮或种子箱施用或通过处理种子用于防治昆虫和/或蛛螨和/或线虫的用途。
本发明还涉及邻氨基苯甲酰胺衍生物用于增强植物对非生物胁迫的胁迫耐受性,特别是用于增强植物生长和/或提高植物产量和/或提高对干旱和干燥条件的耐受性的用途。已知植物以特异性或非特异性防御机理对自然胁迫条件例如低温、热、干燥条件、损伤、被病原体(病毒、细菌、真菌、昆虫)等攻击产生反应,而且对除草剂产生反应[Pflanzenbiochemie,第393-462页,Spektrum Akademischer Verlag,Heidelberg,Berlin,Oxford,Hans W.Heldt,1996.;Biochemistry and Molecular Biology ofPlants,第1102-1203页,American Society of Plant Physiologists,Rockville,Maryland,eds.Buchanan,Gruissem,Jones,2000]。
已知植物中存在大量的蛋白质,和对其进行编码的基因,其参与对非生物胁迫(例如低温、热、干燥条件、盐、涝)的防御反应。其中的一些形成信号传导链(例如转录因子、激酶、磷酸酶)的一部分或者引起植物细胞的生理响应(例如离子运输、活性氧簇的失活)。非生物胁迫反应的信号链基因包括DREB和CBF类的转录因子(Jaglo-Ottosen et al.,1998,Science 280:104-106)。对盐度胁迫的反应包括ATPK和MP2C类的磷酸酶。此外,在盐度胁迫的情况下,通常激活渗透物质如脯氨酸或蔗糖的生物合成。这包括例如蔗糖合酶和脯氨酸运载体(Hasegawa et al.,2000,Annu Rev Plant Physiol Plant Mol Biol 51:463-499)。植物对冷和干旱的胁迫防御使用某些相同的分子机理。存在被称为晚期胚胎富集蛋白(LEA 蛋白质)的已知累积物,其包括作为一个重要类别的脱水素(Ingram and Bartels,1996,Annu Rev Plant Physiol Plant Mol Biol 47:277-403,Close,1997,PhysiolPlant 100:291-296)。这些是在被胁迫的植物中稳定泡囊、蛋白质和膜结构的伴侣蛋白。此外,通常存在醛脱氢酶的诱导,其使在氧化胁迫情况下形成的活性氧簇(ROS)失活(Kirchet al.,2005,Plant Mol Biol 57:315-332)。
热休克因子(HSF)和热休克蛋白质(HSP)在热胁迫的情况下被激活并且在此作为伴侣蛋白起到与在冷和干旱胁迫的情况下脱水素类似的作用(Yu et al.,2005,Mol Cells19:328-333)。
已知许多参与胁迫耐受或病原体防御的植物内源信号物质。此处的实例包括水杨酸、苯甲酸、茉莉酮酸或乙烯[Biochemistry and Molecular Biology of Plants,第850-929页,American Society of Plant Physiologists,Rockville,Maryland,eds.Buchanan,Gruissem,Jones,2000]。这些物质中的一些或其稳定的合成衍生物及其衍生结构在外用至植物或拌种中也是有效的,并且激活了引发植物提高的胁迫耐受性或病原体耐受性的防御反应[Sembdner,and Parthier,1993,Ann.Rev.Plant Physiol.PlantMol.Biol.44:569-589)。水杨酸酯介导的防御特别针对植物致病真菌、细菌和病毒(Ryalset al.,The Plant Cell 8,1809–1819,1996)。
另外已知化学物质能够提高植物对非生物胁迫的耐受性。这类物质通过拌种、通过叶面喷撒或通过土壤处理施用。例如,记载了通过用系统获得性抗性(SAR)激发子、脱落酸衍生物或azibenzolar-S-methyl的处理,作物植物的非生物胁迫耐受性提高(Schadingand Wei,WO-200028055,Abrams and Gusta,US-5201931,Churchill et al.,1998,PlantGrowth Regul 25:35-45)。类似的效果还可以在施用杀真菌剂(尤其是源自strobilurin类杀真菌剂)或琥珀酸脱氢酶抑制剂时观察到,并且还通常伴随着产量提高(Draber et al.,DE-3534948,Bartlett et al.,2002,Pest Manag Sci 60:309)。还已知低剂量的除草剂草甘膦(glyphosate)刺激某些植物种类的生长(Cedergreen,Env.Pollution 2008,156,1099)。
此外,已有记载生长调节剂对作物植物的胁迫耐受性的效果(Morrison andAndrews,1992,J Plant Growth Regul 11:113-117,RD-259027)。在渗透胁迫的情况下,观察到由于施用渗透物质(例如甘氨酸甜菜碱或其生物化学前体例如胆碱衍生物)的保护作用(Chen et al.,2000,Plant Cell Environ 23:609-618,Bergmann et al.,DE-4103253)。也已经记载了抗氧化剂(例如萘酚和黄嘌呤)提高植物中非生物胁迫耐受性的效果(Bergmann et al.,DD-277832,Bergmann et al.,DD-277835)。然而,这些物质的抗胁迫作用的分子原因基本上是未知的。
还已知植物对非生物胁迫的耐受性可以通过改性内源性聚-ADP-核糖聚合酶(PARP)或聚-(ADP-核糖)糖基水解酶(PARG)的活性而提高(de Block et al.,The PlantJournal,2005,41,95;Levine et al.,FEBS Lett.1998,440,1;WO0004173;WO04090140)。
因此已知植物具有多种内源性反应机制,其引起对多种不同的有害生物和/或天然非生物胁迫的有效防御。
然而,由于对于现代作物处理组合物的生态需求和经济需求不断增长,例如关于毒性、选择性、施用率、残留物形成和有利的制造,因此持续需要开发新的作物处理组合物,其至少在一些方面优于已知的组合物。
邻氨基苯甲酰胺衍生物已经记载于WO 2007/144100。这些文件也记录了杀虫活性。出人意料地,现已发现邻氨基苯甲酰胺衍生物极其适于通过灌注、土混、犁沟处理、滴注施用、在水培体系中通过栽植穴处理,在浸渍施用至根、块茎或球茎后,使用水培体系或土壤注射以及通过茎杆或花注射、浸渍施用、漂浮或种子箱施用或通过处理种子来防治昆虫和/或蛛螨和/或线虫。
也已经发现,通过使用邻氨基苯甲酰胺衍生物可以增强植物对非生物胁迫的胁迫耐受性,使得邻氨基苯甲酰胺衍生物可特别用于增强植物生长和/或提高植物产量和/或提高对干旱和干燥条件的耐受性。
因此,本发明涉及邻氨基苯甲酰胺衍生物通过灌注、与基质混合、犁沟处理、在水培和灌溉体系中作为滴注施用、栽植穴处理或作为浸渍施用至例如根、块茎或球茎、或通过土壤、茎杆或花注射来用于防治昆虫和/或蛛螨和/或线虫,并用于处理种子。本发明还涉及在天然基质(土壤)或人造基质(例如岩棉、玻璃棉、石英砂、砂砾、膨胀粘土、蛭石)、户外或在密闭体系中(例如温室或在防护罩下)和一年生(例如大田作物、蔬菜、香料、观赏植物)或多年生(例如柑桔植物(citrus plant)、水果、热带作物、香料、坚果、葡萄、针叶树和观赏植物)作物中的施用形式。
本发明还涉及邻氨基苯甲酰胺衍生物用于增加植物对非生物胁迫的耐受性的用途。仅宽泛描述的待保护的作物将在下文更详细地描述并具体说明。例如,关于用途,大田作物应理解为是指
谷类作物例如小麦、大麦、黑麦、燕麦、小黑麦,以及玉米、棉花、大豆、黍和稻,
以及油菜(油菜籽(canola))、马铃薯、甘蔗、糖用甜菜和向日葵。
例如,关于用途,蔬菜应理解为是指例如果菜类蔬菜和作为蔬菜的花序,例如铃状椒、辣椒、番茄、茄子、黄瓜、南瓜、小胡瓜、蚕豆、红花菜豆和矮菜豆、豌豆、洋蓟;
以及叶菜,例如成头莴苣(head-forming lettuce)、菊苣、苣荬菜、各种类型的水芹、紫花南芥、野苣(lamb’s lettuce)、卷心莴苣、韭葱、菠菜、甜菜;
此外还有结节状、根和茎杆的蔬菜,例如根芹菜、红甜菜根、胡萝卜、萝卜、辣根、婆罗门参、芦笋、芜青、棕榈叶芽、竹笋、此外还有葱蒜类蔬菜,例如洋葱、韭葱、茴香、大蒜;
此外还有芸薹苔属蔬菜如花椰菜、青花椰菜、球茎甘蓝、红球甘蓝、白球甘蓝、羽衣甘蓝、皱叶甘蓝(Savoy cabbage)、孢子甘蓝、大白菜。
关于用途,多年生作物应理解为是指柑桔类,例如桔、柚子、橘、柠檬、来檬、酸橙、金桔、蜜柑;
以及梨果,例如苹果、梨和榅桲,和核果,例如桃、油桃、樱桃、李子、quetsch、杏;
此外还有葡萄藤、葎草、橄榄、茶和热带作物,例如芒果、番木瓜、无花果、菠萝、海枣、香蕉、榴莲、柿、椰子、可可、咖啡、鳄梨、荔枝、maracujas、番石榴,
此外还有杏仁和坚果,例如榛子、核桃、开心果、腰果、巴西果(para nut)、山核桃、灰胡桃、栗、山核桃坚果、澳洲坚果、花生,
此外以及浆果,例如红醋栗、醋栗、悬钩子、黑莓、蓝莓、草莓、越橘包括美国越橘、猕猴桃。
关于用途,观赏植物应理解为是指一年生和多年生植物,例如切花例如玫瑰、康乃馨、非洲菊、百合花、木茼蒿、菊花、郁金香、水仙花、银莲花、罂粟、朱顶红、大丽花、杜鹃花、锦葵,
以及例如花坛植物、盆栽植物和多年生植物例如玫瑰、万寿菊、violas、天竺葵、倒挂金钟、芙蓉、菊花、凤仙花、仙客来、非洲堇、向日葵、秋海棠。
此外例如灌木和针叶树,例如榕木、杜鹃、冷杉、云杉、松树,包括日本金松、紫杉、刺柏、夹竹桃。
关于用途,香料应理解为是指一年生和多年生植物,例如茴香子、辣椒、红胡椒(capsicum)、胡椒、香草、马郁兰、百里香、丁香、杜松子、肉桂、龙嵩、胡荽、藏红花、生姜。可根据本发明用作杀虫剂和/或杀螨剂和/或杀线虫剂的邻氨基苯甲酰胺由通式(I)定义:
其中
R1代表氢、氨基、羟基或代表C1-C6-烷基、C2-C6-烯基、C2-C6-炔基或C3-C6-环烷基,其各自任选地被相同或不同的取代基单取代或多取代,其中所述取代基彼此独立地可选自卤素、氰基、硝基、羟基、C1-C4-烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、(C1-C4-烷氧基)羰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C3-C6-环烷基氨基和(C1-C4-烷基)-C3-C6-环烷基氨基,
R2代表氢、C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C4-烷氧基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C3-C6-环烷基氨基、C1-C6-烷氧基羰基或C1-C6-烷基羰基,
R3代表氢或代表C1-C6-烷基、C1-C6-烷氧基、C2-C6-烯基、C2-C6-炔基、C3-C12-环烷基、C3-C12-环烷基-C1-C6-烷基,其各自任选地被相同或不同的取代基单取代或多取代,其中所述取代基彼此独立地可选自氨基、C3-C6-环烷基氨基、卤素、氰基、羧基、氨基甲酰基、硝基、羟基、C1-C6-烷基、C1-C6-卤代烷基、C3-C6-环烷基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C6-烷氧基羰基、C1-C6-烷基羰基、C3-C6-三烷基甲硅烷基和饱和的或部分饱和的杂环、芳族或杂芳族环或饱和的、部分饱和的或芳族杂双环,其中所述环或环体系任选地被选自以下基团的相同或不同的取代基单取代或多取代,所述基团为:SF5、卤素、氰基、硝基、羟基、氨基、羧基、氨基甲酰基、氨基磺酰基、C1-C6-烷基、C3-C6-环烷基、C1-C4-烷氧基、C1-C6-卤代烷基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-烷基硫亚氨基(alkylsulphimino)、C1-C4-烷基硫亚氨基-C1-C4-烷基、C1-C4-烷基硫亚氨基-C2-C5-烷基羰基、C1-C4-烷基磺亚氨基(alkylsulphoximino)、C1-C4-烷基磺亚氨基-C1-C4-烷基、C1-C4-烷基磺亚氨基-C2-C5-烷基羰基、C1-C6-烷氧基羰基、C1-C6-烷基羰基、C3-C6-三烷基甲硅烷基、苯甲基C2-C6-烯基、C2-C6-炔基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C3-C6-环烷基氨基,或3元至6元环,其中所述环可任选地被C1-C6-烷基、卤素、氰基、硝基、卤代-(C1-C6)-烷基、C1-C6-烷氧基或卤代-(C1-C6)-烷氧基取代,或
R3代表C1-C6-烷氧基羰基、C1-C6-烷基羰基、C1-C6-烷基氨基羰基或二-(C1-C6)烷基氨基羰基,或
R3还代表5元或6元芳族或杂芳族环、4元、5元或6元部分饱和的环或饱和的杂环,或饱和的、部分饱和的或芳族杂双环,所述环可任选地包括一至三个选自O、S和N的杂原子,所述环被相同或不同的取代基单取代或多取代,其中所述取代基彼此独立地选自SF5、卤素、氰基、硝基、羟基、氨基、羧基、氨基甲酰基、C1-C6-烷基、C3-C6-环烷基、C1-C4-烷氧基、C1-C6-卤代烷基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-烷基硫亚氨基、C1-C4-烷基硫亚氨基-C1-C4-烷基、C1-C4-烷基硫亚氨基-C1-C5-烷基羰基、C1-C4-烷基磺亚氨基、C1-C4-烷基磺亚氨基-C1-C4-烷基、C1-C4-烷基磺亚氨基-C2-C5-烷基羰基、C1-C6-烷氧基羰基、C1-C6-烷基羰基、C3-C6-三烷基甲硅烷基、C2-C6-烯基、C2-C6-炔基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基和C3-C6-环烷基氨基,或3元至6元环,其中所述环可任选地被C1-C6-烷基、卤素、氰基、硝基、卤代-(C1-C6)-烷基、C1-C6-烷氧基或卤代-(C1-C6)-烷氧基所取代,
R2和R3可通过两个至六个碳原子彼此连接并且成环,所述环任选地还包含另一个氮、硫或氧原子且所述环可任选地被C1-C2-烷基、C1-C2-卤代烷基、卤素、氰基、氨基、C1-C2-烷氧基或C1-C2-卤代烷氧基单取代至四取代,
R2、R3还一起代表=S(C1-C4-烷基)2或=S(O)(C1-C4-烷基)2,
