CN115279189A - 具有杀有害生物效用的组合物及与其相关的方法 - Google Patents
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Classifications
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- A—HUMAN NECESSITIES
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- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P5/00—Nematocides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/02—Acaricides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P7/00—Arthropodicides
- A01P7/04—Insecticides
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P9/00—Molluscicides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Insects & Arthropods (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本公开涉及以下的领域:对节肢动物门、软体动物门和线虫动物门中的有害生物具有杀有害生物效用的分子,生产此类分子的方法,含有此类分子的杀有害生物组合物,以及使用此类杀有害生物组合物对抗此类有害生物的方法。这些杀有害生物组合物可以例如用作杀螨剂、杀昆虫剂、杀螨药、杀软体动物剂、和杀线虫剂。此文档公开了具有下式的分子。
Description
技术领域
本公开涉及以下的领域:对节肢动物门、软体动物门和线虫动物门中的有害生物具有杀有害生物效用的分子,生产此类分子的方法,含有此类分子的杀有害生物组合物,以及使用此类杀有害生物组合物对抗此类有害生物的方法。这些杀有害生物组合物可以例如用作杀螨剂(acaricide)、杀昆虫剂、杀螨药(miticide)、杀软体动物剂、和杀线虫剂。
背景技术
“许多最危险的人类疾病都是通过昆虫介体传播的”(Rivero等人)。“在历史上,疟疾、登革热、黄热病、鼠疫、丝虫病、虱传斑疹伤寒、锥虫病(trypanomiasis)、利什曼病、和其他介体传播的疾病在17世纪至20世纪初造成的人类疾病和死亡超过所有其他原因的总和”(Gubler)。介体传播的疾病占全球寄生虫和感染性疾病的约17%。仅疟疾每年就造成超过800,000人死亡,其中85%发生于五岁以下的儿童。每年有约5千万至约1亿例登革热病例。每年还发生250,000至500,000例登革出血热(Matthews)。介体防治在感染性疾病的预防和防治中起着至关重要的作用。然而,在作为人类疾病的主要介体的所有昆虫物种中都出现了对杀昆虫剂的抗性,包括对多种杀昆虫剂的抗性(Rivero等人)。最近,超过550种节肢动物物种已产生了对至少一种杀有害生物剂的抗性(Whalon等人)。此外,昆虫抗性的案例到目前为止继续在超过除草剂和杀真菌剂抗性的案例的数目(Sparks等人)。
每年,昆虫、植物病原体、和杂草破坏了所有食品生产中的多于40%。尽管应用了杀有害生物剂并且使用了多种多样的非化学防治措施(诸如轮作)和生物防治措施,这种损失仍然发生。如果可以仅挽救此食物中的一部分,则可以将其用来养活世界上多于三十亿营养不良的人(Pimental)。
植物寄生线虫是最普遍的有害生物之一,并且通常是最隐蔽且最昂贵的有害生物之一。据估计,可归因于线虫的损失为从发达国家的约9%至不发达国家的约15%。然而,在美国对35个州关于各种作物的调查指示,由线虫引起的损失高达25%(Nicol等人)。
值得注意的是,腹足类(蛞蝓和蜗牛)是比其他节肢动物或线虫经济重要性低的有害生物,但在某些地方,它们可能大幅降低产率,严重影响收获产品的品质,并且传播人类、动物、和植物疾病。尽管仅几十种腹足类物种是严重的区域性有害生物,而少数物种是在全球范围上的重要有害生物。特别地,腹足类会影响多种多样的农业和园艺作物,诸如可耕地、牧场(pastoral)、和纤维作物;蔬菜;灌木和树木果实;药草;以及观赏植物(Speiser)。
白蚁类对所有类型的私有结构和公共结构以及农业和林业资源造成损害。据估计,2005年,白蚁类每年在全球范围内造成超过500亿美元的损害(Korb)。
因此,出于许多原因(包括上述那些),对高昂(2010年估计每种杀有害生物剂约2.56亿美元)、耗时(每种杀有害生物剂平均约10年)并且困难地开发新杀有害生物剂的需求持续存在(美国植保协会(CropLife America))。
本公开中引用的某些参考文献
CropLife America[美国植保协会],The Cost of New Agrochemical ProductDiscovery,Development&Registration,and Research&Development predictions forthe Future[新农用化学品发现、开发和注册以及未来研究与开发预测的成本],2010。
Drewes,M.,Tietjen,K.,Sparks,T.C.,High-Throughput Screening inAgrochemical Research,Modern Methods in Crop Protection Research,Part I,Methods for the Design and Optimization of New Active Ingredients[农业化学研究中的高通量筛选,作物保护研究中的现代方法,第I部分,用于设计和优化新活性成分的方法],由Jeschke,P.,Kramer,W.,Schirmer,U.,和Matthias W.编辑,第1-20页,2012。
Gubler,D.,Resurgent Vector-Borne Diseases as a Global Health Problem,Emerging Infectious Diseases[作为全球健康问题的复现的介体传播的疾病,新出现的感染性疾病],第4卷,第3号,第442-450页,1998。
Korb,J.,Termites,Current Biology[白蚁类,现代生物学],第17卷,第23号,2007。
Matthews,G.,Integrated Vector Management:Controlling Vectors ofMalaria and Other Insect Vector Borne Diseases[综合的介体管理:防治疟疾介体和其他昆虫介体传播的疾病],第1章,第1页,2011。
Nicol,J.,Turner S.,Coyne,L.,den Nijs,L.,Hocksland,L.,Tahna-Maafi,Z.,Current Nematode Threats to World Agriculture,Genomic and Molecular Geneticsof Plant-Nematode Interactions[当前对世界农业的线虫威胁,植物的基因组和分子遗传学-线虫相互作用],第21-43页,2011。
Pimental,D.,Pest Control in World Agriculture,Agricultural Sciences[世界农业中的有害生物防治,农业科学]-第II卷,2009。
Rivero,A.,Vezilier,J.,Weill,M.,Read,A.,Gandon,S.,Insect Control ofVector-Borne Diseases:When is Insect Resistance a Problem?Public Library ofScience Pathogens[介体传播的疾病的昆虫防治:何时昆虫抗性成为问题?科学病原体公共图书馆],第6卷,第8期,第1-9页,2010。
Sparks T.C.,Nauen R.,IRAC:Mode of action classification andinsecticide resistance management,Pesticide Biochemistry and Physiology(2014)available online 4December 2014[IRAC:作用方式分类和杀昆虫剂抗性管理,杀有害生物剂生物化学和生理学(2014),可在线访问,2014年12月4日]。
Speiser,B.,Molluscicides,Encyclopedia of Pest Management[杀软体动物剂,有害生物管理百科全书],第219章,第506-508页,2002。
Whalon,M.,Mota-Sanchez,D.,Hollingworth,R.,Analysis of GlobalPesticide Resistance in Arthropods,Global Pesticide Resistance in Arthropods[全球节肢动物的杀有害生物剂抗性的分析,节肢动物的全球杀有害生物剂抗性],第1章,第5-33页,2008。
本公开中使用的定义
这些定义中给出的实例通常是非详尽的,并且不得解释为限制本公开。可以理解的是,取代基应相对于与其附接的特定分子遵从化学键合规则和空间相容性约束。这些定义仅用于本公开的目的。
短语“活性成分”意指具有可用于防治有害生物的活性的材料和/或可用于帮助使其他材料具有较好的防治有害生物的活性的材料,此类材料的实例包括但不限于杀螨剂、杀藻剂、拒食剂、杀鸟剂、杀细菌剂、驱鸟剂、化学不育剂、杀真菌剂、除草剂安全剂、除草剂、昆虫引诱剂、驱昆虫剂、杀昆虫剂、驱哺乳动物剂、交配干扰剂、杀软体动物剂、杀线虫剂、植物激活剂、植物生长调节剂、杀啮齿动物剂、增效剂、和杀病毒剂(参见alanwood.net)。此类材料的实例包括但不限于活性成分组α中所列出的材料。
短语“活性成分组α”(在下文中为“AIGA”)共同意指以下材料:
(1)(3-乙氧基丙基)溴化汞、1,2-二溴乙烷、1,2-二氯乙烷、1,2-二氯丙烷、1,3-二氯丙烯、1-MCP、1-甲基环丙烯、1-萘酚、2-(辛基硫基)乙醇、2,3,3-TPA、2,3,5-三碘苯甲酸、2,3,6-TBA、2,4,5-T、2,4,5-TB、2,4,5-TP、2,4-D、2,4-DB、2,4-DEB、2,4-DEP、2,4-DES、2,4-DP、2,4-MCPA、2,4-MCPB、2iP、2-甲氧乙氯汞、2-苯基苯酚、3,4-DA、3,4-DB、3,4-DP、3,6-二氯吡啶甲酸、4-氨基吡啶、4-CPA、4-CPB、4-CPP、4-羟基苯乙醇、8-羟基喹啉硫酸盐、8-苯基巯基氧基喹啉、阿维菌素、阿维菌素氨甲基、脱落酸、ACC、乙酰甲胺磷、灭螨醌、啶虫脒、家蝇磷、乙草胺、三氯杀虫酯、乙酯磷、乙酰虫腈、阿拉酸式苯、三氟羧草醚、苯草醚、ACN、阿莱普、氟丙菊酯、丙烯醛、丙烯腈、阿西非那比(acynonapyr)、阿普泰克、双丙环虫酯(afidopyropen)、阿福拉纳、甲草胺、抑草生、棉铃威、阿苯达唑、涕灭威、涕灭威砜、阿迪吗啉、涕灭砜威、艾氏剂、丙烯菊酯、蒜素、草毒死、阿洛氨菌素、禾草灭、烯丙醇、除害威、五氯戊酮酸、α-氯氰菊酯、α-硫丹、甲体氯氰菊酯、六甲蜜胺、磷化铝、磷化铝(aluminumphosphide)、辛唑嘧菌胺、胺嗪酮、莠灭净(ametryn)、莠灭净(ametryne)、特草嗪酮、氨唑草酮、拌种灵、赛果、磺胺螨酯、酰嘧磺隆、灭害威、环丙嘧啶酸、氯氨基吡啶酸、氨基吡芬、氨基三唑、甲基胺草磷、胺草磷、甲基-胺草磷、吲唑磺菌胺、胺吸磷、双甲脒、杀草强、氨基磺酸铵、代森铵、气相二氧化硅、无定形二氧化硅、氨丙膦酸、AMS、新烟碱、嘧啶醇、敌菌灵、莎稗磷、疏草隆、蒽醌、安妥、唑磷嗪、杀螨特、残杀威、三氧化二砷、福美砷、阿司匹林、黄草灵、乙基杀扑磷、阿特拉通、阿特拉津、金色制酶素、阿维菌素B1、AVG、艾维激素、阿扎康唑、印苦楝子素、草芬定、甲基吡啶磷、灭蚜松、四唑嘧磺隆、益棉磷(azinphosethyl)、益棉磷(azinphos-ethyl)、保棉磷(azinphosmethyl)、保棉磷(azinphos-methyl)、叠氮津(aziprotryn)、叠氮津、氧化福美双、偶氮苯、三唑锡、偶氮磷、嘧菌酯、菊乙胺酯、燕麦灵(barban)、燕麦灵(barbanate)、六氟硅酸钡、多硫化钡、氟硅酸钡、熏菊酯、碱式碳酸铜、碱式氯化铜、碱式硫酸铜、BCPC、氟丁酰草胺、氟丁酰草胺-M、苯霜灵、精苯霜灵、草除灵、苯卡巴腙、苯氯噻、苯哒嗪丙酯(bendaqingbingzhi)、噁虫威、苯达松、倍尼芬(benefin)、氟草胺、丙硫克百威、呋草黄、苯嘧磺草胺、麦锈灵、苯菌灵、解草酮、苯噁磷、敌菌腙、苄嘧磺隆、地散磷、杀虫磺、苯它隆、噻草平、灭草松、苯噻菌胺、苯噻硫氰、禾草灭、苯草灭、胺酸杀、苯扎氯铵、苄烯酸、异恶草胺、抑菌啉、六氯化苯、双苯嘧草酮、苯甲亚胺、芐草胺、苯并双环酮、硫丹、吡草酮、氟磺胺草、基异羟肟酸、苯螨特(benzomate)、苯并磷酸盐(benzophosphate)、苯并噻二唑、苯丙烯氟菌唑、苯螨特(benzoximate)、新燕灵、苯并嘧啶烷(benzpyrimoxan)、苯噻隆、苯唑草酮(benzuocaotong)、苯甲酸苄酯、苄腺嘌呤、小蘖碱、β-氟氯氰菊酯、β-氯氰菊酯、苯噻嗪、BHC、双丙氨膦、双环吡喃酮、联苯肼酯、必芬诺、联苯菊酯、吡氟菌酯、毕拉草、乐杀螨、病氰硝、生物丙烯菊酯、戊环苄呋菊酯、生物氯菊酯、生物苄呋菊酯、联苯、吡杀兹、噻枯唑、噻枯唑铜、亚甲基二(x-萘-y-磺酸)二苯汞(bisphenylmercury methylenedi(x-naphthalene-y-sulphonate))、双草醚、双三氟虫脲、杀虫双、比多农、硫双二氯酚、必杀吩、比克罗宗、杀稻瘟菌素S、硼砂、波尔多混合液、硼酸、白可列、BPPS、芸苔素内酯、乙基芸苔素内酯、小蠹性信息素、溴鼠灵、溴氟醚菊酯(brofenprox)、溴灭菊酯、溴氟酰胺、溴氟菊酯、除草定、溴敌隆、二溴磷(bromchlophos)、溴鼠胺、溴苄呋菊酯、溴苯烯磷、溴乙酰胺、糠草腈、溴丁酰草胺、溴西克林、溴烯杀、溴-DDT、杀草全、溴硫磷(bromofos)、溴甲烷、溴硫磷(bromophos)、乙基溴硫磷、溴螨酯、溴菌腈、溴苯腈、溴莠敏、糠菌唑、溴硝醇、BRP、BTH、增效特、合杀威、特克草、布瑞莫、噻嗪酮、伯更狄混合液、白消安(busulfan)、白消安(busulphan)、畜虫威、丁草胺、氟丙嘧草酯、牧草胺、抑草磷、丁烷氟虫腈、特嘧硫磷、丁烯草胺、丁烯氟虫腈、苄烯菊酯、特咪唑草、丁硫啶、丁噻隆、脱叶亚磷(butifos)、丁酮威、丁酯磷、避蚊酮、丁酮砜威、地乐胺、叶锈特、丁苯草酮、炔草隆、丁胺、丁草敌、丁酯磷(butylchlorophos)、丁烯氟虫腈、二甲胂酸、硫线磷、唑草胺、钙化醇、砷酸钙、氯酸钙、氰胺钙、氰化钙、多硫化钙、敌敌钙、克草胺酯、毒杀芬、樟脑、敌菌丹、克菌丹、威百亩、吗菌威、氯灭杀威、卡巴立(carbaril)、西维因、卡巴草灵、卡巴松、贝芬替、多菌灵、长杀草、卡波硫磷、克百威、二硫化碳、四氯化碳、硫化羰、三硫磷、马拉硫磷(carbophos)、丁硫克百威、甲草威、环二混剂、萎锈灵、唑草酮、环丙酰菌胺、杀螟丹、香芹酚、香芹酮、CAVP、CDAA、CDEA、CDEC、叶枯炔、CEPC、赛拉罗、敌菌腙、沙巴草、切欣特混合液、奎硫磷(chinalphos)、甲基爱奎硫磷(chinalphos-méthyl)、灭螨猛(chinomethionat)、灭螨猛(chinomethionate)、赤拉灵、壳聚糖、灭瘟唑、甲氧除草醚、氯醛糖、草灭平、氯胺磷、氯霉素、双胺灵、四氯化苯醌、丁酰草胺、氯虫苯甲酰胺、炔禾灵、可乐津、氯杀螨、灭幼脲、冰片丹、氯溴隆、氯炔灵、氯丹、十氯酮、杀虫脒、氯烯炔菊酯、玉雄杀、乙烯利、虫脒、盐酸杀虫脒、伐草克、虫螨腈、苯咪唑菌、杀螨醇、灭草隆、燕麦酯、杀螨酯、敌螨特、毒虫畏、甲基毒虫畏、定虫隆、氟啼杀、氯甲丹、氯芴羧酸、氯芴素、氯草敏、氯嘧磺隆、氯化物、氯-IPC、氯甲磷、矮壮素、磺草酮、甲氧除草醚、氯乙灵、草枯醚、氯乙酸、乙酯杀螨醇、氯二硝萘、杀螨酯、氯仿、伊托明、灭虫脲、地茂散、氯敌鼠、敌百虫、氯化苦、三氯丙酸、氯炔丙菊酯、丙酯杀螨醇、百菌清、氯麦隆、氯醚隆(chloroxifenidim)、枯草隆(chloroxuron)、羟敌草腈、三丁氯苄膦、氯辛硫磷、氯吡唑磷、草败死、氯苯胺灵、毒死蜱、甲基毒死蜱、四氯喹噁啉、氯磺隆、敌草索、草克乐、虫螨磷、绿麦隆、克氯得、壳聚糖、胆钙化醇、氯化胆碱、环虫酰肼、环己米特、抗倒酯(cimectacarb)、抗倒酯(cimetacarb)、瓜菊酯I、瓜菊酯II、瓜菊酯、吲哚酮草酯、环庚草醚、醚磺隆、津奥啉、氰苯酰胺、咯草隆、顺式苄呋菊酯、氯酰草膦、环苯草酮、克仑吡林、氯苯氢吡咯(clenpyrin)、克草同、氯咪巴唑、碘氯啶酯、炔草酸、地虫威、苯哒嗪酸、滴滴涕、四螨嗪、氯芬磷、降固醇酸、草氯丙酸、广灭灵、稗草胺、贝螺杀、坐果安、氯丙氧定、毕克草、解毒喹、氯酯磺草胺酸、氯氰碘柳胺、噻虫胺、克霉唑、坐果酸、克拉垦(cloxylacon)、克扎垦(clozylacon)、CMA、CMMP、CMP、CMU、科得引诱剂、胆骨化醇、噻唑硫磷、8-羟基喹啉铜、醋酸铜、亚砷酸铜、砷酸铜、碳酸铜、碱式、氢氧化铜、环烷酸铜、油酸铜、氧氯化铜、硅酸铜、硫酸铜、碱式硫酸铜、铬酸锌铜、氯杀鼠灵、杀鼠灵、库马磷(coumafos)、克灭鼠、蝇毒磷、杀鼠迷、甲香菌酯、畜虫磷、丁香菌酯、CPMC、CPMF、CPPC、醚草敏、甲酚、甲苯基酸、鼠立死、克罗米通、巴毒磷(crotoxyfos)、丁烯磷(crotoxyphos)、育畜磷、冰晶石、诱蝇酮、硫杂灵、枯草酮(cumyleron)、苄草隆、福美铜氯、氧化亚铜、莪术醇、CVMP、氨腈、氰草净、氰草津、苯腈磷、氰、杀螟腈、果虫磷、氰虫酰胺、三聚氰酸、氰霜唑、洒布净、环菌胺、环丙酸酰胺、环溴虫酰胺、环虫菊酯、环草敌、环己酰亚胺、环螨酯、乙氰菊酯、环吡喃(cyclopyranil)、环哒草特、环磺隆、环杀草、环莠隆、腈吡螨酯、环氟菌胺、丁氟螨酯、氟氯氰菊酯、环卤二酰胺(cyhalodiamide)、氰氟草酯、氯氟氰菊酯、三环锡、螨蜱胺、霜脲氰、解草胺腈、氰菌灵、氯氰菊酯、牧草快、苯醚氰菊酯、环草津、三环塞草胺、环克座、嘧菌环胺、酯菌胺、环丙草胺、可普磺酰胺、环丙马秦、畜蜱磷、多果定、杀草隆、茅草枯、丁酰肼、哒幼酮、棉隆、DBCP、d-樟脑、DCB、DCIP、DCPA(日本)、DCPA(美国)、DCPTA、DCU、DDD、DDPP、DDT、DDVP、咪菌威、癸磷锡、溴氰菊酯(decamethrin)、一甲呋喃丹、避蚊胺、脱氧乙酸、敌草快(deiquat)、异丁草胺、环氧硫磷、溴氰菊酯(deltamethrin)、田乐磷、田乐磷-O、田乐磷-S、内吸磷、甲基内吸磷、内吸磷-O、甲基内吸磷-O、内吸磷-S、甲基内吸磷-S、甲基内吸磷-S砜、内吸磷-S-甲磺酸、DEP、生物丙烯菊酯、鱼藤酮、甜菜安、敌草净(desmetryn)、敌草净(desmetryne)、d-反式卤炔丙菊酯、丁醚脲、氯亚磷、氯亚胺硫磷、燕麦敌(diallate)、燕麦敌(di-allate)、二胺磷、麦草畏(dianat)、硅藻土(diatomaceousearth)、硅藻土(diatomite)、二嗪农、二溴磷、邻苯二甲酸二丁酯、驱虫特、麦草畏(dicamba)、异氯磷、敌草腈、二氯苯噻唑(dichlobentiazox)、除线磷、益发灵、二氯萘醌、氯全隆、二灭幼脲、敌草隆、羧酸芴、二氯茀醇(dichlorflurenol)、苄胺灵、二氯丙烯胺、二氯甲烷、二氯酚、滴丙酸、滴丙酸-P、敌敌畏、菌核利(dichlozolin)、菌核利(dichlozoline)、苄氯三唑醇、二氯西莫、二草氯丙酸、达灭净、氯硝胺、敌克美施、双氯磺草胺、三氯杀螨醇、滴滴涕、双杀鼠灵、敌来死、百治磷、地快乐、双香豆素、地昔尼尔、迪赛隆、狄氏剂、除螨灵、二乙除草双、甘草锁、二爱杀松、乙硫磷(diéthion)、乙霉威、增效磷、乙硫磷(diéthon)、焦碳酸二乙酯、待乙妥、鼠得克、待克利、戊味禾草灵、枯莠隆、苯敌快、噻鼠灵、氟螨嗪、二福隆、吡氟草胺、吡氟酰草胺、二氟吡隆、二氟林、敌草克、双羟丙茶碱、敌玛替夫、四氟甲醚菊酯、甲氟磷、噁唑隆、杀虫双、哌草丹、菌核净、地麦威、混灭威、菌核净、二甲草胺、异戊净、二甲噻草胺、二甲噻草胺-P、噻节因、二甲嘧酚、乐果、达灭芬、苄菌酯、驱蚊灵、二甲基二硫醚、二甲基邻苯二甲酸酯、二甲基亚硝胺、敌蝇威、草灭散、草哒酮、地莫菌胺、灭草灵(dimpropyridaz)、二嗪农、杀草隆、消螨酚、啶菌噁唑、达克利、达克利-M、敌乐胺、二硝基酚、大脱螨、消螨普、消螨普-4、消螨普-6、邻敌螨消、迪乐芬诺、硝戊酯、丙硝酚、戊硝酚、地乐酚、硝辛酯、呋虫胺、特乐酚、硝丁酯、苯虫醚、蔬果磷、二氧威、敌杀磷、敌恶磷、敌鼠(diphacin)、敌鼠(diphacinone)、二苯茚酮、草乃敌(diphenamid)、草乃敌(diphenamide)、二苯砜、二苯胺、二苯硫醚、调呋酸、地乐灵、异丙净、敌百虫、敌派美创、双硫氧吡啶、敌草快、