CN111050559A - 杀有害生物活性吡唑衍生物 - Google Patents
杀有害生物活性吡唑衍生物 Download PDFInfo
- Publication number
- CN111050559A CN111050559A CN201880052290.0A CN201880052290A CN111050559A CN 111050559 A CN111050559 A CN 111050559A CN 201880052290 A CN201880052290 A CN 201880052290A CN 111050559 A CN111050559 A CN 111050559A
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- Prior art keywords
- pyrazol
- spp
- methyl
- ethyl
- species
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- A01N43/48—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
如本文所定义的式(I)的化合物,用于制备所述化合物的方法,包含所述化合物的杀有害生物组合物,特别是杀昆虫、杀螨、杀软体动物以及杀线虫组合物,以及使用所述化合物来对抗和防治诸如昆虫、螨、软体动物和线虫有害生物的有害生物的方法。
Description
本发明涉及吡唑衍生物,用于制备它们的方法,用于制备它们的中间体,包含这些衍生物的杀有害生物组合物,特别是杀昆虫、杀螨、杀软体动物以及杀线虫组合物,以及涉及使用它们来对抗和防治诸如昆虫、螨、软体动物和线虫有害生物的有害生物的方法。
现在已经出人意料地发现某些吡唑衍生物具有高度有效的杀昆虫特性。在此范围内的其他化合物是从WO 2014/122083、WO 2012/107434、WO 2015/067646、WO 2015/067647、WO 2015/067648、WO 2015/150442、WO 2015/193218和WO 2010/051926已知的。
因此,如实施例1,本发明提供了一种式(I)的化合物,
其中
R1选自H、C1-C6-烷基、C2-C6烯基、C2-C6炔基、C3-C7环烷基、C3-C7环烷基-C1-C3-烷基、C1-C6-烷基羰基、C1-C6-烷氧基羰基、芳基(C0-C3)-烷基和杂芳基(C0-C3)-烷基,其中C1-C6-烷基、C3-C6烯基、C3-C6炔基、C3-C7环烷基、C3-C7环烷基-C1-C3-烷基、C1-C6-烷基羰基、C1-C6-烷氧基羰基、芳基(C0-C3)-烷基和杂芳基(C0-C3)-烷基中的每一个是未取代的或被1至5个独立地选自卤素、氰基、C1-C6-烷氧基和C1-C6-烷氧基羰基的取代基取代的;
Q是H或氰基;
A是CH或N;
或其农用化学上可接受的盐或N-氧化物。
如实施例2,提供了根据实施例1所述的化合物,其中R1选自H、异丁基、2,2,2-三氟乙基、-C(=O)CH3、-C(=O)CH2CH3、-C(=O)环丙基、-C(=O)OCH3、-C(=O)OCH2CH3、-C(=O)CH(CH3)(CH3)、-CH2-C-CH、-CH2CN、-CH2-O-CH3、-CH2-O-CH2-CH3、-CH2-环丙基、异丙氧基甲基、乙基、丙基、甲基、异丙基、甲氧基丙基、甲氧基乙基、乙氧基乙基、-C(=O)OCH(CH3)(CH3)、-C(=O)CH2OCH3、-C(=O)OCH(CH3)(CH3)和-C(=O)OCH2Cl。
如实施例2.1,提供了根据实施例1所述的化合物,其中R1选自H、异丁基、2,2,2-三氟乙基、-C(=O)CH3、-C(=O)CH2CH3、-C(=O)环丙基、-C(=O)OCH3、-C(=O)OCH2CH3、-C(=O)CH(CH3)(CH3)、-CH2-C-CH、-CH2CN、-CH2-O-CH3、-CH2-O-CH2-CH3和-CH2-环丙基。
如实施例3,提供了根据实施例1或2所述的化合物,其中R1选自H、异丁基、2,2,2-三氟乙基、环丙基甲基、-C(=O)CH3、-C(=O)OCH3、-C(=O)OCH2CH3、-C(=O)CH(CH3)(CH3)、-CH2-C-CH、-CH2CN和-CH2-O-CH3。
如实施例4,提供了根据实施例1至3中任一项所述的化合物,其中Q是氰基。
如实施例4.1,提供了根据实施例1至4中任一项所述的化合物,其中A是CH。
如实施例5:根据实施例1所述的化合物或盐,其选自
定义:
如本文所用的术语“烷基”(孤立地或作为化学基团的一部分)表示直链或支链的烃,优选具有1至6个碳原子,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙基、1,1-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,2-二甲基丙基、1,3-二甲基丁基、1,4-二甲基丁基、2,3-二甲基丁基、1,1-二甲基丁基、2,2-二甲基丁基、3,3-二甲基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基丁基和2-乙基丁基。具有1至4个碳原子的烷基是优选的,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。
术语“烯基”-孤立地或作为化学基团的一部分-表示直链或支链的烃,优选具有2至6个碳原子和至少一个双键,例如乙烯基、2-丙烯基、2-丁烯基、3-丁烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-甲基-2-丁烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、1-甲基-3-丁烯基、2-甲基-3-丁烯基、3-甲基-3-丁烯基、1,1-二甲基-2-丙烯基、1,2-二甲基-2-丙烯基、1-乙基-2-丙烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基、1-甲基-2-戊烯基、2-甲基-2-戊烯基、3-甲基-2-戊烯基、4-甲基-2-戊烯基、3-甲基-3-戊烯基、4-甲基-3-戊烯基、1-甲基-4-戊烯基、2-甲基-4-戊烯基、3-甲基-4-戊烯基、4-甲基-4-戊烯基、1,1-二甲基-2-丁烯基、1,1-二甲基-3-丁烯基、1,2-二甲基-2-丁烯基、1,2-二甲基-3-丁烯基、1,3-二甲基-2-丁烯基、2,2-二甲基-3-丁烯基、2,3-二甲基-2-丁烯基、2,3-二甲基-3-丁烯基、1-乙基-2-丁烯基、1-乙基-3-丁烯基、2-乙基-2-丁烯基、2-乙基-3-丁烯基、1,1,2-三甲基-2-丙烯基、1-乙基-1-甲基-2-丙烯基和1-乙基-2-甲基-2-丙烯基。具有2至4个碳原子的烯基是优选的,例如2-丙烯基、2-丁烯基或1-甲基-2-丙烯基。
术语“炔基”(孤立地或作为化学基团的一部分)表示直链或支链的烃,优选具有2至6个碳原子和至少一个三键,例如2-丙炔基、2-丁炔基、3-丁炔基、1-甲基-2-丙炔基、2-戊炔基、3-戊炔基、4-戊炔基、1-甲基-3-丁炔基、2-甲基-3-丁炔基、1-甲基-2-丁炔基、1,1-二甲基-2-丙炔基、1-乙基-2-丙炔基、2-己炔基、3-己炔基、4-己炔基、5-己炔基、1-甲基-2-戊炔基、1-甲基-3-戊炔基、1-甲基-4-戊炔基、2-甲基-3-戊炔基、2-甲基-4-戊炔基、3-甲基-4-戊炔基、4-甲基-2-戊炔基、1,1-二甲基-3-丁炔基、1,2-二甲基-3-丁炔基、2,2-二甲基-3-丁炔基、1-乙基-3-丁炔基、2-乙基-3-丁炔基、1-乙基-1-甲基-2-丙炔基和2,5-己二炔基。具有2至4个碳原子的炔基是优选的,例如乙炔基、2-丙炔基或2-丁炔基-2-丙烯基。
术语“环烷基”(孤立地或作为化学基团的一部分)表示饱和的或部分不饱和的单环、二环或三环的烃,优选3至10个碳原子,例如环丙基、环丁基、环戊基、环己基、环庚基、环辛基、二环[2.2.1]庚基、二环[2.2.2]辛基或金刚烷基。
具有3、4、5、6或7个碳原子的环烷基是优选的,例如环丙基或环丁基。
术语“环烷基烷基”表示单环、二环或三环的环烷基烷基,优选4至10个或4至7个碳原子,例如环丙基甲基、环丁基甲基、环戊基甲基、环己基甲基和环戊基乙基。具有4、5或7个碳原子的环烷基烷基是优选的,例如环丙基甲基或环丁基甲基。
术语“卤素”或“卤代”表示氟、氯、溴或碘,特别是氟、氯或溴。被卤素取代的化学基团,例如卤烷基、卤代环烷基、卤代烷氧基、卤代烷基硫烷基、卤代烷基亚磺酰基或卤代烷基磺酰基是被卤素取代一次或直到最大数量的取代基。如果“烷基”、“烯基”或“炔基”被卤素取代,则卤素原子可以是相同或不同的并且可以是结合在同一碳原子或者不同的碳原子上。
术语“卤代环烷基”表示单环、二环或三环的卤代环烷基,优选具有3至10个碳原子,例如1-氟-环丙基、2-氟-环丙基或1-氟-环丁基。优选的卤代环烷基具有3、5或7个碳原子。
术语“卤代烷基”、“卤代烯基”或“卤代炔基”表示被卤素取代的烷基、烯基或炔基,优选被1至9个相同或不同的卤素原子取代,例如单卤代烷基(=单卤烷基)像CH2CH2CI、CH2CH2F、CHCICH3、CHFCH3、CH2CI、CH2F;全卤代烷基,如CCl3或CF3或CF2CF3;多卤代烷基,如CHF2、CH2F、CH2CHFCI、CF2CF2H、CH2CF3。这同样适用于卤代烯基和被卤素取代的其他基团。
卤代烷氧基的实例是例如OCF3、OCHF2、OCH2F、OCF2CF3、OCH2CF3、OCF3、OCHF2、OCH2F、OCF2CF3、OCH2CF3。
卤代烷基的另外的实例是三氯甲基、氯二氟甲基、二氯氟甲基、1-氟乙基、2-氟乙基、2,2-二氟乙基、2,2,2-三氟乙基、2,2,2-三氯乙基、2-氯-2,2-二氟乙基、五氟乙基和五氟-叔丁基。
具有1至4个碳原子和1至9个、优选1至5个相同或不同的选自氟、氯或溴的卤素原子的卤代烷基是优选的。
具有1或2个碳原子和1至5个相同或不同的选自氟或氯的卤素原子的卤代烷基,例如二氟甲基、三氟甲基或2,2-二氟乙基,是特别优选的。
术语“烷氧基”表示直链或支链的O-烷基,优选具有1至6个碳原子,例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基和叔丁氧基。具有1至4个碳原子的烷氧基是优选的。
术语“卤代烷氧基”表示被卤素取代的直链或支链O-烷基,优选具有1至6个碳原子,例如二氟甲氧基、三氟甲氧基、2,2-二氟乙氧基、1,1,2,2-四氟乙氧基、2,2,2-三氟乙氧基和2-氯-1,1,2-三氟乙氧基。
具有1至4个碳原子的卤代烷氧基是优选的。
术语“烷基羰基”表示直链或支链的烷基-C(=O),优选具有2至7个碳原子,例如甲基羰基、乙基羰基、正丙基羰基、异丙基羰基、仲丁基羰基和叔丁基羰基。
具有1至4个碳原子的烷基羰基是优选的。