R4代表氢、卤素、氰基、硝基C1-C4-烷基、C1-C4-卤代烷基、C2-C6-烯基、C2-C6-卤代烯基、C2-C6-炔基、C1-C4-烷氧基、C1-C4-卤代烷氧基、SF5、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C3-C6-环烷基氨基、(C1-C4-烷氧基)亚氨基、(C1-C4-烷基)(C1-C4-烷氧基)亚氨基、(C1-C4-卤代烷基)(C1-C4-烷氧基)亚氨基或C3-C6-三烷基甲硅烷基,或
两个R4通过相邻的碳原子形成代表-(CH2)3-、-(CH2)4-、-(CH2)5-、-(CH=CH-)2-、-OCH2O-、-O(CH2)2O-、-OCF2O-、-(CF2)2O-、-O(CF2)2O-、-(CH=CH-CH=N)-或-(CH=CH-N=CH)-的环,
两个R4还通过相邻的碳原子形成以下稠环,所述稠环任选地被相同或不同的取代基单取代或多取代,其中所述取代基彼此独立地可选自氢、C1-C6-烷基、C3-C6-环烷基、C1-C6-卤代烷基、C3-C6-卤代环烷基、卤素、C1-C6-烷氧基、C1-C4-烷硫基(C1-C6-烷基)、C1-C4-烷基亚磺酰基(C1-C6-烷基)、C1-C4-烷基磺酰基(C1-C6-烷基)、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基和C3-C6-环烷基氨基,
n代表0至3,
R5代表C1-C6-烷基、C3-C6-环烷基、C1-C6-卤代烷基、C1-C6-卤代环烷基、C2-C6-烯基、C2-C6-卤代烯基、C2-C6-炔基、C2-C6-卤代炔基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基、卤素、氰基、硝基或C3-C6-三烷基甲硅烷基,
QX代表芳族或杂芳族5元或6元环,其任选地被相同或不同的R7取代基单取代或多取代并且可包括1至3个选自N、S和O的杂原子,
A代表任选地单取代的或多取代的-(C1-C6-亚烷基)-、-(C2-C6-亚烯基)-、-(C2-C6-亚炔基)-、-R8-(C3-C6-环烷基)-R8-、-R8-O-R8-、-R8-S-R8-、-R8-S(=O)-R8-、-R8-S(=O)2-R8-、-R8-N(C1-C6-烷基)-R8-、-R8-C=NO(C1-C6-烷基)-R8、-CH[CO2(C1-C6-烷基)-、-R8-C(=O)-R8、-R8-C(=O)NH-R8、R8-C(=O)N(C1-C6-烷基)-R8、-R8-C(=O)NHNH-R8-、-R8-C(=O)N(C1-C6-烷基)-NH-R8-、-R8-C(=O)NHN(C1-C6-烷基)-R8、-R8-O(C=O)-R8、-R8-O(C=O)NH-R8、-R8-O(C=O)N(C1-C6-烷基)-R8、-R8-S(=O)2NH-R8、-R8-S(=O)2N(C1-C6-烷基)-R8、-R8-S(C=O)-R8、-R8-S(C=O)NH-R8、-R8-S(C=O)N(C1-C6-烷基)-R8、-R8-NHNH-R8、-R8-NHN(C1-C6-烷基)-R8、-R8-N(C1-C6-烷基)-NH-R8、-R8-N(C1-C6-烷基)-N(C1-C6-烷基)-R8、-R8-N=CH-O-R8、-R8-NH(C=O)O-R8、-R8-N(C1-C6-烷基)-(C=O)O-R8、-R8-NH(C=O)NH-R8、-R8-NH(C=S)NH-R8、-R8-NHS(=O)2-R8、R8-NH-R8、R8-C(=O)-C(=O)-R8、R8-C(OH)-R8、R8-NH(C=O)-R8、R8-Qz-R8、R8-C(=N-NR’2)-R8、R8-C(=C-R’2)-R8或-R8-N(C1-C6-烷基)S(=O)2-R8,
其中取代基彼此独立地可选自卤素、氰基、硝基、羟基、C1-C6-烷基、C1-C6-烷氧基、卤代-C1-C6-烷基、氨基、(C1-C6-烷基)氨基、二-(C1-C6-烷基)氨基和C3-C6-环烷基
其中环中的-(C3-C6-环烷基)-可任选地包含1个或2个选自N、S和O的杂原子,
R8代表直链或支链的-(C1-C6-亚烷基)-或代表直接键合,
其中多个R8彼此独立地代表直链或支链的-(C1-C6-亚烷基)-或代表直接键合,
例如,R8-O-R8-代表-(C1-C6-亚烷基)-O-(C1-C6-亚烷基)-、-(C1-C6-亚烷基)-O-、-O-(C1-C6-亚烷基)-,或-O-,
其中R’代表烷基、烷基羰基、烯基、炔基,其可任选地被卤素单取代或多取代,
Qz代表3元或4元部分饱和的或饱和的或5元或6元部分饱和的、饱和的或芳族环或代表6元至10元双环体系,
其中所述环或双环体系可任选地包含1-3个选自N、S和O的杂原子,
其中所述环或双环体系任选地被相同或不同的取代基单取代或多取代并且其中所述取代基彼此独立地可选自氢、C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、氨基甲酰基、硝基、羟基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C3-C6-环烷基氨基、(C1-C6-烷基)羰基、(C1-C6-烷氧基)羰基、(C1-C6-烷基)氨基羰基和二-(C1-C4-烷基)氨基羰基,
QY代表5元或6元部分饱和或饱和的杂环或杂芳环或芳族8元、9元或10元稠合杂双环体系,其中所述环或环体系任选地被相同的或不同的取代基单取代或多取代并且所述取代基彼此独立地可选自氢、C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、羧基、氨基甲酰基、硝基、羟基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C3-C6-环烷基氨基、(C1-C6-烷基)羰基、(C1-C6-烷氧基)羰基、(C1-C6-烷基)氨基羰基、二-(C1-C4-烷基)氨基羰基、三(C1-C2)烷基甲硅烷基和(C1-C4-烷基)(C1-C4-烷氧基)亚氨基,
或者其中所述取代基彼此独立地可选自苯基和5元或6元杂芳环,其中苯基或所述环可任选地被选自C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、硝基、羟基、C1-C4-烷氧基和C1-C4-卤代烷氧基的相同或不同取代基单取代或多取代,
R7代表氢、C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C3-C6-环烷氧基或
R9彼此独立地代表氢、C1-C6-烷基、C3-C6-环烷基、C1-C6-卤代烷基、卤素、氰基、硝基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基或C1-C4-卤代烷硫基,
p代表0至4,
Z代表N、CH、CF、CCl、CBr或Cl,
通式(I)的化合物还包括N-氧化物和盐。
对于本发明而言,优选、特别优选、非常特别优选或尤其优选的是这样的式(I)的活性化合物,其中
R1 优选代表氢、C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、氰基(C1-C6-烷基)、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C1-C4-烷氧基-C1-C4-烷基、C1-C4-烷硫基-C1-C4-烷基、C1-C4-烷基亚磺酰基-C1-C4-烷基或C1-C4-烷基磺酰基-C1-C4-烷基,
R1 特别优选代表氢、甲基、环丙基、氰基甲基、甲氧基甲基、甲硫基甲基、甲基亚磺酰基甲基或甲基磺酰基甲基,
R1 非常特别优选代表氢,
R2 优选代表氢或C1-C6-烷基。
R2 特别优选代表氢或甲基。
R2 非常特别优选代表氢。
R3 优选代表氢或代表C1-C4-烷基、C1-C4-烷氧基、C2-C4-烯基、C2-C4-炔基、C3-C6-环烷基,其各自任选地被相同或不同的取代基单取代或多取代,其中所述取代基彼此独立地可选自卤素、氰基、羧基、氨基甲酰基、硝基、羟基、C1-C4-烷基、C1-C4-卤代烷基、C3-C6-环烷基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-烷氧基羰基、C1-C4-烷基羰基或苯环或4元、5元或6元芳族、部分饱和或饱和的杂环,其中所述苯环或杂环任选地被相同的或不同的取代基单取代或多取代并且其中所述取代基彼此独立地可选自氢、C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、羧基、氨基甲酰基、NO2、羟基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C3-C6-环烷基氨基、(C1-C6-烷基)羰基、(C1-C6-烷氧基)羰基或
R3 优选代表C2-C4-烷氧基羰基、C2-C4-烷基羰基、C2-C4-烷基氨基羰基或C2-C4-二烷基氨基羰基,或
R3 优选代表苯环、5元或6元芳族杂环或4元、5元或6元部分饱和或饱和的杂环,其可以包含1-3个选自N、S和O的杂原子,其中所述苯环或杂环任选地被相同或不同的取代基单取代或多取代,并且其中所述取代基彼此独立地可选自氢、C1-C4-烷基、C2-C4-烯基、C2-C4-炔基、C3-C6-环烷基、C1-C4-卤代烷基、C2-C4-卤代烯基、C2-C4-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、羧基、氨基甲酰基、NO2、羟基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基、C1-C4-烷基氨基、二-(C1-C4-烷基)氨基、C3-C6-环烷基氨基、(C1-C4-烷基)羰基和(C1-C4-烷氧基)羰基,
R3 特别优选代表氢或代表C1-C4-烷基或C3-C6-环烷基,其各自任选地被相同或不同的取代基单取代或多取代,其中所述取代基彼此独立地可选自卤素、氰基、羧基、羟基、C1-C4-烷基、C1-C4-卤代烷基、C3-C6-环烷基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C2-C4-烷氧基羰基、C2-C6-烷基羰基和苯环和4元、5元或6元芳族、部分饱和或饱和的杂环,其中所述苯环或杂环任选地被相同的或不同的取代基单取代或多取代,并且其中所述取代基彼此独立地可选自氢、C1-C4-烷基、C3-C6-环烷基、C1-C4-卤代烷基、C2-C4-卤代烯基、C2-C4-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、羟基、C1-C4-烷氧基和C1-C4-卤代烷氧基,或
R3 特别优选代表C2-C4-烷氧基羰基、C2-C4-烷基羰基或C2-C4-烷基氨基羰基,或
R3 特别优选代表苯环、5元或6元芳族杂环或4元、5元或6元部分饱和或饱和的杂环,其可包含1-3个选自N、S和O的杂原子,其中所述苯环或杂环任选地被相同的或不同的取代基单取代或多取代,并且其中所述取代基彼此独立地可选自氢、C1-C4-烷基、C2-C4-烯基、C2-C4-炔基、C3-C6-环烷基、C1-C4-卤代烷基、C2-C4-卤代烯基、C2-C4-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、氨基甲酰基、NO2、羟基、C1-C4-烷氧基和C1-C4-卤代烷氧基,或
R3 非常特别优选代表氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、环丙基、环丁基、氮杂环丁烷、氧杂环丁烷、硫杂环丁烷(thietane)、吡咯烷、吡唑烷、咪唑烷、咪唑烷酮、四氢呋喃、四氢噻吩、四氢噻吩二氧化物、噻唑啉、噻唑烷、哌啶、哌嗪、四氢吡喃、二氢呋喃酮、二氧杂环己烷、吗啉、硫代吗啉、硫代吗啉二氧化物、苯基或吡啶基,或
R3 尤其优选代表氢、甲基、异丙基、环丙基或叔丁基。
R4 优选代表氢、C1-C4-烷基、C1-C4-卤代烷基、卤素、氰基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基或C1-C4-卤代烷硫基,
两个相邻的基团R4还优选代表-(CH2)3-、-(CH2)4-、-(CH2)5-、-(CH=CH-)2-、-OCH2O-、-O(CH2)2O-、-OCF2O-、-(CF2)2O-、-O(CF2)2O-、-(CH=CH-CH=N)-或-(CH=CH-N=CH)-,
R4 特别优选代表氢、C1-C4-烷基、C1-C2-卤代烷基、卤素、氰基或C1-C2-卤代烷氧基,
两个相邻的基团R4 特别优选代表-(CH2)4-、-(CH=CH-)2-、-O(CH2)2O-、-O(CF2)2O-、-(CH=CH-CH=N)-或-(CH=CH-N=CH)-,
R4 非常特别优选代表氢、甲基、三氟甲基、氰基、氟、氯、溴、碘或三氟甲氧基。此外,两个相邻的基团R4非常特别优选代表-(CH2)4-或-(CH=CH-)2-。
R4 尤其优选代表氯、氟或溴,
R4还尤其优选代表碘或氰基。
两个相邻的基团R4 尤其优选代表-(CH=CH-)2
n优选代表0、1或2,
n特别优选代表1或2,
n非常特别优选代表1,
R5 优选代表C1-C4-烷基、C3-C6-环烷基、C1-C4-卤代烷基、C1-C6-卤代环烷基、C2-C6-烯基、C2-C4-卤代烯基、C2-C4-炔基、C2-C4-卤代炔基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基、卤素、氰基、硝基或C3-C6-三烷基甲硅烷基,
R5 特别优选代表C1-C4-烷基、C3-C6-环烷基、C1-C4-卤代烷基、C1-C6-卤代环烷基、C2-C6-烯基、C2-C4-卤代烯基、C2-C4-炔基、C2-C4-卤代炔基、C1-C4-烷氧基、C1-C4-卤代烷氧基、氟、氯、溴、碘、氰基、硝基或C3-C6-三烷基甲硅烷基,
R5 非常特别优选代表甲基、氟、氯、溴或碘,
R5 尤其优选代表甲基或氯,
Qx优选代表5元或6元杂芳环,其任选地被相同或不同的R7单取代或多取代并且可包含1-3个选自N、O和S的杂原子,或代表苯基,
Qx特别优选代表选自呋喃、噻吩、三唑、咪唑、噻唑、噁唑、异噁唑、异噻唑、噻二唑、噁二唑、吡咯、吡啶、嘧啶、哒嗪、吡嗪、苯基或吡唑的5元或6元环,所述环任选地被相同或不同的R7单取代或多取代,
Qx非常特别优选代噻唑、噁唑、吡咯、咪唑、三唑、嘧啶、苯基或代表被基团R7单取代的吡唑,
其中Z、R和p可以具有上面给出的一般定义或以下给出的优选或特别优选的定义,