四硼酸盐、杀虫双、雌舞毒蛾引诱剂、麦草畏甲酯、赛松、双硫仑、乙拌磷、灭菌磷、腈硫醌、噻喃磷、二甲基二硫醚、甲基乙拌磷、氟硫草定、达有龙、双黄药、d-柠檬烯、DMDS、DMPA、DNOC、吗菌灵、多地辛、多宁、苯氧炔螨、十二烷基胍醋酸盐、谷蠢引诱剂、多拉克汀、DPC、敌菌酮、DSMA、右旋反式丙烯菊酯、右旋反式苄呋菊酯、毒氟磷、莎扑隆、EBEP、EBP、硫线磷、脱皮甾酮、氯唑灵、EDB、EDC、EDDP、克瘟散、甘草津、甲氨基阿维菌素、EMPC、烯炔菊酯、烯腺嘌呤、硫丹、草多索、草藻灭、因毒磷、安特灵、烯肟菌酯(enestroburin)、恩康唑、烯肟菌酯(enoxastrobin)、螨净、EPN、丙酰芸苔素内酯、保幼醚、依普座、依立诺克丁、磺唑草、ε-甲氧苄氟菊酯、ε-莫氟杀林、EPTC、抑草蓬、麦角钙化醇、二氯己酰草胺、生物烯丙菊酯、高氰戊菊酯、ESP、戊草丹、乙烯硅、乙环唑、依他伏杀、代森硫、噻唑菌胺、克草胺、乙丁烯氟灵、胺苯磺隆、杀草胺、乙烯利、噻二唑隆、杀虫丹、抑草威、爱杀松、乙嗪草酮、乙虫腈、依瑞莫、益硫、乙氧本草胺、乙呋草黄、驱蚊醇、灭克磷、普伏松、氯氟草醚、促长啉、乙氧嘧磺隆、吲熟酯、甲酸乙酯、乙基焦磷酸盐、乙滴滴、乙基-DDD、乙烯、二溴乙烯、二氯乙烯、氧化乙烯、乙蒜素、2,3-二羟基丙基硫醇化乙基汞、乙酸乙基汞、溴化乙基汞、氯化乙基汞、磷酸乙基汞、硝草酚、ETM、乙胺草醚、乙氧苯草胺、依芬普司、乙螨唑、依得利、乙嘧硫磷(etrimfos)、乙嘧硫磷(étrimphos)、丁香酚、EXD、凡杀同、氨磺磷、伐草克、咪唑菌酮、敌克松、烯肟菌胺、芬灭松、咪菌腈、芬瑞莫、酰苯磺威(fenasulam)、抗螨唑、喹螨醚、芬克座、苯丁锡、解草唑、皮蝇硫磷、芬氯磷、解草啶、乙苯威、五氟苯菊酯、甲呋酰胺、环酰菌胺、非草隆、种衣酯、扑灭松、除螨酯、酚菌酮、仲丁威、毒菌锡、涕丙酸、苯硫威、非诺克林、氰菌胺、噁唑禾草灵、噁唑禾草灵-P、异噁苯砜、芬诺克、拌种咯、芬哌沙米(fenpicoxamid)、吡氯氰菊酯、甲氰菊酯、苯锈啶、芬普福、胺苯吡菌酮、唑螨酯、芬奎三酮、哒嗪抑雄素、除螨酯、丰索磷、氯苯氧乙醇、噻唑禾草灵、芬杀松、乙基芬杀松、噻唑禾草灵、三苯锡、四唑酰草胺、芳氟胺、非草隆、非草隆-TCA、氰戊菊酯、福美铁、富米综、磷酸铁、硫酸亚铁、氟虫腈、氟燕灵、氟燕灵-M、嘧啶磺隆、氟鼠灵、氟美托奎、氟啶虫酰胺、双氟磺草胺、氯氟吡啶酯、氟吡草胺(florylpicoxamid)、嘧螨酯、三氟咪啶酰胺(fluazaindolizine)、吡氟禾草灵、吡氟禾草灵-P、扶吉胺、异丙吡草酯、氟佐隆、氟虫双酰胺、氟螨噻、溴氟菊酯、氟酮磺隆、氟吡磺隆、氟消草、伏康脲、氟环脲、氟氰菊酯、护汰宁、联氟螨(fluénéthyl)、联氟螨(fluenetil)、氟噻虫砜、氟噻草胺、氟芬内林、吡氟草胺、氟虫脲、氟菌螨酯、三氟醚、氟哒嗪草酯、氟螨嗪、丁烯氟虫腈、氟己芬、氟茚唑菌胺(fluindapyr)、氟氯苯菊酯、氟酰菌胺、氟节胺、唑嘧磺草胺、氟默嗪、氟烯草酸、丙炔氟草胺、氟米丙平、氟吗啉、伏草隆、氟吡菌胺、氟吡胺(fluopimomide)、氟吡菌酰胺、氟杀螨、增糖胺、氟乙酰胺、氟乙酸、氟咯草酮、消草醚、乙羧氟草醚、唑呋草、氟氯菌核利(fluoromide)、唑唆草、氟除草醚、氯氟吡氧乙酸、氟硫隆、三氟苯唑、氟氧杂吡乙酮(fluoxapiprolin)、氟嘧菌酯、氟胺草唑、氟丙嘧草、氟鼠啶、四氟丙酸、氟吡呋喃酮、氟嘧啶(flupyrimin)、氟啶嘧磺隆、氟喹唑、氟拉蓝那、解草安、抑草丁、羧芴素、氟啶草酮、氟咯草酮、氟定咪、氟草定、调嘧醇、氟磺酰胺、呋草酮、护硅得、氟硫灭、氟螨嗪、嗪草酸、氟噻草胺、氟替尼、福多果定、护汰芬、氟胺氰菊酯、氟甲酰胺(fluxametamide)、氟唑菌酰胺、肟草安、福尔培(folpel)、灭菌丹(folpet)、氟磺胺草醚、地虫磷、甲酰嘧磺隆、氟吡脲、甲醛、伐虫脒、安果、胺甲威、杀木膦、福赛得、丁苯硫磷、福司吡酯、噻唑磷、丁硫环磷、弗罗塔林、四氯苯酞、麦穗灵、氟草净、氟草醚、氟菌螨酯(fujunmanzhi)、氟氯醚(fulumi)、氟乙酰胺、氟萘禾草灵、呋苯硫脲、乙二醇缩糖醛、呋霜灵、炔呋菊酯、福拉比、呋喃虫酰肼、呋线威、二甲呋酰胺、氟康唑、顺式氟康唑、抗虫菊、糠醛、呋喃解草唑、拌种胺、呋菌隆、呋氧草醚、γ-BHC、γ-氯氟氰菊酯、γ-HCH、格螨酯、赤霉酸、赤霉素A3、激勃素、鼠甘伏(gliftor)、鼠甘伏(glitor)、氯醛糖、草铵膦、草铵膦-P、果绿定、乙二肟、草甘膦、草甘二膦、棉红铃虫性诱剂、诱杀烯混剂、灰黄霉素、胍诺克汀、双胍盐、丙烯酸喹啉酯、氟氯吡啶酯、苄螨醚、氯虫酰肼、氟硝磺酰胺、氯吡嘧磺隆、氟啶草、吡氟氯禾灵、吡氟氯禾灵-P、吡氟氯禾灵-R、HCA、HCB、HCH、六甲密胺、六甲磷、HEOD、七氯、禾他氟林、庚烯磷、增产肟、除莠霉素、除莠霉素A、速杀硫磷、六氯、六氯环己烷、六氯丙酮、六氯苯(hexachlorobenzene)、六氯丁二烯、六氯苯(hexachlorophene)、菲克利、氟铃脲、六氟拉敏、六氟砷酸钾、己诱剂、己酰胺、六嗪同、己硫磷、噻螨酮、HHDN、霍洛硫、高油菜素内酯、环草肟、环虫腈(huanchongjing)、磺草灵、环菌唑、氟蚁腙、汞加芬、水合石灰、氨腈化氢、氰化氢、烯虫乙酯、土菌消、恶霉灵、奋淋威、IAA、IBA、IBP、埃卡瑞丁、伊米萨利、咪草酸、甲氧咪草烟、甲基咪草烟、依灭草、灭草喹、咪草烟、唑吡嘧磺隆、亚胺唑、新烟磷、吡虫啉、氯噻啉、克热净、炔咪菊酯、依纳素、茚草酮、茚嗪氟草胺、茚虫威、枯瘟净、纤毛虫土(infusorial earth)、茚吡氟西姆(inpyrfluxam)、碘草腈、碘克威、碘硫磷、碘甲烷、碘甲磺隆、优芬磺隆、碘苯腈、抑草津、IPC、种菌唑、艾分卡巴腙、艾分氟康唑、伊匹芬喹(ipflufenoquin)、丙基喜乐松、依普同、缬霉威、丙草定、齿小蠹二烯醇、小蠹烯醇、IPSP、IPX、氯唑磷、依杀松、碳氯灵、丁咪胺、丁咪胺、水胺硫磷、异草定、异环斯兰(isocycloseram)、异艾氏剂、异柳磷、甲基异柳磷、艾索非他米、异氟普兰(isoflucypram)、异索威、丁嗪草酮、异草完隆、异派磷、氮草草、叶蝉散、异草定、异乐灵、异丙吡草酯、稻瘟灵、异丙隆、异吡瑞沙、异嘧醇、异拌磷、异噻菌胺、异恶隆、异酰菌酮、异噁酰草胺、异恶氯草酮、双苯噁唑酸、异噁唑草酮、异恶草醚、异噁唑磷、异恶隆、伊维菌素、异恶草胺、浸种磷(izopamfos)、浸种磷(izopamphos)、日本丽金龟引诱剂、喃烯菊酯、茉莉菊酯I、茉莉菊酯II、茉莉酸、甲磺虫腙、甲基增效磷、甲香菌酯、解草烷、解草烯、井岗霉素A、碘硫磷、保幼激素I、保幼激素II、保幼激素III、噻嗯菊酯、κ-联苯菊酯、κ-七氟菊酯、卡草灵、卡日塔赞、春日霉素、克菌灵、氯戊环、克螺多、硅藻土(kieselguhr)、活动素、烯虫炔酯、精苯霜灵、克收欣、喹草烯、乳氟禾草灵、λ-氯氟氰菊酯、兰考三酮(lancotrione)、拉替鲁尔、砒酸铅、环草定、雷皮菌素、溴苯磷、联苯腈酯(lianbenjingzhi)、石硫合剂、灵丹、三甲基二氧三环壬烷、利谷隆、啶虫磷、夜蛾性诱剂、粉纹夜蛾性诱剂、洛替拉纳(lotilaner)、氯芬奴隆、氯氟氰虫酰胺(lüfuqingchongxianan)、氯酰草磷(lüxiancaolin)、氯啶菌酯、氯氟醚菊酯(lvfumijvzhi)、氯酰草膦、噻唑磷、M-74、M-81、MAA、磷化镁、马拉硫磷(malathion)、马拉硫磷(maldison)、马来酰肼、丙螨氰、麦芽糊精、MAMA、代森锰铜、代森锰锌、曼得罗宾、双炔酰菌胺、锰乃浦、苦参碱、叠氮磷、MCC、MCP、MCPA、MCPA-硫代乙基、MCPB、MCPP、灭锈胺、灭蚜磷、甲威苯咪、甲基减蚜磷、甲氯丙酸、甲氯丙酸-P、杀螨脒、地乐施、诱杀酯、苯噻酰草胺、精甲霜灵、吡唑解草酸、甲芬氟康唑(mefentrifluconazole)、氟磺酰草胺、美加特酸、蜂花醇、双杀鼠灵、MEMC、灭蚜松、MEP、嘧菌胺、氯氟醚菊酯、灭芬酯、地安磷、壮棉素、灭普宁、消螨多、灭虫威、倍硫磷、倍硫磷硫醇(mercaptophos thiol)、马拉硫磷(mercaptothion)、氯化汞、氧化汞、氯化亚汞、脱叶亚磷、氧化脱叶亚磷、灭莠津、甲基二磺隆、甲基磺草酮、甲硫芬(mesulfen)、甲亚砜磷(mesulfenfos)、甲硫芬(mesulphen)、间甲酚、氰氟虫胺、甲霜灵、甲霜灵-M、蜗牛敌、威百亩、恶唑酰草胺、苯嗪草酮、甲基对硫磷、灭他熏、吡草胺、双醚氯吡嘧磺隆、间氯敌菌酮、美卡芬(metcamifen)、灭特座、甲基涕巴、二甲达草伏、噻噻隆、虫螨畏、美索丙铂林、威百亩、甲胺磷、灭速克、灭草唑、呋菌胺、甲草苯隆、杀扑磷、甲硫苯威、灭赐克、甲硫嘧磺隆、甲硫涕巴、甲硫唑啉、灭草恒、杀虫乙烯磷、速灭威、醚草通、灭多威、甲氧普林、格草净、盖草津、丁基奎纳克林、甲醚菊酯、甲氧滴滴涕、甲氧虫酰胼、去草酮、甲基唑磷嗪、甲基溴、甲基丁香酚、甲基碘、异硫氰酸甲酯、甲基对硫磷、甲基乙酯磷、甲基氯仿、二硫代氨基甲酯、甲基杀草隆、二氯甲烷、甲基异柳磷、甲基倍硫磷、氧化甲基倍硫磷、甲基倍硫磷硫醇、甲基汞苯甲酸盐、氰胍甲汞、甲基汞五氯酚盐、甲基新癸胺、杀螟硫磷、保棉磷、甲硫唑啉、代森联、代森联锌、吡喃隆、溴谷隆、甲氧苄氟菊酯、异丙甲草胺、速灭威、苯磺隆、苯氧菌胺、磺草唑胺、恶虫酮、甲氧隆、灭芬农、代森联、赛克津、美曲磷脂、敌百虫、噻菌胺、甲磺隆、metyltetraprole、速灭磷、兹克威、灭除威(miechuwei)、灭鼠安、灭蚊菊酯(miewenjuzhi)、米尔螨素、米尔贝肟、代森环、醚螨胺(mimanan)、丙胺氟磷、MIPC、灭蚁灵、MNAF、蘑菇醇、草达灭、杀虫单、莫氟杀林、庚酰草胺、特噁唑隆(monisuron)、单甲脒、单氯乙酸、久效磷、绿谷隆、杀虫单(monomehypo)、舒非仑、嘧磺隆、杀虫单(monosultap)、灭草隆、灭草隆-TCA、伐草快、吗啉脒胍、茂果、莫兹得、莫昔克丁、MPMC、MSMA、MTMC、家蝇引诱剂、腈菌唑、米克啉、蜂花基醇、N-(乙基汞)-对甲苯磺酰苯胺、NAA、NAAm、钠乃浦、萘酞磷、二溴磷、萘、萘乙酰胺、萘酸酐、萘肽磷、萘氧基乙酸、萘乙酸、萘基茚满-1,3-二酮、萘氧基乙酸、萘丙胺、敌草胺、敌草胺-M、萘草胺、游霉素、NBPOS、草不隆(neburea)、草不隆(neburon)、异狄氏剂、毒藜碱、对氯硫磷(nichlorfos)、除草醚、氯硝柳胺、啶酰菌胺、烟嘧磺隆、烟碱、硫酸烟碱、氟蚁灵、尼克霉素、NIP、氟氯草胺、吡氯草胺(nipyralofen)、烯啶虫胺、硝乙脲噻唑、磺乐灵、氯啶、戊氰威、除草醚、三氟甲草醚、硝基苯乙烯、异丙消、灭鼠宁、壬醇、鼠特灵、草完隆、达草灭、降烟碱、草完隆、氟酰脲、多氟脲、NPA、尼瑞莫、奴南酮(nuranone)、OCH、八氯二丙醚、辛噻酮、邻二氯苯、呋酰胺、氧乐果、邻苯基苯酚、坪草丹、欧福绿、旱草丹、邻二氯苯、嘧苯胺磺隆、奥克绿、肟醚菌胺、氨磺乐灵、蛇床子素(osthol)、蛇床子素(osthole)、欧斯摧蒙(ostramone)、欧威壮(ovatron)、杀螨酯、解草腈、丙炔噁草酮、噁草酮、欧杀斯、草胺酸盐、欧杀灭、草哒松(oxapyrazon)、草哒松(oxapyrazone)、环氧嘧磺隆、奥赛普林、噁嗪草酮、噁唑硫(oxazosulfyl)、喹啉铜(oxine-copper)、喹啉铜(oxine-Cu)、欧索林酸、噁咪唑、氧化萎锈灵、甲基砜吸磷、异亚砜磷、砜拌磷、羟烯腺嘌呤、乙氧氟草醚、氧化苦参碱、土霉素、氧化克杀螨、PAC、巴克素、哌虫啶、丙烯除虫菊、PAP、对二氯苯、对氟隆、百草枯、对硫磷、甲基对硫磷、苯吡醇、巴黎绿、PCNB、PCP、PCP-钠、对二氯苯、PDJ、克草猛、消螨酚、披扶座、天竺葵酸、平克座、宾克隆、二甲戊乐灵、三氯杀虫酯、喷福芬、氟幼脲、二甲戊乐灵、平速烂、五氯苯酚、五氯苯基月桂酸盐、戊酰苯草胺、吡噻菌胺、戊烯氰氯菊酯、环戊噁草酮、灭蚁灵、氟草磺胺、苄氯菊酯、烯草胺、PHC、氰烯菌酯、乙基氰烯菌酯、敌磺钠(phénaminosulf)、叶枯净、双乙威(phénétacarbe)、棉胺宁、芬硫磷、甜菜宁、乙基甜菜宁、稀草隆、酚硫杀、苯醚菊酯、苯螨醚、稻丰散、苯汞脲、乙酸苯基汞、氯化苯基汞、邻苯二酚的苯基汞衍生物、硝酸苯基汞、水杨酸苯基汞、甲拌磷、毒鼠磷(phosazetim)、伏杀磷、磷灭丁(phosametine)、毒鼠磷(phosazetim)、毒鼠磷(phosazetin)、三磷锡、氯瘟磷、霉疫净(phosethyl)、硫环磷、甲基硫环磷、甘氨硫磷、亚胺硫磷、对氯硫磷、磷酰胺、磷胺、磷烷、草丁膦、磷虫威、磷、三磷锡、辛硫磷、甲基辛硫磷、四氯苯酞、萘酞磷(phthalophos)、似虫菊、皮卡布西、派卡瑞丁、毒莠定、氟吡草胺、啶氧菌酯、匹马菌素、杀鼠酮、唑啉草酯、粉病灵、哌嗪、胡椒基丁醚、胡椒基环己烯酮、哌草磷、哌壮素(piproctanly)、哌壮素、增效醛、甲胺啼磷(pirimetaphos)、比加普、灭鼠优、嘧啶氧磷、乙基虫螨磷、甲基虫螨磷、鼠完(pival)、杀鼠酮、三氯杀虫酯、PMA、PMP、聚丁烯、聚氨基甲酸酯、毒杀芬、聚乙氧基喹啉、多氧菌素D、多氧菌素(polyoxins)、保粒霉素、多噻烷、亚砷酸钾、叠氮化钾、氰酸钾、氰化钾、乙基黄酸钾、环烷酸钾、多硫化钾、硫氰酸钾、pp′-DDT、丙炔菊酯、早熟素I、早熟素II、早熟素III、丙草胺、乙酰嘧啶磷、氟嘧磺隆、扑杀热、咪酰胺、丙氯醇、环丙腈津、扑灭宁、氨氟乐灵、丙溴磷、氟唑草胺、环丙氟灵、丙氟菊酯、环苯草酮、杀虫胺、甘扑津、调环酸、茉莉酮、蜱虱威、猛杀威、扑灭通、扑草净(prometryn)、扑草净(prometryne)、捕灭鼠、拿草特、前尼替丁(pronitridine)、扑草胺、丙虫磷、普罗帕脒、霜霉威、敌稗、丙虫磷、喔草酯、克螨特、扑虫菊、扑灭津、巴胺磷、苯胺灵、普克利、丙匹定(propidine)、甲基锌乃浦、异丙草胺、安丹、丙苯磺隆、增效酯、丙嘧磺隆、戊炔草胺、丙氧喹啉、补骨内酯、甲硫磺乐灵、苄草丹、氟磺隆、乙噻唑磷、硫菌威、丙硫菌唑、普硫松、发硫磷、丙苯烃菊酯、扑灭生、派密多磷(prymidophos)、广草胺、补骨脂素(psoralen)、补骨脂素(psoralene)、比达农、氟唑菌酰羟胺(pydiflumetofen)、派氟丁胺、派灭净、比锈灵、吡唑硫磷、双唑草腈、百克敏、吡草醚、氟虫腈、嘧啶威、唑胺菌酯、唑菌酯、吡丙炔(pyrapropoyne)、磺酰草吡唑、派拉氟胺、吡唑特(pyrazolate)、吡唑特(pyrazolynate)、杀草敏、白粉松、吡嘧磺隆、硫吡唑磷、苄草唑、反灭虫菊、必列宁I、必列宁II、除虫菊精、异丙酯草醚、丙酯草醚、吡菌苯威、嘧啶肟草醚、稗草丹、氯草定、哒螨灵、吡啶氯甲基(pyridachlometyl)、吡啶达醇、啶虫丙醚、哒嗪硫磷(pyridaphenthion)、哒嗪硫磷(pyridaphenthione)、哒草特、啶菌腈、比芬诺、氟虫吡喹、环酯草醚、派灭他磷(pyrimétaphos)、嘧霉胺、抗蚜威、嘧螨醚、嘧草醚、嘧螨胺、乙基嘧啶磷、甲基嘧啶磷、嘧啶硫蕃、嘧硫磷、灭鼠优、派瑞芬酮、派瑞乐、吡啶醇、吡丙醚、啶菌噁唑、嘧硫草醚、吡唑威、百快隆、嘧氧砜、甲氧磺草胺、吡氯灵、吡氧呋、嗪草酸(qincaosuan)、氰枯灵(qingkuling)、苦木素、羟基喹啉基乙酮、喹硫磷、甲基喹硫磷、醌菌腙、二氯喹啉酸、喹克唑、喹草酸、灭藻醌、奎诺夫林(quinofumelin)、灭螨猛、氯藻胺、畜宁磷、快诺芬、喹硫磷、五氯硝基苯、喹禾灵、喹禾灵-P、驱蚊酯、驱蝇定、吡咪唑、碘醚柳胺、R-达克利、热必得、敌草快、雷度隆(renriduron)、红圆介壳虫引诱剂、灭虫菊、硫氰苯乙胺、闹羊花毒素III、病毒唑、砜嘧磺隆、丁烯氟虫腈(rizazole)、R-甲霜灵、硫氰苯胺(rodéthanil)、皮蝇磷、鱼藤酮、鱼尼丁、藜芦碱、苯嘧磺草胺、噻菌茂、噻森铜、水杨酰苯胺、氟硅菊酯、血根碱、散道宁、S-生物丙烯菊酯、八甲磷、海葱糖苷、另丁津、密草通、氟唑环菌胺、司拉克丁、单甲脒、增效菊、芝麻林素、赛松、西杀草、西维因、双甲胺草磷、双碱胺草磷(shuangjianancaolin)、S-烯虫乙酯、环草隆、四氟醚菊酯(sifumijvzhi)、诱虫环、硅护芬、毒鼠硅、二氧化硅气凝胶、硅胶、硅噻菌胺(silthiofam)、硅噻菌胺(silthiopham)、硅噻菌胺(silthiophan)、三氯苯氧丙酸、西玛津、硅氟唑、西玛通、西草净(simetryn)、西草净(simetryne)、杀雄啉、S-烯虫炔酯、消石灰、SMA、S-甲氧普林、S-异丙甲草胺、亚砷酸钠、叠氮化钠、氯酸钠、氰化钠、氟化钠、氟乙酸钠、六氟硅酸钠、环烷酸钠、邻苯基苯酚钠、正苯基苯酚钠、五氯苯酚钠、五氯苯酚氧化钠、多硫化钠、氟硅酸钠、硫代碳酸钠、硫氰酸钠、蔬草灭、苏硫磷、乙基多杀菌素、赐诺杀、螺螨酯、螺甲螨酯、甲氧哌啶乙酯(spiropidion)、螺虫乙酯、螺环菌胺、司替罗磷、链霉素、番木鳖碱、食菌甲诱醇、磺苯醚隆、磺草酮、草克死、甲磺草胺、舒非仑、氟虫胺、磺噻隆(sulfodiazole)、甲嘧磺隆、草硫膦、磺酰磺隆、治螟磷(sulfotep)、硫特普(sulfotepp)、氟啶虫胺腈、亚砜、硫肟醚、硫、硫酸、氟化硫酰、吖庚磺酯、草硫膦、硫丙磷、戊苯砜、灭草灵、τ-氟胺氰菊酯、稗草烯、噻螨威、TBTO、TBZ、TCA、TCBA、TCMTB、TCNB、TDE、得克利、虫酰肼、吡螨胺、特普弗洛奎(tebufloquin)、丁基嘧啶磷、牧草胺、丁噻隆、克枯烂、四氯硝基苯、福美双联、三氯杀螨砜、得福隆、七氟菊酯、特呋喃隆、环磺酮、替美福司、双硫磷、涕巴、TEPP、吡喃草酮(tepraloxydim)、吡喃草酮(teproloxydim)、环戊烯菊酯、特草定、特草灵、猛杀草、特丁硫磷、甲氧去草净、特丁津、芽根灵、去草净(terbutryn)、去草净(terbutryne)、五氯硝基苯、土霉素(terramicin)、土霉素(terramycin)、特效烯、四氟吡咯烷(tetflupyrolimet)、四氯虫酰胺、四氯乙烷、司替罗磷、四克利、三氯杀螨砜、杀螨好(tetradisul)、四氟隆、胺菊酯、四氟醚菊酯、四胺、杀螨素、氟氰虫酰胺、四氟丙酸钠、杀螨好、硫酸铊、硫酸亚铊、甲氧噻草胺、θ-氯氰菊酯、腐绝、噻虫啉、噻二嗪、噻二氟、噻虫嗪、噻磺隆、噻丙腈、噻氟隆(thiazafluron)、噻氟隆(thiazfluron)、噻酮、噻草定、苯噻硫磷、噻菌腈、噻二唑胺、噻苯隆、噻酮磺隆、噻吩磺隆、赛氟灭、硫柳汞、甲拌磷、禾草丹、抗虫威、硫氯苯亚胺、硫氯苯亚胺(thiochlorphenphime)、硫氰基二硝基苯(thiocyanatodinitrobenzenes)、杀虫环、硫丹、噻菌铜、硫敌克、久效威(thiofanocarb)、久效威(thiofanox)、硫氟肟醚、噻赫派(thiohempa)、硫柳汞、甲基乙拌磷、硫磷嗪、多保净、乙基多保净、甲基多保净、对硫磷、克杀螨、氨基硫脲、杀虫双、噻替派、杀线威(thioxamyl)、福美双、秋兰姆、苏云金素、噻苯达唑、汰敌宁、汰芬那、调节安、TIBA、螨蜱胺、仲草丹、替可里姆(tioclorim)、替噁杀芬(tioxazafen)、硫氰苯甲酰胺、威线肟、TMTD、甲基脱克松、唑虫酰胺、托普洛卡(tolprocarb)、托吡拉特(tolpyralate)、甲苯氟磺胺、甲基益发灵、乙酸甲苯汞、托玛琳(tomarin)、苯吡唑草酮、毒杀芬、TPN、肟草酮、溴氯氰菊酯、四溴菊酯、吡咯腈、拜富宁、反式苄氯菊酯、不孕津、三十烷醇、三泰芬、三泰隆、氟酮磺草胺、野麦畏(triallate)、野麦畏(tri-allate)、威菌磷、抑芽唑、苯螨噻、嘧菌醇、醚苯磺隆、唑蚜威、叶锈特、三嗪氟草胺、三唑硫磷、三唑磷(triazothion)、咪唑嗪、三元氯化铜、三元硫酸铜、苯磺隆、脱叶磷、三丁基氧化锡、杀草畏、水杨菌胺、三氯吡氧乙酸(trichlopyr)、敌百虫、异皮蝇磷-3、毒壤膦(trichloronat)、毒壤膦(trichloronate)、三氯三硝基苯(Trichlorotrinitrobenzenes)、敌百虫(trichlorphon)、绿草定、氯啶菌酯、三甲酚、三环唑、三环己基氢氧化锡、三得芬、灭草环、草达津、蜗螺净、三氯丙氧磷、三氟敏、三氟啶磺隆、三氟地杀嗪、三氟苯嘧啶、赛福座、三福隆、氟乐灵、氟胺磺隆、翠福、三氟禾草肟(trifopsime)、赛福宁、三羟基三嗪、特诱酮、混灭威、三甲隆、抗倒酯、三苯基锡、烯虫硫酯、弗草酮、雷公藤内酯、草达克、杀虫钉、灭菌唑、三氟甲磺隆、创克考、脱叶磷(tuoyelin)、泰勒吡氟(tyclopyrazoflor)、烯效唑、烯效唑-P、福美甲胂、乌瑞替派、戊酸酯、维利微素、维利微素A、霜霉灭、异杀鼠酮、蚜灭多、抑霉胺、凡尼普罗、灭草猛、免克宁、维生素D3、华法林、硝虫硫磷、辛菌胺、烯肟菌胺、锡我菌酯(xiwojunzhi)、XMC、二甲苯草胺、二甲苯酚、灭杀威、杀灭唑(xymiazole)、抑食肼、氰菌胺、玉米素、增效胺、增效磷(zengxiaolin)、ζ-氯氰菊酯、环烷酸锌、磷化锌、噻唑锌(zinc thiazole)、噻唑锌(zinc thiozole)、三氯酚锌、三氯酚锌(zinc trichlorophenoxide)、锌乃浦、福美锌、佐拉普磷、杀鼠灵、苯酰菌胺、唑胺菌酯(zuoanjunzhi)、唑草胺(zuocaoan)、唑菌酯(zuojunzhi)、唑嘧磺隆、α-氯醇、α-蜕皮激素、α-木替翠汀、α-萘乙酸、和β-蜕皮激素;以及