术语“环烷基羰基”表示环烷基-羰基,优选在环烷基部分中3至10个碳原子,例如环丙基羰基、环丁基羰基、环戊基羰基、环己基-羰基、环庚基-羰基、环辛基羰基、二环[2.2.1]庚基、二环[2.2.2]辛基羰基和金刚烷基羰基。在环烷基部分中具有3、5或7个碳原子的环烷基羰基是优选的。
术语“烷氧基羰基”(孤立地或作为化学基团的一部分)表示直链或支链烷氧基羰基,优选在烷氧基部分中具有1至6个碳原子或1至4个碳原子,例如甲氧基羰基、乙氧基羰基、正丙氧基羰基、异丙氧基羰基、仲丁氧基羰基和叔丁氧基羰基。
术语“烷基氨基羰基”表示在烷基部分中具有优选1至6个碳原子或1至4个碳原子的直链或支链烷基氨基羰基,例如甲基氨基羰基、乙基氨基羰基、正丙基氨基羰基、异丙基-氨基羰基、仲丁基氨基羰基和叔丁基氨基羰基。
术语“芳基”表示具有优选6至14个、更优选6至10个环碳原子的单环、二环或多环的芳族体系,例如苯基、萘基、蒽基、菲基,优选苯基。“芳基”还表示多环体系,例如四氢萘基、茚基、茚满基、芴基、联苯基。芳烷基是取代的芳基的实例,其可以进一步在芳基或烷基部分均被相同或不同的取代基取代。苄基和1-苯基乙基是此类芳烷基的实例。
术语“杂芳基”表示杂芳族基团,即完全不饱和的芳族杂环基团,其落入上述杂环的定义中。具有5至7元环的“杂芳基”,具有1至3个,优选1或2个选自N、O和S的相同或不同的杂原子。“杂芳基”的实例是呋喃基,噻吩基,吡唑基,咪唑基,1,2,3-和1,2,4-三唑基,异噁唑基,噻唑基,异噻唑基,1,2,3-、1,3,4-、1,2,4-和1,2,5-噁二唑基,氮杂卓基,吡咯基,吡啶基,哒嗪基,嘧啶基,吡嗪基,1,3,5-、1,2,4-和1,2,3-三嗪基,1,2,4-、1,3,2-、1,3,6-和1,2,6-噁嗪基,氧杂环庚三烯基,硫杂环庚三烯基,1,2,4-三唑酮基和1,2,4-二氮杂卓基。
术语“杂环基”、“杂环”或“杂环体系”表示具有至少一个环的碳环系统,在该环中至少一个碳原子被杂原子取代,该杂原子优选选自N、O、S、P、B、Si、Se,并且该环是饱和的、不饱和的或部分饱和的,并且该环是未取代的或被取代基Z取代的,其中连接键位于环原子处。除非另外定义,否则该杂环具有优选3至9个环原子、优选3至6个环原子,以及在该杂环中的一个或多个、优选1至4个、更优选1、2或3个杂原子,该杂原子优选选自N、O和S,其中没有可以彼此相邻定位的O原子。杂环通常含有不超过4个氮,和/或不超过2个氧原子和/或不超过2个硫原子。在杂环取代基或杂环被进一步取代的情况下,它可以进一步与其他杂环成环。
具有至少一个碱性中心的根据实施例1至5中任一项所述的化合物可以与以下酸形成例如酸加成盐,这些酸为:例如强无机酸,诸如矿物酸,例如高氯酸、硫酸、硝酸、亚硝酸、磷酸或氢卤酸;强有机羧酸,诸如未取代的或例如被卤素取代的C1-C4烷羧酸(例如乙酸),诸如饱和或不饱和的二羧酸(例如草酸、丙二酸、琥珀酸、马来酸、富马酸或邻苯二甲酸),诸如羟基羧酸(例如抗坏血酸、乳酸、苹果酸、酒石酸或柠檬酸),或诸如苯甲酸;或有机磺酸,诸如未取代的或例如被卤素取代的C1-C4烷-或芳基磺酸(例如甲烷-或对甲苯磺酸)。具有至少一个酸性中心的根据实施例1至5中任一项所述的化合物可以例如与碱形成盐,例如矿物盐,诸如碱金属或碱土金属盐,例如钠盐、钾盐或镁盐;或与氨或有机胺形成盐,该有机胺为诸如吗啉,哌啶,吡咯烷,单、二或三-低级烷基胺,例如乙胺、二乙胺、三乙胺或二甲基丙基胺,或单、二或三羟基-低级烷基胺,例如单乙醇胺、二乙醇胺或三乙醇胺。
根据实施例1至5中任一项所述的化合物还包括在盐形成的过程中可以形成的水合物。
如本文所用,当一个实施例通过使用术语“根据……中任一项”(例如“根据实施例1至5中任一项”)提及若干个其他实施例时,则所述实施例不仅是指由整数(例如1和2)所指的实施例还指由具有小数部分(例如1.1、1.2或2.1、2.2、2.3)的数字所指的实施例。例如,“根据实施例1至3中任一项”例如意指根据实施例1、1.1、2、3、3.1、3.2、3.3、3.4、3.5、3.6、3.7中任一项。
根据实施例1至5中任一项所述的化合物可以通过本领域技术人员熟知的或如在方案1中所示的多种方法制造。关于制备的另外说明可在WO 2015/067646、WO 2015/150442、WO 2015/193218、WO 2014/122083以及WO 2012/107434中找到。
例如,式(Ia)或(Ib)的化合物可以根据方案1制备。
方案1:
其中R1’具有与如实施例1至5中任一项中所定义的R1相同的含义,除了R1’不为H之外,A和Q是如实施例1至5中任一项中所定义的,LG表示诸如Cl、Br、I、OMs、OTs或OTf的离去基团。式(1)、(2)、(5)、(8)、(11)和(12)的化合物是可商购的或在化学文献中是已知的。式(3)的化合物可以通过例如根据Synth.Commun.[合成通讯]2004,34,1541的亲核芳族取代由化合物(1)和(2)来制备。式(4)的化合物可以根据例如在WO 07060525(拜耳-维立格(Bayer-Villiger)氧化)中所描述的方法来制备。式(6)的化合物可以根据例如在WO16174052中所描述的方法由式(4)和(5)的化合物来获得。式(7)的化合物可以根据例如在WO 16044446中所描述的方法通过式(6)的化合物的二氟甲基化来获得。式(9)的化合物可以通过式(7)的化合物与式(8)的硼酸、酯(例如频哪醇酯)或三氟硼酸酯之间的经典Suzuki偶联来获得,如在N.Miyaura,A.Suzuki,Chem.Rev[化学综述].1995,95,2457-2483或在G.A.Molander,L.Jean-Gérard,Org.React[有机反应].2013,79,1-316中所述。式(10)的化合物可以例如通过已知的方法通过式(9)的化合物的水解来获得。式(Ia)的化合物可以通过类似于文献方法由化合物(10)和(11)经由已知的肽偶联方法来制备(例如WO 2010/051926和WO 2010/133312)。式(Ib)的化合物可以根据已知的方法在碱的存在下由式(Ia)和(12)的化合物来制备。
可以通过以惯用方式将根据实施例1至5中任一项所述的起始化合物的一个或多个取代基用根据本发明的另一个或其他一个或多个取代基替代来以本身已知的方式将根据实施例1至5中任一项所述的化合物转化为根据实施例1至5中任一项所述的另一种化合物。
取决于所选的适合各自情况的反应条件以及起始材料,有可能例如,在一个反应步骤中仅将一个取代基用根据本发明的另一个取代基替代,或者在同一个反应步骤中可以将多个取代基用根据本发明的其他取代基来替代。
式(I)的化合物的盐能以本身已知的方式来制备。因此,例如,根据实施例1至5中任一项所述的化合物的酸加成盐是通过用合适的酸或合适的离子交换剂试剂进行处理来获得的,并且与碱的盐是通过用合适的碱或用合适的离子交换剂试剂进行处理来获得的。
可以惯用的方式将根据实施例1至5中任一项所述的化合物的盐转化为游离的化合物I、酸加成盐(例如通过用合适的碱性化合物或用合适的离子交换剂试剂进行处理)以及与碱的盐(例如通过用合适的酸或用合适的离子交换剂试剂进行处理)。
可以本身已知的方式将根据实施例1至5中任一项所述的化合物的盐转化为根据实施例1至5中任一项所述的化合物的其他盐、酸加成盐,例如转化成其他酸加成盐,例如通过在合适的溶剂中用酸的合适的金属盐(诸如钠、钡或银的盐,例如用乙酸银)处理无机酸的盐(诸如盐酸盐),在该溶剂中,所形成的无机盐(例如氯化银)是不溶的并且因此从该反应混合物中沉淀出。
取决于程序或反应条件,具有成盐特性的根据实施例1至5中任一项所述的化合物可以游离形式或盐的形式获得。
取决于分子中存在的不对称碳原子的数目、绝对和相对构型和/或取决于分子中存在的非芳族双键的构型,根据实施例1至5中任一项所述的化合物和适当时其互变异构体(在每种情况下呈游离形式或呈盐形式)可以可能的立体异构体之一的形式或作为这些的混合物存在,例如以纯立体异构体(诸如对映异构体和/或非对映异构体)的形式或作为立体异构体混合物,诸如对映异构体混合物(例如外消旋体、非对映异构体混合物或外消旋体混合物)存在;本发明涉及纯立体异构体以及还有所有可能的立体异构体混合物,并且在上文和下文中在每种情况下都应在这种意义上理解,即使当立体化学细节未在每种情况下明确提及时。
可以将呈游离形式或呈盐形式的根据实施例1至5中任一项所述的化合物的非对映异构体混合物或外消旋体混合物(它们的获得可以取决于已选定的起始材料和程序)在这些组分的物理化学差异的基础上,例如通过分步结晶、蒸馏和/或色谱法以已知的方式分离成纯的非对映异构体或外消旋体。
可以类似方式获得的对映异构体混合物(诸如外消旋体)可以通过已知方法拆分成光学对映异构体,例如通过从光学活性溶剂中重结晶;通过在手性吸附剂上的色谱法,例如在乙酰纤维素上的高效液相色谱法(HPLC);借助于合适的微生物,通过用特异性固定化酶裂解;通过形成包含化合物,例如使用手性冠醚,其中仅一个对映异构体被络合;或通过转化成非对映异构体的盐,例如通过使碱性最终产物外消旋体与光学活性酸(诸如羧酸,例如樟脑酸、酒石酸或苹果酸,或磺酸,例如樟脑磺酸)反应,并且例如基于其不同溶解度通过分步结晶将可以这种方式获得的非对映异构体混合物分离,以给出非对映异构体,可以通过合适的试剂(例如碱性试剂)的作用从这些非对映异构体中使所希望的对映异构体变成游离的。
纯的非对映异构体或对映异构体可以根据本发明来获得,不仅是通过分离合适的立体异构体混合物,而且还通过通常已知的非对映立体选择性或对映选择性合成的方法,例如通过用具有合适的立体化学的起始材料进行根据本发明的方法。
可以通过在酸酐(例如三氟乙酸酐)的存在下使根据实施例1至5中任一项所述的化合物与合适的氧化剂(例如H2O2/尿素加合物)反应来制备N-氧化物。此类氧化从文献,例如从J.Med.Chem.[药物化学杂志]32(12),2561-73,1989或WO 00/15615已知。
如果单独组分具有不同的生物活性,则有利的是在每种情况下分离或合成生物学上更有效的立体异构体,例如对映异构体或非对映异构体或立体异构体混合物,例如对映异构体混合物或非对映异构体混合物。
根据实施例1至5中任一项所述的化合物和适当时其互变异构体(在每种情况下呈游离形式或呈盐形式)如果适当的话还可以水合物的形式获得和/或包括其他溶剂,例如可以用于使以固体形式存在的化合物结晶的那些。
以下实例说明但不限制本发明。
本发明的化合物与已知化合物的区别可以在于在低施用率下更大的疗效,这可以由本领域的普通技术人员使用在实例中概述的实验程序,使用更低的施用率(如果必要的话)例如,50ppm、12.5ppm、6ppm、3ppm、1.5ppm或0.8ppm来证实。
本发明还提供了有用于制备根据实施例1至5中任一项所述的化合物的中间体。某些中间体是新颖的并且本身形成本发明的另一个方面。
一组新颖中间体是式(II)的化合物
其中P是羟基、C1-C15-烷氧基或卤素,如溴、氯或氟,并且A是CH或N。
具体地,一种新颖中间体是式(IIa)的化合物
其中A是CH或N。
另一种新颖中间体是式(IIb)的化合物