A优选代表任选地单取代的或多取代的-(C1-C4-亚烷基)-、-(C2-C4-亚烯基)-、-(C2-C4-亚炔基)-、-R8-(C3-C6-环烷基)-R8-、-R8-O-R8-、-R8-S-R8-、-R8-S(=O)-R8-、-R8-S(=O)2-R8-、-R8-NH-(C1-C4-烷基)-、-R8-N(C1-C4-烷基)-R8、-R8-C=NO(C1-C4-烷基)、-R8-C(=O)-R8、-R8-C(=S)-R8、-R8-C(=O)NH-R8、R8-C(=O)N(C1-C4-烷基)-R8、-R8-S(=O)2NH-R8、-R8-S(=O)2N(C1-C4-烷基)-R8、-R8-NH(C=O)O-R8、-R8-N(C1-C4-烷基)-(C=O)O-R8、-R8-NH(C=O)NH-R8、-R8-NHS(=O)2-R8、-R8-N(C1-C4-烷基)S(=O)2-R8、R8-NH-R8、R8-C(=O)-C(=O)-R8、R8-C(OH)-R8或R8-Qz-R8,
其中取代基彼此独立地可选自卤素、氰基、硝基、羟基、C1-C6-烷基、C1-C6-烷氧基和卤代-C1-C6-烷基,
其中Qz可以具有上面给出的一般定义或以下给出的优选或特别优选的定义,
A特别优选代表-CH2-、-CH2O-、-CH2OCH2-、-CH2S-、-CH2SCH2-、-CH2N(C1-C4-烷基)-、-CH2N(C1-C4-烷基)CH2-、-CH(Hal)-、-C(Hal)2-、-CH(CN)-、CH2(CO)-、CH2(CS)-、CH2CH(OH)-、-环丙基-、CH2(CO)CH2-、-CH(C1-C4-烷基)-、-C(二-C1-C6-烷基)-、-CH2CH2-、-CH=CH-、-C≡C-、-C=NO(C1-C6-烷基)或-C(=O)(C1-C4-烷基)-,
A非常特别优选代表-CH2-、-CH(CH3)、C(CH3)2、-CH2CH2-、-CH(CN)-、-CH2O-或-C(=O)-CH2-,
A尤其优选代表CH2、CH(CH3)、-CH2O-或-C(=O)-CH2-,
Qz优选代表3元或4元部分饱和的或饱和的或5元或6元部分饱和、饱和的或芳族环,其中所述环可任选地包含1-3个选自N、S和O的杂原子,
其中所述环任选地被相同或不同的取代基单取代或多取代,并且其中所述取代基彼此独立地可选自氢、C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、羟基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基和C1-C4-卤代烷基磺酰基,
Qz特别优选代表3元或4元部分饱和的或饱和的或5元部分饱和的、饱和的或芳族环,其中所述环可任选地包含1-2个选自N、S和O的杂原子,
其中所述环任选地被相同或不同的取代基单取代或多取代,并且其中所述取代基彼此独立地可选自氢、C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、羟基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基和C1-C4-卤代烷基磺酰基,
Qz非常特别优选代表氮杂环丁烷、氧杂环丁烷或硫杂环丁烷、吡咯烷、吡咯啉、吡唑烷、吡唑啉、咪唑烷、咪唑烷酮、咪唑啉、四氢呋喃、四氢噻吩、噻唑烷、异噻唑烷或异噁唑啉,
其任选地被相同或不同的取代基单取代或多取代,并且其中所述取代基彼此独立地可选自氢、甲基、乙基、异丙基、羟基、甲氧基、三氟甲氧基、氟、氯、溴、氰基、二氟甲基、三氟甲基,
R7优选代表C1-C6-烷基或代表基团
R7还优选地代表C3-C6-环烷氧基,
R7 特别优选代表甲基或代表基团
R9彼此独立地优选代表氢、卤素、氰基、C1-C4-烷基、C1-C4-烷氧基、C1-C4-卤代烷基、C1-C4-卤代烷氧基、C1-C4-卤代烷基磺酰基或(C1-C4-烷基)-C1-C4-烷氧基亚氨基,
R9彼此独立地特别优选代表氢、卤素、氰基或C1-C4-卤代烷基,
R9彼此独立地非常特别优选代表氟、氯或溴,
R9 尤其优选代表氯。
p优选代表1、2或3,
p特别优选代表1或2,
p非常特别优选代表1,
Z优选代表N、CH、CF、CCl、CBr或CI,
Z特别优选代表N、CH、CF、CCl或CBr,
Z非常特别优选代表N、CCl或CH,
R8 优选代表直链或支链的-(C1-C4-亚烷基)-或代表直接键合,
R8 特别优选代表甲基、乙基、丙基、异丙基、正丁基、仲丁基或异丁基或直接键合,
R8 非常特别优选代表甲基或乙基或直接结合,
Qy优选代表5元或6元部分饱和或饱和的杂环或杂芳环或芳族8元、9元或10元稠合杂双环体系,其中杂原子可选自N、S和O,其中所述环或环体系任选地被相同或不同的取代基单取代或多取代并且其中所述取代基彼此独立地可选自氢、C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、羧基、氨基甲酰基、硝基、羟基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C1-C4-烷基亚磺酰基、C1-C4-烷基磺酰基、C1-C4-卤代烷硫基、C1-C4-卤代烷基亚磺酰基、C1-C4-卤代烷基磺酰基,
或者其中所述取代基彼此独立地可选自苯基和5元或6元杂芳环,其中苯基或所述环可任选地被选自C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6- 卤代环烷基、卤素、氰基、硝基、羟基、C1-C4-烷氧基和C1-C4-卤代烷氧基的相同或不同的取代基单取代或多取代,
Qy特别优选代表任选地单取代或多取代的选自Q-1至Q-53和Q-58至Q-59、Q62至Q63的5元或6元杂芳环,芳族9元稠合杂双环体系Q-54至Q-56或5元杂环Q-60至Q-61,其中取代基彼此独立地可选自C1-C3-烷基、C1-C3-卤代烷基、C1-C2-烷氧基、卤素、氰基、羟基、硝基或C1-C2-卤代烷氧基,
或其中所述取代基彼此独立地可选自苯基和5元或6元杂芳环,其中苯基或所述环任选地被选自C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、NO2、羟基、C1-C4-烷氧基和C1-C4-卤代烷氧基的相同或不同的取代基单取代或多取代,
Qy非常特别优选代表任选地单取代或多取代的选自Q-36至Q-40、Q43、Q-58至Q-59、Q62、Q63的5元或6元杂芳环、芳族9元稠合杂双环体系Q-54至Q-56或5元杂环Q-60至Q-61,其中取代基彼此独立地可选自C1-C3-烷基、C1-C3-卤代烷基、C1-C2-烷氧基、卤素、氰基、羟基、硝基或C1-C2-卤代烷氧基,
或其中所述取代基彼此独立地可选自苯基和5元或6元杂芳环,其中苯基或所述环可任选地被选自C1-C6-烷基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C1-C6-卤代烷基、C2-C6-卤代烯基、C2-C6-卤代炔基、C3-C6-卤代环烷基、卤素、氰基、硝基、C1-C4-烷氧基和C1-C4-卤代烷氧基的相同或不同的取代基单取代或多取代,
Qy尤其优选代表选自Q-37、Q-38、Q-39、Q-40、Q43、Q-58、Q-59、Q62和Q63的杂芳环,其任选地被相同或不同的取代基单取代或多取代,或代表5元杂环Q-60,其中所述取代基彼此独立地可选自甲基、乙基、环丙基、叔丁基、氯、氟、碘、溴、氰基、硝基、二氟甲基、三氟甲基、五氟乙基、正七氟丙基和异七氟丙基
或所述取代基可彼此独立地选自苯基或5元或6元杂芳环,所述取代基可彼此独立地选自甲基、乙基、环丙基、叔丁基、氯、氟、碘、溴、氰基、硝基、二氟甲基、三氟甲基、五氟乙基、正七氟丙基和异七氟丙基,
彼此独立地,以上列举的环或环体系可以另外被氧代、硫代、(=O)=NH、(=O)=N-CN、(=O)2取代。四氢噻吩二氧化物和咪唑烷酮可以实例的方式被提及。
在该情况下,作为环碳原子上取代基的氧代基团例如为杂环中的羰基。因此,还优选还包括内酯和内酰胺。氧代基团还可在可以各种氧化态存在的杂环原子上存在例如在N和S中上,在该情况下,其在杂环中形成例如二价基团-N(O)-、-S(O)-(还简写为SO)和-S(O)2-(还简写为SO2)。在–N(O)-和–S(O)-基团的情况下,各自包括两种对映异构体。
在杂环中,除了氧代基团之外的取代基也可以与杂原子相连,例如在氮原子上,如果在所述过程中母体结构的氮原子上的氢原子被取代。在氮原子以及其他杂原子例如硫原子的情况下,也可能进行其他取代形成季铵化合物或锍化合物。
特别地,式(I)化合物可以各种区域异构体(regioisomer)形式存在。例如以具有定义Q62或Q63的化合物的混合物形式或以Q58和Q59的混合物的形式。因此,本发明还包括含有式(I)化合物的混合物的活性化合物结合物,其中Qy具有含义Q62和Q63,以及Q58和Q59并且所述化合物可以各种混合比存在,以及一种或多种组(II)的活性化合物。本发明中优选的是其中基团Qy代表Q62或Q58的式(I)的化合物与其中基团Qy代表Q63或Q59的式(I)的化合物的混合比为60:40至99:1,特别优选70:30至97:3,非常特别优选80:20至95:5。尤其优选为其中Qy具有含义Q62或Q58的式(I)的化合物与其中Qy具有含义Q63或Q59的式(I)的化合物以下混合比:80:20;81:19;82:18;83:17;84:16;85:15,86:14;87:13;88:12;89:11;90:10,91:9;92:8;93:7;96:6;95:5。
在本发明的一个优选实施方案中,式(I)化合物以其中Qy代表Q62和Q63的通式(I)化合物的混合物存在,其中Qy代表Q62的式(I)的化合物与Qy代表Q63的式(I)的化合物的比例为80:20至99:1。
在本发明的一个优选实施方案中,式(I)化合物以其中Qy代表Q58和Q59的通式(I)化合物的混合物存在,其中Qy代表Q58的式(I)的化合物与Qy代表Q59的式(I)的化合物的比例为80:20至99:1。
对于本发明而言,还优选的是式(I-1)的活性化合物
其中
R3代表氢或代表C1-C6-烷基、C1-C6-烷氧基、C2-C6-烯基、C2-C6-炔基、C3-C12-环烷基、C3-C12-环烷基-C1-C6-烷基,其各自任选地被相同或不同的取代基单取代或多取代,其中所述取代基彼此独立地可选自卤素、氨基、氰基、硝基、羟基、C1-C6-烷基、C3-C6-环烷基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C2-C6-烷氧基羰基、C1-C6-烷基羰基C3-C6-环烷基氨基和5元或6元杂芳环,R4代表卤素、氰基或甲基,
R5代表甲基或氯,
Z代表N、CCl或CH,
Qy代表任选地单取代或多取代的选自Q-36至Q-40、Q43、Q-58至Q-59、Q62、Q63的5元或6元杂芳环、芳族9元稠合杂双环体系Q-54至Q-56或5元杂环Q-60至Q-61,其中取代基彼此独立地可选自C1-C3-烷基、C1-C3-卤代烷基、C1-C2-烷氧基、卤素、氰基、羟基、硝基或C1-C2-卤代烷氧基,
其中式(I-1)化合物可以以盐的形式存在。
对于本发明而言,优选、特别优选、非常特别优选或尤其优选的是式(I-1)活性化合物,其中
R3 优选代表氢或代表C1-C6-烷基、C1-C6-烷氧基、C2-C6-烯基、C2-C6-炔基、C3-C6-环烷基、C3-C6-环烷基-C1-C6-烷基,其各自任选地被相同或不同的取代基单取代或多取代,其中所述取代基彼此独立地可选自卤素、氰基、氨基、羟基、C1-C6-烷基、C1-C4-烷氧基、C1-C4-卤代烷氧基、C1-C4-烷硫基、C3-C6-环烷基和包含1-2个选自N、O和S的杂原子的5元或6元杂芳环,其中环中的两个氧原子不相邻,
R3 特别优选代表以下的基团中的一种
R4 优选代表卤素、氰基或甲基,
R4 特别优选代表氯或氰基,
R4 还特别优选代表溴、氟、碘或甲基,
R5 优选且特别优选代表甲基,
Z优选代表N或CH,
Qy优选代表源自Q-37、Q-38、Q-39、Q-40、Q43、Q-58、Q-59、Q62和Q63的杂芳环,所述杂芳环任选被相同或不同的取代基单取代或多取代,或代表5元杂环Q-60,其中所述取代基彼此独立地可选自甲基、乙基、环丙基、叔丁基、氯、氟、碘、溴、氰基、硝基、二氟甲基、三氟甲基、五氟乙基、正七氟丙基和异七氟丙基。
Qy特别优选代表源自Q-58和Q-59的杂芳环,所述杂芳环任选地被相同或不同的取代基单取代或多取代,其中所述取代基彼此独立地可选自甲基、乙基、环丙基、叔丁基、二氟甲基、三氟甲基、五氟乙基、正七氟丙基和异七氟丙基。
特别地,式(I-1)的化合物可以各种区域异构体的形式存在。例如具有定义Q62或Q63的化合物的混合物形式或Q58和Q59混合物的形式。因此,本发明还包括含有式(I-1)化合物的混合物的活性化合物结合物,其中Qy具有含义Q62和Q63,以及Q58和Q59,并且所述化合物可以各种混合比存在,以及一种或多种组(II)的活性化合物。本文中优选的是其中基团Qy代表Q62或Q58的式(I)化合物与其中基团Qy代表Q63或Q59的式(I)化合物的混合比为60:40至99:1,特别优选70:30至97:3,非常特别优选80:20至95:5。尤其优选为其中Qy具有含义Q62或Q58的式(I)化合物与其中Qy具有含义Q63或Q59的式(I)化合物的以下混合比:80:20;81:19;82:18;83:17;84:16;85:15、86:14;87:13;88:12;89:11;90:10、91:9;92:8;93:7;96:6;95:5。
对于本发明而言,特别优选的是以下式(I-1-1)至(I-1-71)的活性化合物
对于本发明而言,还特别优选的是以下式(I-1-1)至(I-1-71)的活性化合物的混合物。
这些混合物优选以80:20至99:1的混合比存在。以示例性的方式,可以提及混合物I-1-1/I-1-7,其中式I-1-1化合物和式I-1-7化合物以80:20至99:1的混合比存在。以示例性的方式,还可以提及混合物I-1-2/I-1-8,其中式I-1-2化合物和式I-1-8化合物以80:20至99:1的混合比存在。
I-1-1-/1-1-7,
1-1-2/1-1-8,
1-1-3/1-1-9,
I-1-4/1-1-10,
I-1-5/1-1-11,
I-1-6/1-1-12,
I-1-13/I-1-1-19,
1-1-14/1-1-20,
I-1-15/I-1-21,
I-1-16/I-1-22,
I-1-17/I-1-23,
I-1-18/I-1-24,
1-1-25/1-1-31,
1-1-26/1-1-32,
I-1-27/I-1-33,
1-1-28/1-1-34,
I-1-29/I-1-35,
I-1-30/I-1-36,
1-1-37/1-1-43,
1-1-38/1-1-44,
I-1-39/I-1-45,
I-1-40/I-1-46,
I-1-41/I-1-47,
I-1-42/I-1-48,
I-1-49/I-1-55,
I-1-50/I-1-56,