(2)表1中的以下分子:
PCT申请公开WO 2010129497 A1中公开了N-(4-氯-2-(吡啶-3-基)噻唑-5-基)-N-乙基-3-(甲基磺酰基)丙酰胺(下文中称为“AI-1”)
PCT申请公开WO 2018071327 A1中公开了反式-5-(3-(3,5-双(三氟甲基)苯基)-2,2-二氯环丙烷-1-甲酰胺基)-2-氯-N-(3-(2,2-二氟乙酰胺基)-2,4-二氟苯基)苯甲酰胺(下文中称为“rac-AI-2”)
PCT申请公开WO 2018071327 A1中公开了5-((1R,3R)-3-(3,5-双(三氟甲基)苯基)-2,2-二氯环丙烷-1-甲酰胺基)-2-氯-N-(3-(2,2-二氟乙酰胺基)-2,4-二氟苯基)苯甲酰胺(下文中称为“R,R-AI-2”),其(R,R)-对映异构体
如本公开中所使用的,以上每一个均是活性成分。对于更多信息,参阅位于Alanwood.net的“杀有害生物剂通用名称大全(Compendium of Pesticide CommonNames)”以及位于bcpcdata.com的各种版本(包括在线版本)的“杀有害生物剂手册(ThePesticide Manual)”中列出的材料。
活性成分的特别优选的选择是1,3-二氯丙烯、氯虫苯甲酰胺、毒死蜱、氰虫酰胺、氟铃脲、灭多威、甲氧虫酰肼、多氟脲、草氨酰、乙基多杀菌素、多杀菌素、氟啶虫胺腈和三氟苯嘧啶(在下文中为“AIGA-2”)。
另外,活性成分的其他特别优选的选择是灭螨醌、啶虫脒、乙酰虫腈、阿维菌素、谷硫磷-甲基、联苯肼酯、联苯菊酯、西维因、克百威、虫螨腈、定虫隆、环虫酰肼、噻虫胺、氟氯氰菊酯、氯氰菊酯、溴氰菊酯、丁醚脲、甲氨基阿维菌素苯甲酸盐、硫丹、高氰戊菊酯、乙虫腈、乙螨唑、氟虫腈、氟啶虫酰胺、嘧螨酯、γ-氯氟氰菊酯、氯虫酰肼、茚虫威、λ-氯氟氰菊酯、虱螨脲、马拉硫磷、灭多威、氟酰脲、苄氯菊酯、啶虫丙醚、嘧螨醚、螺螨酯、虫酰肼、噻虫啉、噻虫嗪、硫双威、唑虫酰胺、和ζ-氯氰菊酯(在下文中为“AIGA-3”)。
术语“生物型杀有害生物剂”意指通常以与化学杀有害生物剂类似的方式应用的微生物类生物型有害生物防治剂。通常,它们是细菌性的,例如芽孢杆菌属物种(Bacillusspp.)、伯克霍尔德菌属物种(Burkholderia spp.)、假单胞菌属物种(Pseudomonas spp.)、Saccaropolyspora属物种、沃巴赫氏菌(Wolbachie pipientis(Zap)),但也有真菌防治剂的实例,包括木霉属物种(Trichoderma spp)和白粉寄生孢(Ampelomyces quisqualis)。一个熟知的生物型杀有害生物剂实例是芽孢杆菌属(Bacillus)物种,鳞翅目、鞘翅目、和双翅目细菌疾病。生物型杀有害生物剂包括基于昆虫病原真菌(例如,球孢白僵菌(Beauveriabassiana)菌株、绿僵菌(Metrahizium anisopliae)菌株F52、玫烟色拟青霉阿波普卡(Paecilomyces fumosoroseus Apopka)菌株97、蜡蚧菌属物种(Lecanicillium spp.)和棒束孢属物种(Isaria spp.))、昆虫病原线虫(例如,夜蛾斯氏线虫(Steinernemafeeliae))、和昆虫病原病毒(例如,苹果蠹蛾颗粒体病毒(Cydia pomonellagranulovirus)(GV)、核多角体病毒(NPV))的产品。昆虫病原生物体的其他实例包括但不限于:杆状病毒例如伪苹果卷叶蛾(Thaumatotibia leucotreta)GV、黎豆夜蛾(Anticarsiagemmatalis)MNPV、和棉铃虫(Helicoverpa armigera)NPV;原生动物;和微孢子虫。一些包括植物精华,包括合成物、提取物、和未精制的油(例如,土荆芥近种臭杏(Chenopodiumambrosioides near ambrosioides)提取物、具有甘油或丙二醇印楝油的脂肪酸单酯)。为了避免疑问,生物型杀有害生物剂是活性成分。对于进一步的信息,参见Kachhawa D,Journal of Entomology and Zoology Studies[昆虫学与动物学研究杂志]2007,5,468-473。
术语“场所”意指有害生物正在生长、可能生长、或可能经过的栖息地、育种地、植物、种子、土壤、材料、或环境。例如,场所可以是:作物、树木、果实、谷类、饲料物种、藤本植物、草皮、和/或观赏植物正在生长的地方;家畜居住的地方;建筑物的内部或外部表面(诸如储存谷物的地方);建筑物中使用的建筑材料(诸如浸渍木材);和建筑物周围的土壤。
短语“MoA材料”意指具有如在IRAC MoA分类v.9.3(位于irac-online.org.)中指示的作用方式(“MoA”)的活性成分,其中描述了以下几组。
(1)乙酰胆碱酯酶(AChE)抑制剂,包括以下活性成分:棉铃威、涕灭威、恶虫威、丙硫克百威、丁酮威、丁酮砜威、西维因、克百威、丁硫克百威、乙硫苯威、仲丁威、伐虫脒、呋线威、异丙威、甲硫威、灭多威、速灭威、草氨酰、抗蚜威、残杀威、硫双威、久效威、唑蚜威、混杀威、XMC、灭杀威、高灭磷、甲基吡啶磷、乙基谷硫磷、甲基谷硫磷、硫线磷、氯氧磷、氯芬磷、氯甲硫磷、毒死蜱、甲基毒死蜱、蝇毒磷、杀螟腈、甲基内吸磷、二嗪磷、敌敌畏/DDVP、百治磷、乐果、甲基毒虫畏、乙拌磷、EPN、乙硫磷、灭线磷、伐灭磷、苯线磷、杀螟硫磷、倍硫磷、噻唑磷、庚烯磷、异丙胺磷、异恶唑磷、马拉硫磷、灭蚜磷、甲胺磷、杀扑磷、速灭磷、久效磷、二溴磷、氧化乐果、砜吸磷、对硫磷、甲基对硫磷、稻丰散、伏杀硫磷、甲拌磷、亚胺硫磷、磷胺、辛硫磷、并溴磷、胺丙畏、丙硫磷、吡唑硫磷、哒嗪硫磷、喹硫磷、治螟磷、丁基嘧啶磷、双硫磷、特丁磷、司替罗磷、甲基乙拌磷、三唑磷、敌百虫、蚜灭磷、甲基嘧啶磷、依米细阿豪斯(Imicyafos)、和O-(甲氧基氨基硫代-磷酰基)水杨酸异丙酯。
(2)GABA门控的氯离子通道阻断剂,包括以下活性成分:氯丹、硫丹、乙虫腈和氟虫腈。
(3)钠通道调节剂,包括以下活性成分:氟丙菊酯、丙烯菊酯、右旋丙烯菊酯、右旋反式丙烯菊酯、联苯菊酯、生物丙烯菊酯、生物丙烯菊酯S-环戊烯基、生物苄呋菊酯、乙氰菊酯、氟氯氰菊酯、β-氟氯氰菊酯、氯氟氰菊酯、λ-氯氟氰菊酯、γ-氯氟氰菊酯、氯氰菊酯、α-氯氰菊酯、β-氯氰菊酯、θ-氯氰菊酯、ζ-氯氰菊酯、苯氰菊酯[(1R)-反式异构体]、溴氰菊酯、烯炔菊酯[(EZ)-(1R)-异构体]、高氰戊菊酯、醚菊酯、甲氰菊酯、氰戊菊酯、氟氰戊菊酯、氟氯苯菊酯、τ-氟胺氰菊酯、噻嗯菊酯、除虫菊酯(除虫菊)、苄螨醚、苯醚菊酯[(1R)-反式异构体]、炔丙菊酯、苄呋菊酯、氟硅菊酯、七氟菊酯、胺菊酯、胺菊酯[(1R)-异构体]、四溴菊酯、四氟苯菊酯、苄氯菊酯、DDT、和甲氧氯。
(4)烟碱型乙酰胆碱受体(nAChR)竞争性调节剂,包括以下活性成分
(4A)啶虫脒、噻虫胺、呋虫胺、吡虫啉、烯啶虫胺、噻虫啉、噻虫嗪
(4B)烟碱,
(4C)氟啶虫胺腈,
(4D)氟吡呋喃酮,和
(4E)三氟苯嘧啶。
(5)烟碱型乙酰胆碱受体(nAChR)变构调节剂-位点I,包括以下活性成分:乙基多杀菌素以及多杀菌素。
(6)谷氨酸门控的氯离子通道(GLUCL)变构调节剂,包括以下活性成分:阿维菌素、埃玛菌素苯甲酸酯、雷皮菌素、和灭螨菌素。
(7)保幼激素模拟物,包括以下活性成分:烯虫乙酯、烯虫炔酯、甲氧普林、苯氧威、和蚊蝇醚。
(8)其他非特异性(多位点)抑制剂,包括以下活性成分:甲基溴、氯化苦、冰晶石、硫酰氟、硼砂、硼酸、八硼酸二钠、硼酸钠、偏硼酸钠、吐酒石、diazomet、和威百亩。
(9)声音反应型器官TRPV通道调节剂,包括以下活性成分:双丙环虫酯、吡蚜酮和氟虫吡喹。
(10)螨类生长抑制剂,包括以下活性成分:四螨嗪、噻螨酮、氟螨嗪、和乙螨唑。
(11)昆虫中肠膜的微生物干扰剂,包括以下活性成分:苏云金芽孢杆菌以色列变种(B.t.var.israelensis)、苏云金杆菌亚莎华变种(B.t.var.aizawai)、苏云金杆菌库斯塔克变种(B.t.var.kurstaki)、苏云金芽孢杆菌拟步行甲变种(B.t.var.tenebrionenis)、以及球形芽孢杆菌。
(12)线粒体ATP合酶的抑制剂,包括以下活性成分:四氯杀螨砜、克螨特、三唑锡、三环锡、苯丁锡、和丁醚脲。
(13)经由破坏质子梯度而产生氧化磷酸化的解偶联剂,包括以下活性成分:溴虫腈、DNOC、和氟虫胺。
(14)烟碱型乙酰胆碱受体(nAChR)通道阻断剂,包括以下活性成分:杀虫磺、巴丹盐酸盐、杀虫环、和杀虫双。
(15)0型壳多糖生物合成抑制剂,包括以下活性成分:双三氟虫脲、定虫隆、除虫脲、氟螨脲、氟虫脲、氟铃脲、虱螨脲、双苯氟脲、多氟脲、氟苯脲、和杀铃脲。
(16)1型壳多糖生物合成抑制剂,包括以下活性成分:噻嗪酮。
(17)双翅目昆虫蜕皮干扰剂,包括以下活性成分:灭蝇胺。
(18)蜕皮激素受体激动剂,包括以下活性成分:环虫酰肼、氯虫酰肼、甲氧虫酰肼、和虫酰肼。
(19)真蛸胺受体激动剂,包括以下活性成分:双甲脒。
(20)线粒体复合体III电子传递抑制剂,包括以下活性成分:氟蚁腙、灭螨醌、联苯肼酯和嘧螨酯。
(21)线粒体复合体I电子传递抑制剂,包括以下活性成分:喹螨醚、唑螨酯、嘧螨醚、哒螨灵、吡螨胺、唑虫酰胺、和鱼藤酮。
(22)电压依赖型钠通道阻断剂,包括以下活性成分:茚虫威和氰氟虫腙。
(23)乙酰CoA羧化酶的抑制剂,包括以下活性成分:螺螨酯、螺甲螨酯、甲氧哌啶乙酯和螺虫乙酯。
(24)线粒体复合体IV电子传递抑制剂,包括以下活性成分:磷化铝、磷化钙、膦、磷化锌、氰化钙、氰化钾和氰化钠。
(25)线粒体复合体II电子传递抑制剂,包括以下活性成分:腈吡螨酯、丁氟螨酯、和吡氟丁酰胺(Pyflubumide)。
(28)利阿诺定受体调节剂,包括以下活性成分:氯虫苯甲酰胺、氰虫酰胺、环溴虫酰胺、氟虫双酰胺、氟氰虫酰胺。
(29)声音反应型器官调节剂-未定义的靶位点,包括以下活性成分:氟啶虫酰胺。
(30)GABA门控的氯离子通道变构调节剂,包括以下活性成分:溴虫氟苯双酰胺(Broflanilide)和氟噁唑酰胺(Fluxametamide)。
(31)杆状病毒,包括以下活性成分:苹果蠹蛾(Cydia pomonella)GV、伪苹果卷叶蛾(Thaumatotibia leucotreta)GV、黎豆夜蛾(Anticarsia gemmatalis)MNPV、和棉铃虫(Helicoverpa armigera)NPV。
(32)烟碱型乙酰胆碱受体(nAChR)变构调节剂-位点II,包括以下活性成分:GS-ω/κHXTX-Hv1a肽。
在此版本的分类方案中未分配组26和27。另外,存在含有作用方式未知或不确定的活性成分的组UN。此组包括以下活性成分:印楝素、苯螨特、溴螨酯、灭螨猛、三氯杀螨醇、石硫合剂、啶虫丙醚、和硫磺。存在含有作用方式未知或不确定的细菌剂(非Bt)的组UNB。此组包括以下活性成分:伯克霍尔德菌属物种、沃巴赫氏菌。存在组UNE,其含有包括合成物、提取物、和未精制的油的植物精华(作用方式未知或不确定)。此组包括以下活性成分:土荆芥近种臭杏提取物、具有甘油或丙二醇印楝油的脂肪酸单酯。存在含有作用方式未知或不确定的真菌剂的组UNF。此组包括以下活性成分:球孢白僵菌菌株、绿僵菌菌株F52、玫烟色拟青霉阿波普卡菌株97。存在含有非特异性机械干扰剂的组UNM。此组包括以下活性成分:硅藻土。
术语“有害生物”意指对人类或人类关注物(诸如农作物、食物、牲畜等)有害的生物体,其中所述生物体来自节肢动物门、软体动物门、或线虫动物门。特别的实例是蚂蚁、蚜虫、臭虫(bed bug)、甲虫、蛀虫、毛毛虫、蟑螂、蟋蟀、蠼螋、跳蚤、苍蝇、草蜢、蛆、大黄蜂、叶蝉科动物(jassids)、叶跳虫(leafhoppers)、虱、蝗虫、蛆虫、粉介壳虫(mealybug)、螨、飞蛾、线虫、盲蝽(plantbug)、飞虱(planthopper)、木虱、叶蜂、介壳虫(scale)、蠹虫、蛞蝓、蜗牛、蜘蛛、跳虫、椿象、综合纲、白蚁、蓟马、扁虱、黄蜂、粉虱和铁线虫。
另外的实例是以下中的有害生物
(1)有螯肢亚门(Chelicerata)、多足亚门(Myriapoda)、和六足亚门(Hexapoda)。
(2)蛛形纲(Arachnida)、综合纲(Symphyla)、和昆虫纲(Insecta)。
(3)虱目(Order Anoplura)。特定属的非详尽列表包括但不限于:血虱属物种(Haematopinus spp.)、甲胁虱属物种(Hoplopleura spp.)、长颚虱属物种(Linognathusspp.)、人虱属物种(Pediculus spp.)、鳞虱属物种(Polyplax spp.)、管虱属物种(Solenopotes spp.)、和新血虱属物种(Neohaematopinis spp.)。特定物种的非详尽列表包括但不限于:驴血虱(Haematopinus asini)、猪血虱(Haematopinus suis)、棘颚虱(Linognathus setosus)、绵羊颚虱(Linognathus ovillus)、人头虱(Pediculus humanuscapitis)、人类体虱(Pediculus humanus humanus)、和耻阴虱(Pthirus pubis)。
(4)鞘翅目(Order Coleoptera)。特定属的非详尽列表包括但不限于:三齿豆象属物种(Acanthoscelides spp.)、叩甲属物种(Agriotes spp.)、花象属物种(Anthonomusspp.)、长喙小象属物种(Apion spp.)、甘蔗金龟属物种(Apogonia spp.)、细角长角象属物种(Araecerus spp.)、守瓜属物种(Aulacophora spp.)、豆象属物种(Bruchus spp.)、天牛属物种(Cerosterna spp.)、豆叶甲属物种(Cerotoma spp.)、龟象属物种(Ceutorhynchusspp.)、凹胫跳甲属物种(Chaetocnema spp.)、叶甲属物种(Colaspis spp.)、Ctenicera属物种、象虫属物种(Curculio spp.)、方头甲属物种(Cyclocephala spp.)、根叶甲属物种(Diabrotica spp.)、竹蠹属物种(Dinoderus spp.)、角谷盗属物种(Gnathocerus spp.)、腹窃蠢属(Hemicoelus)物种、异翅长蠢属(Heterobostruchus)物种、叶象属物种(Hyperaspp.)、齿小蠹属物种(Ips spp.)、粉蠹属物种(Lyctus spp.)、美洲叶甲属物种(Megascelis spp.)、菜花露尾甲属物种(Meligethes spp.)、Mezium属物种、褐蛛甲属物种(Niptus spp.)、耳喙象属物种(Otiorhynchus spp.)、短喙象属物种(Pantomorus spp.)、鳃角金龟属物种(Phyllophaga spp.)、条跳甲属物种(Phyllotreta spp.)、蛛甲属物种(Ptinus spp.)、根鳃金龟属物种(Rhizotrogus spp.)、虎象甲属物种(Rhynchites spp.)、隐颏象属物种(Rhynchophorus spp.)、小蠹属物种(Scolytus spp.)、尖隐喙象属物种(Sphenophorus spp.)、米象属物种(Sitophilus spp.)、拟步行虫属物种(Tenebriospp.)、和拟谷盗属物种(Tribolium spp.)。特定物种的非详尽列表包括但不限于:菜豆象(Acanthoscelides obtectus)、白蜡窄吉丁(Agrilus planipennis)、米扁虫(Ahasverusadvena)、黑菌虫(Alphitobius diaperinus)、光肩星天牛(Anoplophora glabripennis)、棉铃象虫(Anthonomus grandis)、小圆皮蠹(Anthrenus verbasci)、丽黄圆皮蠹(Anthrenus falvipes)、黑绒金龟(Ataenius spretulus)、甜菜隐食甲(Atomarialinearis)、黑皮蠹(Attagenus unicolor)、甜菜象(Bothynoderes punctiventris)、豌豆象(Bruchus pisorum)、四纹豆象(Callosobruchus maculatus)、黄斑露尾甲(Carpophilushemipterus)、甜菜龟甲(Cassida vittata)、方颈扁甲(Cathartus quadricollis)、豆叶甲(Cerotoma trifurcata)、白菜籽龟象(Ceutorhynchus assimilis)、芫菁龟象(Ceutorhynchus napi)、旋梯宽胸金针虫(Conoderus scalaris)、密点宽胸金针虫(Conoderus stigmosus)、李象(Conotrachelus nenuphar)、绿花金龟(Cotinis nitida)、石刁柏负泥虫(Crioceris asparagi)、锈赤扁谷盗
(Cryptolestes ferrugineus)、长角扁谷盗(Cryptolestes pusillus)、土耳其扁谷盗(Cryptolestes turcicus)、密点细枝象(Cylindrocopturus adspersus)、剪叶象甲(Deporaus marginatus)、火腿皮蠹(Dermestes lardarius)、白腹皮蠹(Dermestesmaculatus)、玉米根虫(Diabrotica virgifera virgifera)、墨西哥豆瓢虫(Epilachnavarivestis)、培塔窃蠢(Euvrilletta peltata)、蛀茎象甲(Faustinus cubae)、苍白树皮象(Hylobius pales)、北美家天牛(Hylotrupes bajulus)、紫苜蓿叶象(Hypera postica)、咖啡果小蠹(Hypothenemus hampei)、烟草甲(Lasioderma serricorne)、马铃薯甲虫(Leptinotarsa decemlineata)、灰头叩甲(Limonius canus)、福克金龟(Liogenysfuscus)、苏图金龟(Liogenys suturalis)、稻水象甲(Lissorhoptrus oryzophilus)、暹罗谷盗(Lophocateres pusillus)、南方粉蠹(Lyctus planicollis)、马克拉皮乔利特(Maecolaspis joliveti)、玉米叩甲(Melanotus communis)、油菜花露尾甲(Meligethesaeneus)、大栗鳃金龟(Melolontha melolontha)、赤足椰虫甲(Necrobia rufipes)、短筒天牛(Oberea brevis)、线性筒天牛(Oberea linearis)、椰蛀犀金龟(Oryctes rhinoceros)、大眼锯谷盗(Oryzaephilus mercator)、苏里南锯谷盗(Oryzaephilus surinamensis)、黑角负泥虫(Oulema melanopus)、水稻负泥虫(Oulema oryzae)、六月鳃角金龟(Phyllophagacuyabana)、矮胖木蛀虫(Polycaon stoutti)、日本弧丽金龟(Popillia japonica)、大谷蠹(Prostephanus truncatus)、谷蠹(Rhyzopertha dominica)、条纹根瘤象(Sitonalineatus)、谷象(Sitophilus granarius)、米象(Sitophilus oryzae)、玉米象(Sitophilus zeamais)、药材甲(Stegobium paniceum)、大谷盗(Tenebroidesmauritanicus)、赤拟谷盗(Tribolium castaneum)、杂拟谷盗(Tribolium confusum)、谷斑皮蠹(Trogoderma granarium)、花斑皮蠹(Trogoderma variabile)、红毛窃蠹(Xestobiumrufovillosum)、和玉米距步甲(Zabrus tenebrioides)。
(5)革翅目(Order Dermaptera)。特定物种的非详尽列表包括但不限于:欧洲球螋(Forficula auricularia)。
(6)蜚蠊目(Order Blattaria)。特定物种的非详尽列表包括但不限于:德国小蠊(Blattella germanica)、亚洲蜚蠊(Blattella asahinai)、东方蜚蠊(Blattaorientalis)、樱桃红蜚蠊(Blatta lateralis)、宾夕法尼亚木蠊(Parcoblattapennsylvanica)、美洲大蠊(Periplaneta americana)、澳洲大蠊(Periplanetaaustralasiae)、褐色大蠊(Periplaneta brunnea)、黑胸大蠊(Periplaneta fuliginosa)、蔗蠊(Pycnoscelus surinamensis)、和长须蜚蠊(Supella longipalpa)。