其中A是CH或N。
一组新颖中间体是式(III)的化合物
其中U是氢、卤素(如溴、氯或氟)或硼酸(-B(OH)2)或硼酸酯衍生物(例如-B(OR’)2,其中R’是C1-C8-烷基,如甲基或乙基)。
一组新颖中间体是式(IV)的化合物
其中R1、A和Q是如在实施例1至5中任一项所定义的。R1和Q的优选项是与针对根据实施例1至5中任一项所述的化合物的对应取代基所列出的优选项相同的。
一组新颖中间体是式(V)的化合物
其中R1、A和Q是如在实施例1至5中任一项中所定义的,并且XB是卤素、氨基、氰基、C1-C8烷基磺酰基氧基、C1-C8卤代烷基磺酰基氧基、C1-C8芳基磺酰基氧基、任选地取代的C1-C8芳基磺酰基氧基(芳基优选为苯基)、重氮盐(例如-N2 +Cl-、-N2 +BF4 -、-N2 +Br-、-N2 +PF6 -)、膦酸酯(例如-OP(O)(OR’)2,其中R’是甲基或乙基)或硼酸(-B(OH)2)或硼酸酯衍生物(例如-B(OR’)2,其中R’是C1-C8-烷基,如甲基或乙基),优选地XB是溴、碘、氯、氰基、三氟甲基亚砜基、对甲苯亚砜基和重氮氯化物。R1和Q的优选项是与针对根据实施例1至5中任一项所述的化合物的对应取代基所列出的优选项相同的。
根据实施例1至5中任一项所述的化合物在有害生物防治领域中是有预防和/或治疗价值的活性成分(即使是在低的施用量下),这些成分具有非常有利的杀生物谱并且是温血物种、鱼和植物良好耐受的。根据本发明的活性成分对通常敏感而且还抗性的动物有害生物(诸如昆虫或蜱螨目的代表)的全部或单独的发育阶段起作用。根据本发明的活性成分的杀昆虫或杀螨活性可以本身直接显示,即立即或者仅在过去一些时间之后(例如在蜕皮期间)发生对有害生物的破坏;或间接显示,例如降低产卵和/或孵化率。
以上提及的动物有害生物的实例是:
来自蜱螨目,例如
下毛瘿螨属物种(Acalitus spp)、针刺瘿螨属物种(Aculus spp)、窄瘿螨属物种(Acaricalus spp.)、瘤瘿螨属物种(Aceria spp.)、粗脚粉螨(Acarus siro)、钝眼蜱属物种(Amblyomma spp.)、锐缘蜱属物种(Argas spp.)、牛蜱属物种(Boophilus spp.)、短须螨属物种(Brevipalpus spp.)、苔螨属物种(Bryobia spp)、上三脊瘿螨属物种(Calipitrimerus spp.)、皮螨属物种(Chorioptes spp.)、鸡皮刺螨(Dermanyssusgallinae)、表皮螨属物种(Dermatophagoides spp)、始叶螨属物种(Eotetranychus spp)、瘿螨属物种(Eriophyes spp.)、半跗线螨属物种(Hemitarsonemus spp)、璃眼蜱属物种(Hyalomma spp.)、硬蜱属物种(Ixodes spp.)、小爪螨属物种(Olygonychus spp)、钝缘蜱属物种(Ornithodoros spp.)、侧多食跗线螨(Polyphagotarsone latus)、全爪螨属物种(Panonychus spp.)、桔芸锈螨(Phyllocoptruta oleivora)、植食螨属物种(Phytonemusspp.)、多食跗线螨属物种(Polyphagotarsonemus spp)、痒螨属物种(Psoroptes spp.)、扇头蜱属物种(Rhipicephalus spp.)、根螨属物种(Rhizoglyphus spp.)、疥螨属物种(Sarcoptes spp.)、狭跗线螨属物种(Steneotarsonemus spp)、跗线螨属物种(Tarsonemusspp.)以及叶螨属物种(Tetranychus spp.);
来自虱目,例如
血虱属物种(Haematopinus spp.)、长颚虱属物种(Linognathus spp.)、人虱属物种(Pediculus spp.)、瘿绵蚜属物种(Pemphigus spp.)以及根瘤蚜属物种(Phylloxeraspp.);
来自鞘翅目,例如
叩甲属物种(Agriotes spp.)、欧洲鳃角金龟(Amphimallon majale)、东方异丽金龟(Anomala orientalis)、花象属物种(Anthonomus spp.)、蜉金龟属物种(Aphodiusspp)、玉米拟花萤(Astylus atromaculatus)、金龟属物种(Ataenius spp)、甜菜隐食甲(Atomaria linearis)、甜菜胫跳甲(Chaetocnema tibialis)、萤叶甲属物种(Cerotomaspp)、宽胸叩头虫属物种(Conoderus spp)、根颈象属物种(Cosmopolites spp.)、绿花金龟(Cotinis nitida)、象虫属物种(Curculio spp.)、圆头犀金龟属物种(Cyclocephalaspp)、皮蠹属物种(Dermestes spp.)、根萤叶甲属物种(Diabrotica spp.)、阿根廷兜虫(Diloboderus abderus)、食植瓢虫属物种(Epilachna spp.)、Eremnus属物种、黑异爪蔗金龟(Heteronychus arator)、咖啡果小蠹(Hypothenemus hampei)、Lagria vilosa、马铃薯甲虫(Leptinotarsa decemLineata)、稻水象属物种(Lissorhoptrus spp.)、Liogenys属物种、Maecolaspis属物种、栗色绒金龟(Maladera castanea)、美洲叶甲属物种(Megascelisspp)、油菜花露尾甲(Melighetes aeneus)、鳃金龟属物种(Melolontha spp.)、Myochrousarmatus、锯谷盗属物种(Orycaephilus spp.)、耳喙象属物种(Otiorhynchus spp.)、鳃角金龟属物种(Phyllophaga spp.)、斑象属物种(Phlyctinus spp.)、弧丽金龟属物种(Popillia spp.)、蚤跳甲属物种(Psylliodes spp.)、Rhyssomatus aubtilis、劫根蠹属物种(Rhizopertha spp.)、金龟子科(Scarabeidae)、米象属物种(Sitophilus spp.)、麦蛾属物种(Sitotroga spp.)、伪切根虫属物种(Somaticus spp.)、尖隐喙象属物种(Sphenophorus spp)、大豆茎象(Sternechus subsignatus)、拟步行虫属物种(Tenebriospp.)、拟谷盗属物种(Tribolium spp.)以及斑皮蠹属物种(Trogoderma spp.);
来自双翅目,例如
伊蚊属物种(Aedes spp.)、疟蚊属物种(Anopheles spp)、高梁芒蚊(Antherigonasoccata.)、橄榄果实蝇(Bactrocea oleae)、花园毛蚊(Bibio hortulanus)、迟眼蕈蚊属物种(Bradysia spp.)、红头丽蝇(Calliphora erythrocephala)、小条实蝇属物种(Ceratitis spp.)、金蝇属物种(Chrysomyia spp.)、库蚊属物种(Culex spp.)、黄蝇属物种(Cuterebra spp.)、寡鬃实蝇属物种(Dacus spp.)、地种蝇属物种(Delia spp)、黑腹果蝇(Drosophila melanogaster)、厕蝇属物种(Fannia spp.)、胃蝇属物种(Gastrophilusspp.)、Geomyza tripunctata、舌蝇属物种(Glossina spp.)、皮蝇属物种(Hypodermaspp.)、虱蝇属物种(Hyppobosca spp.)、斑潜蝇属物种(Liriomyza spp.)、绿蝇属物种(Lucilia spp.)、黑潜蝇属物种(Melanagromyza spp.)、家蝇属物种(Musca spp.)、狂蝇属物种(Oestrus spp.)、瘿蚊属物种(Orseolia spp.)、瑞典麦秆蝇(Oscinella frit)、藜泉蝇(Pegomyia hyoscyami)、草种蝇属物种(Phorbia spp.)、绕实蝇属物种(Rhagoletisspp)、Rivelia quadrifasciata、Scatella属物种、尖眼蕈蚊属物种(Sciara spp.)、螫蝇属物种(Stomoxys spp.)、虻属物种(Tabanus spp.)、绦虫属物种(Tannia spp.)以及大蚊属物种(Tipula spp.);
来自半翅目,例如
瘤缘蝽(Acanthocoris scabrator)、拟缘蝽属物种(Acrosternum spp)、苜蓿盲蝽(Adelphocoris lineolatus)、土黄缘蝽(Amblypelta nitida)、海虾盾缘蝽(Bathycoeliathalassina)、土长蝽属物种(Blissus spp)、臭虫属物种(Cimex spp.)、Clavigrallatomentosicollis、盲蝽属物种(Creontiades spp.)、可可瘤盲蝽(Distantiellatheobroma)、Dichelops furcatus、棉红蝽属物种(Dysdercus spp.)、埃德萨属物种(Edessa spp)、美洲蝽属物种(Euschistus spp.)、六斑菜蝽(Eurydema pulchrum)、扁盾蝽属物种(Eurygaster spp.)、茶翅蝽(Halyomorpha halys)、具凹巨股长蝽(Horciasnobilellus)、稻缘蝽属物种(Leptocorisa spp.)、草盲蝽属物种(Lygus spp)、热带硕蚧属物种(Margarodes spp)、卷心菜斑色蝽(Murgantia histrionic)、新长缘蝽属物种(Neomegalotomus spp)、烟盲蝽(Nesidiocoris tenuis)、绿蝽属物种(Nezara spp.)、拟长蝽(Nysius simulans)、海岛蝽象(Oebalus insularis)、皮蝽属物种(Piesma spp.)、壁蝽属物种(Piezodorus spp)、红猎蝽属物种(Rhodnius spp.)、可可褐盲蝽(Sahlbergellasingularis)、栗土蝽(Scaptocoris castanea)、黑蝽属物种(Scotinophara spp.)、Thyanta属物种、锥鼻虫属物种(Triatoma spp.)、木薯网蝽(Vatiga illudens);