I-1-51/I-1-57,
I-1-52/I-1-58,
I-1-53/I-1-59,
I-1-54/I-1-60。
对于本发明而言,非常特别优选的是式(I-1)的活性化合物或以下列举的式(I-1-1)至(I-1-71)的活性化合物混合物:
(I-1-1)、(I-1-2)、(I-1-3)、(I-1-61)、(I-1-62)、(I-1-63)、(I-1-64)、(I-1-65)、(I-1-66)、(I-1-67)、(I-1-68)、(I-1-69)、(I-1-70)、(I-1-71)、I-1-1/1-1-7、1-1-2/1-1-8、1-1-3/1-1-9。本发明的邻氨基苯甲酰胺衍生物的用途是抵抗宽范围的动物有害物,特别是在农业、园艺业、林业和园林以及休闲设施中遇到的昆虫、蛛形纲动物、蠕虫、线虫和软体动物,抵抗通常敏感和抗性的物种,以及抵抗所有或个别发育阶段。这些害虫包括:
节肢动物门(Arthropoda)害虫,特别是蛛形纲(Arachnida)例如粉螨属(Acarusspp.)、柑橘瘤瘿螨(Aceria sheldoni)、刺皮瘿螨属(Aculops spp.)、刺瘿瘿螨属(Aculusspp.)、花蜱属(Amblyomma spp.)、山楂叶螨(Amphitetranychus viennensis)、锐缘蜱属(Argas spp.)、牛蜱属(Boophilus spp.)、短须螨属(Brevipalpus spp.)、Bryobiagraminum、苜蓿苔螨(Bryobia praetiosa)、Centruroides spp.、皮螨属(Chorioptesspp.)、鸡皮刺螨(Dermanyssus gallinae)、特嗜皮螨(Dermatophagoidespteronissimus)、法嗜皮螨(Dermatophagoides farinae)、革蜱属(Dermacentor spp.)、始叶螨属(Eotetranychus spp.)、梨上瘿螨(Epitrimerus pyri)、真叶螨属(Eutetranychusspp.)、瘿螨属(Eriophyes spp.)、Glycyphagus domesticus、赤足夜螨(Halotydeusdestructor)、半跗线螨属(Hemitarsonemus spp.)、璃眼蜱属(Hyalomma spp.)、硬蜱属(Ixodes spp.)、毒蛛属(Latrodectus spp.)、隐蛛属(Loxosceles spp.)、Metatetranychus spp.、Neutrombicula autumnalis、Nuphersa spp.、小爪螨属(Oligonychus spp.)、钝缘蜱属(Ornithodoros spp.)、禽刺螨属(Ornithonyssus spp.)、全爪螨属(Panonychus spp.)、桔芸锈螨(Phyllocoptruta oleivora)、侧多食跗线螨(Polyphagotarsonemus latus)、痒螨属(Psoroptes spp.)、扇头蜱属(Rhipicephalusspp.)、根螨属(Rhizoglyphus spp.)、疥螨属(Sarcoptes spp.)、中东金蝎(Scorpiomaurus)、狭趺线螨种(Stenotarsonemus spp.)、Steneotarsonemus spinki、跗线螨属(Tarsonemus spp.)、叶螨属(Tetranychus spp.)、Trombicula alfreddugesi、Vaejovisspp.、Vasates lycopersici。
唇足纲(Chilopoda),例如,地蜈蚣属(Geophilus spp.)、蚰蜒属(Scutigeraspp.)。
弹尾目(Collembola)或弹尾纲,例如,武装棘跳虫(Onychiurus armatus)。
倍足纲(Diplopoda),例如,千足虫(Blaniulus guttulatus)。
昆虫纲,例如蜚蠊目(Blattodea),例如,亚洲蠊(Blattella asahinai)、德国蠊(Blattella germanica)、东方蜚蠊(Blatta orientalies)、马德拉蜚蠊(Leucophaeamaderae)、角腹蠊属(Panchlora spp.)、木蠊属(Parcoblatta spp.)、大蠊属(Periplanetaspp.)、棕带蜚蠊(Supella longipalpa)。
鞘翅目(Coleoptera),例如,黄瓜条纹叶甲(Acalymma vittatum)、菜豆象(Acanthoscelides obtectus)、喙丽金龟属(Adoretus spp.)、杨树萤叶甲(Agelasticaalni)、叩甲属(Agriotes spp.)、黑菌虫(Alphitobius diaperinus)、马铃薯鳃角金龟(Amphimallon solstitialis)、家具窃蠹(Anobium punctatum)、星天牛属(Anoplophoraspp.)、花象属(Anthonomus spp.)、圆皮蠹属(Anthrenus spp.)、长喙小象属(Apionspp.)、阿鳃金龟属(Apogonia spp.)、Atomaria spp.、毛皮蠹属(Attagenus spp.)、恶条豆象(Bruchidius obtectus)、豆象属(Bruchus spp.)、龟甲属(Cassida spp.)、菜豆萤叶甲(Cerotoma trifurcata)、龟象属(Ceuthorhynchus spp.)、凹胫跳甲属(Chaetocnemaspp.)、Cleonus mendicus、宽胸叩头虫属(Conoderus spp.)、根颈象属(Cosmopolitesspp.)、褐新西兰肋翅鳃角金龟(Costelytra zealandica)、叩甲属(Ctenicera spp.)、象虫属(Curculio spp.)、锈赤扁谷盗(Cryptolestes ferrugineus)、杨干隐喙象(Cryptorhynchus lapathi)、细枝象属(Cylindrocopturus spp.)、皮蠹属(Dermestesspp.)、叶甲属(Diabrotica spp.)、蛀野螟属(Dichocrocis spp.)、水稻铁甲(Dicladispaarmigera)、Diloboderus spp.、食植瓢虫属(Epilachna spp.)、毛跳甲属(Epitrix spp.)、Faustinus spp.、裸蛛甲(Gibbium psylloides)、阔角谷盗(Gnathocerus cornutus)、菜心野螟(Hellula undalis)、黑异爪蔗金龟(Heteronychus arator)、寡节鳃金龟属(Heteronyx spp.)、Hylamorpha elegans、北美家天牛(Hylotrupes bajulus)、紫苜蓿叶象(Hypera postica)、蓝绿象(Hypomeces squamosus)、Hypothenemus spp.、甘蔗大褐齿爪鳃金龟(Lachnosterna consanguinea)、烟草甲(Lasioderma serricorne)、长头谷盗(Latheticus oryzae)、Lathridius spp.、Lema spp.、马铃薯甲虫(Leptinotarsadecemlineata)、纹潜蛾属(Leucoptera spp.)、稻根象(Lissorhoptrus oryzophilus)、筒喙象属(Lixus spp.)、Luperodes spp.、粉蠹属(Lyctus spp.)、美洲叶甲属(Megascelisspp.)、Melanotus spp.、油菜花露尾甲(Meligethes aeneus)、鳃金龟属(Melolonthaspp.)、Migdolus spp.、墨天牛属(Monochamus spp.)、Naupactus xanthographus、隐跗郭公虫属(Necrobia spp.)、黄蛛甲(Niptus hololeucus)、椰蛀犀金龟(Oryctesrhinoceros)、锯谷盗(Oryzaephilus surinamensis)、Oryzaphagus oryzae、耳喙象属(Otiorrhynchus spp.)、小青花金龟(Oxycetonia jucunda)、辣根猿叶虫(Phaedoncochleariae)、食叶鳃金龟属(Phyllophaga spp.)、Phyllophaga helleri、菜跳甲属(Phyllotreta spp.)、日本弧丽金龟(Popillia japonica)、象甲属(Premnotrypes spp.)、大谷蠹(Prostephanus truncatus)、跳甲属(Psylliodes spp.)、蛛甲属(Ptinus spp.)、暗色瓢虫(Rhizobius ventralis)、谷蠹(Rhizopertha dominica)、谷象属(Sitophilusspp.)、米象(Sitophilus oryzae)、尖隐喙象属(Sphenophorus spp.)、药材甲(Stegobiumpaniceum)、茎干象属(Sternechus spp.)、Symphyletes spp.、纤毛象属(Tanymecusspp.)、黄粉虫(Tenebrio molitor)、大谷盗(Tenebrioides mauretanicus)、拟谷盗属(Tribolium spp.)、斑皮蠹属(Trogoderma spp.)、籽象属(Tychius spp.)、脊虎天牛属(Xylotrechus spp.)、距步甲属(Zabrus spp.)。
双翅目(Diptera),例如,伊蚊属(Aedes spp.)、潜蝇属(Agromyza spp.)、按实蝇属(Anastrepha spp.)、按蚊属(Anopheles spp.)、瘿蚊属(Asphondylia spp.)、果实蝇属(Bactrocera spp.)、花园毛蚊(Bibio hortulanus)、红头丽蝇(Calliphoraerythrocephala)、红头丽蝇(Calliphora vicina)、地中海蜡实蝇(Ceratitis capitata)、摇蚊属(Chironomus spp.)、金蝇属(Chrysomyia spp.)、斑虻属(Chrysops spp.)、高额麻虻(Chrysozona pluvialis)、锥蝇属(Cochliomyia spp.)、Contarinia spp.、人皮蝇(Cordylobia anthropophaga)、树真环足摇蚊(Cricotopus sylvestris)、库蚊属(Culexspp.)、库蠓属(Culicoides spp.)、脉毛蚊属(Culiseta spp.)、黄蝇属(Cuterebra spp.)、橄榄大实蝇(Dacus oleae)、Dasyneura spp.、地种蝇属(Delia spp.)、人肤蝇(Dermatobiahominis)、果蝇属(Drosophila spp.)、稻象属(Echinocnemus spp.)、厕蝇属(Fanniaspp.)、胃蝇属(Gastrophilus spp.)、舌蝇属(Glossina spp.)、麻虻属(Haematopotaspp.)、毛眼水蝇属(Hydrellia spp.)、麦叶毛眼水蝇(Hydrellia griseola)、黑蝇属(Hylemya spp.)、虱蝇属(Hippobosca spp.)、皮蝇属(Hypoderma spp.)、斑潜蝇属(Liriomyza spp.)、绿蝇属(Lucilia spp.)、Lutzomyia spp.、Mansonia spp.、家蝇属(Musca spp.)、狂蝇属(Oestrus spp.)、瑞典麦秆蝇(Oscinella frit)、拟长跗摇蚊属(Paratanytarsus spp.)、Paralauterborniella subcincta、藜泉蝇(Pegomyia spp.)、白蛉属(Phlebotomus spp.)、草种蝇属(Phorbia spp.)、伏蝇属(Phormia spp.)、酪蝇(Piophila casei)、Prodiplosis spp.、胡萝卜茎蝇(Psila rosae)、绕实蝇属(Rhagoletisspp.)、麻蝇属(Sarcophaga spp.)、蚋属(Simulium spp.)、螫蝇属(Stomoxys spp.)、虻属(Tabanus spp.)、根斑蝇属(Tetanops spp.)、大蚊属(Tipula spp.)。
异翅目(Heteroptera),例如,南瓜缘蝽(Anasa tristis)、拟丽蝽属(Antestiopsis spp.)、Boisea spp.、土长蝽属(Blissus spp.)、俊盲蝽属(Calocorisspp.)、Campylomma livida、异背长蝽属(Cavelerius spp.)、臭虫属(Cimex spp.)、Collaria spp.、Creontiades dilutus、胡椒缘蝽(Dasynus piperis)、Dichelopsfurcatus、厚氏长棒网蝽(Diconocoris hewetti)、棉红蝽属(Dysdercus spp.)、美洲蝽属(Euschistus spp.)、扁盾蝽属(Eurygaster spp.)、Heliopeltis spp.、Horciasnobilellus、稻缘蝽属(Leptocorisa spp.)、Leptocorisa varicornis、叶喙缘蝽(Leptoglossus phyllopus)、草盲蝽属(Lygus spp.)、蔗黑长蝽(Macropes excavatus)、盲蝽科(Miridae)、金光绿盲蝽(Monalonion atratum)、绿蝽属(Nezara spp.)、Oebalusspp.、蝽科(Pentomidae)、方背皮蝽(Piesma quadrata)、壁蝽属(Piezodorus spp.)、杂盲蝽属(Psallus spp.)、Pseudacysta persea、红猎蝽属(Rhodnius spp.)、可可褐盲蝽(Sahlbergella singularis)、Scaptocoris castanea、黑蝽属(Scotinophora spp.)、梨冠网蝽(Stephanitis nashi)、Tibraca spp.、锥猎蝽属(Triatoma spp.)。