(7)双翅目(Order Diptera)。特定属的非详尽列表包括但不限于:伊蚊属物种(Aedes spp.)、潜蝇属物种(Agromyza spp.)、按实蝇属物种(Anastrepha spp.)、疟蚊属物种(Anopheles spp.)、果实蝇属物种(Bactrocera spp.)、蜡实蝇属物种(Ceratitisspp.)、斑虻属物种(Chrysops spp.)、锥蝇属物种(Cochliomyia spp.)、康瘿蚊属物种(Contarinia spp.)、库蚊属物种(Culex spp.)、库蠓属物种(Culicoides spp.)、叶瘿蚊属物种(Dasineura spp.)、地种蝇属物种(Delia spp.)、果蝇属物种(Drosophila spp.)、厕蝇属物种(Fannia spp.)、种蝇属物种(Hylemya spp.)、斑潜蝇属物种(Liriomyza spp.)、家蝇属物种(Musca spp.)、草种蝇属物种(Phorbia spp.)、粉蝇属物种(Pollenia spp.)、毛蠓属物种(Psychoda spp.)、蚋属物种(Simulium spp.)、虻属物种(Tabanus spp.)和大蚊属物种(Tipula spp.)。特定物种的非详尽列表包括但不限于:紫苜蓿潜蝇(Agromyzafrontella)、加勒比按实蝇(Anastrepha suspensa)、墨西哥按实蝇(Anastrepha ludens)、西印度按实蝇(Anastrepha obliqua)、瓜实蝇(Bactrocera cucurbitae)、东方果实蝇(Bactrocera dorsalis)、入侵实蝇(Bactrocera invadens)、桃实蝇(Bactrocerazonata)、地中海实蝇(Ceratitis capitata)、油菜叶瘿蚊(Dasineura brassicae)、灰地种蝇(Delia platura)、黄腹厕蝇(Fannia canicularis)、灰腹厕蝇(Fannia scalaris)、肠胃蝇(Gasterophilus intestinalis)、Gracillia perseae、东方臂蝇(Haematobiairritans)、纹皮蝇(Hypoderma lineatum)、菜潜蝇(Liriomyza brassicae)、美洲斑潜蝇(Liriomyza sativa)、绵羊虱蝇(Melophagus ovinus)、秋家蝇(Musca autumnalis)、普通家蝇(Musca domestica)、羊狂蝇(Oestrus ovis)、黑麦秆蝇(Oscinella frit)、甜菜泉蝇(Pegomya betae)、酪蝇(Piophila casei)、胡萝卜蝇(Psila rosae)、樱桃绕果实蝇(Rhagoletis cerasi)、苹果果实蝇(Rhagoletis pomonella)、蓝橘绕实蝇(Rhagoletismendax)、麦红吸浆虫(Sitodiplosis mosellana)和厩螫蝇(Stomoxys calcitrans)。
(8)半翅目(Order Hemiptera)。特定属的非详尽列表包括但不限于:球蚜属物种(Adelges spp.)、白轮盾介壳虫属物种(Aulacaspis spp.)、沫蝉属物种(Aphrophoraspp.)、蚜属物种(Aphis spp.)、小粉虱属物种(Bemisia spp.)、蜡介壳虫属物种(Ceroplastes spp.)、雪盾介壳虫属物种(Chionaspis spp.)、褐圆盾介壳虫属物种(Chrysomphalus spp.)、软介壳虫属物种(Coccus spp.)、小绿叶蝉属物种(Empoascaspp.)、美洲蝽属物种(Euschistus spp.)、牡蛎介壳虫属物种(Lepidosaphes spp.)、蝽属物种(Lagynotomus spp.)、草盲蝽属物种(Lygus spp.)、长管蚜属物种(Macrosiphumspp.)、黑尾叶蝉属物种(Nephotettix spp.)、稻绿蝽属物种(Nezara spp.)、褐飞虱属物种(Nilaparvata spp.)、长沫蝉属物种(Philaenus spp.)、植盲蝽属物种(Phytocorisspp.)、璧蝽属物种(Piezodorus spp.)、臀纹粉介壳虫属物种(Planococcus spp.)、粉介壳虫属物种(Pseudococcus spp.)、缢管蚜属物种(Rhopalosiphum spp.)、黑盔介壳虫属物种(Saissetia spp.)、彩斑蚜属物种(Therioaphis spp.)、龟纹蜡介壳虫属物种(Toumeyellaspp.)、桔蚜属物种(Toxoptera spp.)、粉虱属物种(Trialeurodes spp.)、锥蝽属物种(Triatoma spp.)和矢尖介壳虫属物种(Unaspis spp.)。特定属的非详尽列表包括但不限于:喜绿蝽(Acrosternum hilare)、豌豆蚜(Acyrthosiphon pisum)、欧洲甘蓝粉虱(Aleyrodes proletella)、螺旋粉虱(Aleurodicus dispersus)、软毛粉虱(Aleurothrixusfloccosus)、二点小绿叶蝉(Amrasca biguttula biguttula)、红园介壳虫(Aonidiellaaurantii)、豆卫矛蚜(Aphis fabae)、棉蚜(Aphis gossypii)、大豆蚜(Aphisglycines)、苹果蚜(Aphis pomi)、马铃薯长须蚜(Aulacorthum solani)、马铃薯尖翅木虱(Bactericera cockerelli)、黄星菘蝽(Bagrada hilaris)、银叶粉虱(Bemisiaargentifolii)、烟粉虱(Bemisia tabaci)、多毛长蝽(Blissus leucopterus)、槭姬缘蝽(Boisea trivittata)、天门冬小管蚜(Brachycorynella asparagi)、水稻粉红粉介壳虫(Brevennia rehi)、甘蓝蚜(Brevicoryne brassicae)、梨木虱(Cacopsylla pyri)、梨木虱(Cacopsylla pyricola)、马铃薯盲蝽(Calocoris norvegicus)、红蜡介壳虫(Ceroplastesrubens)、热带臭虫(Cimex hemipterus)、温带臭虫(Cimex lectularius)、桔软蜡蚧(Coccus pseudomagnoliarum)、法思图盲蝽(Dagbertus fasciatus)、绿腹椿象(Dichelopsfurcatus)、麦双尾蚜(Diuraphis noxia)、柑橘木虱(Diaphorina citri)、车前圆尾蚜(Dysaphis plantaginea)、美棉红蝽(Dysdercussuturellus)、埃德萨美邦达(Edessameditabunda)、假眼小绿叶蝉(Empoasca vitis)、苹果绵蚜(Eriosoma lanigerum)、葡萄叶星斑叶蝉(Erythroneura elegantula)、莫拉扁盾蝽(Eurygaster maura)、斑点美洲蝽(Euschistus conspersus)、希罗美洲蝽(Euschistus heros)、褐臭蝽(Euschistusservus)、茶翅蝽(Halyomorpha halys)、腰果刺盲蝽(Helopeltis antonii)、桃粉大尾蚜(Hyalopterus pruni)、腰果刺盲蝽(Helopeltis antonii)、茶角盲蝽(Helopeltistheivora)、吹绵介壳虫(Icerya purchasi)、檬果褐叶蝉(Idioscopus nitidulus)、小绿叶蝉(Jacobiasca formosana)、灰飞虱(Laodelphax striatellus)、水土坚蚧(Lecaniumcorni)、大稻缘蝽(Leptocorisa oratorius)、异稻缘蝽(Leptocorisa varicornis)、豆荚草盲蝽(Lygus hesperus)、木槿曼粉介壳虫(Maconellicoccus hirsutus)、大戟长管蚜(Macrosiphum euphorbiae)、麦长管蚜(Macrosiphum granarium)、蔷薇长管蚜(Macrosiphum rosae)、二叉叶蝉(Macrosteles quadrilineatus)、覆盆子沫蝉(Mahanarvafrimbiolata)、筛豆龟蝽(Megacopta cribraria)、麦无网长管蚜(Metopolophiumdirhodum)、长角缘蝽(Mictis longicornis)、桃蚜(Myzus persicae)、莴苣蚜(Nasonoviaribisnigri)、黑尾叶蝉(Nephotettix cincticeps)、长盲蝽(Neurocolpuslongirostris)、稻绿蝽(Nezara viridula)、褐稻虱(Nilaparvata lugens)、木瓜粉蚧(Paracoccus marginatus)、马铃薯木虱(Paratrioza cockerelli)、糠片盾介壳虫(Parlatoria pergandii)、黑片盾介壳虫(Parlatoria ziziphi)、玉米蜡蝉(Peregrinusmaidis)、根瘤蚜(Phylloxera vitifoliae)、去杉球介壳虫(Physokermes piceae)、加洲植盲蝽(Phytocoris californicus)、亲缘植盲蝽(Phytocoris relativus)、吉尔德璧蝽(Piezodorus guildinii)、橘臀纹粉蚧(Planococcus citri)、无花果臀纹粉蚧(Planococcus ficus)、四线盲蝽(Poecilocapsus lineatus)、越橘盲蝽(Psallusvaccinicola)、鳄梨网蝽(Pseudacysta perseae)、菠萝粉介壳虫(Pseudococcusbrevipes)、梨圆盾介壳虫(Quadraspidiotus perniciosus)、玉米蚜(Rhopalosiphummaidis)、禾谷缢管蚜(Rhopalosiphum padi)、橄榄黑盔介壳虫(Saissetia oleae)、栗盾蝽(Scaptocoriscastanea)、麦二叉蚜(Schizaphis graminum)、麦长管蚜(Sitobionavenae)、白背飞虱(Sogatella furcifera)、温室白粉虱(Trialeurodes vaporariorum)、青麻白粉虱(Trialeurodes abutiloneus)、矢尖介壳虫(Unaspis yanonensis)和恩特那叶蝉(Zulia entrerriana)。
(9)膜翅目(Order Hymenoptera)。特定属的非详尽列表包括但不限于:顶切叶蚁属物种(Acromyrmex spp.)、美洲切叶蚁属物种(Atta spp.)、弓背蚁属物种(Camponotusspp.)、松叶蜂属物种(Diprion spp.)、长黄胡蜂属物种(Dolichovespula spp.)、蚁属物种(Formica spp.)、小家蚁属物种(Monomorium spp.)、新松叶蜂属物种(Neodiprion spp.)、立毛蚁属物种(Paratrechina spp.)、大头蚁属物种(Pheidole spp.)、收获蚁属物种(Pogonomyrmex spp.)、马蜂属物种(Polistes spp.)、火蚁属物种(Solenopsis spp.)、狡臭蚁属物种(Technomyrmex spp.)、铺道蚁属物种(Tetramorium spp.)、黄胡蜂属物种(Vespula spp.)、胡蜂属物种(Vespa spp.)和木蜂属物种(Xylocopa spp.)。特定物种的非详尽列表包括但不限于:中国新疆菜叶蜂(Athalia rosae)、德州切叶蚁(Atta texana)、梨樱叶蜂(Caliroa cerasi)、美洲榆叶蜂(Cimbex americana)、阿根廷虹臭蚁(Iridomyrmexhumilis)、阿根廷蚁(Linepithema humile)、东非蜜蜂(Mellifera Scutellata)、小黑蚁(Monomorium minimum)、小黄家蚁(Monomorium pharaonis)、欧洲新松叶蜂(Neodiprionsertifer)、红火蚁(Solenopsis invicta)、热带火蚁(Solenopsis geminata)、贼蚁(Solenopsis molesta)、黑火蚁(Solenopsis richtery)、南方火蚁(Solenopsis xyloni)、酸臭蚁(Tapinoma sessile)和小火蚁(Wasmannia auropunctata)。
(10)等翅目(Order Isoptera)。特定属的非详尽列表包括但不限于:乳白蚁属物种(Coptotermes spp.)、角象白蚁属物种(Cornitermes spp.)、堆砂白蚁属物种(Cryptotermes spp.)、异白蚁属物种(Heterotermes spp.)、木白蚁属物种(Kalotermesspp.)、楹白蚁属物种(Incisitermes spp.)、大白蚁属物种(Macrotermes spp.)、缘木白蚁属物种(Marginitermes spp.)、锯白蚁属物种(Microcerotermes spp.)、原角白蚁属物种(Procornitermes spp.)、散白蚁属物种(Reticulitermes spp.)、长鼻白蚁属物种(Schedorhinotermes spp.)和古白蚁属物种(Zootermopsis spp.)。特定物种的非详尽列表包括但不限于:大家白蚁(Coptotermes curvignathus)、大唇乳白蚁(Coptotermesfrenchi)、中国台湾乳白蚁(Coptotermes formosanus)、格斯特家白蚁(Coptotermesgestroi)、麻头堆砂白蚁(Cryptotermes brevis)、金色异白蚁(Heterotermes aureus)、甘蔗白蚁(Heterotermes tenuis)、小楹白蚁(Incisitermes minor)、斯氏楹白蚁(Incisitermes snyderi)、甘蔗白蚁(Microtermes obesi)、具角象白蚁(Nasutitermescorniger)、黑翅土白蚁(Odontotermes formosanus)、根土白蚁(Odontotermes obesus)、班努斯散白蚁(Reticulitermes banyulensis)、格拉塞散白蚁(Reticulitermesgrassei)、黄胸散白蚁(Reticulitermes flavipes)、哈根散白蚁(Reticulitermeshageni)、西方散白蚁(Reticulitermes hesperus)、桑特散白蚁(Reticulitermessantonensis)、栖北散白蚁(Reticulitermes speratus)、黑胫散白蚁(Reticulitermestibialis)和南方散白蚁(Reticulitermes virginicus)。
(11)鳞翅目(Order Lepidoptera)。特定属的非详尽列表包括但不限于:卷叶蛾属物种(Adoxophyes spp.)、地老虎属物种(Agrotis spp.)、带卷蛾属物种(Argyrotaeniaspp.)、卷叶蛾属物种(Cacoecia spp.)、丽细蛾属物种(Caloptilia spp.)、水稻螟虫属物种(Chilo spp.)、锞纹夜蛾属物种(Chrysodeixis spp.)、豆粉蝶属物种(Colias spp.)、草螟属物种(Crambus spp.)、绢野螟属物种(Diaphania spp.)、螟属物种(Diatraea spp.)、钻夜蛾属物种(Earias spp.)、粉斑螟属物种(Ephestia spp.)、尺蠖蛾属物种(Epimecisspp.)、脏切夜蛾属物种(Feltia spp.)、角剑夜蛾属物种(Gortyna spp.)、铃夜蛾属物种(Helicoverpa spp.)、实夜蛾属物种(Heliothis spp.)、根蠹属物种(Indarbela spp.)、潜夜细蛾属物种(Lithocolletis spp.)、切根虫属物种(Loxagrotis spp.)、天幕毛虫属物种(Malacosoma spp.)、谷蛾属物种(Nemapogon spp.)、疆夜蛾属物种(Peridroma spp.)、小潜细蛾属物种(Phyllonorycter spp.)、粘虫属物种(Pseudaletia spp.)、菜蛾属物种(Plutella spp.)、蛀茎夜蛾属物种(Sesamia spp.)、夜盗蛾属物种(Spoaoptera spp.)、透翅蛾属物种(Synanthedon spp.)和巢蛾属物种(Yponomeuta spp.)。特定物种的非详尽列表包括但不限于:飞扬阿夜蛾(Achaea janata)、棉褐带卷蛾(Adoxophyesorana)、小地老虎(Agrotis ipsilon)、棉叶波纹叶蛾(Alabama argillacea)、鳄梨楔卷蛾(Amorbiacuneana)、脐橙螟蛾(Amyelois transitella)、棕斑灰蛾(Anacamptodesdefectaria)、桃条麦蛾(Anarsia lineatella)、黄麻桥夜蛾(Anomis sabulifera)、黎豆夜蛾(Anticarsiagemmatalis)、果树黄卷蛾(Archips argyrospila)、玫瑰黄卷蛾(Archips rosana)、桔带卷蛾(Argyrotaenia citrana)、伽马纹夜蛾(Autographa gamma)、苹果小卷叶蛾(Bonagotacranaodes)、禾弄蝶(Borbo cinnara)、棉潜蛾(Bucculatrix thurberiella)、烟卷蛾(Capua reticulana)、桃小食心虫(Carposina niponensis)、横线尾夜蛾(Chlumetiatransversa)、蔷薇斜条卷叶蛾(Choristoneura rosaceana)、稻纵卷叶螟(Cnaphalocrocismedinalis)、可可细蛾(Conopomorpha cramerella)、米蛾(Corcyracephalonica)、芳香木蠹蛾(Cossus cossus)、胡桃小卷蛾(Cydia caryana)、李小食心虫(Cydia funebrana)、梨小食心虫(Cydia molesta)、豌豆小卷蛾(Cydia nigricana)、苹果蠹蛾(Cydiapomonella)、荨麻毛虫(Darna diducta)、黄瓜绢野螟(Diaphanianitidalis)、小蔗杆草螟(Diatraea saccharalis)、西南玉米螟(Diatraea grandiosella)、埃和钻夜蛾(Eariasinsulana)、翠纹钻夜蛾(Earias vittella)、橙色小卷蛾(Ecdytolopha aurantianum)、南美玉米苗斑螟(Elasmopalpus lignosellus)、粉斑螟(Ephestia cautella)、烟草粉斑螟(Ephestia elutella)、地中海斑螟(Ephestia kuehniella)、菜豆小卷蛾(Epinotiaaporema)、苹淡褐卷蛾(Epiphyas postvittana)、香蕉弄蝶(Erionota thrax)、盐泽灯蛾(Estigmene acrea)、葡萄螟蛾(Eupoecilia ambiguella)、原切根虫(Euxoa auxiliaris)、大蜡螟(Galleria mellonella)、东方果实蛾(Grapholita molesta)、三纹螟蛾(Hedyleptaindicata)、棉铃虫(Helicoverpa armigera)、谷实夜蛾(Helicoverpa zea)、美洲烟叶蛾(Heliothis virescens)、菜螟(Hellula undalis)、番茄蠹蛾(Keiferialycopersicella)、茄黄斑螟(Leucinodes orbonalis)、咖啡点潜蛾(Leucopteracoffeella)、旋纹潜蛾(Leucopteramalifoliella)、葡萄浆果小卷蛾(Lobesia botrana)、豆白隆切根虫(Loxagrotisalbicosta)、舞毒蛾(Lymantria dispar)、窄翅潜叶蛾(Lyonetia clerkella)、油棕榈结草虫(Mahasena corbetti)、甘蓝夜蛾(Mamestrabrassicae)、烟草天蛾(Manduca sexta)、豆荚野螟(Maruca testulalis)、袋蛾(Metisaplana)、秘夜蛾粘虫(Mythimna unipuncta)、番茄草螟蛾(Neoleucinodes elegantalis)、稻三点螟(Nymphula depunctalis)、冬尺蠖蛾(Operophtera brumata)、欧洲玉米螟(Ostrinia nubilalis)、Oxydia vesulia、葡萄褐卷蛾(Pandemis cerasana)、苹褐卷蛾(Pandemis heparana)、非洲达摩凤蝶(Papilio demodocus)、红铃虫(Pectinophoragossypiella)、豆杂角夜蛾(Peridroma saucia)、咖啡潜叶蛾(Perileucopteracoffeella)、马铃薯块茎蛾(Phthorimaea operculella)、柑橘潜叶蛾(Phyllocnistiscitrella)、斑幕潜叶蛾(Phyllonorycter blancardella)、菜粉蝶(Pieris rapae)、苜蓿绿夜蛾(Plathypena scabra)、苹果芽小卷蛾(Platynota idaeusalis)、印度谷螟(Plodiainterpunctella)、小菜蛾(Plutella xylostella)、浆果小卷蛾(Polychrosis viteana)、桔果巢蛾(Prays endocarpa)、油橄榄巢蛾(Prays oleae)、一星粘虫(Pseudaletiaunipuncta)、大豆尺夜蛾(Pseudoplusia includens)、薄荷灰夜蛾(Rachiplusia nu)、三化螟(Scirpophaga incertulas)、大螟(Sesamia inferens)、茎螟(Sesamia nonagrioides)、荨麻毛虫(Setora nitens)、麦蛾(Sitotroga cerealella)、葡萄长须卷叶蛾(Sparganothis pilleriana)、甜菜夜蛾(Spodoptera exigua)、草地贪夜蛾(Spodopterafrugiperda)、亚热带粘虫(Spodoptera eridania)、菠萝钻心虫(Thecla basilides)、袋谷蛾(Tinea pellionella)、衣蛾(Tineola bisselliella)、粉纹夜蛾(Trichoplusia ni)、番茄斑潜蝇(Tuta absoluta)、咖啡木蠹蛾(Zeuzera coffeae)和梨豹蠹蛾(Zeuzea pyrina)。