豌豆无网长管蚜(Acyrthosium pisum)、Adalges属物种、Agalliana ensigera、塔尔吉隆脉木虱(Agonoscena targionii)、粉虱属物种(Aleurodicus spp.)、刺粉虱属物种(Aleurocanthus spp.)、甘蔗穴粉虱(Aleurolobus barodensis)、软毛粉虱(Aleurothrixus floccosus)、甘蓝粉虱(Aleyrodes brassicae)、棉叶蝉(Amarascabiguttula)、檬果长突叶蝉(Amritodus atkinsoni)、肾圆盾蚧属物种(Aonidiella spp.)、蚜科(Aphididae)、蚜属物种(Aphis spp.)、蚧属物种(Aspidiotus spp.)、茄沟无网蚜(Aulacorthum solani)、马铃薯/番茄木虱(Bactericera cockerelli)、小粉虱属物种(Bemisia spp)、短尾蚜属物种(Brachycaudus spp.)、甘蓝蚜(Brevicoryne brassicae)、喀木虱属物种(Cacopsylla spp)、双尾蚜(Cavariella aegopodii Scop.)、蜡蚧属物种(Ceroplaster spp.)、黑褐圆盾蚧(Chrysomphalus aonidium)、橙褐圆盾蚧(Chrysomphalus dictyospermi)、大叶蝉属物种(Cicadella spp)、大白叶蝉(Cofanaspectra)、隐瘤蚜属物种(Cryptomyzus spp)、叶蝉属物种(Cicadulina spp)、褐软蚧(Coccus hesperidum)、玉米黄翅叶蝉(Dalbulus maidis)、裸粉虱属物种(Dialeurodesspp)、柑橘木虱(Diaphorina citri)、麦双尾蚜(Diuraphis noxia)、西圆尾蚜属物种(Dysaphis spp)、小绿叶蝉属物种(Empoasca spp.)、苹果绵蚜(Eriosoma larigerum)、葡萄斑叶蝉属物种(Erythroneura spp.)、Gascardia属物种、赤桉木虱(Glycaspisbrimblecombei)、菜缢管蚜(Hyadaphis pseudobrassicae)、大尾蚜属物种(Hyalopterusspp.)、超瘤蚜种(Hyperomyzus pallidus)、檬果绿叶蝉(Idioscopus clypealis)、非洲叶蝉(Jacobiasca lybica)、灰飞虱属物种(Laodelphax spp.)、水土坚蚧(Lecanium corni)、蛎盾蚧属物种(Lepidosaphes spp.)、萝卜蚜(Lopaphis erysimi)、Lyogenys maidis、长管蚜属物种(Macrosiphum spp.)、沫蝉属物种(Mahanarva spp)、蛾蜡蝉科(Metcalfapruinosa)、麦无网蚜(Metopolophium dirhodum)、麦蜡蝉(Myndus crudus)、瘤蚜属物种(Myzus spp.)、新声蚜属物种(Neotoxoptera sp)、黑尾叶蝉属物种(Nephotettix spp.)、褐飞虱属物种(Nilaparvata spp.)、梨大绿蚜(Nippolachnus piri Mats)、Odonaspisruthae、甘蔗棉蚜(Oregma lanigera Zehnter)、杨梅缘粉虱(Parabemisia myricae)、考氏木虱(Paratrioza cockerelli)、片盾蚧属物种(Parlatoria spp.)、瘿绵蚜属物种(Pemphigus spp.)、玉米蜡蝉(Peregrinus maidis)、扁角飞虱属物种(Perkinsiellaspp)、忽布疣蚜(Phorodon humuli)、根瘤蚜属物种(Phylloxera spp)、动性球菌属物种(Planococcus spp.)、桑白盾蚧属物种(Pseudaulacaspis spp.)、粉蚧属物种(Pseudococcus spp.)、棉跳盲蝽(Pseudatomoscelis seriatus)、木虱属物种(Psyllaspp.)、棉蚧(Pulvinaria aethiopica)、齿盾蚧属物种(Quadraspidiotus spp.)、Quesadagigas、电光叶蝉(Recilia dorsalis)、缢管蚜属物种(Rhopalosiphum spp.)、黑盔蚧属物种(Saissetia spp.)、带叶蝉属物种(Scaphoideus spp.)、二叉蚜属物种(Schizaphisspp.)、麦蚜属物种(Sitobion spp.)、白背飞虱(Sogatella furcifera)、三角苜蓿跳虫(Spissistilus festinus)、条斑飞虱(Tarophagus Proserpina)、声蚜属物种(Toxopteraspp)、粉虱属物种(Trialeurodes spp)、Tridiscus sporoboli、葵粉蚧属物种(Trionymusspp.)、非洲木虱(Trioza erytreae)、矢尖蚧(Unaspis citri)、火焰斑叶蝉(Zyginaflammigera)、Zyginidia scutellaris;
来自膜翅目,例如
顶切叶蚁属物种(Acromyrmex)、三节叶蜂属物种(Arge spp.)、切叶蚁属物种(Atta spp.)、茎叶蜂属物种(Cephus spp.)、松叶蜂属物种(Diprion spp.)、锯角叶蜂科(Diprionidae)、松叶蜂(Gilpinia polytoma)、实叶蜂属物种(Hoplocampa spp.)、毛蚁属物种(Lasius spp.)、小黄家蚁(Monomorium pharaonis)、新松叶蜂属物种(Neodiprionspp.)、农蚁属物种(Pogonomyrmex spp)、红火蚁(Slenopsis invicta)、水蚁属物种(Solenopsis spp.)以及胡蜂属物种(Vespa spp.);
来自等翅目,例如
家白蚁属物种(Coptotermes spp)、白蚁(Corniternes cumulans)、楹白蚁属物种(Incisitermes spp)、大白蚁属物种(Macrotermes spp)、澳白蚁属物种(Mastotermesspp)、小白蚁属物种(Microtermes spp)、散白蚁属物种(Reticulitermes spp.);热带火蚁(Solenopsis geminate)
来自鳞翅目(Lepidoptera),例如,
长翅卷蛾属物种(Acleris spp.)、褐带卷蛾属物种(Adoxophyes spp.)、透翅蛾属物种(Aegeria spp.)、地夜蛾属物种(Agrotis spp.)、棉叶虫(Alabama argillaceae)、Amylois属物种、黎豆夜蛾(Anticarsia gemmatalis)、黄卷蛾属物种(Archips spp.)、银蛾属物种(Argyresthia spp.)、带卷蛾属物种(Argyrotaenia spp.)、丫纹夜蛾属物种(Autographa spp.)、棉潜蛾(Bucculatrix thurberiella)、玉米楷夜蛾(Busseolafusca)、粉斑螟蛾(Cadra cautella)、桃蛀果蛾(Carposina nipponensis)、禾草螟属物种(Chilo spp.)、色卷蛾属物种(Choristoneura spp.)、越蔓桔草螟(Chrysoteuchiatopiaria)、葡萄果蠹蛾(Clysia ambiguella)、卷叶螟属物种(Cnaphalocrocis spp.)、云卷蛾属物种(Cnephasia spp.)、纹卷蛾属物种(Cochylis spp.)、鞘蛾属物种(Coleophoraspp.)、篱笆豆粉蝶(Colias lesbia)、小造桥夜蛾(Cosmophila flava)、草螟属物种(Crambus spp)、大菜螟(Crocidolomia binotalis)、苹果异形小卷蛾(Cryptophlebialeucotreta)、黄杨木蛾(Cydalima perspectalis)、小卷蛾属物种(Cydia spp.)、黄杨绢野螟(Diaphania perspectalis)、杆草螟属物种(Diatraea spp.)、苏丹棉铃虫(Diparopsiscastanea)、钻夜蛾属物种(Earias spp.)、甘薯杆螟(Eldana saccharina)、粉斑螟属物种(Ephestia spp.)、叶小卷蛾属物种(Epinotia spp.)、盐泽灯蛾(Estigmene acrea)、Etiella zinckinella、花小卷蛾属物种(Eucosma spp.)、环针单纹卷蛾(Eupoeciliaambiguella)、黄毒蛾属物种(Euproctis spp.)、切根虫属物种(Euxoa spp.)、Feltiajaculiferia、小食心虫属物种(Grapholita spp.)、云雾广翅小卷蛾(Hedya nubiferana)、实夜蛾属物种(Heliothis spp.)、菜螟(Hellula undalis)、切叶野螟属物种(Herpetogramma spp.)、美国白蛾(Hyphantria cunea)、番茄蠹蛾(Keiferialycopersicella)、Lasmopalpus lignosellus、旋纹潜叶蛾(Leucoptera scitella)、潜叶细蛾属物种(Lithocollethis spp.)、葡萄花翅小卷蛾(Lobesia botrana)、Loxostegebifidalis、毒蛾属物种(Lymantria spp.)、潜蛾属物种(Lyonetia spp.)、幕枯叶蛾属物种(Malacosoma spp.)、甘蓝夜蛾(Mamestra brassicae)、烟草天蛾(Manduca sexta)、光腹夜蛾属物种(Mythimna spp.)、夜蛾属物种(Noctua spp)、秋尺蛾属物种(Operophteraspp.)、Orniodes indica、欧洲玉米螟(Ostrinia nubilalis)、超小卷蛾属物种(Pammenespp.)、褐卷蛾属物种(Pandemis spp.)、小眼夜蛾(Panolis flammea)、蛀茎夜蛾(Papaipema nebris)、红铃麦蛾(Pectinophora gossypiela)、咖啡潜叶蛾(Perileucoptera coffeella)、一星黏虫(Pseudaletia unipuncta)、马铃薯麦蛾(Phthorimaea operculella)、菜粉蝶(Pieris rapae)、粉蝶属物种(Pieris spp.)、小菜蛾(Plutella xylostella)、小白巢蛾属物种(Prays spp.)、尺叶蛾属物种(Pseudoplusiaspp)、薄荷灰夜蛾(Rachiplusia nu)、西方豆地香(Richia albicosta)、白禾螟属物种(Scirpophaga spp.)、蛀茎夜蛾属物种(Sesamia spp.)、长须卷蛾属物种(Sparganothisspp.)、灰翅夜蛾属物种(Spodoptera spp.)、棉大卷叶螟(Sylepta derogate)、兴透翅蛾属物种(Synanthedon spp.)、异舟蛾属物种(Thaumetopoea spp.)、卷蛾属物种(Tortrixspp.)、粉纹夜蛾(Trichoplusia ni)、番茄斑潜蝇(Tuta absoluta)、以及巢蛾属物种(Yponomeuta spp.);