同翅目(Homoptera),例如,Acizzia acaciaebaileyanae、Acizzia dodonaeae、Acizzia uncatoides、狭背蚱蜢(Acrida turrita)、无网长管蚜属(Acyrthosipon spp.)、Acrogonia spp.、Aeneolamia spp.、隆脉木虱属(Agonoscena spp.)、甘蓝粉虱(Aleyrodesproletella)、蔗粉虱属(Aleurolobus barodensis)、软毛粉虱(Aleurothrixusfloccosus)、Allocaridara malayensis、杧果叶蝉属(Amrasca spp.)、Anuraphis cardui、肾圆盾蚧属(Aonidiella spp.)、苏联黄粉蚜(Aphanostigma piri)、蚜属(Aphis spp.)、葡萄叶蝉(Arboridia apicalis)、Arytainilla spp.、小圆盾蚧属(Aspidiella spp.)、圆盾蚧属(Aspidiotus spp.)、Atanus spp.、茄沟无网蚜(Aulacorthum solani)、木薯粉虱(Bemisia tabaci)、Blastopsylla occidentalis、Boreioglycaspis melaleucae、李短尾蚜(Brachycaudus helichrysii)、Brachycolus spp.、甘蓝蚜(Brevicoryne brassicae)、Cacopsylla spp.、小褐稻虱(Calligypona marginata)、丽黄头大叶蝉(Carneocephalafulgida)、甘蔗粉角蚜(Ceratovacuna lanigera)、沫蝉科(Cercopidae)、蜡蚧属(Ceroplastes spp.)、草莓钉蚜(Chaetosiphon fragaefolii)、蔗黄雪盾蚧(Chionaspistegalensis)、茶绿叶蝉(Chlorita onukii)、棉蝗(Chondracris rosea)、核桃黑斑蚜(Chromaphis juglandicola)、黑褐圆盾蚧(Chrysomphalus ficus)、玉米叶蝉(Cicadulinambila)、Coccomytilus halli、软蚧属(Coccus spp.)、茶藨隐瘤蚜(Cryptomyzus ribis)、Cryptoneossa spp.、Ctenarytaina spp.、Dalbulus spp.、柑桔粉虱(Dialeurodescitri)、Diaphorina citri、白背盾蚧属(Diaspis spp.)、履绵蚧属(Drosicha spp.)、西圆尾蚜属(Dysaphis spp.)、灰粉蚧属(Dysmicoccus spp.)、小绿叶蝉属(Empoasca spp.)、绵蚜属(Eriosoma spp.)、Erythroneura spp.、Eucalyptolyma spp.、Euphyllura spp.、Euscelis bilobatus、拂粉蚧属(Ferrisia spp.)、咖啡地粉蚧(Geococcus coffeae)、Glycaspis spp.、Heteropsylla cubana、Heteropsylla spinulosa、假桃病毒叶蝉(Homalodisca coagulata)、梅大尾蚜(Hyalopterus arundinis)、吹绵蚧属(Iceryaspp.)、片角叶蝉属(Idiocerus spp.)、扁喙叶蝉属(Idioscopus spp.)、灰飞虱(Laodelphax striatellus)、Lecanium spp.、蛎盾蚧属(Lepidosaphes spp.)、萝卜蚜(Lipaphis erysimi)、长管蚜属(Macrosiphum spp.)、二点叶蝉(Macrostelesfacifrons)、Mahanarva spp.、高粱蚜(Melanaphis sacchari)、Metcalfiella spp.、麦无网蚜(Metopolophium dirhodum)、黑缘平翅斑蚜(Monellia costalis)、Monelliopsispecanis、瘤蚜属(Myzus spp.)、莴苣衲长管蚜(Nasonovia ribisnigri)、黑尾叶蝉属(Nephotettix spp.)、Nettigoniclla spectra、褐飞虱(Nilaparvata lugens)、Oncometopia spp.、Orthezia praelonga、Oxya chinensis、芽瘿木虱属(Pachypsyllaspp.)、杨梅缘粉虱(Parabemisia myricae)、Paratrioza spp.、片盾蚧属(Parlatoriaspp.)、瘿绵蚜属(Pemphigus spp.)、玉米蜡蝉(Peregrinus maidis)、绵粉蚧属(Phenacoccus spp.)、杨平翅绵蚜(Phloeomyzus passerinii)、忽布疣蚜(Phorodonhumuli)、葡萄根瘤蚜属(Phylloxera spp.)、苏铁褐点并盾蚧(Pinnaspis aspidistrae)、臀纹粉蚧属(Planococcus spp.)、Prosopidopsylla flava、梨形原绵蚧(Protopulvinariapyriformis)、桑白盾蚧(Pseudaulacaspis pentagona)、粉蚧属(Pseudococcus spp.)、Psyllopsis spp.、木虱属(Psylla spp.)、金小蜂属(Pteromalus spp.)、Pyrilla spp.、笠圆盾蚧属(Quadraspidiotus spp.)、Quesada gigas、平刺粉蚧属(Rastrococcus spp.)、缢管蚜属(Rhopalosiphum spp.)、黑盔蚧属(Saissetia spp.)、葡萄带叶蝉(Scaphoidestitanus)、麦二叉蚜(Schizaphis graminum)、苏铁刺圆盾蚧(Selenaspidusarticulatus)、长唇基飞虱属(Sogata spp.)、白背飞虱(Sogatella furcifera)、Sogatodes spp.、Stictocephala festina、Siphoninus phillyreae、Tenalapharamalayensis、Tetragonocephela spp.、Tinocallis caryaefoliae、广胸沫蝉属(Tomaspisspp.)、声蚜属(Toxoptera spp.)、温室粉虱(Trialeurodes vaporariorum)、个木虱属(Trioza spp.)、小叶蝉属(Typhlocyba spp.)、尖盾蚧属(Unaspis spp.)、葡萄根瘤虱(Viteus vitifolii)、么叶蝉属(Zygina spp.)。
膜翅目(Hymenoptera),例如,Acromyrmex spp.、菜叶蜂属(Athalia spp.)、Attaspp.、松叶蜂属(Diprion spp.)、实叶蜂属(Hoplocampa spp.)、毛蚁属(Lasius spp.)、小家蚁(Monomorium pharaonis)、树蜂属(Sirex spp.)、红外来火蚁(Solenopsis invicta)、Tapinoma spp.、角树蜂属(Urocerus spp.)、胡蜂属(Vespa spp.)、黑树蜂属(Xerisspp.)。
等足目(Isopoda),例如,鼠妇(Armadillidium vulgare)、栉水虱(Oniscusasellus)、球鼠妇(Porcellio scaber)。
等翅目(Isoptera),例如,家白蚁属(Coptotermes spp.)、堆角白蚁(Cornitermescumulans)、堆砂白蚁属(Cryptotermes spp.)、楹白蚁属(Incisitermes spp.)、稻麦小白蚁(Microtermes obesi)、土白蚁属(Odontotermes spp.)、散白蚁属(Reticulitermesspp.)。
鳞翅目(Lepidoptera),例如,小蜡螟(Achroia grisella)、桑剑纹夜蛾(Acronicta major)、褐带卷蛾属(Adoxophyes spp.)、烦夜蛾(Aedia leucomelas)、地老虎属(Agrotis spp.)、Alabama spp.、脐橙螟(Amyelois transitella)、条麦蛾属(Anarsiaspp.)、干煞夜蛾属(Anticarsia spp.)、条小卷蛾属(Argyroploce spp.)、甘蓝夜蛾(Barathra brassicae)、台湾单带弄蝶(Borbo cinnara)、棉潜蛾(Bucculatrixthurberiella)、松尺蠖(Bupalus piniarius)、蛀褐夜蛾属(Busseola spp.)、黄卷蛾属(Cacoecia spp.)、茶丽细蛾(Caloptilia theivora)、Capua reticulana、苹果小卷蛾(Carpocapsa pomonella)、桃蛀果蛾(Carposina niponensis)、冬尺蛾(Cheimatobiabrumata)、禾草螟属(Chilo spp.)、色卷蛾属(Choristoneura spp.)、葡萄果蠹蛾(Clysiaambiguella)、Cnaphalocerus spp.、稻纵卷叶螟(Cnaphalocrocis medinalis)、云卷蛾属(Cnephasia spp.)、Conopomorpha spp.、球细颈象属(Conotrachelus spp.)、Copitarsiaspp.、Cydia spp.、Dalaca noctuides、绢野螟属(Diaphania spp.)、小蔗杆草螟(Diatraeasaccharalis)、金刚钻属(Earias spp.)、Ecdytolopha aurantium、南美玉米苗斑螟(Elasmopalpus lignosellus)、甘薯杆螟(Eldana saccharina)、粉斑螟属(Ephestiaspp.)、叶小卷蛾属(Epinotia spp.)、苹淡褐卷蛾(Epiphyas postvittana)、荚斑螟属(Etiella spp.)、棕卷蛾属(Eulia spp.)、女贞细卷蛾(Eupoecilia ambiguella)、黄毒蛾属(Euproctis spp.)、切根虫属(Euxoa spp.)、脏切夜蛾属(Feltia spp.)、大蜡螟(Galleria mellonella)、细蛾属(Gracillaria spp.)、小食心虫属(Grapholitha spp.)、Hedylepta spp.、棉铃虫属(Helicoverpa spp.)、实夜蛾属(Heliothis spp.)、褐织蛾(Hofmannophila pseudospretella)、同斑螟属(Homoeosoma spp.)、长卷蛾属(Homonaspp.)、苹果巢蛾(Hyponomeuta padella)、柿举枝蛾柿蒂虫(Kakivoria flavofasciata)、贪夜蛾属(Laphygma spp.)、梨小食心虫(Laspeyresia molesta)、茄白翅野螟(Leucinodesorbonalis)、纹潜蛾属(Leucoptera spp.)、潜叶细蛾属(Lithocolletis spp.)、绿果冬夜蛾(Lithophane antennata)、花翅小蛾属(Lobesia spp.)、豆白隆切根虫(Loxagrotisalbicosta)、毒蛾属(Lymantria spp.)、潜蛾属(Lyonetia spp.)、黄褐天幕毛虫(Malacosoma neustria)、豆野螟(Maruca testulalis)、甘蓝夜蛾(Mamestra brassicae)、暮眼蝶(Melanitis leda)、毛胫夜蛾属(Mocis spp.)、Monopis obviella、粘虫(Mythimnaseparata)、橡长角蛾(Nemapogon cloacellus)、水螟属(Nymphula spp.)、Oiketicusspp.、Oria spp.、瘤丛螟属(Orthaga spp.)、秆野螟属(Ostrinia spp.)、水稻负泥虫(Oulema oryzae)、小眼夜蛾(Panolis flammea)、稻弄蝶属(Parnara spp.)、红铃虫属(Pectinophora spp.)、Perileucoptera spp.、茄麦蛾属(Phthorimaea spp.)、桔潜蛾(Phyllocnistis citrella)、Phyllonorycter spp.、菜粉蝶属(Pieris spp.)、苹果纹卷叶蛾(Platynota stultana)、印度谷螟(Plodia interpunctella)、金翅夜蛾属(Plusiaspp.)、菜蛾(Plutella xylostella)、小白巢蛾属(Prays spp.)、斜纹夜蛾属(Prodeniaspp.)、Protoparce spp.、Pseudaletia spp.、粘虫(Pseudaletia unipuncta)、大豆夜蛾(Pseudoplusia includens)、玉米螟(Pyrausta nubilalis)、Rachiplusia nu、禾螟属(Schoenobius spp.)、白禾螟属(Scirpophaga spp.)、稻白禾螟(Scirpophaga innotata)、Scotia segetum、蛀茎夜蛾属(Sesamia spp.)、稻蛀茎夜蛾(Sesamia inferens)、长须卷蛾属(Sparganothis spp.)、灰翅夜蛾属(Spodoptera spp.)、Spodoptera praefica、举肢蛾属(Stathmopoda spp.)、花生麦蛾(Stomopteryx subsecivella)、Synanthedon spp.、Tecia solanivora、Thermesia gemmatalis、Tinea cloacella、袋谷蛾(Tineapellionella)、幕谷蛾(Tineola bisselliella)、卷蛾属(Tortrix spp.)、毛毡衣蛾(Trichophaga tapetzella)、粉夜蛾属(Trichoplusia spp.)、三化螟(Tryporyzaincertulas)、番茄斑潜蝇(Tuta absoluta)、灰蝶属(Virachola spp.)。
直翅目(Orthoptera)或跳跃目(Saltatoria),例如,家蟋(Acheta domesticus)、Dichroplus spp.、蝼蛄属(Gryllotalpa spp.)、蔗蝗属(Hieroglyphus spp.)、飞蝗属(Locusta spp.)、黑蝗属(Melanoplus spp.)、沙漠蝗(Schistocerca gregaria)。