(12)食毛目(Order Mallophaga)。特定属的非详尽列表包括但不限于:细鹅虱属物种(Anaticola spp.)、牛毛虱属物种(Bovicola spp.)、大火鸡虱属物种(Chelopistesspp.)、鸡角羽虱属物种(Goniodes spp.)、鸡虱属物种(Menacanthus spp.)和犬毛虱属物种(Trichodectes spp.)。特定物种的非详尽列表包括但不限于:牛羽虱(Bovicolabovis)、山羊住牛虱(Bovicola caprae)、绵羊虱(Bovicola ovis)、大火鸡虱(Chelopistesmeleagridis)、鸡角羽虱(Goniodes dissimilis)、大角羽虱(Goniodes gigas)、雏鸡羽虱(Menacanthus stramineus)、鸡羽虱(Menopon gallinea)和犬啮毛虱(Trichodectescanis)。
(13)直翅目(Order Orthoptera)。特定属的非详尽列表包括但不限于:黑蝗属物种(Melanoplus spp.)和树螽属物种(Pterophylla spp.)。特定物种的非详尽列表包括但不限于:家蟋蟀(Acheta domesticus)、摩门虫斯(Anabrus simplex)、非洲蝼蛄(Gryllotalpa africana)、南方蝼蛄(Gryllotalpa australis)、黑短蝼蛄(Gryllotalpabrachyptera)、欧洲痣蟋蟀(Gryllotalpa hexadactyla)、东亚飞蝗(Locustamigratoria)、角翅虫斯(Microcentrum retinerve)、沙漠蝗(Schistocerca gregaria)和叉尾灌丛树虫(Scudderia furcata)。
(14)啮虫目(Order Psocoptera)。特定物种的非详尽列表包括但不限于:无色书虱(Liposcelis decolor)、嗜虫书虱(Liposcelis entomophila)、Lachesill aquercus和Trogium pulsatorium。
(15)蚤目(Order Siphonaptera)。特定物种的非详尽列表包括但不限于:鸡角叶蚤(Ceratophyllus gallinae)、黑角叶蚤(Ceratophyllus niger)、犬栉头蚤(Ctenocephalides canis)、猫栉头蚤(Ctenocephalides felis)和人蚤(Pulexirritans)。
(16)缨翅目(Order Thysanoptera)。特定属的非详尽列表包括但不限于:巢针蓟马属物种(Caliothrips spp.)、花蓟马属物种(Frankliniella spp.)、硬蓟马属物种(Scirtothrips spp.)和蓟马属物种(Thrips spp.)。特定物种的非详尽列表包括但不限于:双刺花蓟马(Frankliniella bispinosa)、烟草褐蓟马(Frankliniella fusca)、苜蓿蓟马(Frankliniella occidentalis)、梳缺花蓟马(Frankliniella schultzei)、东方花蓟马(Frankliniella tritici)、玉米蓟马(Frankliniella williamsi)、温室蓟马(Heliothrips haemorrhoidalis)、腹钩蓟马(Rhipiphorothrips cruentatus)、柑桔硬蓟马(Scirtothrips citri)、茶黄蓟马(Scirtothrips dorsalis)、锤角带蓟马(Taeniothrips rhopalantennalis)、黄胸蓟马(Thrips hawaiiensis)、豆黄蓟马(Thripsnigropilosus)、东方蓟马(Thrips orientalis)、南黄蓟马(Thrips palmi)和烟蓟马(Thrips tabaci)。
(17)缨尾目(Order Thysanura)。特定属的非详尽列表包括但不限于:衣鱼属物种(Lepisma spp.)和灶衣鱼属物种(Thermobia spp.)。
(18)蜱螨目(Order Acarina)。特定属的非详尽列表包括但不限于:刺皮节蜱属物种(Aculops spp.)、锐缘蜱属物种(Argus spp.)、牛壁虱属物种(Boophilus spp.)、蠕形螨属物种(Demodex spp.)、革蜱属物种(Dermacentor spp.)、上瘿螨属物种(Epitimerusspp.)、节蜱属物种(Eriophyes spp.)、硬蜱属物种(Ixodes spp.)、赤叶螨属物种(Oligonychus spp.)、全爪螨属物种(Panonychus spp.)、扇头蜱属物种(Rhizoglyphusspp.)和叶螨属物种(Tetranychus spp.)。特定物种的非详尽列表包括但不限于:气管螨(Acarapis woodi)、粗脚粉螨(Acarus siro)、芒果瘿螨(Aceria mangiferae)、番茄刺皮瘿螨(Aculops lycopersici)、柑橘刺瘿螨(Aculus pelekassi)、苹刺瘿螨(Aculusschlechtendali)、美洲花蜱(Amblyomma americanum)、卵形短须螨(Brevipalpusobovatus)、紫红短须螨(Brevipalpus phoenicis)、变异矩头蜱(Dermacentorvariabilis)、屋尘螨(Dermatophagoides pteronyssinus)、鹅耳枥始叶螨(Eotetranychuscarpini)、吸血异脂刺螨(Liponyssoides sanguineus)、猫背肛螨(Notoedres cati)、咖啡小爪螨(Oligonychus coffeae)、冬青小爪螨(Oligonychus ilicis)、柏氏禽刺螨(Ornithonyssus bacoti)、橘全爪螨(Panonychus citri)、苹果红蜘蛛(Panonychusulmi)、柑橘锈螨(Phyllocoptruta oleivora)、多食跗线螨(Polyphagotarsonemuslatus)、血红扇头蜱(Rhipicephalus sanguineus)、疥螨(Sarcoptes scabiei)、鳄梨顶冠节蜱(Tegolophus perseaflorae)、棉叶螨(Tetranychus urticae)、长食酪螨(Tyrophaguslongior)和狄氏瓦螨(Varroa destructor)。
(19)蜘蛛目(Order Araneae)。特定属的非详尽列表包括但不限于:平甲蛛属物种(Loxosceles spp.)、寇蛛属物种(Latrodectus spp.)和澳毒蜘蛛属物种(Atrax spp.)。特定物种的非详尽列表包括但不限于:裼皮斜蛛(Loxosceles reclusa)、红斑寇蛛(Latrodectus mactans)和悉尼漏斗网蜘蛛(Atrax robustus)。
(20)综合纲(Class Symphyla)。特定物种的非详尽列表包括但不限于:白松虫(Scutigerella immaculata)。
(21)弹尾亚纲(Subclass Collembola)。特定物种的非详尽列表包括但不限于:庭园圆跳虫(Bourletiella hortensis)、武装棘跳虫(Onychiurus armatus)、嗜粪棘跳虫(Onychiurus fimetarius)和绿圆跳虫(Sminthurus viridis)。
(22)线虫动物门(Phylum Nematoda)。特定属的非详尽列表包括但不限于:刺线虫属物种(Belonolaimus spp.)、小环线虫属物种(Criconemella spp.)、茎线虫属物种(Ditylenchus spp.)、球胞囊线虫属物种(Globodera spp.)、孢囊线虫属物种(Heteroderaspp.)、潜根线虫属物种(Hirschmanniella spp.)、纽带线虫属物种(Hoplolaimus spp.)、根瘤线虫属物种(Meloidogyne spp.)、根腐线虫属物种(Pratylenchus spp.)和内侵线虫属物种(Radopholus spp.)。特定物种的非详尽列表包括但不限于:犬恶丝虫(Dirofilariaimmitis)、马铃薯白线虫(Globodera pallida)、大豆胞囊线虫(Heterodera glycines)、玉米胞囊线虫(Heterodera zeae)、南方根结线虫(Meloidogyne incognita)、爪哇根结线虫(Meloidogyne javanica)、盘尾丝虫(Onchocerca volvulus)、穿刺短体线虫(Pratylenchus penetrans)、香蕉穿孔线虫(Radopholus similis)和肾形线虫(Rotylenchulus reniformis)。
(23)软体动物门(Phylum Mollusca)。特定物种的非详尽列表包括但不限于:散布大蜗牛(Cornu aspersum)、网纹野蛞蝓(Deroceras reticulatum)、黄蛞蝓(Limaxflavus)、温室蛞蝓(Milax gagates)和福寿螺(Pomacea canaliculata)。
特别优选的要防治的有害生物组是取食汁液的有害生物。取食汁液的有害生物通常具有刺穿和/或吸吮式口器并且以植物的汁液和内部植物组织为食。农业上特别关注的取食汁液的有害生物的实例包括但不限于蚜虫、叶跳虫、介壳虫、蓟马、木虱、飞虱、粉介壳虫、椿象、和粉虱。具有农业上关注的取食汁液的有害生物的目的具体实例包括但不限于虱目和半翅目。农业上关注的半翅目的具体实例包括但不限于白轮盾蚧属物种、沫蝉属物种、蚜属物种、小粉虱属物种、软蜡蚧属物种、美洲蝽属物种、草盲蝽属物种、长管蚜属物种、稻绿蝽属物种、缢管蚜属物种、白背飞虱属物种(Sogatella spp.)、褐飞虱属物种、和黑尾叶蝉属物种。
另一个特别优选的要防治的有害生物组是咀嚼有害生物。咀嚼有害生物通常具有允许其咀嚼包括根、茎、叶、芽、和生殖组织(包括但不限于花、果实、和种子)的植物组织的口器。农业上特别关注的咀嚼有害生物的实例包括但不限于毛毛虫、甲虫、草蜢、和蝗虫。具有农业上关注的咀嚼有害生物的目的具体实例包括但不限于:鞘翅目、鳞翅目、和直翅目。农业上关注的鞘翅目的具体实例包括但不限于花象属物种、豆叶甲属物种、凹胫跳甲属物种、叶甲属物种、方头甲属物种、根叶甲属物种、叶象属物种、鳃角金龟属物种、条跳甲属物种、尖隐喙象属物种、米象属物种。
短语“杀有害生物有效量”意指对有害生物实现可观测的作用所需的杀有害生物剂的量,所述作用例如坏死、死亡、阻滞、预防、消除、摧毁、或在其他方面减少有害生物在场所作用中的出现和/或活动的。当有害生物群体从场所被驱逐、有害生物在场所中或周围丧失能力、和/或有害生物在场所中或周围被根除时,这种作用可以出现。当然,可出现这些作用的组合。通常,有害生物群体、活动、或两者希想地减少超过五十百分比、优选地超过90百分比、并且最优选地超过99百分比。通常,出于农业目的的杀有害生物有效量为约0.0001克/公顷至约5000克/公顷、优选约0.0001克/公顷至约500克/公顷、并且其甚至更优选为约0.0001克/公顷至约50克/公顷。可替代地,针对有害生物可以使用约150克/公顷至约250克/公顷。
具体实施方式
本文档公开了分子N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲基磺酰基)丙酰胺:
式一,也称为F1
式一可以以不同的几何或光学异构体或不同的互变异构形式存在。可以存在一个或多个手性中心,在这种情况下,式一可以以纯对映异构体、对映异构体混合物、纯非对映异构体或非对映异构体混合物的形式存在。本领域技术人员将理解,一种立体异构体可以比其他立体异构体更具活性。单独的立体异构体可以通过已知的选择性合成程序、通过使用拆分的起始材料的常规合成程序、或通过常规拆分程序获得。可以存在互变异构中心。本公开涵盖所有此类异构体、互变异构体、和其呈所有比例的混合物。为清楚起见,本公开中公开的结构可以仅以一种几何形式绘制,但旨在表示所述分子的所有几何形式。
式一(F1)的合成
在不进一步纯化的情况下,使用从商业来源获得的起始材料、试剂、和溶剂。无水溶剂作为Sure/SealTM购买自奥德里奇公司(Aldrich)并且按所收到的原样使用。在ThomasHoover Unimelt毛细管熔点装置或来自斯坦福研究系统(Stanford Research Systems)的OptiMelt自动熔点系统上获得熔点,并且不经校正。使用“室温”的实例是在气候控制实验室中进行的,温度范围是约20℃至约24℃。分子被给予它们已知的名称,根据ISIS Draw、ChemDraw、或ACD Name Pro中的命名程序命名。如果此类程序不能命名分子,则使用常规命名规则命名此类分子。1H NMR光谱数据按ppm(δ)计并且在300、400、500、或600MHz记录;13CNMR光谱数据按ppm(δ)计并且在75、100或150MHz记录;并且19F NMR光谱数据按ppm(δ)计并且在376MHz记录,除非另行说明。
本领域技术人员应认识到,可以通过以与所描述的顺序不同的顺序执行合成路线的一些步骤来实现所希望的分子的合成。本领域技术人员还将认识到,可以在所需分子上进行标准的官能团互换或取代反应以引入或修饰取代基。
实例1:3-氯-1-(吡啶-3-基)-1H-吡唑-4-胺(C5)的制备
步骤1-3-氯-1H-吡唑-4-胺盐酸盐(C2)的制备:在2升(L)三颈圆底烧瓶上固定顶置式搅拌器、温度探针、加料漏斗和氮气入口。向此三颈烧瓶中添加乙醇(600毫升(mL))和4-硝基-1H-吡唑(C1;50.6克(g),447毫摩尔(mmol))。向此溶液中一次性添加浓盐酸(HCl;368mL)(注:15℃至39℃快速放热),并且将所得混合物用氮气(N2)吹扫5分钟(min)。添加在氧化铝上的钯(5%w/w)(2.6g),并且将混合物在室温下搅拌,同时在4小时(h)内逐滴添加三乙基硅烷(208g,1789mmol)。将在2h内从35℃开始缓慢自热至55℃的反应混合物搅拌总共16h。通过塞将混合物真空过滤,并且收集两相混合物。将所述两相混合物转移至分液漏斗中,并且收集底部水层,并且借助乙腈(3×350mL)旋转蒸发(60℃,50mmHg)至干燥。将所得黄色固体悬浮在乙腈(150mL)中,并且允许在室温下静置2h,然后在冰箱中于0℃下静置1h。将固体过滤并且用乙腈(100mL)洗涤以得到呈白色固体的标题化合物(84g,97%产率,80%纯度):mp 190℃-193℃;1H NMR(400MHz,DMSO-d6)δ10.46-10.24(br s,2H),8.03(s,0.54H),7.75(s,0.46H),5.95(br s,1H);13C-NMR(101MHz,DMSO-d6)δ128.24,125.97,116.71。
步骤2-(3-氯-1H-吡唑-4-基)氨基甲酸叔丁酯(C3)的制备:向2L圆底烧瓶中添加3-氯-1H-吡唑-4-胺盐酸盐(C2;100g,649mmol)和四氢呋喃(THF;500mL)。向此混合物中依序添加二碳酸二叔丁酯(156g,714mmol)、碳酸氢钠(120g,1429mmol)和水(50.0mL)。将混合物搅拌16h,用水(500mL)和乙酸乙酯(EtOAc;500mL)稀释,并且转移至分液漏斗中。这给出三个层:a)底层-白色凝胶状沉淀物;b)中层-浅黄色水性液体;和c)顶层-赤褐色有机液体。分离各相,将底层和中层(即,水相)一起收集。将水相用EtOAc(2×200mL)萃取,并且将有机萃取物合并,用盐水(200mL)洗涤,经无水硫酸钠干燥,过滤并且通过旋转蒸发浓缩以给出浓稠的赤褐色油状物(160g)。将所述浓稠的油状物悬浮在己烷(1000mL)中,并且在55℃下搅拌2h。这给出浅棕色悬浮液。将混合物冷却至0℃,并且通过真空过滤收集固体,并且用己烷(2×10mL)冲洗。将样品进行空气干燥至恒定质量以得到呈浅棕色固体的标题化合物(103g,72%产率,80%纯度):mp 137℃-138℃;1H NMR(400MHz,CDCl3)δ10.69(s,1H),7.91(s,1H),1.52(s,9H)。
步骤3-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)氨基甲酸叔丁酯(C4)的制备:为干燥的2L三颈圆底烧瓶配备机械搅拌器、氮气入口、温度计和回流冷凝器。向此烧瓶中添加3-碘吡啶(113g,551mmol)、(3-氯-1H-吡唑-4-基)氨基甲酸叔丁酯(C3;100g,459mmol)、粉末状磷酸钾(195g,919mmol)和氯化铜(3.09g,23mmol)。依序添加乙腈(1L)和N1,N2-二甲基乙烷-1,2-二胺(101g,1149mmol),并且将混合物加热至81℃持续4h。将混合物冷却至室温,并且通过床过滤。将滤液转移至配备有机械搅拌器的4L锥形烧瓶中,并且用水稀释直至总体积为约4L。将混合物在室温下搅拌30min,并且通过真空过滤收集所得固体。将固体用水洗涤并且在40℃下在真空中烘箱干燥若干天至恒定重量以给出呈棕褐色固体的标题化合物(117.8g,87%产率,80%纯度):mp 140℃-143℃;1H NMR(400MHz,CDCl3)δ8.96(s,1H),8.53(dd,J=4.7,1.2Hz,1H),8.36(s,1H),7.98(ddd,J=8.3,2.7,1.4Hz,1H),7.38(dd,J=8.3,4.8Hz,1H),6.37(s,1H),1.54(s,9H);ESIMS m/z338([M-t-Bu]+),220([M-O-t-Bu]-)。
步骤4-3-氯-1-(吡啶-3-基)-1H-吡唑-4-胺(C5)的制备:将三氟乙酸(TFA;6.79mL)添加到在二氯甲烷(DCM;6.79mL)中的(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)氨基甲酸叔丁酯(C4;2g,6.79mmol)中,并且将混合物在室温下搅拌2h。添加甲苯(12mL),并且将反应混合物在真空中浓缩至接近干燥。将浓缩的反应混合物倒入含有饱和碳酸氢钠水溶液的分液漏斗中,并且用DCM(3×10mL)萃取。将合并的有机层浓缩以给出呈白色固体的标题化合物(0.954g,72%):mp 137.9℃-139.9℃;1H NMR(400MHz,CDCl3)δ8.84(d,J=2.4Hz,1H),8.50(dd,J=4.7,1.4Hz,1H),7.95(ddd,J=8.3,2.7,1.5Hz,1H),7.52(s,1H),7.37(ddd,J=8.4,4.7,0.7Hz,1H),3.18(s,2H);ESIMS m/z 196([M+H]+)。
实例2:N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲基磺酰基)丙酰胺(式一)的制备