来自食毛目(Mallophaga),例如,
畜虱属物种(Damalinea spp.)和啮毛虱属物种(Trichodectes spp.);
来自直翅目(Orthoptera),例如,
蠊属物种(Blatta spp.)、小蠊属物种(Blattella spp.)、蝼蛄属物种(Gryllotalpa spp.)、马德拉蜚蠊(Leucophaea maderae)、飞蝗属物种(Locusta spp.)、北痣蟋蟀(Neocurtilla hexadactyla)、大蠊属物种(Periplaneta spp.)、痣蟋蟀属物种(Scapteriscus spp.)、以及沙漠蝗属物种(Schistocerca spp.);
来自啮虫目(Psocoptera),例如,
虱啮属物种(Liposcelis spp.);
来自蚤目(Siphonaptera),例如,
角叶蚤属物种(Ceratophyllus spp.)、栉头蚤属物种(Ctenocephalides spp.)以及开皇客蚤(Xenopsylla cheopis);
来自缨翅目(Thysanoptera),例如,
Calliothrips phaseoli、花蓟马属物种(Frankliniella spp.)、阳蓟马属物种(Heliothrips spp)、褐带蓟马属物种(Hercinothrips spp.)、单亲蓟马属物种(Parthenothrips spp.)、非洲桔硬蓟马(Scirtothrips aurantii)、大豆蓟马(Sericothrips variabilis)、带蓟马属物种(Taeniothrips spp.)、蓟马属物种(Thripsspp);
来自缨尾目(Thysanura),例如,衣鱼(Lepisma saccharina)。
根据本发明的活性成分可用于控制、即遏制或破坏上述类型的有害生物,这些有害生物特别出现在植物上,尤其是在农业中、在园艺中以及在林业中的有用的植物和观赏植物上,或者在这些植物的器官上,例如果实、花、叶、茎、块茎或根,并且在一些情况下,甚至在一个随后的时间点形成的植物器官仍保持受保护以抵抗这些有害生物。
适合的目标作物是,特别地是,谷类,如小麦、大麦、黑麦、燕麦、水稻、玉米或高粱;甜菜,诸如糖用甜菜或饲料甜菜;水果,例如梨果、核果或无核小果,诸如苹果、梨、李子、桃、杏、樱桃或浆果,例如草莓、覆盆子或黑莓;豆科作物,诸如菜豆、小扁豆、豌豆或大豆;油料作物,诸如油菜、芥菜、罂粟、橄榄、向日葵、椰子、蓖麻、可可豆或落花生;瓜类作物,诸如南瓜、黄瓜或甜瓜;纤维植物,诸如棉花、亚麻、大麻或黄麻;柑橘类水果,诸如橙、柠檬、葡萄柚或橘子;蔬菜,诸如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、番茄、马铃薯或灯笼椒;樟科,诸如鳄梨、肉桂(Cinnamonium)或樟脑;以及还有烟草、坚果、咖啡、茄子、甘蔗、茶、胡椒、葡萄藤、蛇麻草、车前草科、胶乳植物以及观赏植物。
根据本发明的这些活性成分尤其适合于防治棉花、蔬菜、玉米、水稻以及大豆作物上的扁豆蚜(Aphis craccivora)、黄瓜条叶甲(Diabrotica balteata)、烟芽夜蛾(Heliothis virescens)、桃蚜(Myzus persicae)、小菜蛾(Plutella xylostella)以及海灰翅夜蛾(Spodoptera littoralis)。根据本发明的这些活性成分另外尤其适合于控制甘蓝夜蛾(优选地在蔬菜上)、苹果蠹蛾(优选地在苹果上)、小绿叶蝉(优选地在蔬菜、葡萄园里)、马铃薯叶甲(优选地在马铃薯上)以及二化螟(优选地在水稻上)。
在另一方面中,本发明还可涉及一种防治由植物寄生线虫(内寄生线虫、半内寄生线虫和外寄生线虫)对植物及其部分的损害的方法,尤其是以下植物寄生线虫,如根结线虫(root knot nematodes)、北方根结线虫(Meloidogyne hapla)、南方根结线虫(Meloidogyne incognita)、爪哇根结线虫(Meloidogyne javanica)、花生根结线虫(Meloidogyne arenaria)以及其他根结线虫属物种;孢囊形成线虫(cyst-formingnematodes)、马铃薯金线虫(Globodera rostochiensis)以及其他球孢囊线虫属(Globodera)物种;禾谷孢囊线虫(Heterodera avenae)、大豆孢囊线虫(Heteroderaglycines)、甜菜孢囊线虫(Heterodera schachtii)、红三叶异皮线虫(Heteroderatrifolii)、以及其他异皮线虫属(Heterodera)物种;种瘿线虫(Seed gall nematodes)、粒线虫属(Anguina)物种;茎及叶面线虫(Stem and foliar nematodes)、滑刃线虫属(Aphelenchoides)物种;刺毛线虫(Sting nematodes)、长尾刺线虫(Belonolaimuslongicaudatus)以及其他刺线虫属(Belonolaimus)物种;松树线虫(Pine nematodes)、松材线虫(Bursaphelenchus xylophilus)以及其他伞滑刃属(Bursaphelenchus)物种;环形线虫(Ring nematodes)、环线虫属(Criconema)物种、小环线虫属(Criconemella)物种、轮线虫属(Criconemoides)物种、中环线虫属(Mesocriconema)物种;茎及鳞球茎线虫(Stemand bulb nematodes)、腐烂茎线虫(Ditylenchus destructor)、鳞球茎茎线虫(Ditylenchus dipsaci)以及其他茎线虫属(Ditylenchus)物种;维线虫(Awl nematodes)、锥线虫属(Dolichodorus)物种;螺旋线虫(Spiral nematodes)、多头螺旋线虫(Heliocotylenchus multicinctus)以及其他螺旋线虫属(Helicotylenchus)物种;鞘及鞘形线虫(Sheath and sheathoid nematodes)、鞘线虫属(Hemicycliophora)物种以及半轮线虫属(Hemicriconemoides)物种;潜根线虫属(Hirshmanniella)物种;支线虫(Lancenematodes)、冠线虫属(Hoploaimus)物种;假根结线虫(false rootknot nematodes)、珍珠线虫属(Nacobbus)物种;针状线虫(Needle nematodes)、横带长针线虫(Longidoruselongatus)以及其他长针线虫属(Longidorus)物种;大头针线虫(Pin nematodes)、短体线虫属(Pratylenchus)物种;腐线虫(Lesion nematodes)、花斑短体线虫(Pratylenchusneglectus)、穿刺短体线虫(Pratylenchus penetrans)、弯曲短体线虫(Pratylenchuscurvitatus)、古氏短体线虫(Pratylenchus goodeyi)以及其他短体线虫属(Pratylenchus)物种;柑桔穿孔线虫(Burrowing nematodes)、香蕉穿孔线虫(Radopholussimilis)以及其他内侵线虫属(Radopholus)物种;肾状线虫(Reniform nematodes)、罗柏氏盘旋线虫(Rotylenchus robustus)、肾形盘旋线虫(Rotylenchus reniformis)以及其他盘旋线虫属(Rotylenchus)物种;盾线虫属(Scutellonema)物种;短粗根线虫(Stubby rootnematodes)、原始毛刺线虫(Trichodorus primitivus)以及其他毛刺线虫属(Trichodorus)物种、拟毛刺线虫属(Paratrichodorus)物种;矮化线虫(Stuntnematodes)、马齿苋矮化线虫(Tylenchorhynchus claytoni)、顺逆矮化线虫(Tylenchorhynchus dubius)以及其他矮化线虫属(Tylenchorhynchus)物种;柑桔线虫(Citrus nematodes)、穿刺线虫(Tylenchulus)物种;短剑线虫(Dagger nematodes)、剑线虫属(Xiphinema)物种;以及其他植物寄生线虫物种,如亚粒线虫属物种(Subanguinaspp.)、根结线虫属物种(Hypsoperine spp.)、大刺环线虫属物种(Macroposthonia spp.)、矮化线虫属物种(Melinius spp.)、刻点胞囊属物种(Punctodera spp.)、以及五沟线虫属物种(Quinisulcius spp.)。
根据实施例1至5中任一项所述的化合物还可以具有抵抗软体动物的活性。其实例包括例如福寿螺科(Ampullariidae);蛞蝓科(Arion)(黑蛞蝓(A.ater)、环状蛞蝓(A.circumscriptus)、棕阿勇蛞蝓(A.hortensis)、红蛞蝓(A.rufus));巴蜗牛科(Bradybaenidae)(灌木巴蜗牛(Bradybaena fruticum));葱蜗牛属(Cepaea)(花园葱蜗牛(C.hortensis)、森林葱蜗牛(C.Nemoralis));ochlodina;野蛞蝓属(Deroceras)(野灰蛞蝓(D.agrestis)、D.empiricorum、光滑野蛞蝓(D.laeve)、网纹野蛞蝓(D.reticulatum));圆盘螺属(Discus)(圆形圆盘蜗牛(D.rotundatus));Euomphalia;土蜗属(Galba)(截口土蜗(G.trunculata));小蜗牛属(Helicelia)(伊塔拉小蜗牛(H.itala)、布维小蜗牛(H.obvia));大蜗牛科(Helicidae)(Helicigona arbustorum);Helicodiscus;大蜗牛(Helix)(开口大蜗牛(H.aperta));蛞蝓属(Limax)(利迈科斯蛞蝓(L.cinereoniger)、黄蛞蝓(L.flavus)、边缘蛞蝓(L.marginatus)、大蛞蝓(L.maximus)、柔蛞蝓(L.tenellus));椎实螺属(Lymnaea);Milax(小蛞蝓科)(黑色小蛞蝓(M.gagates)、边缘小蛞蝓(M.marginatus)、硕氏小蛞蝓(M.sowerbyi));钻螺属(Opeas);瓶螺属(Pomacea)(福寿螺(P.canaticulata));瓦娄蜗牛属(Vallonia)和Zanitoides。
术语“作物”应当理解为还包括已经通过使用重组DNA技术而被这样转化使其能够合成一种或多种选择性作用毒素的作物植物,这些毒素是如已知例如来自于产毒素细菌,尤其是芽孢杆菌属的那些细菌。