虱目(Phthiraptera),例如畜虱属(Damalinia spp.)、血虱属(Haematopinusspp.)、毛虱属(Linognathus spp.)、虱属(Pediculus spp.)、Phylloera vastatrix、阴虱(Phthirus pubis)、嚼虱属(Trichodectes spp.)。
啮虫目(Psocoptera),例如,Lepinatus spp.、粉啮虫属(Liposcelis spp.)。
蚤目(Siphonaptera),例如,角叶蚤属(Ceratophyllus spp.)、栉首蚤属(Ctenocephalides spp.)、人蚤(Pulex irritans)、穿皮潜蚤(Tunga penetrans)、印鼠客蚤(Xenopsylla cheopis)。
缨翅目(Thysanoptera),例如,玉米黄呆蓟马(Anaphothrips obscurus)、稻蓟马(Baliothrips biformis)、葡萄镰蓟马(Drepanothris reuteri)、Enneothrips flavens、花蓟马属(Frankliniella spp.)、网蓟马属(Heliothrips spp.)、温室条篱蓟马(Hercinothrips femoralis)、卡蓟葡萄蓟马(Rhipiphorothrips cruentatus)、硬蓟马属(Scirtothrips spp.)、Taeniothrips cardamoni、蓟马属(Thrips spp.)。
缨尾目(Zygentoma,=Thysanura),例如,栉衣鱼属(Ctenolepisma spp.)、衣鱼(Lepisma saccharina)、盗火虫(Lepismodes inquilinus)、家衣鱼(Thermobiadomestica)。
综合目(Symphyla),例如,Scutigerella spp.。
软体动物门(Mollusca)害虫,特别是双壳软体动物(Bivalva)纲,例如,饰贝属(Dreissena spp.)以及腹足纲(Gastropoda),例如,Arion spp.、双脐螺属(Biomphalariaspp.)、小泡螺属(Bulinus spp.)、野蛞蝓属(Deroceras spp.)、土蜗属(Galba spp.)、椎实螺属(Lymnaea spp.)、钉螺属(Oncomelania spp.)、Pomacea spp.、琥珀螺属(Succineaspp.)。
扁形动物门(Plathelminthe)和线虫门(Nematoda)动物寄生虫,例如十二指肠钩口线虫(Ancylostoma duodenale)、斯里兰卡钩口线虫(Ancylostoma ceylanicum)、巴西钩口线虫(Acylostoma braziliensis)、钩口线虫属(Ancylostoma spp.)、蛔虫属(Ascarisspp.)、马来布鲁线虫(Brugia malayi)、帝汶布鲁线虫(Brugia timori)、仰口线虫属(Bunostomum spp.)、夏柏特线虫属(Chabertia spp.)、枝睾吸虫属(Clonorchis spp.)、古柏线虫属(Cooperia spp.)、双腔吸虫属(Dicrocoelium spp.)、丝状网尾线虫(Dictyocaulus filaria)、阔节裂头绦虫(Diphyllobothrium latum)、麦地那龙线虫(Dracunculus medinensis)、细粒棘球绦虫(Echinococcus granulosus)、多房棘球绦虫(Echinococcus multilocularis)、蠕形住肠蛲虫(Enterobius vermicularis)、Faciolaspp.、血毛线虫属(Haemonchus spp.)、异刺线虫属(Heterakis spp.)、矮小啮壳绦虫(Hymenolepis nana)、猪圆线虫属(Hyostrongulus spp.)、罗阿罗阿线虫(Loa Loa)、细颈线虫属(Nematodirus spp.)、结节线虫属(Oesophagostomum spp.)、后睾吸虫属(Opisthorchis spp.)、旋盘尾丝虫(Onchocerca volvulus)、奥斯脱线虫属(Ostertagiaspp.)、并殖吸虫属(Paragonimus spp.)、Schistosomen spp.、富氏类圆线虫(Strongyloides fuelleborni)、粪类圆线虫(Strongyloides stercoralis)、粪圆线虫属(Stronyloides spp.)、牛带绦虫(Taenia saginata)、猪带绦虫(Taenia solium)、旋毛形线虫(Trichinella spiralis)、本地毛形线虫(Trichinella nativa)、株布氏旋毛虫(Trichinella britovi)、南方旋毛虫(Trichinella nelsoni)、Trichinellapseudopsiralis、毛圆线虫属(Trichostrongulus spp.)、毛首鞭形线虫(Trichuristrichuria)、班氏吴策线虫(Wuchereria bancrofti)。
线虫门的植物有害物,即,植物寄生线虫类,特别是滑刃线虫属(Aphelenchoidesspp.)、伞滑刃线虫属(Bursaphelenchus spp.)、茎线虫属(Ditylenchus spp.)、球异皮线虫属(Globodera spp.)、异皮线虫属(Heterodera spp.)、长针线虫属(Longidorus spp.)、根结线虫属(Meloidogyne spp.)、短体线虫属(Pratylenchus spp.)、穿孔线虫属(Radopholus spp.)、毛刺线虫属(Trichodorus spp.)、小垫刃线虫属(Tylenchulusspp.)、剑线虫属(Xiphinema spp.)、螺旋线虫属(Helicotylenchus spp.)、矮化线虫属(Tylenchorhynchus spp.)、盾线虫属(Scutellonema spp.)、副毛刺线虫属(Paratrichodorus spp.)、Meloinema spp.、异真滑刃线虫属(Paraphelenchus spp.)、Aglenchus spp.、刺线虫属(Belonolaimus spp.)、珍珠线虫属(Nacobbus spp.)、小盘旋线虫属(Rotylenchulus spp.)、盘旋线虫属(Rotylenchus spp.)、Neotylenchus spp.、异真滑刃线虫属(Paraphelenchus spp.)、椎线虫属(Dolichodorus spp.)、纽带线虫属(Hoplolaimus spp.)、Punctodera spp.、Criconemella spp.、Quinisulcius spp.、半环苔虫属(Hemicycliophora spp.)、蟃线虫属(Anguina spp.)、亚蟃线虫属(Subanguinaspp.)、半轮线虫属(Hemicriconemoides spp.)、Psilenchus spp.、Pseudohalenchusspp.、轮线虫属(Criconemoides spp.)、Cacopaurus spp.。
还可以防治原生动物(protozoa)亚门,球虫目(Coccidia),例如艾美虫属(Eimeria spp.)。
本发明还提供用于处理植物的施用溶液,包含有效用于增强植物对非生物胁迫因子抗性用量的至少一种选自通式(I)的邻氨基苯甲酰胺衍生物的化合物。可以相对化的非生物胁迫条件可以包括例如干旱、冷和热条件、渗透胁迫、水涝、高土壤盐度、高矿物暴露、臭氧条件、强光条件、有限的氮营养素可用度、有限的磷营养素可用度。
在一个实施方案中,例如,根据本发明提供的邻氨基苯甲酰胺衍生物可通过施用至合适的待处理的植物或植物部位而施用。本发明所设想的使用本发明化合物(I)优选以剂量为0.0005至3kg/ha,更优选为0.001至2kg/ha,尤其优选为0.005至1kg/ha进行。
术语“对非生物胁迫的抗性”在本文中理解为意指对于植物的各种优势。这些有利的特性表现为例如以下改进的植物特性:在表面积和深度方面的改进的根系生长、增加的匍匐丝和分蘖形成、更强的和更多产的匍匐丝和分蘖、增进芽生长、增加的抗倒伏性,增加的芽基直径,增加的叶面积,营养物和组分例如碳水化合物、脂肪、油类、蛋白质、维生素、矿物质、精油、染料、纤维的更高产量、更好的纤维品质、更早开花、增加的开花数量、降低的毒性产物如真菌毒素的含量、降低的残留物或任何种类的不利组分含量、或更好的可消化性、采收材料改进的储存稳定性、改进的对不利的温度的耐受性、改进的对干旱和干燥的耐受性、和改进的对水涝引起的缺氧的耐受性、改进的对土壤和水中高盐度的耐受性、增强的对臭氧胁迫的耐受性、改进的对于除草剂和其他作物处理组合物的相容性、改进的吸水性和光合作用性能、有利的植物性能,例如加快成熟、更均匀成熟、对有利动物更大的吸引性、改进的授粉或本领域技术人员已知的其他优势。
更具体地,本发明的用途表现出在施用至植物和植物部位时所述的优势。
对于本发明而言,还可以将对植物成熟起作用的已知的物质与本发明的邻氨基苯甲酰胺衍生物相结合。在本文中,可以提及例如以下活性化合物(所述化合物或根据国际标准化组织(ISO)的“通用名称”或根据化学名称或根据编号而提及),各自包括所有使用形式,如酸、盐、酯和异构体,如立体异构体和旋光异构体。在本文中,例如,提及一种且在某些情况下多种使用形式:
根瘤菌毒素(rhizobitoxine)、2-氨基乙氧基乙烯基甘氨酸(AVG)、甲氧基乙烯基甘氨酸(MVG)、乙烯基甘氨酸、氨基氧乙酸、西奈芬净(sinefungin)、s-腺苷高半胱氨酸、硫代丁酸2-酮基-4-甲酯、(异亚丙基)氨基氧乙酸2-(甲氧基)-2-氧代乙酯、(异亚丙基)氨基氧乙酸2-(己氧基)-2-氧代乙酯、(环亚己基)氨基氧乙酸2-(异丙基氧基)-2-氧代乙酯、腐胺、亚精胺、精胺、1,8-二氨基-4-氨基乙基辛烷、L-刀豆酸、丁酰肼、1-氨基环丙基-1-羧酸甲酯、N-甲基-1-氨基环丙基-1-羧酸、1-氨基环丙基-1-甲酰胺、如记载于DE3335514、EP30287、DE2906507或US5123951中的取代1-氨基环丙基-1-羧酸衍生物、1-氨基环丙基-1-异羟肟酸、1-甲基环丙烯、3-甲基环丙烯、1-乙基环丙烯、1-正丙基环丙烯、1-环丙烯基甲醇、贡蒿酮、丁子香酚
可用于本发明化合物的混合物制剂或在桶混制剂中的配伍组分为,例如基于抑制以下物质的已知活性化合物:例如1-氨基环丙烷-1-羧酸盐合酶、1-氨基环丙烷-1-羧酸盐氧化酶和乙烯受体,例如ETR1、ETR2、ERS1、ERS2或EIN4,例如记载于Biotechn.Adv.2006,24,357-367;Bot.Bull.Acad.Sin.199,40,1-7或Plant Growth Reg.1993,13,41-46以及其中所引用的文献。
对于本发明而言,邻氨基苯甲酰胺衍生物还可以与提高植物对非生物胁迫耐受性的已知的物质结合,所述已知的物质例如为脱落酸及其类似物(植物激素)(Jones andMansfield,1970,J.Exp.Botany 21:714-719;Bonham-Smith et al.,1988,PhysiologiaPlantarum 73:27-30);杀真菌剂,特别是源自strobilurin或琥珀酸酯脱氢酶抑制剂类、除草剂草甘膦、渗透物质例如甘氨酸甜菜碱或其生物化学前体,例如胆碱衍生物(Chen etal.,2000,Plant Cell Environ 23:609-618,Bergmann et al.,DE-4103253);抗氧化剂例如萘酚和黄嘌呤、吡咯类例如甲基吡咯如多效唑(Morrison and Andrews,1992,J PlantGrowth Regul 11:113-117;Imperial Chemical Industries PLC,1985,ResearchDisclosure 259:578-582);苯并噻二唑(CGA 245704;通用名称:acibenzolar-S-methyl;商品名称:)(Achuo et al.,Plant Pathology 53(1),65–72,2004;Tamblyn etal.,Pesticide Science 55(6),676–677,1999;EP-OS 0313512);乙酰基水杨酸、磺亚胺,源自氧化脂类(oxylipin)例如茉莉酸(Walling,J.Plant Growth Regul.19,195–216,2000);源自新烟碱类(氯代烟碱类)杀虫剂,特别是吡虫啉(imidacloprid)(Brown et al.,Beltwide Cotton Conference Proceedings 2231–2237,2004)。
如所已知的,上面所提及的对植物的各种优势可部分结合,并且可以使用常规可应用的术语描述它们。这类术语为例如以下名称:植物毒性效应、对胁迫因素的抗性、较小的植物胁迫、植物保健(health)、健康的植物、植物适应性(fitness)、植物健康(wellness)、植物概念、活力效应、胁迫防护、保护性防护、作物保健、作物保健性能、作物保健产品、作物保健管理、作物保健疗法、植物保健、植物保健性能、植物保健产品、植物保健管理、植物保健疗法、绿化效应或再绿化效应、鲜度或本领域技术人员相当熟悉的其他术语。
在本发明的上下文中,对非生物胁迫抗性的良好作用应理解为表示(但不作为限制):
·至少萌芽改进通常3%,尤其高于5%,特别优选高于10%,
·至少产量提高通常3%,尤其高于5%,特别优选高于10%,
·至少根系发育改进通常3%,尤其高于5%,特别优选高于10%,
·至少芽尺寸提高通常3%,尤其高于5%,特别优选高于10%,
·至少叶面积提高通常3%,尤其高于5%,特别优选高于10%,
·至少萌芽改进通常3%,尤其高于5%,特别优选高于10%,
·至少光合作用性能改进通常3%,尤其高于5%,特别优选高于10%,和/或
·至少花形成改进通常3%,尤其高于5%,特别优选高于10%,所述效应可以单独出现,或者以两种以上效应的任何结合出现。
本发明还提供用于处理植物的施用溶液,包含有效增强植物对非生物胁迫因素抗性用量的至少一种通式(I)的化合物。所述施用溶液可以包含其他常规组分,如溶剂、制剂助剂,尤其是水。其他组分可以包括下面描述的农用化学活性化合物。
本发明还提供相应的施用溶液用于提高植物对非生物胁迫因素抗性的用途。下面的说明同时适用于通式(I)化合物本身的本发明的用途和相应的施用溶液。