步骤1-N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲硫基)丙酰胺(C7)的制备:向3-氯-1-(吡啶-3-基)-1H-吡唑-4-胺(C5;0.1g,0.514mmol)和2-(甲硫基)丙酸(C6;0.185g,1.541mmol)在DCM(1.713mL)中的悬浮液中依序添加N,N-二甲基吡啶-4-胺(0.220g,1.798mmol)和N1-((乙基亚氨基)亚甲基)-N3,N3-二甲基丙烷-1,3-二胺盐酸盐(0.305g,1.593mmol)。将反应混合物在环境温度下搅拌18h并且浓缩。通过硅胶色谱法(0-100%EtOAc/己烷)纯化给出呈白色固体的标题化合物(116mg,72%):mp 129℃-132℃;1HNMR(400MHz,CDCl3)δ8.98(d,J=2.4Hz,1H),8.63(s,1H),8.58-8.53(m,1H),8.03-7.96(m,1H),7.43-7.37(m,1H),3.59-3.48(m,1H),2.18(s,3H),1.59(d,J=7.3Hz,3H);ESIMS m/z297([M+1]+)。
步骤2-N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲基磺酰基)丙酰胺(式一)的制备:向100mL圆底烧瓶中添加N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲硫基)丙酰胺(C7;882mg,2.97mmol)、乙酸(6.0mL)和过硼酸钠四水合物(915mg,5.94mmol)。将反应混合物在惰性气氛下在温热至50℃的加热块中搅拌过夜。然后将反应混合物倒入盐水溶液中,并且用DCM(3x20mL)萃取。将合并的有机提取物经硫酸镁干燥,过滤,并且浓缩。通过硅胶色谱法(在DCM中的0-10%甲醇)纯化所得残余物,给出呈白色泡沫的标题化合物(734mg,74%):1H NMR(400MHz,DMSO-d6)δ10.41(s,1H),9.07(d,J=2.7Hz,1H),8.94(s,1H),8.55(dd,J=4.7,1.4Hz,1H),8.23(ddd,J=8.4,2.8,1.4Hz,1H),7.55(ddd,J=8.4,4.8,0.7Hz,1H),4.41(q,J=7.0Hz,1H),3.07(s,3H),1.57(d,J=7.1Hz,3H);ESIMS m/z 329([M+H]+);IR(薄膜)1680cm-1。
对比分子的合成
实例3:3-氯-N-甲基-1-(吡啶-3-基)-1H-吡唑-4-胺(C9)的制备
步骤1-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)(甲基)氨基甲酸叔丁酯(C8)的制备:向在0℃下的3-氯-1-(吡啶-3-基)-1H-吡唑-4-基氨基甲酸叔丁酯(C4;1.0g,3.39mmol)在N,N-二甲基甲酰胺(16.96mL)中的溶液中添加氢化钠(0.163g,4.07mmol)。30min后,将烧瓶温热至环境温度,并且将反应混合物再搅拌30min。将碘甲烷(0.232mL,3.73mmol)添加到烧瓶中,并且将反应混合物在环境温度下搅拌2h。通过添加饱和氯化铵将反应淬灭。将反应混合物用叔丁基甲基醚萃取两次。将有机层经硫酸钠干燥,过滤并且浓缩。通过硅胶柱色谱法(0-100%EtOAc/己烷)纯化,给出呈黄色油状物的标题化合物(983mg,94%):1H NMR(400MHz,CDCl3)δ8.91(d,J=2.5Hz,1H),8.64-8.48(m,1H),8.01(d,J=7.5Hz,1H),7.90(s,1H),7.41(dd,J=8.3,4.8Hz,1H),3.23(s,3H),1.58-1.25(m,9H);ESIMS m/z 309([M+H]+);IR(薄膜)1693cm-1。
步骤2-3-氯-N-甲基-1-(吡啶-3-基)-1H-吡唑-4-胺(C9)的制备:向在DCM(5.4mL)中的3-氯-1-(吡啶-3-基)-1H-吡唑-4-基(甲基)氨基甲酸叔丁酯(C8;1.65g,5.34mmol)中添加三氟乙酸(TFA;5.4mL),并且将溶液在室温下搅拌1h。添加甲苯,并且将反应混合物在真空中浓缩至接近干燥。将浓缩的反应混合物倒入含有饱和碳酸氢钠的分液漏斗中,并且将混合物用EtOAc(3×20mL)萃取。将萃取物合并,经硫酸镁干燥,过滤,并且浓缩至干燥。分离出呈淡黄色固体的标题化合物(0.92g,83%):mp 108℃-118℃;1H NMR(400MHz,CDCl3)δ8.88(d,J=2.4Hz,1H),8.48(dd,J=4.7,1.4Hz,1H),7.96(ddd,J=8.3,2.7,1.4Hz,1H),7.41-7.29(m,2H),2.87(s,3H);EIMS m/z 208。
实例4:N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-N-甲基-2-(甲基磺酰基)丙酰胺的制备(对比实例1,也称为CE1)
步骤1-N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-N-甲基-2-(甲硫基)丙酰胺(C10)的制备:向2-(甲硫基)丙酸(C6;481mg,4.00mmol)在DCM(6mL)中的溶液中添加草酰二氯(0.384mL,4.40mmol)和一滴二甲基甲酰胺。观察到剧烈的鼓泡,并且继续搅拌30分钟。将粗酰氯反应混合物(C6b)在真空中浓缩至接近干燥。将浓缩的反应混合物(C6b)溶解在DCM(3mL)中,并且缓慢地(经约5min)添加至3-氯-N-甲基-1-(吡啶-3-基)-1H-吡唑-4-胺(C9;417mg,2mmol)和N-乙基-N-异丙-2-胺(0.751mL,4.40mmol)在DCM(3mL)中的冰冷溶液中。将所得深橙色溶液经0.5小时缓慢温热至室温,并且在环境温度下搅拌1.5小时。通过添加饱和碳酸氢钠溶液将反应混合物淬灭。将反应混合物用DCM(3×10mL)萃取。通过硅胶色谱法(0-100%EtOAc/己烷)纯化残余物,给出呈白色固体的标题化合物(495mg,76%):mp 128℃-133℃;1H NMR(400MHz,CDCl3)δ8.94(d,J=2.4Hz,1H),8.62(d,J=3.8Hz,1H),8.15(s,1H),8.03(d,J=8.3Hz,1H),7.46(dd,J=8.3,4.8Hz,1H),3.34(q,J=6.8Hz,1H),3.26(s,3H),2.10(s,3H),1.45(d,J=6.9Hz,3H);ESIMS m/z 311([M+1]+)。
步骤2-N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-N-甲基-2-(甲基磺酰基)丙酰胺的制备(对比实例1):向20mL小瓶中依序添加N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-N-甲基-2-(甲硫基)丙酰胺(C10;306mg,0.985mmol)、乙酸(2mL)和过硼酸钠四水合物(333mg,2.17mmol)。将溶液在65℃下加热3h,冷却,并且通过缓慢添加饱和碳酸氢钠溶液淬灭。将溶液用DCM(3x 10mL)萃取,并且将合并的有机萃取物干燥并且浓缩。通过硅胶色谱法(在DCM中的0-10%甲醇)纯化所得混合物,给出呈灰白色固体的标题化合物(221mg,62%):1H NMR(400MHz,CDCl3)δ8.97(dd,J=2.7,0.7Hz,1H),8.64(dd,J=4.7,1.5Hz,1H),8.22(s,1H),8.00(ddd,J=8.4,2.7,1.5Hz,1H),7.45(ddd,J=8.4,4.8,0.8Hz,1H),4.14-3.94(m,1H),3.33(s,3H),3.02(d,J=0.8Hz,3H),1.65(d,J=7.0Hz,3H);ESIMS m/z 343([M+1]+);IR(薄膜)1657cm-1。
实例5:N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-N-甲基-2-(甲基磺酰基)乙酰胺的制备(对比实例2,也称为CE2):
步骤1-N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-N-甲基-2-(甲硫基)乙酰胺(C12)的制备:向20mL小瓶中依序添加3-氯-N-甲基-1-(吡啶-3-基)-1H-吡唑-4-胺(C9;417mg,2mmol)、2-(甲硫基)乙酸(C11;318mg,3mmol)、N1-((乙基亚氨基)亚甲基)-N3,N3-二甲基丙烷-1,3-二胺盐酸盐(767mg,4mmol)、N,N-二甲基吡啶-4-胺(611mg,5mmol)、和二氯乙烷(6mL)。将溶液在室温下搅拌18h并且浓缩。通过硅胶色谱法(0-100%EtOAc/己烷)纯化,提供呈淡黄色油状物的标题化合物(517mg,83%):1H NMR(400MHz,CDCl3)δ8.95(d,J=2.5Hz,1H),8.62(dd,J=4.8,1.4Hz,1H),8.13(s,1H),8.04(ddd,J=8.3,2.7,1.4Hz,1H),7.50-7.43(m,1H),3.26(s,3H),3.12(s,2H),2.24(s,3H);13C NMR(101MHz,CDCl3)δ170.00,148.61,140.15,140.03,135.68,126.56,126.42,125.33,124.15,37.16,34.94,16.22;ESIMS m/z 297([M+H]+)。
步骤2-N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-N-甲基-2-(甲基磺酰基)乙酰胺的制备(对比实例2):向7mL小瓶中依序添加N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-N-甲基-2-(甲硫基)乙酰胺(C12;262mg,0.883mmol)、乙酸(1.5mL)、和过硼酸钠四水合物(299mg,1.942mmol)。将混合物在65℃下搅拌2h,然后通过添加饱和碳酸氢钠溶液淬灭。将反应混合物用DCM(3×10mL)萃取。将合并的有机萃取物干燥并且浓缩。通过硅胶色谱法(在DCM中的0-10%甲醇)纯化所得混合物,得到呈白色半固体的标题化合物(192mg,62.8%):1H NMR(500MHz,CDCl3)δ8.97(d,J=2.6Hz,1H),8.64(dd,J=4.9,1.3Hz,1H),8.24(s,1H),8.00(ddd,J=8.4,2.8,1.4Hz,1H),7.45(dd,J=8.4,4.8Hz,1H),3.96(s,2H),3.33(s,3H),3.20(s,3H);ESIMS m/z 329([M+H]+);IR(薄膜)1664cm-1。
实例6:N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲基磺酰基)乙酰胺的制备(式二,也称为CE3)
步骤1-N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲硫基)乙酰胺(C14)的制备:向3-氯-1-(吡唑-3-基)-1H-吡啶-4-胺(C5;1.0g,5.14mmol)、N,N-二甲基吡啶-4-胺(628mg,5.14mmol)、和2-(甲硫基)乙酸(C13;654mg,6.17mmol)在二氯乙烷(6mL)中的悬浮液中添加N1-((乙基亚氨基)亚甲基)-N3,N3-二甲基丙烷-1,3-二胺盐酸盐(1.477mg,7.71mmol)。将反应混合物在环境温度下搅拌24h。将混合物用DCM稀释并且用饱和氯化铵水溶液和盐水洗涤,经硫酸镁干燥,并且在真空中浓缩以给出棕色胶状物。通过硅胶色谱法(DCM-甲醇)纯化胶状物,给出呈白色固体的标题化合物(1.268g,87%):1H NMR(400MHz,CDCl3)δ9.06-8.90(m,1H),8.74(s,1H),8.64(s,1H),8.57-8.45(m,1H),8.05-7.90(m,1H),7.46-7.33(m,1H),3.41(s,2H),2.24(s,3H);ESIMS m/z 283([M+H]+)。
步骤2-N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲基磺酰基)乙酰胺(式二)的制备:向N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲硫基)乙酰胺(C14;160mg,0.566mmol)在乙酸(1.5mL)中的溶液中添加过硼酸钠四水合物(183mg,1.188mmol)。将反应混合物在60℃下搅拌2h。将反应混合物冷却并且然后倒入过量的饱和碳酸氢钠溶液中,并且用DCM萃取。通过硅胶色谱法(在DCM中的0-10%甲醇)纯化所得残余物,给出呈白色固体的标题化合物(101mg,53.9%)和呈白色固体的N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲基亚硫酰基)乙酰胺(C15)(40mg,22.5%)。
N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲基磺酰基)乙酰胺(式二):1H NMR(300MHz,CDCl3)δ8.95(dd,J=2.7,0.8Hz,1H),8.66(d,J=0.6Hz,1H),8.53(dd,J=4.8,1.4Hz,1H),8.04(ddd,J=8.4,2.7,1.4Hz,1H),7.45(ddd,J=8.3,4.8,0.7Hz,1H),4.23(q,J=0.8Hz,2H),3.21(t,J=0.8Hz,3H);ESIMS m/z 315([M+H]+);IR(薄膜)1677cm-1。
N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲基亚硫酰基)乙酰胺(C15):1HNMR(300MHz,CDCl3)δ8.95(dd,J=2.7,0.8Hz,1H),8.65(d,J=0.7Hz,1H),8.53(dd,J=4.8,1.4Hz,1H),8.04(ddd,J=8.4,2.7,1.5Hz,1H),7.45(ddd,J=8.4,4.8,0.8Hz,1H),3.93(d,J=13.9Hz,1H),3.71(d,J=13.8Hz,1H),2.80(s,3H);ESIMS m/z 299([M+H]+);IR(薄膜)1673cm-1。
实例7:N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-(甲基磺酰基)乙酰胺(式三,也称为CE4)的制备
步骤1-2-甲基-2-(甲硫基)丙酰氯(C17)的制备:向100mL圆底烧瓶中装入2-甲基-2-(甲硫基)丙酸乙酯(C16;500mg,3.08mmol)、氢氧化锂水合物(400mg,9.53mmol)、THF(6.0mL)、甲醇(2.0mL)和水(2.0mL)。允许将反应混合物在室温下搅拌过夜。将反应混合物用2当量浓度(N)HCl调至酸性,并且用EtOAc(3×15mL)萃取。将合并的有机提取物经硫酸镁干燥,过滤,并且浓缩。
如在Liu,Aiping;Ren,Yeguo;Huang,Lu;Pei,Hui;Hu,Zhibin;Lin,Xuemei;Cheng,Sixi;Huang,Mingzhi;Zhu,Xiaoxing;Wei,Tianlong CN101928271,2010中从上面的酸制备标题化合物。将其分离(不经纯化),呈无色固体(394mg,83%):1H NMR(500MHz,DMSO-d6)δ2.05(s,3H),1.39(s,6H);13C NMR(126MHz,DMSO-d6)δ174.01,45.08,24.31,11.73;IR(薄膜)3394,1652,1204,1040,1024,995cm-1。
步骤2-N-(3-氯-1-(吡啶-3-基)-1H-吡唑-4-基)-2-甲基-2-(甲硫基)丙酰胺(C18)的制备:向50-mL圆底烧瓶中装入来自步骤1的2-甲基-2-(甲硫基)丙酰氯(C17;200mg,1.310mmol)、3-氯-1-(吡啶-3-基)-1H-吡唑-4-胺(C5;255mg,1.310mmol)和二氯乙烷(6.552mL)。在惰性气氛下添加N-乙基-N-异丙-2-胺(456μL,2.62mmol)。将反应混合物在室温下搅拌3h并且浓缩。通过倒入盐水溶液中将反应淬灭,并且将反应混合物用DCM(2×15mL)萃取。将合并的有机提取物经硫酸镁干燥,过滤,并且浓缩。用硅胶色谱法(0-80%EtOAc/己烷)纯化所得残余物,给出呈浅橙色残余物的标题化合物(191mg,46.4%):1H NMR(400MHz,DMSO-d6)δ9.37(s,1H),9.07(dd,J=2.8,0.7Hz,1H),8.78(s,1H),8.55(dd,J=4.7,1.4Hz,1H),8.22(ddd,J=8.3,2.7,1.4Hz,1H),7.56(ddd,J=8.4,4.8,0.8Hz,1H),2.10(s,3H),1.53(s,6H);13C NMR(126MHz,DMSO-d6)δ171.99,147.05,138.78,136.62,134.86,125.02,124.85,123.72,119.01,47.13,24.99,11.65;IR(薄膜)1675,1484,1388,1353,947,800,702cm-1;ESIMS m/z 311([M+H]+)。
步骤3-N-(3-氯-1-(吡啶-3-基)-1H-吡啶-4-基)-2-甲基-2-(甲基磺酰基)丙酰胺(式三)的制备:向25mL小瓶中装入N-(3-氯-1-(吡啶-3-基)-1H-吡啶-4-基)-2-甲基-2-(甲硫基)丙酰胺(C18;75mg,0.241mmol)、过硼酸钠四水合物(74mg,0.483mmol),并且添加乙酸(2.0mL)。将反应混合物在加热块中在50℃下搅拌3h。将反应混合物用水(7mL)稀释,并用DCM(3×7mL)萃取。将合并的有机提取物经硫酸镁干燥,过滤,并且浓缩。通过硅胶色谱法(0-75%EtOAc/己烷)纯化所得残余物提供呈白色固体的标题化合物(47mg,56.2%):1HNMR(400MHz,DMSO-d6)δ9.50(s,1H),9.07(d,J=2.6Hz,1H),8.83(s,1H),8.56(dd,J=4.7,1.4Hz,1H),8.23(ddd,J=8.4,2.8,1.4Hz,1H),7.68-7.49(m,1H),3.10(s,3H),1.66(s,6H);13C NMR(101MHz,DMSO-d6)δ167.92,148.27,139.99,137.59,135.89,126.34,126.09,124.77,119.33,67.49,36.97,19.76;IR(薄膜)1678,1292,1108,946,800,701cm-1;ESIMSm/z 343([M+H]+)。
生物测定
对作为针对宽范围的取食汁液的有害生物的良好指示物种的绿桃蚜(GreenPeach Aphid)(桃蚜(Myzus persicae))和甘薯粉虱(Sweetpotato Whitefly)(烟粉虱(Bemisia tabaci))进行以下生物测定。这两种指示物种的结果显示出式一在防治取食汁液的昆虫中宽的有用性。
测试溶液:
将F1、CE1、CE2、CE3、和CE4(各2mg)各自溶解在2mL丙酮/甲醇(1:1)溶剂中,形成每种测试分子1000ppm的储备溶液。将储备溶液用在水中的0.025%20稀释5倍以获得每种测试分子200ppm的测试溶液。随后使用在含有0.025%20和10%丙酮/甲醇(1:1)的水中的4倍稀释液以产生对于剂量反应所希望的浓度。每种测定使用最少5种浓度的每种测试分子。
生物测定1:绿桃蚜(桃蚜,MYZUPE)(“GPA”)。
GPA是桃树的最重要的蚜虫类有害生物,会导致生长下降、叶枯萎、和各种组织的死亡。桃蚜也是危险的,因为它充当将植物病毒(诸如马铃薯病毒Y和马铃薯卷叶病毒)传播至茄科/马铃薯科(nightshade/potato family Solanaceae)的成员以及将各种花叶病毒传播至许多其他粮食作物的介体。除其他作物外,GPA尤其侵袭诸如以下的植物:西兰花、牛蒡、卷心菜、胡萝卜、花椰菜、白萝卜、茄子、青豆、莴苣、夏威夷果、木瓜、辣椒、甘薯、蕃茄、西洋菜、和西葫芦。GPA还侵袭许多观赏作物,诸如康乃馨、菊花、开花白球甘蓝、一品红、和玫瑰。GPA已对许多杀有害生物剂产生抗性。目前,它是所报道的昆虫抗性案例数量第三大的有害生物(Sparks等人)。因此,由于以上因素,防治这种有害生物是重要的。另外,防治这种被称为取食汁液的有害生物的有害生物(GPA)的分子可用于防治以从植物吸汁为食的其他有害生物。
使用以下程序针对GPA测试如上所描述制备的式一和对比实例的测试溶液。
将在3英寸盆中生长的带2-3片的小(3-5cm)真叶的甘蓝幼苗用作测试基质。在化学应用前一天,用20-50个GPA(无翅成虫和若虫阶段)来感染幼苗。每种处理使用具有单独幼苗的四个盆。使用手持抽吸式喷雾器,向甘蓝叶的两面喷洒溶液直到产生径流。仅用稀释剂(在水中的0.025%20和10%丙酮/甲醇(1:1))喷雾参考植物(溶剂检查)。在分级之前,将经处理的植物在大约25℃和环境相对湿度(RH)下在保藏室内保藏3天。通过以下方式进行评估:在处理后三天在显微镜下对活蚜虫数/株植物进行计数。使用如下雅培校正式(W.S.Abboot,“A Method of Computing the Effectiveness of an Insecticide[计算杀昆虫剂有效性的方法]”,J.Econ.Entomol.[经济昆虫学期刊]18(1925),第265-267页)测量防治百分比:
经校正的%防治=100*(X-Y)/X
其中X=在溶剂检查植物上的活蚜虫数,并且Y=在经处理的植物上的活蚜虫数。结果在以下表2中给出。
生物测定2:甘薯粉虱(烟粉虱,BEMITA)(“SPW”)。
甘薯粉虱对于棉花是主要破坏性有害生物。它对于许多蔬菜作物(诸如瓜类、芸苔属作物、蕃茄、和结球莴苣)以及观赏植物也是严重的有害生物。SPW通过直接取食损害和病毒传播两者造成损害。SPW是取食汁液的昆虫,并且其取食会除去植物的营养物。这可能导致棉花的生长萎缩、脱叶、产率减少、和棉铃脱落。SPW产生大量蜜露,所述蜜露支持烟霉在植物叶片上的生长。SPW也是诸如棉花皱叶病毒和番茄黄化曲叶病毒的病毒的介体。
使用以下程序针对SPW测试如上所描述制备的式一和对比实例的测试溶液。
将在3英寸盆中生长的棉花幼苗用作测试基质,所述棉花幼苗被修剪成使得仅保留一片真叶。允许烟粉虱(B.tabaci)成虫在这些植物上定植并且产卵24小时,之后使用压缩空气将所有成虫从植物中移出。监测植物的卵发育,并且当爬虫(crawler)羽化在进行中时(基于使用显微镜的目视检查,>25%羽化),使用上面针对绿桃蚜(GPA)所描述的测试溶液和方法对植物进行喷雾。在分级之前,将经处理的植物在大约25℃和环境相对湿度(RH)下在保藏室内保藏。通过以下方式进行评估:在处理后7-9天在显微镜下对发育的2-3龄若虫数/株植物进行计数。使用如下雅培校正式(W.S.Abboot,“A Method of Computing theEffectiveness of an Insecticide[计算杀昆虫剂有效性的方法]”,J.Econ.Entomol.[经济昆虫学期刊]18(1925),第265-267页)测量防治百分比:
经校正的%防治=100*(X-Y)/X
其中X=在溶剂检查植物上的活若虫数,并且Y=在经处理的植物上的活若虫数。结果在以下表2中给出。
生物测定分析
表2中示出了F1、CE1、CE2、CE3、和CE4生物测定结果。#列示出了进行的各生物测定的重复数。平均LC50指示百万分率。%列示出了所需的平均LC50的增加百分比。例如,在桃蚜生物测定中,将CE4与F1比较,增加百分比为((2.17-0.07)/0.07)*100=3000%,这意味着与F1相比,实现相同的作用采用多得多的CE4。
鉴于上面的生物测定,所有生物测定的平均%是((15+331+421+100+314+643+(-29)+3000)/8),为约599%。这指示,多需要平均约599%杀有害生物剂,以便与F1一样有效。考虑到所测试的分子,这是出乎意料的。
农业上可接受的酸加成盐、盐衍生物、溶剂化物、酯衍生物、多晶型物、同位素物和放射性核素
可以将式一配制成农业上可接受的酸加成盐。作为非限制性实例,胺官能团可与盐酸、氢溴酸、硫酸、磷酸、乙酸、苯甲酸、柠檬酸、丙二酸、水杨酸、苹果酸、反丁烯二酸、乙二酸、丁二酸、酒石酸、乳酸、葡萄糖酸、抗坏血酸、顺丁烯二酸、天冬氨酸、苯磺酸、甲磺酸、乙磺酸、羟基甲磺酸、和羟基乙磺酸形成盐。
可以将式一配制成盐衍生物。作为非限制性实例,可通过使游离碱与足以产生盐的量的所希望的酸接触来制备盐衍生物。可以通过将所述盐用合适的稀碱水溶液(诸如稀氢氧化钠、碳酸钾、氨、和碳酸氢钠水溶液)处理来再生游离碱。例如,在许多情况下,通过将杀有害生物剂(诸如2,4-D)转化成其二甲胺盐而使其更可溶于水。
可以将式一与溶剂一起配制成稳定复合物,使得所述复合物在除去非复合溶剂之后保持完整。这些复合物常称为“溶剂化物”。然而,特别希望的是使用水作为溶剂以形成稳定的水合物。
可以将式一制成为多种多晶型物。多晶型现象在农用化学品开发中是重要的,因为相同分子的不同晶体多晶型物或结构可具有大大不同的物理特性和生物性能。
可以用不同的同位素制造式一。特别重要的是具有2H(也称为氘)或3H(也称为氚)代替1H的分子。可以用不同放射性核素制造式一。特别重要的是具有14C(也称为放射性碳)的分子。具有氘、氚、或14C的式一可用于允许在化学和生理过程中追踪的生物学研究、和半衰期研究、以及MoA研究。
组合
在本发明的另一个实施例中,式一可以与一种或多种活性成分组合使用(诸如以组分混合物形式、或同时或依序应用)。
在本发明的另一个实施例中,式一可以与一种或多种活性成分组合使用(诸如以组分混合物形式、或同时或依序应用),所述一种或多种活性成分各自具有与式一的MoA相同、类似、或优选不同的MoA。
在另一个实施例中,式一可以与具有杀螨、杀藻、杀鸟、杀细菌、杀真菌、除草、杀昆虫、杀软体动物、杀线虫、杀啮齿动物、和/或杀病毒特性的一种或多种分子组合使用(诸如在组分混合物中或同时或依序应用)。
在另一个实施例中,式一可以与作为拒食剂、驱鸟剂、化学不育剂、除草剂安全剂、昆虫引诱剂、驱昆虫剂、驱哺乳动物剂、交配干扰剂、植物激活剂、植物生长调节剂、植物健康刺激剂或促进剂、硝化作用抑制剂、和/或增效剂的一种或多种分子组合使用(诸如在组分混合物中或同时或依序应用)。
在另一个实施例中,式一也可以与一种或多种生物型杀有害生物剂组合使用(诸如以组分混合物形式、或同时或依序应用)。
在另一个实施例中,在杀有害生物组合物中,式一和活性成分的组合可以以多种多样的重量比率使用。例如,在双组分混合物中,式一与活性成分的重量比率可以使用表3中的重量比率。然而,通常,小于约10:1至约1:10的重量比率是优选的。
表3 |
式一:活性成分的重量比率 |
100:1至1:100 |
50:1至1:50 |
20:1至1:20 |
10:1至1:10 |
5:1至1:5 |
3:1至1:3 |
2:1至1:2 |
1:1 |
具有式一的分子与活性成分的重量比率也可描绘为X:Y;其中X是式一的重量份并且Y是活性成分的重量份。X的重量份的数值范围为0<X≤100并且Y的重量份的数值范围为0<Y≤100,并且图表地示出于表4中。作为非限制性实例,式一与活性成分的重量比率可以是20:1。
式一与活性成分的重量比率的范围可以描绘为X1:Y1至X2:Y2,其中X和Y是如上定义的。
在一个实施例中,重量比率的范围可以是X1:Y1至X2:Y2,其中X1>Y1并且X2<Y2。作为非限制性实例,式一与活性成分的重量比率的范围可以是3:1至1:3,包括端点。
在另一个实施例中,重量比率的范围可以是X1:Y1至X2:Y2,其中X1>Y1且X2>Y2。作为非限制性实例,式一与活性成分的重量比率的范围可以是15:1至3:1,包括端点。
在另一个实施例中,重量比率的范围可以是X1:Y1至X2:Y2,其中X1<Y1且X2<Y2。作为非限制性实例,式一与活性成分的重量比率的范围可以是约1:3至约1:20,包括端点。
配制品
杀有害生物剂经常不适于以其纯形式应用。通常必需添加其他物质,使得杀有害生物剂可以在所需浓度下并且以适当的形式使用,从而允许易于应用、操作、运输、储存和最大杀有害生物活性。因此,将杀有害生物剂配制成例如诱饵、浓缩乳液、粉尘剂、可乳化浓缩物、熏剂、凝胶、颗粒剂、微胶囊、种子处理剂、悬浮液浓缩物、悬乳剂、片剂、水溶性液体、水可分散颗粒剂或干燥可流动剂、可湿性粉剂、和超低容量溶液。
杀有害生物剂最常以由此类杀有害生物剂的浓缩配制品制备的水性悬浮液或乳液形式应用。此类水溶性、水可悬浮性、或可乳化配制品可以是通常被称为可湿性粉剂、水可分散颗粒剂的固体,通常被称为可乳化浓缩物或水性悬浮液的液体。可压实形成水可分散颗粒剂的可湿性粉剂包含杀有害生物剂、载体和表面活性剂的紧密混合物。杀有害生物剂的浓度通常为约10重量%至约90重量%。载体通常选自绿坡缕石(attapulgite)粘土、蒙脱石(montmorillonite)粘土、硅藻土、或纯化硅酸盐。占可湿性粉剂的约0.5%至约10%的有效表面活性剂被发现于磺化木质素、缩合萘磺酸盐、萘磺酸盐、烷基苯磺酸盐、烷基硫酸盐、和诸如烷基苯酚的环氧乙烷加合物的非离子表面活性剂。
杀有害生物剂的可乳化浓缩物包含适宜浓度的溶解于载体中的杀有害生物剂(如约50至约500克/升液体),所述载体是水混溶性溶剂或水不可混溶性有机溶剂和乳化剂的混合物。可用的有机溶剂包括芳香族化合物(尤其是二甲苯)和石油馏分(尤其是石油的高沸点萘和烯部分,诸如重芳香族石脑油)。也可以使用其他有机溶剂,诸如包括松香衍生物的萜烯溶剂、诸如环己酮的脂族酮、和诸如2-乙氧基乙醇的复杂醇。用于可乳化浓缩物的合适乳化剂选自常规的阴离子表面活性剂和非离子表面活性剂。
水性悬浮液包括水不溶性杀有害生物剂以约5重量%至约50重量%的浓度分散在水性载体中的悬浮液。悬浮液通过以下方式制备:精细研磨杀有害生物剂并且将其剧烈混合到由水和表面活性剂构成的载体中。还可以添加诸如无机盐和合成胶或天然胶的成分以增加水性载体的密度和粘度。通过在例如砂磨机、球磨机、或活塞型均化器的器具中制备水性混合物并且使其均化来同时研磨和混合杀有害生物剂通常是最有效的。可以将呈悬浮液的杀有害生物剂微包封在塑料聚合物中。
油分散体(OD)包括有机溶剂不溶性杀有害生物剂以约2重量%至约50重量%的浓度精细分散于有机溶剂和乳化剂的混合物中的悬浮液。一种或多种杀有害生物剂可以溶解于有机溶剂中。可用的有机溶剂包括芳香族化合物(尤其是二甲苯)和石油馏分(尤其是石油的高沸点萘和烯部分,诸如重芳香族石脑油)。其他溶剂可以包括植物油、种子油、和植物油和种子油的酯。用于油分散体的合适乳化剂选自常规的阴离子表面活性剂和非离子表面活性剂。在油分散体的配制中添加增稠剂或胶凝剂以改变液体的流变性或流动特性以及防止分散颗粒或液滴的分离和沉降。
杀有害生物剂也可以以颗粒组合物的形式应用,所述颗粒组合物特别可用于应用于土壤。颗粒组合物通常含有约0.5重量%至约10重量%的杀有害生物剂,所述杀有害生物剂分散于包含粘土或类似物质的载体中。通常通过将杀有害生物剂溶解于合适的溶剂中并且将其应用到已预先形成在约0.5mm至约3mm的适当粒度的颗粒载体中来制备此类组合物。也可以通过制造载体和分子的粘团或糊状物并且然后挤压并且干燥以获得所希望的颗粒粒度来配制此类组合物。颗粒的另一种形式是水可乳化颗粒剂(EG)。它是由颗粒剂组成的配制品,所述配制品有待以一种或多种活性成分在水中崩解和溶解之后溶解或稀释于有机溶剂中的常规水包油乳液形式应用。水可乳化颗粒剂包含溶解或稀释于合适的有机溶剂中的一种或若干种活性成分,所述一种或若干种活性成分被吸收在水溶性聚合物壳或一些其他类型的可溶性或不溶性基质中。
通过将呈粉末状形式的杀有害生物剂与合适的粉尘状农业载体(诸如高岭土、研磨的火山岩等)紧密混合来制备含有杀有害生物剂的粉尘剂。粉尘剂可以适当含有约1%至约10%的杀有害生物剂。粉尘剂可以以拌种的形式或以使用喷粉机的叶面应用的形式进行应用。
同样实用的是以在适当的有机溶剂(通常为石油)中的溶液形式应用杀有害生物剂,诸如广泛用于农业化学的喷淋油。
杀有害生物剂也可以气溶胶组合物的形式应用。在此类组合物中,杀有害生物剂溶解或分散于作为产生压力的推进剂混合物的载体中。将气溶胶组合物包装在通过雾化阀分配混合物的容器中。
当杀有害生物剂与食品或引诱剂或两者混合时,形成杀有害生物剂诱饵。当有害生物食用诱铒时,它们也食用杀有害生物剂。诱饵可以呈颗粒剂、凝胶、可流动粉末、液体、或固体的形式。诱饵可用于有害生物庇护处。
熏剂是具有相对高蒸气压并且因此可以足够浓度的气体形式存在以杀死土壤或封闭空间中的有害生物的杀有害生物剂。熏剂的毒性与其浓度和暴露时间成比例。它们通过良好的扩散能力表征并且通过渗透有害生物的呼吸系统或经由有害生物的表皮吸收而起作用。应用熏剂以防治在气密薄片下、在气封室或建筑物中或在特定腔室中的积谷有害生物(stored product pest)。
可以通过将杀有害生物剂颗粒或液滴悬浮于多种类型的聚合物中来将杀有害生物剂微包封。通过改变聚合物的化学性质或通过改变加工中的因素,可以形成具有各种尺寸、溶解度、壁厚和渗透程度的微胶囊。这些因素管控内部的活性成分释放的速度,其继而影响产品的残余性能、作用速度、和气味。微胶囊可以配制为悬浮液浓缩物或水可分散颗粒剂。
油溶液浓缩物是通过将杀有害生物剂溶解于将使杀有害生物剂保持在溶液中的溶剂中来制造。杀有害生物剂的油溶液通常比其他配制品更快击溃并且杀死有害生物,因为溶剂本身具有杀有害生物作用并且覆盖外皮的蜡质的溶解增加杀有害生物剂摄取的速度。油溶液的其他优点包括更好的储存稳定性、更好的裂隙渗透性和更好的对油脂表面的粘附性。
另一个实施例是水包油乳液,其中所述乳液包含各自具备层状液晶包衣并且分散在水相中的油性小珠,其中每个油性小珠包含至少一种具有农业活性的分子并且单独地被单层状层或多层状的层包覆,所述单层状层或多层状的层包含:(1)至少一种非离子亲脂性表面活性剂,(2)至少一种非离子亲水性表面活性剂,和(3)至少一种离子表面活性剂,其中所述小珠的平均粒径小于800纳米。
其他配制品组分
通常,当式一用于配制品时,此类配制品也可以含有其他组分。这些组分包括但不限于(这是非详尽且非互相排他性列表)润湿剂、铺展剂、粘着剂、渗透剂、缓冲剂、螯合剂、减漂剂、相容剂、消泡剂、清洁剂、和乳化剂。接着描述数种组分。
润湿剂是当被添加到液体中时通过减小液体与其所铺展的表面之间的表面张力而增加液体的铺展或渗透能力的物质。润湿剂因以下两个主要功能用于农用化学配制品:在加工和制造期间,增加粉末在水中润湿的速率以制造可溶性液体或悬浮液浓缩物;以及在产品与水在喷洒罐中混合期间,减少可湿性粉剂的润湿时间并且改进水到水可分散颗粒剂中的渗透。用于可湿性粉剂、悬浮液浓缩物和水可分散颗粒剂配制品的润湿剂的实例是:月桂基硫酸钠、二辛基磺基琥珀酸钠、烷基酚乙氧基化物、和脂族醇乙氧基化物。
分散剂是吸附于颗粒表面上,有助于保持颗粒的分散状态并且防止其再聚集的物质。将分散剂添加到农用化学配制品中以促进在制造期间的分散和悬浮并且确保颗粒再分散于喷洒罐中的水中。它们广泛用于可湿性粉剂、悬浮液浓缩物、和水可分散颗粒剂中。用作分散剂的表面活性剂具有强烈吸附于颗粒表面上并且提供针对颗粒再聚集的带电荷的或空间屏障的能力。最常用的表面活性剂是阴离子表面活性剂、非离子表面活性剂、或两种类型的混合物。对于可湿性粉剂配制品,最常见的分散剂是木质素磺酸钠。对于悬浮液浓缩物,使用聚电解质(诸如萘磺酸钠甲醛缩合物)获得非常好的吸附性和稳定性。也使用三苯乙烯基苯酚乙氧基化物磷酸酯。诸如烷基芳基环氧乙烷缩合物和EO-PO嵌段共聚物的非离子表面活性剂有时与作为分散剂的阴离子表面活性剂组合用于悬浮液浓缩物。近年来,已开发出新型的非常高分子量聚合物表面活性剂作为分散剂。其具有非常长的疏水性“主链”和大量环氧乙烷链,形成“梳型”表面活性剂的“齿”。这些高分子量聚合物可以赋予悬浮液浓缩物非常好的长期稳定性,因为疏水性主链具有在颗粒表面上的许多锚点。用于农用化学配制品的分散剂的实例是:木质素磺酸钠、萘磺酸钠甲醛缩合物、三苯乙烯基苯酚乙氧基化物磷酸酯、脂族醇乙氧基化物、烷基乙氧基化物、EO-PO嵌段共聚物、和接枝共聚物。
乳化剂是使一种液相的液滴在另一个液相中的悬浮液稳定的物质。在无乳化剂的情况下,可以将两种液体分成两种不可混溶的液相。最常用的乳化剂共混物含有具有十二个或更多个环氧乙烷单元的烷基酚或脂族醇和油溶性的十二烷基苯磺酸钙盐。约8至约18的亲水亲油平衡(“HLB”)值将正常提供良好的稳定乳液。乳液稳定性可以有时通过添加少量EO-PO嵌段共聚物表面活性剂来改进。
增溶剂是将以高于临界胶束浓度的浓度在水中形成胶束的表面活性剂。所述胶束然后能够溶解或增溶胶束的疏水性部分内的水不溶性材料。通常用于增溶的表面活性剂的类型为非离子表面活性剂:脱水山梨醇单油酸酯;脱水山梨醇单油酸酯乙氧基化物;和油酸甲酯。
表面活性剂有时单独地或与作为用于喷洒罐混合的辅助剂的其他添加剂(诸如矿物油或植物油)一起使用,以改进杀有害生物剂对于标靶的生物性能。用于生物增强的表面活性剂的类型通常取决于杀有害生物剂的性质和作用方式。然而,它们通常是非离子表面活性剂,诸如:烷基乙氧基化物、直链脂族醇乙氧基化物、和脂族胺乙氧基化物。
农业配制品中的载体或稀释剂是添加到杀有害生物剂中以给出所需强度的产品的材料。载体通常是具有高吸收能力的材料,而稀释剂通常是具有低吸收能力的材料。载体和稀释剂用于粉尘剂、可湿性粉剂、颗粒剂、和水可分散颗粒剂的配制。
有机溶剂主要用于配制可乳化浓缩物、水包油乳液、悬乳剂、油分散体和超低容量配制品,并且在较小程度上用于配制颗粒配制品。有时使用溶剂混合物。第一主组的溶剂是脂族石蜡油,诸如煤油或精制石蜡。第二主组的(并且最常用的)溶剂包括芳香族溶剂,诸如二甲苯和较高分子量的C9和C10芳香族溶剂馏分。氯化烃可用作助溶剂以便当配制品乳化在水中时防止杀有害生物剂结晶。醇有时用作助溶剂以增加溶解能力。其他溶剂可以包括植物油、种子油、和植物油和种子油的酯。
增稠剂或胶凝剂主要用于配制悬浮液浓缩物、油分散体、乳液和悬乳剂,以改变液体的流变或流动特性和防止分散的颗粒或液滴的分离和沉降。增稠剂、胶凝剂和防沉剂通常分成两个类别,即水不溶性颗粒和水溶性聚合物。可以使用粘土和二氧化硅来制备悬浮液浓缩物和油分散体配制品。这些类型的材料的实例包括但不限于蒙脱石、膨润土、硅酸镁铝、和绿坡缕石。在水基悬浮液浓缩物中的水溶性多糖已作为增稠-胶凝剂使用了许多年。最常用的多糖类型是种子和海藻的天然提取物或是纤维素的合成衍生物。这些类型的材料的实例包括但不限于瓜耳胶、刺槐豆胶、角叉菜胶、海藻酸盐、甲基纤维素、羧甲基纤维素钠(SCMC)、和羟乙基纤维素(HEC)。其他类型的防沉剂是基于改性淀粉、聚丙烯酸酯、聚乙烯醇、和聚环氧乙烷的。另一种良好的防沉剂是黄原胶。
微生物可以导致配制产品的腐败。因此,使用防腐剂消除或减轻其作用。此类药剂的实例包括但不限于:丙酸及其钠盐、山梨酸及其钠或钾盐、苯甲酸及其钠盐、对羟基苯甲酸钠盐、对羟基苯甲酸甲酯、和1,2-苯并异噻唑啉-3-酮(BIT)。
表面活性剂的存在通常在生产和通过喷洒罐应用中的混合操作期间导致水基配制品起泡。为了减少起泡的倾向,通常在生产阶段期间或在填充至瓶中之前添加消泡剂。通常,存在两种类型的消泡剂,即硅酮和非硅酮。硅酮通常是二甲基聚硅氧烷的水性乳液,而非硅酮消泡剂是水不溶性油(诸如辛醇和壬醇)或二氧化硅。在两种情况下,消泡剂的功能是使表面活性剂从空气-水界面移位。
“绿色”剂(例如辅助剂、表面活性剂、溶剂)可以减少作物保护配制品的整体环境足迹。绿色剂是可生物降解的并且通常源于天然和/或可持续源,例如植物源和动物源。具体实例是:植物油、种子油、及其酯,以及烷氧基化烷基聚葡萄糖苷。
应用
式一可以应用于任何场所。应用此类分子的特定场所包括苜蓿、杏仁、苹果、大麦、豆类、低芥酸菜籽、玉米、棉花、十字花科植物、花卉、饲料物种(黑麦草、苏丹草(SudanGrass)、高羊茅(Tall Fescue)、肯塔基蓝草(Kentucky Blue Grass)和三叶草)、水果、莴苣、燕麦、油籽作物、柑橘、花生、梨、胡椒、马铃薯、水稻、高梁、大豆、草莓、甘蔗、糖用甜菜、向日葵、烟草、蕃茄、小麦(例如,硬红冬小麦(Hard Red Winter Wheat)、软红冬小麦(SoftRed Winter Wheat)、白冬小麦(White Winter Wheat)、硬红春小麦(Hard Red SpringWheat)和杜伦春小麦(Durum Spring Wheat))以及其他有价值的作物生长或要种植其种子的场所。
式一也可以应用于植物(诸如作物)生长的地方和存在低水平(甚至实际不存在)的可商业上损害此类植物的有害生物的地方。在此类场所应用此类分子将有益于植物在此类场所生长。此类有益效果可包括但不限于:帮助植物生长更好的根系;帮助植物更好地承受应激生长条件;改进植物的健康状况;改进植物的产率(例如,增加的生物量和/或增加的有价值成分的含量);改进植物的活力(例如,改进的植物生长和/或更绿的叶);改进植物的品质(例如,改进某些成分的含量或组成);以及改进植物的对非生物和/或生物应激的耐受性。
当生长多种植物时,可以将式一与硫酸铵一起应用,因为这可以提供另外的益处。
可以将式一应用于以下植物上、中或周围,包括地上部分及地下部分:经遗传修饰以表达特定性状(诸如苏云金芽孢杆菌(例如,Cry1Ab、Cry1Ac、Cry1Fa、Cry1A.105、Cry2Ab、Vip3A、mCry3A、Cry3Ab、Cry3Bb、Cry34Ab1/Cry35Ab1))、其他杀昆虫毒素的植物,或表达除草剂耐受性的植物,或具有表达杀昆虫毒素、除草剂耐受性、营养增强或任何其他有益性状的“堆叠”外源基因的植物。
可以将式一应用于植物的叶和/或结实部分以防治有害生物。此类分子将与有害生物直接接触,或有害生物将在食用植物时或在汲取植物的汁液或其他营养物时食用此类分子。
也可以将式一应用于土壤,并且当以这种方式应用时,可以防治食用根和茎的有害生物。根可吸收此类分子,由此将其向上输送至植物的叶部分以防治地面上的咀嚼有害生物和取食汁液的有害生物。
可以利用植物中杀有害生物剂的系统性移动来通过将具有式一的分子应用(例如,通过喷洒场所)于植物的不同部分而防治在植物的一个部分上的有害生物。例如,叶取食的昆虫的防治可以通过滴灌或沟施、通过用例如种植前或种植后土壤浸液处理土壤、或通过在种植之前处理植物种子来实现。