可由此类转基因植物表达的毒素包括例如杀昆虫蛋白,例如来自蜡样芽胞杆菌(Bacillus cereus)或日本金龟子芽孢杆菌(Bacillus popilliae)的杀昆虫蛋白;或者来自苏云金芽孢杆菌(Bacillus thuringiensis)的杀昆虫蛋白,诸如δ-内毒素,例如Cry1Ab、Cry1Ac、Cry1F、Cry1Fa2、Cry2Ab、Cry3A、Cry3Bb1或Cry9C,或者营养期杀昆虫蛋白(Vip),例如Vip1、Vip2、Vip3或Vip3A;或细菌定植线虫的杀昆虫蛋白,例如光杆状菌属某些种(Photorhabdus spp.)或致病杆菌属某些种(Xenorhabdus spp.),诸如发光杆菌(Photorhabdus luminescens)、嗜线虫致病杆菌(Xenorhabdus nematophilus);由动物产生的毒素,诸如蝎毒素、蛛毒素、蜂毒素和其他昆虫特异性神经毒素;由真菌产生的毒素,诸如链霉菌毒素,植物凝集素类(lectin),诸如豌豆凝集素、大麦凝集素或雪花莲凝集素;凝集素(agglutinin);蛋白酶抑制剂,诸如胰蛋白酶抑制剂、丝蛋白酶抑制剂、马铃薯糖蛋白、胱抑素、木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),诸如蓖麻毒素、玉米-RIP、相思豆毒素、丝瓜籽蛋白、皂草素或异株泻根毒蛋白;类固醇代谢酶,诸如3-羟基类固醇氧化酶、蜕化类固醇-UDP-糖基-转移酶、胆固醇氧化酶、蜕化素抑制剂、HMG-COA-还原酶、离子通道阻断剂诸如钠通道或钙通道阻断剂、保幼激素酯酶、利尿激素受体、芪合酶、联苄合酶、几丁质酶和葡聚糖酶。
在本发明的背景下,δ-内毒素(例如Cry1Ab、Cry1Ac、Cry1F、Cry1Fa2、Cry2Ab、Cry3A、Cry3Bb1或Cry9C)或营养期杀虫蛋白(Vip)(例如Vip1、Vip2、Vip3或Vip3A)应理解为显然还包括混合型毒素、截短的毒素和经修饰的毒素。混合型毒素是通过那些蛋白的不同结构域的新组合重组产生的(参见例如,WO 02/15701)。截短的毒素,例如截短的Cry1Ab是已知的。在经修饰的毒素的情况下,天然存在的毒素的一个或多个氨基酸被置换。在这种氨基酸置换中,优选将非天然存在的蛋白酶识别序列插入毒素中,例如像在Cry3A055的情况下,一种组织蛋白酶-G-识别序列被插入Cry3A毒素中(参见WO 03/018810)。
此类毒素或能够合成此类毒素的转基因植物的实例披露于例如EP-A-0 374 753、WO 93/07278、WO 95/34656、EP-A-0 427 529、EP-A-451 878以及WO 03/052073中。
用于制备这样的转基因植物的方法通常是本领域技术人员已知的并且描述在例如以上提及的公开物中。CryI型脱氧核糖核酸及其制备例如从WO 95/34656、EP-A-0 367474、EP-A-0 401 979和WO 90/13651中已知。
包括在转基因植物中的毒素使得植物对有害昆虫有耐受性。这样的昆虫可以存在于任何昆虫分类群,但尤其常见于甲虫(鞘翅目)、双翅昆虫(双翅目)和蛾(鳞翅目)。
包含一种或多种编码杀昆虫剂抗性并且表达一种或多种毒素的基因的转基因植物是已知的并且其中一些是可商购的。此类植物的实例是:(玉米品种,表达Cry1Ab毒素);YieldGard (玉米品种,表达Cry3Bb1毒素);YieldGard(玉米品种,表达Cry1Ab和Cry3Bb1毒素);(玉米品种,表达Cry9C毒素);(玉米品种,表达Cry1Fa2毒素和获得对除草剂草铵膦铵的耐受性的酶膦丝菌素N-乙酰基转移酶(PAT));NuCOTN(棉花品种,表达Cry1Ac毒素);Bollgard(棉花品种,表达Cry1Ac毒素);Bollgard(棉花品种,表达Cry1Ac和Cry2Ab毒素);(棉花品种,表达Vip3A和Cry1Ab毒素); (马铃薯品种,表达Cry3A毒素);GT Advantage(GA21耐草甘膦性状)、CB Advantage(Bt11玉米螟(CB)性状)以及
此类转基因作物的另外的实例是:
1.Bt11玉米,来自先正达种子公司(Syngenta Seeds SAS),霍比特路(Chemin del'Hobit)27,F-31 790圣苏维尔(St.Sauveur),法国,登记号C/FR/96/05/10。遗传修饰的玉蜀黍,通过转基因表达截短的Cry1Ab毒素,使之能抵抗欧洲玉米螟(玉米螟和粉茎螟)的侵袭。Bt11玉米还转基因表达PAT酶以获得对除草剂草铵膦铵盐的耐受性。
2.Bt176玉米,来自先正达种子公司,霍比特路27,F-31 790圣苏维尔,法国,登记号C/FR/96/05/10。遗传修饰的玉蜀黍,通过转基因表达Cry1Ab毒素,使之能抵抗欧洲玉米螟(玉米螟和粉茎螟)的侵袭。Bt176玉米还转基因表达酶PAT以获得对除草剂草铵膦铵盐的耐受性。
3.MIR604玉米,来自先正达种子公司,霍比特路27,F-31 790圣苏维尔,法国,登记号C/FR/96/05/10。通过转基因表达经修饰的Cry3A毒素使之具有昆虫抗性的玉米。此毒素是通过插入组织蛋白酶-G-蛋白酶识别序列而经修饰的Cry3A055。此类转基因玉米植物的制备描述于WO 03/018810中。
4.MON 863玉米,来自孟山都欧洲公司(Monsanto Europe S.A.),270-272特弗伦大道(Avenue de Tervuren),B-1150布鲁塞尔,比利时,登记号C/DE/02/9。MON 863表达Cry3Bb1毒素,并且对某些鞘翅目昆虫有抗性。
5.IPC 531棉花,来自孟山都欧洲公司,270-272特弗伦大道(Avenue deTervuren),B-1150布鲁塞尔,比利时,登记号C/ES/96/02。
6.1507玉米,来自先锋海外公司(Pioneer Overseas Corporation),特德斯科大道(Avenue Tedesco),7B-1160布鲁塞尔,比利时,登记号C/NL/00/10。遗传修饰的玉米,表达蛋白质Cry1F以获得对某些鳞翅目昆虫的抗性,并且表达PAT蛋白质以获得对除草剂草丁膦铵的耐受性。
7.NK603×MON 810玉米,来自孟山都欧洲公司(Monsanto Europe S.A.),270-272特弗伦大道(Avenue de Tervuren),B-1150布鲁塞尔,比利时,登记号C/GB/02/M3/03。通过将遗传修饰的品种NK603和MON 810杂交,由常规育种的杂交玉米品种构成。NK603×MON810玉米转基因地表达由土壤杆菌属菌株CP4获得的蛋白质CP4 EPSPS,使之耐除草剂(含有草甘膦),以及还有由苏云金芽孢杆菌库尔斯塔克亚种获得的Cry1Ab毒素,使之耐某些鳞翅目昆虫,包括欧洲玉米螟。
抗昆虫的植物的转基因作物还描述于BATS(瑞士,巴塞尔(Basel)4058,克拉斯崔舍(Clarastrasse)13,Zentrum für Biosicherheit und Nachhaltigkeit,Zentrum BATS)报告2003中(https://bats.ch)。
术语“作物”应理解为还包括已经通过使用重组DNA技术而被这样转化使其能够合成具有选择性作用的抗病原物质的作物植物,这些抗病原物质是例如像所谓的“病程相关蛋白”(PRP,参见例如EP-A-0 392 225)。此类抗病原物质和能够合成此类抗病原物质的转基因植物的实例是例如从EP-A-0 392 225、WO 95/33818和EP-A-0 353 191已知的。生产此类转基因植物的方法对于本领域技术人员而言通常是已知的并且描述于例如以上提及的公开物中。
作物也可以经修饰以增加对真菌(例如镰孢霉属、炭疽病或疫霉属)、细菌(例如假单胞菌属)或病毒(例如马铃薯卷叶病毒、番茄斑萎病毒、黄瓜花叶病毒)病原体的抗性。
作物还包括对线虫(如大豆异皮线虫)具有增加的抗性的那些作物。
具有对非生物性胁迫的耐受性的作物包括例如通过表达NF-YB或本领域中已知的其他蛋白质而对干旱、高盐、高温、寒冷、霜或光辐射具有增加的耐受性的那些作物。
可由此类转基因植物表达的抗病原物质包括例如离子通道阻断剂,诸如钠通道和钙通道的阻断剂,例如病毒KP1、KP4或KP6毒素;芪合酶;联苄合酶;几丁质酶;葡聚糖酶;所谓“病程相关蛋白”(PRP;参见例如EP-A-0 392 225);由微生物产生的抗病原物质,例如肽抗生素或杂环抗生素(参见例如WO 95/33818)或参与植物病原体防御的蛋白质或多肽因子(所谓“植物疾病抗性基因”,如WO 03/000906中所描述的)。
根据本发明的组合物的其他使用范围是保护所储存的物品和储存室以及保护原材料,诸如木材、纺织品、地板或建筑物,以及还在卫生领域中,尤其是保护人类、家畜以及生产性牲畜免受所提及类型的有害生物的侵袭。
本发明还提供了一种用于防治有害生物(诸如蚊和其他疾病媒介物;同样参见https://www.who.int/malaria/vector_control/irs/en/)的方法。在一个实施例中,用于控制有害生物的方法包括通过涂刷、轧制、喷雾、涂布或浸渍,向目标有害生物、它们的场所或表面或基底施用本发明的组合物。通过举例,通过本发明的方法考虑到了表面(如墙、天花板或地板表面)的IRS(室内滞留喷雾)施用。在另一个实施例中,考虑到了将此类组合物施用于如下基底,如无纺或织物材料,该材料处于网织品、被覆物、被褥、窗帘以及帐篷的形式(或可以用于在这些物品的制造中使用)。
在另一个实施例中,用于防治此类有害生物的方法包括向目标有害生物、它们的场所或表面或基质施用杀有害生物有效量的本发明的组合物,以便于在该表面或基质上提供有效的滞留的杀有害生物活性。这样的施用可以通过涂刷、轧制、喷雾、涂布或浸渍本发明的杀有害生物组合物来进行。通过举例,通过本发明的方法考虑到了表面(如墙、天花板或地板表面)的IRS施用,以便于在该表面上提供有效的滞留的杀有害生物活性。在另一个实施例中,考虑了施用此类组合物以用于在基底上的有害生物的残留控制,该基底是如处于网织品、被覆物、被褥、窗帘以及帐篷的形式(或可以用于在这些物品的制造中)的织物材料。
有待处理的基底(包括无纺物、织物或网织品)可以由天然纤维,如棉花、拉菲亚树叶纤维、黄麻、亚麻、剑麻、粗麻布或羊毛,或者合成纤维,如聚酰胺、聚酯、聚丙烯、聚丙烯腈等等制成。聚酯是特别适合的。纺织品处理的方法是已知的,例如WO 2008/151984、WO2003/034823、US 5631072、WO 2005/64072、WO 2006/128870、EP 1724392、WO 2005113886或WO 2007/090739。
根据本发明的组合物的其他使用范围是针对所有观赏树木连同所有种类的果树和坚果树的树木注射/树干处理领域。
在树木注射/树干处理领域中,根据本发明的化合物尤其适合于对抗来自如上提及的鳞翅目和来自鞘翅目的钻木昆虫,尤其是对抗下表A和B中列出的钻木虫:
表A.具有经济重要性的外来蛀木虫的实例。