所有植物和植物部位均可根据本发明处理。在本文中植物理解为意指所有植物和植物种群,如想要和不想要的野生植物或作物植物(包括天然存在的作物植物)。作物植物可以是通过常规育种和优选法或通过生物技术和基因工程法或通过前述方法的结合而得到的植物,包括转基因植物并包括受和不受品种权(varietal property rights)保护的植物品种。植物部位的含义理解为意指植物所有的地上和地下部位和植物器官,如芽、叶、花和根,可提及的实例为叶、针叶、茎、干、花、子实体、果实、种子以及根、块茎和根茎。植物部位也包括采收物以及无性和有性繁殖物,例如插枝、块茎、根茎、分株和种子。
如上所提及,可根据本发明处理所有植物及其部位。在一个优选的实施方案中,处理了野生植物种和植物栽培种,或由常规生物育种方法(如杂交或原生质体融合)而得到的植物种和植物栽培种及其部位。在另一个优选的实施方案中,处理由基因工程——如果合适与常规方法相结合——而得到的转基因植物和植物栽培种(遗传修饰生物)及其部位。术语“部位”、“植物的部位”或“植物部位”已在上文做出解释。
更优选地,根据本发明处理各自市售可得或正在使用的植物栽培种的植物。植物栽培种理解为意指由常规育种、诱变或重组DNA技术获得的具有新特性(“特征”)的植物。这些植物可以是栽培种、生物型和基因型。
根据植物种或植物栽培种、其种植地点和生长条件(土壤、气候、生长期、营养),本发明的处理也可产生超加和(“协同”)效应。例如,超过实际预期的效果可能性包括:降低可根据本发明使用的化合物和组合物的施用率和/或加宽其活性谱和/或提高其活性、改善植物生长、提高对高温或低温耐受性、提高对干旱或对水或土壤中含盐量的耐受性、提高开花品质、使采收更简易、加速成熟、提高产量、提高采收产品的品质和/或提高其营养价值、改善采收产品的贮存期和/或其加工性能。
依据本发明处理的优选的转基因植物或植物栽培种(通过遗传工程而获得的那些)包括通过遗传修饰而接受了遗传物质的所有植物,所述遗传物质将特别有利的有用特性(“特征”)赋予这些植物。所述特性的实例为更好的植物生长、提高对高温或低温的耐受性、提高对干旱或者对水或土壤含盐量的耐受性、提高开花品质、使采收更简易、加速成熟、提高产量、提高采收产品的品质和/或提高其营养价值、改善采收产品的贮存期和/或其加工性能。其它特别强调的所述特征的实例为改善植物对动物和微生物有害物的抵抗力,如对昆虫、螨虫、植物致病真菌、细菌和/或病毒的抵抗力,以及提高植物对某些除草活性化合物的耐受性。可提及的转基因植物的实例为重要的作物植物,如谷物(小麦、稻)、玉米、大豆、马铃薯、棉花、烟草、油菜和果实植物(果实为苹果、梨、柑橘类水果和葡萄),且特别强调的是玉米、大豆、马铃薯、棉花、烟草和油菜。特别强调的特征为通过在植物体内形成毒素,特别是由苏云金芽孢杆菌(Bacillus thuringiensis)的遗传物质(例如由基因CryⅠA(a)、CryⅠA(b)、CryⅠA(c)、CryⅡA、CryⅢA、CryⅢB2、Cry9c、Cry2Ab、Cry3Bb和CryⅠF及其结合)在植物体内形成的毒素,来提高植物对昆虫、蛛形纲动物、线虫和蛞蝓以及蜗牛的抵抗力(以下称为“Bt植物”)。还特别强调的特征为通过系统获得性抗性(SAR)、系统素、植物抗毒素、引发物和抗性基因以及相应的表达蛋白质和毒素来提高植物对真菌、细菌和病毒的抵抗力。还特别强调的特征为提高植物对某些除草活性化合物(例如咪唑啉酮类、磺酰脲类、草甘膦或草丁膦)(例如“PAT”基因)的耐受性。赋予所述所需特征的基因也可在转基因植物体内相互结合而存在。“Bt植物”的实例包括市售的商品名称为YIELD(例如玉米、棉花、大豆)、(例如玉米)、(例如玉米)、(棉花)、(棉花)和(马铃薯)的玉米品种、棉花品种、大豆品种和马铃薯品种。可提及的除草剂耐受性植物的实例为市售的商品名称为Roundup(具有草甘膦耐受性,例如玉米、棉花、大豆)、Liberty (具有草丁膦耐受性,例如油菜)、(具有咪唑啉酮耐受性)和(具有磺酰脲耐受性,例如玉米)的玉米品种、棉花品种和大豆品种。可提及的具有除草剂抗性植物(以常规的除草剂耐受性方式育种的植物)包括名为(例如玉米)的市售品种。当然,以上叙述也适用于具有所述基因特征或仍待开发基因特征的植物栽培种,所述植物栽培种将在未来进行开发和/或上市。
还可以根据本发明处理的植物和植物品种为对一种或多种非生物胁迫因素具有抗性的那些植物。非生物胁迫条件可以包括例如干旱、低温暴露、热暴露、渗透胁迫、水涝、高土壤盐度、高矿物暴露、臭氧暴露、强光暴露、有限的氮营养素可用度、有限的磷营养素可用度或避阴。
还可以根据本发明处理的植物和植物品种是以提高的产率性能为特征的那些植物。所述植物中提高的产率可以是以下因素的结果:例如,改良的植物生理学、生长和发育,如水分利用率、水分保留率、改进的氮的利用、提高的碳素同化、增强的光合作用、提高的发芽率和加速成熟。产率还可以通过改进植物构造来实现(在胁迫和非胁迫条件下),包括提早开花、对杂交种子生产的开花控制、秧苗活力、植株大小、节间数和节间距、根系生长、种子大小、果实大小、荚果大小、荚数或穗数、每个荚或穗的种子数量、种子质量、增强种子的填充、减少种子的散播、减少荚裂开以及抗倒伏。其他的产率特征包括种子组分,如碳水化合物含量、蛋白质含量、油含量和组成、营养价值、减少抗营养化合物、改善可加工性和较好的贮存稳定性。
还可以根据本发明处理的植物是已经表达出杂交优势特性或杂交优势作用的杂交植物,杂交优势特性或杂交优势作用通常导致更高的产量、更加茁壮、更加健康和更好的对生物和非生物胁迫因素的抵抗力。这种植物通常是将一种自交雄性不育亲本系(母本)与另一种自交雄性能育亲本系(父本)杂交而制得。杂交种子通常收获自雄性不育植物然后出售给种植者。雄性不育植物有时(例如在玉米中)可以通过去雄(即机械移除雄性生殖器官或雄花)而制得,但是,更通常地,雄性不育性是植物基因组中遗传定子的结果。在这种情况下,尤其是当种子是从杂交植物上收获的所需产品时,通常有用的是确保充分恢复含有负责雄性不育性的遗传决定因子的杂交植物的雄性能育性。这可以通过确保父本具有适当的育性恢复基因而实现,该基因能够恢复含有造成雄性不育性的遗传定子的杂交植物的雄性可育性。雄性不育的遗传定子可以位于细胞质中。细胞质雄性不育(CMS)实例例如在芸苔属种(Brassica species)中已被描述(WO 1992/005251、WO 1995/009910、WO 1998/27806、WO2005/002324、WO 2006/021972和US 6,229,072)。然而,雄性不育的遗传定子也可以位于细胞核基因组中。雄性不育植物也可通过植物生物技术方法例如基因工程获得。一种获取雄性不育植物的特别有用的方法记载于WO 89/10396中,其中,例如,核糖核酸酶例如芽孢杆菌RNA酶在雄蕊中的绒毡层细胞中选择性地表达。随后可通过在绒毡层细胞中表达核糖核酸酶抑制剂如芽孢杆菌RNA酶抑制剂来恢复能育性(例如WO 1991/002069)。
邻氨基苯甲酰胺衍生物可以转化为常规制剂,例如溶液剂、乳剂、可湿性粉末剂、悬浮剂、粉末剂、尘剂、膏剂、可溶性粉剂、颗粒剂、悬乳浓缩剂、经活性化合物浸渍的天然和合成材料、以及聚合物材料中的微胶囊剂。
因此,本发明还涉及作为作物保护组合物和/或农药的制剂以及由其制得的使用形式,例如灌注、滴注和喷撒液体,所述制剂和使用形式包含至少一种本发明的活性化合物。在某些情况下,所述使用形式包含其他作物保护组合物和/或农药和/或增强作用的助剂,如:渗透剂,例如植物油,例如菜籽油、葵花籽油、矿物油,例如石蜡油、植物脂肪酸的烷基酯,例如菜籽油甲酯或豆油甲酯、或烷醇烷氧基化合物和/或铺展剂(spreader),例如烷基硅氧烷和/或盐,例如有机或无机铵盐或鏻盐,例如硫酸铵或磷酸氢二铵和/或保持促进剂,例如磺基琥珀酸二辛酯或羟丙基瓜耳胶聚合物和/或保湿剂,例如甘油和/或肥料,例如含铵、钾或磷的肥料。
常规制剂有,例如水溶性液体剂(SL)、乳油(EC)、水乳剂(EW)、悬浮剂(SC、SE、FS、OD)、水分散颗粒剂(WG)、颗粒剂(GR)和胶囊浓缩剂(CS);这些和其它可能的制剂类型由例如Crop Life International描述并记载于Pesticide Specifications,Manual ondevelopment and use of FAO and WHO specifications for pesticides,FAO PlantProduction and Protection第173页,由FAO/WHO Joint Meeting on PesticideSpecifications制定,2004,ISBN:9251048576中。所述制剂除一种或多种本发明活性化合物之外还任选地包含其他的农用化学活性化合物。
这些优选为包含助剂的制剂或使用形式,所述助剂例如填充剂、溶剂、自发性促进剂、载体、乳化剂、分散剂、防冻剂、生物灭杀剂、增稠剂和/或其它助剂,例如佐剂。本上下文中佐剂是增强制剂的生物效果而其本身并无生物效果的组分。佐剂的实例有促进保持、铺展、附着于叶片表面或渗透的试剂。
这些制剂以已知方式制备,例如通过将活性化合物与助剂例如填充剂、溶剂和/或固体载体和/或其他助剂例如表面活性剂混合。这些制剂或在合适的装置中制备,或在施用前或施用过程中制备。
使用的助剂可以为能够赋予活性化合物制剂或由这些制剂制备的施用形式(如即用型作物保护组合物,例如灌注、滴注、喷撒液体或拌种剂)以特定性能(如某些物理、技术和/或生物性能)的物质。
合适的填充剂为,例如水、极性和非极性有机化学液体,例如芳烃类和非芳香烃类(如石蜡、烷基苯、烷基萘、氯苯)、醇类和多元醇类(如果合适,其也可被取代、醚化和/或酯化)、酮类(如丙酮、环己酮)、酯类(包括脂肪和油)以及(聚)醚类、未被取代的和取代的胺类、酰胺类、内酰胺类(如N-烷基吡咯烷酮)以及内酯类、砜类和亚砜类(如二甲亚砜)。
如果所用填充剂为水,还可使用例如有机溶剂作为助溶剂。合适的液体溶剂基本上是:芳族化合物如二甲苯、甲苯或烷基萘;氯代芳烃和氯代脂族烃如氯苯、氯乙烯或二氯甲烷、脂族烃如环己烷或石蜡,例如矿物油馏分、矿物油和植物油、醇类如丁醇或乙二醇及其醚和酯、酮类如丙酮、甲基乙基酮、甲基异丁基酮或环己酮、强极性溶剂如二甲基甲酰胺和二甲基亚砜,以及水。
原则上可以使用所有合适的溶剂。合适的溶剂的实例为芳烃,如二甲苯、甲苯或烷基萘、氯代芳烃或氯代脂族烃,如氯苯、氯乙烯或二氯甲烷、脂族烃如环己烷、石蜡、石油馏分、矿物油和植物油、醇如甲醇、乙醇、异丙醇、丁醇或乙二醇及其醚和酯、酮如丙酮、甲基乙基酮、甲基异丁基酮或环己酮、强极性溶剂如二甲基亚砜,以及水。
原则上可以使用所有合适的载体。有用的载体特别包括:例如铵盐,及粉碎的天然矿物如高岭土、粘土、滑石、白垩、石英、绿坡缕石、蒙脱石或硅藻土,以及粉碎的合成材料如细碎的二氧化硅、氧化铝以及天然或合成的硅酸盐、树脂、蜡和/或固体肥料。还可以使用所述载体的混合物。用于颗粒剂的有用的载体包括:例如粉碎并分级的天然岩石如方解石、大理石、浮石、海泡石、白云石,以及无机和有机粉的合成颗粒,以及有机材料如锯屑、纸、椰壳、玉米穗轴和烟草茎的颗粒。
还可以使用液化气体填充剂或溶剂。特别合适的填充剂或载体是在环境温度和大气压力下为气体的那些,例如气雾推进剂气体,如卤代烃,以及丁烷、丙烷、氮气和二氧化碳。
乳化剂和/或发泡剂、具有离子或非离子特性的分散剂或润湿剂,或这些表面活性剂混合物的实例为聚丙烯酸盐、木素磺酸盐、酚磺酸盐或萘磺酸盐、环氧乙烷与脂肪醇或与脂肪酸或与脂肪胺,与取代酚(优选烷基酚或芳基酚)的缩聚物、磺基琥珀酸酯的盐、牛磺酸衍生物(优选烷基牛磺酸)、聚乙氧基化醇或酚的磷酸酯、多元醇的脂肪酯,和包括硫酸盐、磺酸盐和磷酸盐的化合物的衍生物例如烷芳基聚乙二醇醚、烷基磺酸盐、烷基硫酸盐、芳基磺酸盐、蛋白质水解产物、木素亚硫酸盐废液和甲基纤维素。如果一种活性化合物和/或一种惰性载体在水中不溶并且当施用在水中进行时,表面活性剂的存在是有利的。
可以使用着色剂如无机颜料,例如氧化铁、氧化钛和普鲁士蓝,和有机染料如茜素染料、偶氮染料和金属酞菁染料,以及微量营养素如铁盐、锰盐、硼盐、铜盐、钴盐、钼盐和锌盐作为制剂及由其衍生的使用形式的额外助剂。
还可存在稳定剂,如低温稳定剂、防腐剂、抗氧化剂、光稳定剂或其它改进化学和/或物理稳定性的试剂。还可以存在发泡剂或防沫剂。
还可以存在增稠剂如羧甲基纤维素和粉末、颗粒或胶乳形式的天然和合成聚合物,如阿拉伯树胶、聚乙烯醇和聚乙酸乙烯酯、或天然磷脂如脑磷脂和卵磷脂和合成磷脂作为制剂和由及其衍生的使用形式中的额外助剂。其他可能的助剂有矿物油和植物油。
如果合适,制剂及由其衍生的使用形式还可以包括其他助剂。这类添加剂的实例包括香料、保护胶体、粘合剂、胶粘剂、增稠剂、触变剂、渗透剂、保持促进剂、稳定剂、螯合剂、络合剂、保湿剂和铺展剂。通常,活性化合物可与常规用于制剂目的的任何固体或液体添加剂相结合。
有用的保持促进剂包括所有降低动态表面张力的那些物质,例如磺基琥珀酸二辛酯,或增加粘弹性的那些物质,例如羟丙基瓜耳胶聚合物。
本文中有用的渗透剂为所有的通常用于改进农用化学活性化合物对植物渗透性的那些物质。本文中渗透剂由其从(通常为水性的)施用液体和/或从喷雾涂层渗透进入植物表皮并因此增加活性化合物在表皮中的迁移性的能力而定义。可使用文献中(Baur etal.,1997,Pesticide Science 51,131-152)记载的方法来测定该特性。实例包括醇烷氧基化物,如椰子脂肪酸乙氧基化物(10)或异十三烷基乙氧基化物(12)、脂肪酸酯,例如油菜籽油甲酯或豆油甲酯;脂肪胺烷氧基化物,例如牛油胺乙氧基化物(15);或铵盐和/或鏻盐,例如硫酸铵或磷酸氢二铵。
由市售可得的制剂制备的使用形式的活性化合物的含量可以在宽的范围内变化。使用形式的活性化合物浓度可以为0.0000001至95重量%活性化合物,优选0.0001至1重量%。本发明的邻氨基苯甲酰胺的用途为通过灌注、土混、犁沟处理、在水培或灌溉体系中通过滴注施用至土壤或其他基质、通过土壤、茎或花注射、通过栽植穴处理或通过浸渍施用至例如繁殖材料如球茎、块茎或根、漂浮或种子箱施用,特别是在种子的情况下通过单层或多层包衣施用。
根据本发明优选的是处理种子。例如,由害虫引起的对作物植物的大多数损害早在种子在贮存期间被侵扰时和将种子引入土壤中之后,以及在植物发芽期间和刚发芽之后出现。该阶段特别关键因为生长植物的根和芽特别敏感并且即使最小的损害也会导致整个植物的死亡。因此通过使用合适的组合物保护种子和萌芽植物受到特别关注。
通过处理植物的种子而防治害虫为长期已知并且是不断改进的主题。然而,处理种子会引发一系列不能总以令人满意的方式解决的问题。因此,需要开发用于保护种子和萌芽植物的方法,该方法省却了在播种或植物发芽后额外施用作物保护产品。还需要以这样一种方式优化所用活性化合物的量:为种子和正在发芽的植物提供最佳的保护以免受害虫的侵袭,但所用活性化合物不会损伤植物本身。特别地,为了施用最少的作物保护产品而实现种子和萌芽植物的最优化保护,处理种子的方法还应该考虑转基因植物固有的杀虫特性。