式一可以与诱饵和引诱剂一起使用。通常对于诱饵而言,将诱饵置于例如白蚁可与诱铒接触和/或被引诱至诱铒处的地面。也可以将诱饵应用于例如蚂蚁、白蚁、蟑螂和苍蝇可与诱铒接触和/或被引诱至诱铒处的建筑物的表面(水平、竖直或倾斜表面)。
可以将式一包封于胶囊内部或置于胶囊表面上。胶囊的尺寸可以是纳米尺寸(约100-900纳米直径)至微米尺寸(约10-900微米直径)。
可以将式一应用于有害生物的卵。由于一些有害生物的卵抵抗某些杀有害生物剂的独特能力,因此可能希望重复应用此类分子以防治新出现的幼虫。
式一可以作为种子处理剂来应用。可以将种子处理剂应用于所有类型的种子,包括经遗传修饰以表达特定性状的植物的将从其萌发的种子。代表性实例包括表达对无脊椎有害生物(诸如苏云金芽孢杆菌)具有毒性的蛋白质或其他杀昆虫毒素的那些,表达除草剂耐受性的那些(诸如“Roundup Ready”种子),或具有表达杀昆虫毒素、除草剂耐受性、营养增强、抗旱性或任何其他有益性状的“堆叠”外源基因的那些。此外,具有式一的此类种子处理剂可以进一步增强植物更好地经受应激生长条件的能力。这导致更健康、更有活力的植物,这可以在收获时间导致较高的产率。通常,约0.0025mg式一/个种子至约2.0mg式一/个种子是可用的,约0.01mg式一/个种子至约1.75mg式一/个种子的量是可用的,0.1mg式一/个种子至约1.5mg式一/个种子的量是可用的,0.25mg式一/个种子至约0.75mg式一/个种子的量是可用的。通常,约0.5mg式一/个种子的量是可用的。
可以将式一与土壤改善剂中的一种或多种活性成分一起应用。
式一可以在兽医学领域中或在非人类动物饲养领域中用于防治体内寄生虫和体表寄生虫。可以将此类分子通过以下列方式应用:以例如片剂、胶囊、饮料、颗粒剂的形式口服施用,以例如蘸涂、喷洒、倾倒、点样和喷粉的形式经皮应用,和以例如注射液的形式非肠道施用。
式一也可以有利地用于家畜饲养,例如牛、鸡、鹅、山羊、猪、绵羊和火鸡。它们也可以有利地用于宠物,诸如马、犬和猫。要防治的具体有害生物可以是令此类动物生厌的苍蝇、跳蚤、和扁虱。合适的配制品与饮用水或饮食一起口服施用于动物。合适的剂量和配制品取决于物种。
式一也可以用于防治以上列出的动物中(尤其肠)的寄生虫。
式一也可以用于人类健康护理的治疗方法。此类方法包括但限于以例如片剂、胶囊、饮料、颗粒剂的形式口服施用,和经皮应用。
式一也可以应用于侵入性有害生物。全世界的有害生物已迁移至新环境(对于此类有害生物而言)并且此后变成此类新环境的新侵入性物种。此类分子也可以用于此类新侵入性物种以在此类新环境中对其进行防治。
植物病毒每年在全球造成作物产率损失估计600亿美元。许多植物病毒需要通过介体传播,最经常是昆虫,其实例是叶跳虫和飞虱。然而,还已经显示线虫会传播病毒。线虫通过以根为食来传播植物病毒。也可以将式一应用于植物,以便抑制携带植物病毒的有害生物,使得这减少此类植物病毒从有害生物传播到植物的机会。
因此,鉴于以上内容,提供以下另外的非详尽的细节(D)。
1D.一种组合物,其包含:
(a)具有式一(F1)的分子及其N-氧化物、农业上可接受的酸加成盐、盐衍生物、溶剂化物、酯衍生物、多晶型物、同位素、拆分的立体异构体、和互变异构体
式一,也称为F1,和
(b)第二分子及其N-氧化物、农业上可接受的酸加成盐、盐衍生物、溶剂化物、酯衍生物、多晶型物、同位素、拆分的立体异构体、互变异构体、和放射性核素,其中所述第二分子选自由以下组成的组:
(i)N-(4-氯-2-(吡啶-3-基)噻唑-5-基)-N-乙基-3-(甲基磺酰基)丙酰胺(AI-1)
(ii)反式-5-(3-(3,5-双(三氟甲基)苯基)-2,2-二氯环丙烷-1-甲酰胺基)-2-氯-N-(3-(2,2-二氟乙酰胺基)-2,4-二氟苯基)苯甲酰胺(rac-AI-2)
(iii)5-((1R,3R)-3-(3,5-双(三氟甲基)苯基)-2,2-二氯环丙烷-1-甲酰胺基)-2-氯-N-(3-(2,2-二氟乙酰胺基)-2,4-二氟苯基)苯甲酰胺(R,R-AI-2)
2D.根据1D所述的组合物,其中所述第二分子是N-(4-氯-2-(吡啶-3-基)噻唑-5-基)-N-乙基-3-(甲基磺酰基)丙酰胺(AI-1)
3D.根据1D所述的组合物,其中所述第二分子是反式-5-(3-(3,5-双(三氟甲基)苯基)-2,2-二氯环丙烷-1-甲酰胺基)-2-氯-N-(3-(2,2-二氟乙酰胺基)-2,4-二氟苯基)苯甲酰胺(rac-AI-2)
4D.根据1D所述的组合物,其中所述第二分子是5-((1R,3R)-3-(3,5-双(三氟甲基)苯基)-2,2-二氯环丙烷-1-甲酰胺基)-2-氯-N-(3-(2,2-二氟乙酰胺基)-2,4-二氟苯基)苯甲酰胺(R,R-AI-2)
5D.根据前述细节中任一项所述的组合物,所述组合物还包含载体。
6D.根据前述细节中任一项所述的组合物,所述组合物进一步包含活性成分,所述活性成分选自:杀螨剂、杀藻剂、拒食剂、杀鸟剂、杀细菌剂、驱鸟剂、化学不育剂、杀真菌剂、除草剂安全剂、除草剂、昆虫引诱剂、驱昆虫剂、杀昆虫剂、驱哺乳动物剂、交配干扰剂、杀软体动物剂、杀线虫剂、植物激活剂、植物健康刺激剂或促进剂、硝化作用抑制剂、植物生长调节剂、杀啮齿动物剂、增效剂、和杀病毒剂。
7D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自AIGA的活性成分。
8D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自表1的分子。
9D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自AIGA-2的活性成分。
10D.根据前述细节中任一项所述的组合物,所述组合物进一步包含AIGA-3。
11D.根据前述细节中任一项所述的组合物,所述组合物进一步包含生物型杀有害生物剂。
12D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自乙酰胆碱酯酶(AChE)抑制剂的活性成分。
13D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自GABA门控的氯离子通道阻断剂的活性成分。
14D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自钠通道调节剂的活性成分。
15D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自烟碱型乙酰胆碱受体(nAChR)竞争性调节剂的活性成分。
16D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自烟碱型乙酰胆碱受体(nAChR)变构调节剂-位点I的活性成分。
17D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自谷氨酸门控的氯离子通道(GLUCL)变构调节剂的活性成分。
18D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自保幼激素模拟物的活性成分。
19D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自其他非特异性(多位点)抑制剂的活性成分。
20D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自声音反应型器官TRPV通道调节剂的活性成分。
21D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自螨生长抑制剂的活性成分。
22D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自昆虫中肠膜的微生物干扰剂的活性成分。
23D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自线粒体ATP合酶抑制剂的活性成分。
24D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自经由扰乱质子梯度的氧化磷酸化的解偶联剂的活性成分。
25D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自烟碱型乙酰胆碱受体(nAChR)通道阻断剂的活性成分。
26D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自0型壳多糖生物合成抑制剂的活性成分。
27D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自1型壳多糖生物合成抑制剂的活性成分。
28D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自双翅目昆虫蜕皮干扰剂的活性成分。
29D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自蜕皮激素受体激动剂的活性成分。
30D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自真蛸胺受体激动剂的活性成分。
31D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自线粒体复合体III电子传递抑制剂的活性成分。
32D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自线粒体复合体I电子传递抑制剂的活性成分。
33D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自电压依赖的钠通道阻断剂的活性成分。
34D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自乙酰CoA羧化酶的抑制剂的活性成分。
35D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自线粒体复合体IV电子传递抑制剂的活性成分。
36D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自线粒体复合体II电子传递抑制剂的活性成分。
37D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自利阿诺定受体调节剂的活性成分。
38D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自声音反应型器官调节剂-未定义的靶位点的活性成分。
39D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自GABA门控的氯离子通道变构调节剂的活性成分。
40D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自杆状病毒的活性成分。
41D.根据前述细节中任一项所述的组合物,所述组合物进一步包含烟碱型乙酰胆碱受体(nAChR)变构调节剂-位点II。
42D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自组UN的活性成分。
43D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自组UNB的活性成分。
44D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自组UNE的活性成分。
45D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自组UNF的活性成分。
46D.根据前述细节中任一项所述的组合物,所述组合物进一步包含选自组UNM的活性成分。
47D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氯虫苯甲酰胺。
48D.根据前述细节中任一项所述的组合物,所述组合物进一步包含毒死蜱。
49D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氰虫酰胺。
50D.根据前述细节中任一项所述的组合物,所述组合物进一步包含灭多威。
51D.根据前述细节中任一项所述的组合物,所述组合物进一步包含甲氧虫酰肼。
52D.根据前述细节中任一项所述的组合物,所述组合物进一步包含草氨酰。
53D.根据前述细节中任一项所述的组合物,所述组合物进一步包含乙基多杀菌素。
54D.根据前述细节中任一项所述的组合物,所述组合物进一步包含多杀菌素。
55D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氟啶虫胺腈。
56D.根据前述细节中任一项所述的组合物,所述组合物进一步包含三氟苯嘧啶。
57D.根据前述细节中任一项所述的组合物,所述组合物进一步包含β-氟氯氰菊酯。
58D.根据前述细节中任一项所述的组合物,所述组合物进一步包含噻虫胺。
59D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氟氯氰菊酯。
60D.根据前述细节中任一项所述的组合物,所述组合物进一步包含三氟咪啶酰胺。
61D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氟虫双酰胺。
62D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氟吡菌酰胺。
63D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氟吡呋喃酮。
64D.根据前述细节中任一项所述的组合物,所述组合物进一步包含吡虫啉。
65D.根据前述细节中任一项所述的组合物,所述组合物进一步包含螺甲螨酯。
66D.根据前述细节中任一项所述的组合物,所述组合物进一步包含螺虫乙酯。
67D.根据前述细节中任一项所述的组合物,所述组合物进一步包含螺螨酯。
68D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氟氰虫酰胺。
69D.根据前述细节中任一项所述的组合物,所述组合物进一步包含硫双威。
70D.根据前述细节中任一项所述的组合物,所述组合物进一步包含噻虫啉。
71D.根据前述细节中任一项所述的组合物,所述组合物进一步包含α-氯氰菊酯。
72D.根据前述细节中任一项所述的组合物,所述组合物进一步包含丁氟螨酯。
73D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氟虫腈。
74D.根据前述细节中任一项所述的组合物,所述组合物进一步包含氰氟虫腙。
75D.根据前述细节中任一项所述的组合物,所述组合物进一步包含ζ-氯氰菊酯。
76D.根据前述细节中任一项所述的组合物,所述组合物进一步包含双丙环虫酯。
77D.根据前述细节中任一项所述的组合物,所述组合物包含(a)F1;(b)AI-1;和(c)rac-AI-2或R,R-AI-2。
78D.根据前述细节中任一项所述的组合物,其中(a)具有式一(F1)的分子与(b)第二分子的重量比率是100:1至1:100。
79D.根据前述细节中任一项所述的组合物,其中所述(a)具有式一(F1)的分子与(b)第二分子的重量比率是50:1至1:50。
80D.根据前述细节中任一项所述的组合物,其中所述(a)具有式一(F1)的分子与(b)第二分子的重量比率是20:1至1:20。
81D.根据前述细节中任一项所述的组合物,其中所述(a)具有式一(F1)的分子与(b)第二分子的重量比率是10:1至1:10。
82D.根据前述细节中任一项所述的组合物,其中所述(a)具有式一(F1)的分子与(b)第二分子的重量比率是5:1至1:5。
83D.根据前述细节中任一项所述的组合物,其中所述(a)具有式一(F1)的分子与(b)第二分子的重量比率是3:1至1:3。
84D.根据前述细节中任一项所述的组合物,其中所述(a)具有式一(F1)的分子与(b)第二分子的重量比率是2:1至1:2。
85D.根据前述细节中任一项所述的组合物,其中所述(a)具有式一(F1)的分子与(b)第二分子的重量比率是1:1。
86D.根据前述细节中任一项所述的组合物,其中所述(a)具有式一(F1)的分子与(b)第二分子的重量比率是X:Y;其中X是(a)具有式一(F1)的分子的重量份并且Y是(b)第二分子的重量份;进一步其中X的重量份的数值范围为0<X≤100并且Y的重量份的数值范围为0<Y≤100;并且进一步其中X和Y选自表4。
87D.根据前述细节中任一项所述的组合物,其中所述(a)具有式一(F1)的分子与(b)第二分子的重量比率是X:Y;其中X是(a)具有式一(F1)的分子的重量份并且Y是(b)第二分子的重量份;进一步其中X是50并且Y的重量份是20;并且进一步其中X和Y选自表4。
88D.一种防治有害生物的方法,所述方法包括向场所应用杀有害生物有效量的根据前述细节1D至87D中任一项所述的组合物。
89D.根据细节88D所述的方法,其中所述有害生物选自由以下组成的组:蚂蚁、蚜虫、臭虫、甲虫、蛀虫、毛毛虫、蟑螂、蟋蟀、蠼螋、跳蚤、苍蝇、草蜢、蛆、叶跳虫、虱、蝗虫、盲蝽、蛆虫、粉介壳虫、螨、蚊子、线虫、飞虱、木虱、根虫、叶蜂、介壳虫、蠹虫、蛞蝓、蜗牛、蜘蛛、跳虫、椿象、综合纲、白蚁、蓟马、扁虱、黄蜂、粉虱、蛴螬和铁线虫。
90D.根据细节88D所述的方法,其中所述有害生物是取食汁液的有害生物。
91D.根据细节88D所述的方法,其中所述有害生物是蚜虫。
92D.根据细节88D所述的方法,其中所述有害生物是飞虱。
93D.根据细节88D所述的方法,其中所述有害生物来自
虱目或半翅目。
94D.根据细节88D所述的方法,其中将所述组合物应用于土壤。
95D.根据细节88D所述的方法,其中将所述组合物应用于植物的叶部分。
96D.根据细节88D所述的方法,其中在所述场所中水稻、香蕉、玉米、咖啡豆、大豆、棉花、坚果、花生、马铃薯、高粱、甘蔗、卡诺拉油菜(canola)、茶树、葡萄、草皮、观赏植物、小麦、大麦、苜蓿、木本果(tree fruit)、热带果树、油棕、栽培作物、或其他果树或蔬菜正在生长。
97D.根据前述细节1D至87D中任一项所述的组合物,所述组合物进一步包含种子。
98D.根据细节97D所述的组合物,其中所述种子是棉花种子、向日葵种子、水稻种子、糖用甜菜种子、油菜种子、玉米种子、小麦种子、大麦种子、粟种子、高粱种子、荞麦种子、燕麦种子、黑麦种子、大豆种子、或藜麦种子。
99D.根据细节97D所述的组合物,其中使用约0.0025mg的(a)具有式一的分子和(b)第二分子/种子至约2.0mg的(a)具有式一的分子和(b)第二分子/种子。
100D.一种组合物,其包含:
(a)具有式一(F1)的分子及其N-氧化物、农业上可接受的酸加成盐、盐衍生物、溶剂化物、酯衍生物、多晶型物、同位素、拆分的立体异构体、和互变异构体
式一,也称为F1,和
(b)选自由以下组成的组的活性成分:氰化钾,伯克霍尔德菌属物种,沃巴赫氏菌,球孢白僵菌菌株,玫烟色拟青霉阿波普卡菌株97,伪苹果卷叶蛾GV,黎豆夜蛾MNPV,棉铃虫NPV,包括合成物、提取物、和未精制的油的植物精华(例如,土荆芥近种臭杏提取物、具有甘油或丙二醇印楝油的脂肪酸单酯),和GS-ω/κHXTX-Hv1a肽。
本文档中的标题仅是为了方便,并且不得用于解释其任何部分。
Claims (10)
1.一种组合物,其包含:
(a)具有式一(F1)的分子
及其N-氧化物、农业上可接受的酸加成盐、盐衍生物、溶剂化物、酯衍生物、多晶型物、同位素、拆分的立体异构体、互变异构体、和放射性核素,以及
(b)第二分子及其N-氧化物、农业上可接受的酸加成盐、盐衍生物、溶剂化物、酯衍生物、多晶型物、同位素、拆分的立体异构体、互变异构体、和放射性核素,其中所述第二分子选自由以下组成的组:
(i)N-(4-氯-2-(吡啶-3-基)噻唑-5-基)-N-乙基-3-(甲基磺酰基)丙酰胺(AI-1)
(ii)反式-5-(3-(3,5-双(三氟甲基)苯基)-2,2-二氯环丙烷-1-甲酰胺基)-2-氯-N-(3-(2,2-二氟乙酰胺基)-2,4-二氟苯基)苯甲酰胺(rac-AI-2)
(iii)5-((1R,3R)-3-(3,5-双(三氟甲基)苯基)-2,2-二氯环丙烷-1-甲酰胺基)-2-氯-N-(3-(2,2-二氟乙酰胺基)-2,4-二氟苯基)苯甲酰胺(R,R-AI-2)
5.根据前述权利要求中任一项所述的组合物,其还包含载体。
6.根据前述权利要求中任一项所述的组合物,所述组合物进一步包含选自AIGA的活性成分。
7.根据前述权利要求中任一项所述的组合物,所述组合物进一步包含选自AIGA-2的活性成分。
8.根据前述权利要求中任一项所述的组合物,所述组合物进一步包含选自AIGA-3的活性成分。
9.根据前述权利要求中任一项所述的组合物,其中,(a)具有式一(F1)的分子与(b)第二分子的重量比率是100:1至1:100。
10.一种防治有害生物的方法,所述方法包括向场所应用杀有害生物有效量的根据前述权利要求1至9中任一项所述的组合物。
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