表B.具有经济重要性的本地蛀木虫的实例。
在卫生领域中,根据本发明的组合物有效地对抗外寄生虫如硬蜱、软蜱、疥螨、秋螨、蝇(叮咬和舔舐)、寄生性蝇幼虫,虱、发虱、鸟虱和跳蚤。
此类寄生虫的实例是:
虱目:血虱属物种(Haematopinus spp.)、长腭虱属物种(Linognathus spp.)、人虱属物种(Pediculus spp.)以及阴虱属物种(Phtirus spp.)、管虱属物种(Solenopotesspp.)。
食毛目:毛羽虱属物种(Trimenopon spp.)、短羽虱属物种(Menopon spp.)、鸭虱属物种(Trinoton spp.)、牛羽虱属物种(Bovicola spp.)、Werneckiella属物种、Lepikentron属物种、畜虱属物种(Damalina spp.)、啮毛虱属物种(Trichodectes spp.)以及猫羽虱属物种(Felicola spp.)。
双翅目(Diptera)及长角亚目(Nematocerina)和短角亚目(Brachycerina),例如伊蚊属物种(Aedes spp.)、疟蚊属物种(Anopheles spp.)、库蚊属物种(Culex spp.)、蚋属物种(Simulium spp.)、真蚋属物种(Eusimulium spp.)、白蛉属物种(Phlebotomus spp.)、罗蛉属物种(Lutzomyia spp.)、库蠓属物种(Culicoides spp.)、斑虻属物种(Chrysopsspp.)、驼背虻属物种(Hybomitra spp.)、黄虻属物种(Atylotus spp.)、虻属物种(Tabanusspp.)、麻虻属物种(Haematopota spp.)、Philipomyia属物种、蜂虱蝇属物种(Braulaspp.)、家蝇属物种(Musca spp.)、齿股蝇属物种(Hydrotaea spp.)、螫蝇属物种(Stomoxysspp.)、黑角蝇属物种(Haematobia spp.)、莫蝇属物种(Morellia spp.)、厕蝇属物种(Fannia spp.)、舌蝇属物种(Glossina spp.)、丽蝇属物种(Calliphora spp.)、绿蝇属物种(Lucilia spp.)、金蝇属物种(Chrysomyia spp.)、污蝇属物种(Wohlfahrtia spp.)、麻蝇属物种(Sarcophaga spp.)、狂蝇属物种(Oestrus spp.)、皮蝇属物种(Hypodermaspp.)、胃蝇属物种(Gasterophilus spp.)、虱蝇属物种(Hippobosca spp.)、羊虱蝇属物种(Lipoptena spp.)和蜱蝇属物种(Melophagus spp.)。
蚤目(Siphonapterida),例如蚤属物种(Pulex spp.)、栉头蚤属物种(Ctenocephalides spp.)、客蚤属物种(Xenopsylla spp.)、角叶蚤属物种(Ceratophyllusspp.)。
异翅目(Heteropterida),例如臭虫属物种(Cimex spp.)、锥鼻虫属物种(Triatoma spp.)、红猎蝽属物种(Rhodnius spp.)、锥蝽属物种(Panstrongylus spp.)。
蜚蠊目(Blattarida),例如东方蜚蠊(Blatta orientalis)、美洲大蠊(Periplaneta americana)、德国小蠊(Blattelagermanica)以及夏柏拉蟑螂属物种(Supella spp.)。
蜱螨(Acaria)亚纲(螨科(Acarida))和后气门目(Meta-stigmata)和中气门目(Meso-stigmata),例如锐缘蜱属物种(Argas spp.)、钝缘蜱属物种(Ornithodorus spp.)、耳蜱属物种(Otobius spp.)、硬蜱属物种(Ixodes spp.)、钝眼蜱属物种(Amblyommaspp.)、牛蜱属物种(Boophilus spp.)、革蜱属物种(Dermacentor spp.)、血蜱属物种(Haemophysalis spp.)、璃眼蜱属物种(Hyalomma spp.)、扇头蜱属物种(Rhipicephalusspp.)、皮刺螨属物种(Dermanyssus spp.)、刺利螨属物种(Raillietia spp.)、肺刺螨属物种(Pneumonyssus spp.)、胸刺螨属物种(Sternostoma spp.)和瓦螨属物种(Varroaspp.)。
轴螨目(Actinedida)(前气门亚目(Prostigmata))和粉螨目(Acaridida)(无气门亚目(Astigmata)),例如蜂盾螨属物种(Acarapis spp.)、姬螯螨属物种(Cheyletiellaspp.)、禽螯螨属物种(Ornithocheyletia spp.)、肉螨属物种(Myobia spp.)、疮螨属物种(Psorergates spp.)、蠕形螨属物种(Demodex spp.)、恙螨属物种(Trombicula spp.)、牦螨属物种(Listrophorus spp.)、粉螨属物种(Acarus spp.)、食酪螨属物种(Tyrophagusspp.)、嗜木螨属物种(Caloglyphus spp.)、颈下螨属物种(Hypodectes spp.)、翅螨属物种(Pterolichus spp.)、痒螨属物种(Psoroptes spp.)、皮螨属物种(Chorioptes spp.)、耳痒螨属物种(Otodectes spp.)、疥螨属物种(Sarcoptes spp.)、耳螨属物种(Notoedresspp.)、鸟疥螨属物种(Knemidocoptes spp.)、胞螨属物种(Cytodites spp.)以及鸡雏螨属物种(Laminosioptes spp.)。
根据本发明的组合物还适用于保护在如木材、纺织品、塑料、粘合剂、胶、漆料、纸张和卡片、皮革、地板和建筑等情况下的材料免受昆虫侵染。
根据本发明的组合物可用于,例如,对抗以下有害生物:甲虫,诸如北美家天牛(Hylotrupes bajulus)、长毛天牛(Chlorophorus pilosis)、家具窃蠹(Anobiumpunctatum)、红毛窃蠹(Xestobium rufovillosum)、梳角细脉窃蠹(Ptilinuspecticornis)、Dendrobium pertinex、松芽枝窃蠹(Ernobius mollis)、Priobium carpini、褐粉蠹(Lyctus brunneus)、非洲粉蠹(Lyctus africanus)、南方粉蠹(Lyctus planicollis)、栎粉蠹(Lyctus linearis)、柔毛粉蠹(Lyctus pubescens)、胸粉蠹(Trogoxylon aequale)、鳞毛粉蠹(Minthesrugicollis)、材小蠹属物种(Xyleborusspec.)、条木小蠹属物种(Tryptodendron spec.)、咖啡黑长蠹(Apate monachus)、槲长蠹(Bostrychus capucins)、棕异翅长蠹(Heterobostrychus brunneus)、双棘长蠢属物种(Sinoxylon spec.)以及竹长蠹(Dinoderus minutus),以及还有膜翅类,诸如蓝黑树蜂(Sirex juvencus)、大树蜂(Urocerus gigas)、泰加大树蜂(Urocerus gigas taignus)和Urocerus augu,以及白蚁类,诸如欧洲木白蚁(Kalotermes flavicollis)、麻头堆砂白蚁(Cryptotermes brevis)、印巴结构木异白蚁(Heterotermes indicola)、黄胸散白蚁(Reticulitermes flavipes)、桑特散白蚁(Reticulitermes santonensis)、欧洲散白蚁(Reticulitermes lucifugus)、达尔文澳白蚁(Mastotermes darwiniensis)、内华达古白蚁(Zootermopsis nevadensis)与家白蚁(Coptotermes formosanus),以及蛀虫,诸如衣鱼(Lepisma saccharina)。
在一个方面中,本发明因此还涉及杀有害生物组合物,诸如可乳化性浓缩物、悬浮液浓缩物、微乳液、油分散剂、直接可喷雾或可稀释的溶液、可涂抹的糊剂、稀乳液、可溶性粉剂、可分散性粉剂、可湿性粉剂、尘剂、颗粒剂或在聚合物物质中的包囊剂,这些杀有害生物组合物包含根据实施例1至5中任一项所述的活性成分中的-至少-一种并且这些杀有害生物组合物以适于预期目标和普遍环境来选择。在这些组合物中,活性成分是以纯形式(例如呈特定粒度的固体活性成分)或优选地与在配制品领域中常规使用的助剂中的-至少-一种一起使用的,这些助剂诸如增量剂,例如溶剂或固体载体,或诸如表面活性化合物(表面活性剂)。
合适的溶剂的实例是:未氢化的或部分氢化的芳族烃,优选是C8至C12的烷基苯部分,诸如二甲苯混合物、烷基化的萘或四氢化萘;脂肪族或脂环族烃,诸如石蜡或环己烷;醇,诸如乙醇、丙醇或丁醇;二醇及其醚和酯,诸如丙二醇、二丙二醇醚、乙二醇或乙二醇单甲醚或己二醇单乙醚;酮,诸如环己酮、异佛尔酮或双丙酮醇;强极性溶剂,诸如N-甲基吡咯烷-2-酮、二甲亚砜或N,N-二甲基甲酰胺、水;未环氧化的或环氧化的植物油,诸如未环氧化的或环氧化的菜籽油、蓖麻油、椰子油或大豆油;以及硅油。
用于例如尘剂和可分散性粉剂的固体载体通常是经研磨的天然矿物,诸如方解石、滑石、高岭土、蒙脱石或凹凸棒石。为了改进物理特性,添加高度分散的二氧化硅或高度分散的吸收性聚合物也是可能的。用于颗粒剂的合适的吸附性载体是多孔型的,诸如浮石、砖砾、海泡石或膨润土,并且合适的非吸附性载体材料是方解石或沙。此外,可以使用大量无机或有机天然物的颗粒化材料,特别是白云石或粉碎的植物残余物。
取决于待配制的活性成分的类型,合适的表面活性化合物是非离子型、阳离子型和/或阴离子型表面活性剂或表面活性剂混合物,它们具有良好的乳化、分散和润湿特性。下面提及的表面活性剂应仅看作实例;许多配制品领域常用的并且根据本发明合适的其他表面活性剂描述于相关文献中。
合适的非离子型表面活性剂尤其是脂肪族或环脂肪族醇、饱和或不饱和脂肪酸或烷基酚的聚乙二醇醚衍生物,这些衍生物可以含有大约3至大约30个乙二醇醚基团并且在(环)脂肪族烃基团中含有大约8至大约20个碳原子或在烷基酚的烷基部分中含有大约6至大约18个碳原子。还合适的是水溶性聚环氧乙烷与聚丙二醇、乙二氨基聚丙二醇或烷基聚丙二醇的加合物,这些加合物在烷基链中具有1至大约10个碳原子和大约20至大约250个乙二醇醚基团以及大约10至大约100个丙二醇醚基团。通常,上述化合物含有每个丙二醇单元1至大约5个乙二醇单元。可以提及的实例是壬基苯氧基聚乙氧基乙醇、蓖麻油聚乙二醇醚、聚丙二醇/聚环氧乙烷加合物、三丁基苯氧基聚乙氧基乙醇、聚乙二醇或辛基苯氧基聚乙氧基乙醇。还合适的是聚氧乙烯脱水山梨醇的脂肪酸酯,诸如聚氧乙烯脱水山梨醇三油酸酯。