因此本发明还特别涉及一种通过使用本发明的活性化合物处理种子,而保护种子和萌芽植物免受害虫侵袭的方法。本发明还涉及邻氨基苯甲酰胺处理种子用于保护种子和由其得到的植物免受害虫侵袭的用途。此外,本发明涉及根据本发明处理以提供免受害虫侵袭的保护的种子。
本发明的优势之一是邻氨基苯甲酰胺衍生物特殊的内吸性能意味着用这些活性化合物处理种子不仅保护种子本身,而且保护萌芽后得到的植物免受害虫侵袭。以此方式,可以省却在播种时或其后不久立即处理作物。
同样,必须被认为有利的是根据本发明邻氨基苯甲酰胺还可特别用于转基因种子,由该种子得到的植物能够表达抵抗害虫的蛋白质。通过处理该种子,某些害虫可以仅通过表达例如杀虫蛋白质而防治,并且另外对种子的损害可以通过本发明的活性化合物而避免。
本发明的邻氨基苯甲酰胺衍生物的用途适于保护以上提及的任何用于农业、温室、林业或园艺中的植物品种的种子。特别地,所述种子可以是玉米、花生、油菜籽、油菜、罂粟、大豆、棉花、甜菜(例如糖用甜菜和饲用甜菜)、稻、黍、小麦、大麦、燕麦、黑麦、向日葵、烟草、马铃薯或蔬菜(例如番茄、卷心菜品种)的种子。本发明的活性化合物同样适于处理以上提及的果实植物和蔬菜的种子。处理玉米、大豆、棉花、小麦、稻和油菜籽或油菜的种子特别重要。
如上所提及,使用本发明的活性化合物处理转基因种子也特别重要。这通常是含有至少一种控制表达具有特定杀虫特性的多肽的异源基因的植物种子。在本文中,转基因种子中的异源基因可源自微生物如杆菌属(Bacillus)、根瘤菌属(Rhizobium)、假单胞菌属(Pseudomonas)、沙雷氏菌属(Serratia)、木霉属(Trichoderma)、棒形杆菌属(Clavibacter)、丛枝菌(Glomus)或粘帚霉属(Gliocladium)。本发明特别适于处理包括至少一种源自杆菌属的异源基因并且其基因产品显示出对欧洲玉米螟(European cornborer)和/或玉米根蠕虫的活性的转基因种子。特别优选源自苏云金芽孢杆菌的异源基因。
用途实施例以下实施例阐述本发明,但不以任何方式限制本发明。
实施例编号A:
皱叶甘蓝上的菜蛾试验;灌注施用
溶剂:4重量份丙酮
乳化剂:1重量份烷芳基聚乙二醇醚
为制备合适的活性化合物制剂,将1重量份的活性化合物与所述用量的溶剂和乳化剂混合,并且用水将浓缩液稀释至所需的浓度。用所述产品的溶液(水的体积:60ml/植物)浇灌皱叶甘蓝(甘蓝(Brassica oleracea))。所述浓度指的是每棵植物的活性化合物的用量。约1周后,用小菜蛾(菜蛾)的幼虫侵染经处理的植物。1周后,测定以%计的活性。100%是指所有的毛虫均被杀死;0%是指没有毛虫被杀死。
在本试验中,以下产品显示出良好的内吸作用:
表A:皱叶甘蓝上的菜蛾
*化合物(I-1-1)/化合物(I-1-7)的测试混合物包含约85%的化合物(I-1-1)和约15%的化合物(I-1-7)。
实施例编号B:
玉米上的草地夜蛾(Spodoptera frugiperda)试验;灌注施用
溶剂:4重量份丙酮
乳化剂:1重量份烷芳基聚乙二醇醚
为制备合适的活性化合物制剂,将1重量份的活性化合物与所述用量的溶剂和乳化剂混合,并且用水将浓缩液稀释至所需的浓度。用所述产品的溶液(水的体积:50ml/植物)浇灌玉米植物(玉米(Zea mays))。所述浓度是指每棵植物的活性化合物的用量。约1周后,用粘虫(草地夜蛾)侵染经处理的植物。1周后,测定以%计的活性。100%是指所有的毛虫均被杀死;0%是指没有粘虫被杀死。
在本试验中,以下产品显示出良好的内吸作用:
表B:玉米上的草地夜蛾
*化合物(I-1-1)/化合物(I-1-7)的测试混合物包含约85%的化合物(I-1-1)和约15%的化合物(I-1-7)。
实施例编号B-1:
玉米上的草地夜蛾试验;灌注施用
溶剂:7重量份二甲基甲酰胺
乳化剂:1重量份烷芳基聚乙二醇醚
为制备合适的活性化合物制剂,将1重量份的活性化合物与所述用量的溶剂和乳化剂混合,并且用水将浓缩液稀释至所需的浓度。
用所述产品的溶液浇灌玉米植物(玉米)并用粘虫(草地夜蛾)侵染。14天后,测定以%计的活性。100%是指所有的毛虫均被杀死;0%是指没有粘虫被杀死。
在本试验中,以下产品显示出良好的内吸作用:
表B–1:玉米上的草地夜蛾
*化合物(I-1-2)/化合物(I-1-8)的测试混合物包含约84%的化合物(I-1-2)和约15%的化合物(I-1-8)。
实施例编号C:
棉花上的棉铃虫(Heliothis armigera)试验;灌注施用
溶剂:4重量份丙酮
乳化剂:1重量份烷芳基聚乙二醇醚
为制备合适的活性化合物制剂,将1重量份的活性化合物与所述用量的溶剂和乳化剂混合,并且用水将浓缩液稀释至所需的浓度。用所述产品的溶液(水的体积:50ml/植物)浇灌棉花植物(棉花(Gossypium hirsutum))。所述浓度是指每棵植物的活性化合物的用量。约1周后,用棉铃幼虫(棉铃虫)侵染经处理的植物。1周后,测定以%计的活性。100%是指所有的毛虫均被杀死;0%是指没有毛虫被杀死。
在本试验中,以下产品显示出良好的内吸作用:
表C:棉花上的棉铃虫
*化合物(I-1-1)/化合物(I-1-7)的测试混合物包含约85%的化合物(I-1-1)和约15%的化合物(I-1-7)。
实施例编号D:
皱叶甘蓝上的桃蚜(Myzus persicae)试验;灌注施用
溶剂:7重量份二甲基甲酰胺
乳化剂:1重量份烷芳基聚乙二醇醚
为制备合适的活性化合物制剂,将1重量份的活性化合物与所述用量的溶剂和乳化剂混合,并且用水将浓缩液稀释至所需的浓度。用所需浓度的产品溶液浇灌被桃蚜(桃蚜)严重侵染的皱叶甘蓝。10天后,测定以%计的活性。100%是指所有的蚜虫均被杀死;0%是指没有蚜虫被杀死。
在本试验中,以下产品显示出良好的内吸作用:
表D:皱叶甘蓝上的桃蚜
*化合物(I-1-1)/化合物(I-1-7)的测试混合物包含约85%的化合物(I-1-1)和约15%的化合物(I-1-7)。
**化合物(I-1-2)/化合物(I-1-8)的测试混合物包含约84%的化合物(I-1-2)和约15%的化合物(I-1-8)。
实施例编号E:
玉米上的带斑黄瓜叶甲(Diabrotica balteata)试验;灌注施用
溶剂:7重量份二甲基甲酰胺
乳化剂:1重量份烷芳基聚乙二醇醚
为制备合适的活性化合物制剂,将1重量份的活性化合物与所述用量的溶剂和乳化剂混合,并且用水将浓缩液稀释至所需的浓度。
用所述产品的溶液浇灌玉米植物(玉米)并用带状黄瓜甲虫(带斑黄瓜叶甲)的幼虫侵染。
8天后,测定以%计的活性。100%是指所有的毛虫均被杀死;0%是指没有毛虫被杀死。
在本试验中,以下产品显示出良好的内吸作用:
表E:玉米上带斑黄瓜叶甲
*化合物(I-1-1)/化合物(I-1-7)的测试混合物包含约95%的化合物(I-1-1)和约5%的化合物(I-1-7)。
**化合物(I-1-2)/化合物(I-1-8)的测试混合物包含约95%的化合物(I-1-2)和约5%的化合物(I-1-8)。
实施例编号F
植物毒素效应
将单子叶和双子叶作物植物的种子置于木质纤维盆中的砂壤土中,用土壤覆盖并在温室内良好的生长条件下培育。在早叶期(BBCH10–BBCH13)处理测试植物。
为了确保胁迫开始前均匀的水供给,在即将开始前通过坝灌溉对盆栽植物提供最大量的水,并在施用后,转移至塑料插入物中以防止随后过快地干燥。将本发明的活性化合物中加入0.2%润湿剂(Agrotin),作为水性悬浮液以600l水/ha(经转化)的施用率喷至植物的绿色部位。施用物质后立即对植物进行胁迫处理(干旱胁迫)。
干燥胁迫通过在以下条件下逐渐干燥而引起:
“白天”:在26℃下光照12小时
“夜晚”:在18℃下无光照12小时
干旱胁迫阶段的持续时间主要由未处理(用不含试验化合物的空白制剂处理)的、受胁迫的对照植物的状态决定并因此随作物不同而在5至7天内变化。
在胁迫阶段结束后进行约7天的恢复阶段,在该期间再次将植物保持在温室中的良好生长条件下。
胁迫阶段结束后(再灌溉之后)和恢复阶段后,损害强度以与相同生长期的未处理的、没有胁迫的对照组(在干旱胁迫的情况下)的目测对比进行评定。损害强度首先以百分比评定(100%=植物已经死亡,0%=与对照植物相同)。然后使用这些数值通过下式计算测试化合物的功效(=由于物质施用使损害强度降低的百分比):
EF:功效(%)
DVus:未处理的、受胁迫的对照组的损害值
DVts:用测试化合物处理的植物的损害值
在本文中,100%的功效是指所有处理的植物是健康的,且0%的功效是指处理的植物已经死亡。
表F–1:
*化合物(I-1-1)/化合物(I-1-7)的测试混合物包含约95%的化合物(I-1-1)和约5%的化合物(I-1-7)。
Claims (3)
1.式(I-1-1)化合物与(I-1-7)化合物的混合物用于增强植物对非生物胁迫的胁迫耐受性的用途,
其中,式(I-1-1)化合物与(I-1-7)化合物的比例为80∶20至99∶1。
2.式(I-1-2)化合物与(I-1-8)化合物的混合物用于增强植物对非生物胁迫的胁迫耐受性的用途,
其中,式(I-1-2)化合物与(I-1-8)化合物的比例为80∶20至99∶1。
3.权利要求1或2的用途,其中待处理的植物选自大田作物、蔬菜、香料、观赏植物、灌木、针叶树、柑桔植物。
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| DE102013012498A1 (de) | 2013-07-26 | 2015-01-29 | Skw Stickstoffwerke Piesteritz Gmbh | Verwendung von einfachen 1,2,4-Triazol-Derivaten als Mittel zur Verbesserung der Trockenstresstoleranz |
| DE102013021933A1 (de) | 2013-12-20 | 2015-06-25 | Skw Stickstoffwerke Piesteritz Gmbh | Verwendung von Pyrazol-Derivaten als Mittel zur Verbesserung der Trockenstresstoleranz |
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- 2011-07-15 AR ARP110102588A patent/AR082255A1/es unknown
- 2011-07-15 CN CN2011800448652A patent/CN103118541A/zh active Pending
- 2011-07-15 KR KR1020137003451A patent/KR101869449B1/ko not_active Expired - Fee Related
- 2011-07-15 JP JP2013520086A patent/JP5908469B2/ja not_active Expired - Fee Related
- 2011-07-15 PH PH1/2013/500130A patent/PH12013500130A1/en unknown
- 2011-07-15 WO PCT/EP2011/062178 patent/WO2012010525A2/de not_active Ceased
- 2011-07-15 MX MX2013000797A patent/MX339683B/es active IP Right Grant
- 2011-07-15 EP EP11731405.4A patent/EP2595486A2/de not_active Withdrawn
- 2011-07-15 CA CA2805806A patent/CA2805806A1/en not_active Abandoned
- 2011-07-19 US US13/186,129 patent/US8658570B2/en not_active Expired - Fee Related
- 2011-07-19 TW TW100125367A patent/TWI516203B/zh not_active IP Right Cessation
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2013
- 2013-01-18 CL CL2013000185A patent/CL2013000185A1/es unknown
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- 2013-02-19 ZA ZA2013/01283A patent/ZA201301283B/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2013531050A (ja) | 2013-08-01 |
| CA2805806A1 (en) | 2012-01-26 |
| CN103118541A (zh) | 2013-05-22 |
| EP2595486A2 (de) | 2013-05-29 |
| WO2012010525A2 (de) | 2012-01-26 |
| CO6690741A2 (es) | 2013-06-17 |
| MX339683B (es) | 2016-06-06 |
| WO2012010525A3 (de) | 2012-08-09 |
| KR101869449B1 (ko) | 2018-06-20 |
| ZA201301283B (en) | 2014-07-30 |
| KR20130126893A (ko) | 2013-11-21 |
| AU2011281679A1 (en) | 2013-02-21 |
| US8658570B2 (en) | 2014-02-25 |
| CL2013000185A1 (es) | 2013-05-17 |
| AR082255A1 (es) | 2012-11-21 |
| MX2013000797A (es) | 2013-02-27 |
| US20120022112A1 (en) | 2012-01-26 |
| TWI516203B (zh) | 2016-01-11 |
| PH12013500130A1 (en) | 2013-03-11 |
| TW201208563A (en) | 2012-03-01 |
| AU2011281679B2 (en) | 2015-09-03 |
| JP5908469B2 (ja) | 2016-04-26 |
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