阳离子型表面活性剂尤其是总体上具有至少一个大约8至大约22个C原子的烷基作为取代基以及(未卤化或卤化的)低级烷基或羟基烷基或苄基作为另外的取代基的季铵盐。这些盐优选是呈卤化物、甲基硫酸盐或乙基硫酸盐的形式。实例是硬脂基三甲基氯化铵和苄基双(2-氯乙基)乙基溴化铵。
合适的阴离子型表面活性剂的实例是水溶性皂类或水溶性合成表面活性化合物。合适的皂类的实例是具有大约10至大约22个碳原子的脂肪酸的碱金属盐、碱土金属盐或(未取代或取代的)铵盐,诸如油酸或硬脂酸的钠盐或钾盐、或可例如从椰子油或妥尔油中获得的天然脂肪酸混合物的钠盐或钾盐;必须提及的还有脂肪酸甲基牛磺酸酯。然而,更常用的是合成表面活性剂,特别是脂肪磺酸盐、脂肪硫酸盐、磺化的苯并咪唑衍生物或烷基芳基磺酸盐。脂肪磺酸盐和脂肪硫酸盐通常以碱金属、碱土金属或(取代或未取代的)铵盐存在,并且它们通常具有含有大约8至大约22个碳原子的烷基,烷基还应理解为包括酰基的烷基部分;可以提及的实例为木质素磺酸、十二烷基硫酸酯或由天然脂肪酸获得的脂肪醇硫酸酯混合物的钠盐或钙盐。此组还包括脂肪醇/环氧乙烷加合物的硫酸酯盐和磺酸盐。磺化的苯并咪唑衍生物优选地含有2个磺酰基和一个大约8至大约22个C原子的脂肪酸基团。烷基芳基磺酸盐的实例是癸基苯磺酸、二丁基萘磺酸或萘磺酸/甲醛缩合物的钠盐、钙盐或三乙醇铵盐。此外,还可能的是合适的磷酸盐,诸如对壬基苯酚/(4-14)环氧乙烷加合物的磷酸酯盐,或磷脂盐。
通常,这些组合物包含0.1%至99%、尤其是0.1%至95%的活性成分以及1%至99.9%、尤其是5%至99.9%的至少一种固体或液体佐剂,原则上可能的是该组合物的0至25%、尤其是0.1%至20%为表面活性剂(在每种情况下%意指重量百分比)。而对于商品而言,倾向于优选的是浓缩的组合物,最终用户通常使用具有实质上更低浓度的活性成分的稀组合物。
典型地,用于叶施用的预混配制品包含0.1%至99.9%、尤其是1%至95%的所希望的成分以及99.9%至0.1%、尤其是99%至5%的固体或液体佐剂(包括例如溶剂,诸如水),其中助剂可以是表面活性剂,其量是基于该预混配制品0至50%、尤其是0.5%至40%。
通常,用于种子处理施用的桶混配制品包含0.25%至80%、尤其是1%至75%的所希望的成分以及99.75%至20%、尤其是99%至25%的固体或液体助剂(包括例如溶剂,诸如水),其中助剂可以是表面活性剂,其量是基于该桶混配制品0至40%、尤其是0.5%至30%。
典型地,用于种子处理施用的预混配制品包含0.5%至99.9%、尤其是1%至95%的所希望的成分以及99.5%至0.1%、尤其是99%至5%的固体或液体佐剂(包括例如溶剂,诸如水),其中助剂可以是表面活性剂,其量是基于该预混配制品0至50%、尤其是0.5%至40%。
而商用的产品将优选地作为浓缩物(例如,预混组合物(配制品))被配制,最终使用者通常将使用稀配制品(例如,桶混组合物)。
优选的种子处理预混配制品是水性悬浮液浓缩物。可以使用常规的处理技术和机器,诸如流化床技术、滚筒碾磨方法、静态转动(rotostatic)种子处理器和转鼓包衣器,将配制品施用到种子上。其他方法(诸如喷出床)也可以是有用的。可以在包衣之前将种子预上浆。包衣之后,将种子典型地进行干燥并且然后转移到上浆机器中以进行上浆。此类程序在本领域是已知的。
总体上,本发明的预混组合物含有按质量计0.5%至99.9%、尤其是1%至95%、有利地是1%至50%的所希望的成分以及按质量计99.5%至0.1%、尤其是99%至5%的固体或液体佐剂(包括例如溶剂,诸如水),其中助剂(或佐剂)可以是表面活性剂,其量是基于该预混配制品的质量按质量计0至50%、尤其是0.5%至40%。
用于预混组合物的叶配制品类型的实例是:
GR:颗粒剂
WP:可湿性粉剂
WG:水可分散性颗粒剂(粉剂)
SG:水溶性颗粒剂
SL:可溶性浓缩物
EC:可乳化浓缩物
EW:水包油乳液
ME:微乳液
SC:水性悬浮液浓缩物
CS:水性胶囊悬浮液
OD:基于油的悬浮液浓缩物,以及
SE:水性悬乳液。
而用于预混组合物的种子处理配制品类型的实例是:
WS:用于种子处理浆料的可湿性粉剂
LS:用于种子处理的溶液
ES:用于种子处理的乳液
FS:用于种子处理的悬浮液浓缩物
WG:水可分散性颗粒剂,以及
CS:水性胶囊悬浮液。
适合于桶混组合物的配制品类型的实例是溶液、稀乳液、悬浮液或其混合物、以及尘剂。
特别地,优选的组合物构成如下(%=重量百分比):
可乳化浓缩物:
活性成分:1%至95%、优选5%至20%
表面活性剂:1%至30%、优选10%至20%
溶剂:5%至98%、优选70%至85%
尘剂:
活性成分:0.1%至10%、优选0.1%至1%
固体载体:99.9%至90%、优选99.9%至99%
悬浮液浓缩物:
活性成分:5%至75%、优选10%至50%
水:94%至24%、优选88%至30%
表面活性剂:1%至40%、优选2%至30%
可湿性粉剂:
活性成分:0.5%至90%、优选1%至80%
表面活性剂:0.5%至20%、优选1%至15%
固体载体:5%至99%、优选15%至98%
颗粒剂:
活性成分:0.5%至30%、优选3%至15%
固体载体:99.5%至70%、优选97%至85%
实例:
根据实施例1的以下化合物可根据本文所述的方法或根据已知的方法制备。
实验
以下实例旨在说明本发明,而不应解释为对其的限制。
“Mp”意指以℃计的熔点。1H NMR测量值在Brucker 400MHz分光计上记录,化学位移相对于TMS标准品以ppm给出。在如指示的氘代溶剂中测量光谱。
LC MS方法A:标准:
光谱记录在来自沃特斯公司的质谱仪(SQD或ZQ单四极杆质谱仪)上,其装备有电喷射源(极性:正离子或负离子,毛细管电压:3.00kV,锥孔范围:30-60V,萃取器:2.00V,源温度:150℃,去溶剂化温度:350℃,锥孔气体流量:0L/Hr,去溶剂化气体流量:650L/Hr,质量范围:100Da至900Da)和来自沃特斯公司的Acquity UPLC:二元泵,加热柱室以及二极管阵列检测器。溶剂脱气装置,二元泵,加热柱室以及二极管阵列检测器。柱:沃特斯UPLC HSST3,1.8μm,30×2.1mm,温度:60℃,DAD波长范围(nm):210至500,溶剂梯度:A=水+5%MeOH+0.05%HCOOH,B=乙腈+0.05%HCOOH:梯度:梯度:0min 0%B,100%A;1.2-1.5min 100%B;流量(ml/min)0.85。
LC MS方法B:标准长(standard long):
光谱记录在来自沃特斯公司的质谱仪(SQD或ZQ单四极杆质谱仪)上,其装备有电喷射源(极性:正离子或负离子,毛细管电压:3.00kV,锥孔范围:30-60V,萃取器:2.00V,源温度:150℃,去溶剂化温度:350℃,锥孔气体流量:0L/Hr,去溶剂化气体流量:650L/Hr,质量范围:100Da至900Da)和来自沃特斯公司的Acquity UPLC:二元泵,加热柱室以及二极管阵列检测器。溶剂脱气装置,二元泵,加热柱室以及二极管阵列检测器。柱:沃特斯UPLC HSST3,1.8μm,30×2.1mm,温度:60℃,DAD波长范围(nm):210至500,溶剂梯度:A=水+5%MeOH+0.05%HCOOH,B=乙腈+0.05%HCOOH:梯度:梯度:0min 0%B,100%A;2.7-3.0min 100%B;流量(ml/min)0.85。
LC MS方法C:非极性:
光谱记录在来自沃特斯公司的质谱仪(SQD或ZQ单四极杆质谱仪)上,其装备有电喷射源(极性:正离子或负离子,毛细管电压:3.00kV,锥孔范围:30-60V,萃取器:2.00V,源温度:150℃,去溶剂化温度:350℃,锥孔气体流量:0L/Hr,去溶剂化气体流量:650L/Hr,质量范围:100Da至900Da)和来自沃特斯公司的Acquity UPLC:二元泵,加热柱室以及二极管阵列检测器。溶剂脱气装置,二元泵,加热柱室以及二极管阵列检测器。柱:沃特斯UPLC HSST3,1.8μm,30×2.1mm,温度:60℃,DAD波长范围(nm):210至500,溶剂梯度:A=水+5%MeOH+0.05%HCOOH,B=乙腈+0.05%HCOOH:梯度:梯度:0min 40%B,60%A;1.2-1.5min 100%B;流量(ml/min)0.85。
实例1:2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四
氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰胺
a)5-(4-溴吡唑-1-基)-1-甲基-吡唑-4-甲醛的制备
向5-氯-1-甲基-吡唑-4-甲醛(7.2g,可商购,根据WO 2008/59370 A2制备)和4-溴-1H-吡唑(7.3g)在乙腈(50mL)中的溶液中添加无水碳酸铯(32g)。将反应混合物在室温下搅拌18h,并且然后加热至60℃持续2h并加热至80℃持续另外的2.5h。将反应混合物冷却至室温然后添加水。将产物用乙酸乙酯萃取,将有机萃取液用水和盐水洗涤,经硫酸镁干燥并蒸发。将粗产物从二氯甲烷/环己烷混合物中重结晶。
1H NMR(400MHz,CDCl3)δppm 3.94(s,3H),7.82(s,1H),8.00(s,1H),8.06(s,1H),9.77(s,1H)。
LC-MS(方法A):tR=0.72min,m/z=255[M+1]。
b)5-(4-溴吡唑-1-基)-1-甲基-吡唑-4-醇的制备
在10min内在60℃-70℃下向5-(4-溴吡唑-1-基)-1-甲基-吡唑-4-甲醛(6.00g)在氯苯(38g)中的搅拌溶液中分批添加不含水的3-氯过氧苯甲酸(5.41g,95%)。将混合物在60℃下搅拌15min,并且然后冷却至40℃。一次性添加氢氧化钠溶液(27mL,2N),并将混合物在45℃下搅拌30min。添加水(10mL)并用1N HCl使反应混合物的pH达到11。将产物用乙酸乙酯(30mL)萃取两次,将合并的萃取液用盐水(10mL)洗涤并蒸发,以得到黄色结晶固体。材料足够纯以直接用于下一步骤。
1H NMR(400MHz,CDCl3)δppm 3.71(s,3H),6.05(br s,1H),7.18(s,1H),7.67(s,1H),7.74(s,1H)。
LC-MS(方法A):tR=0.64min,m/z=241[M-1],243[M+1]。
c)5-(4-溴吡唑-1-基)-1-甲基-3-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-4-醇 的制备
在20min内在62℃-63℃下向5-(4-溴吡唑-1-基)-1-甲基-吡唑-4-醇(1.46g)、1,1,1,2,3,3,3-七氟-2-碘-丙烷(2.66g,9.0mmol)、硫酸铁(II)七水合物(0.36g)和二甲亚砜(13.0g)的搅拌混合物中逐滴地添加30%过氧化氢溶液(2.05g)。由于不完全转化,因此在70℃-75℃下添加了更多的1,1,1,2,3,3,3-七氟-2-碘-丙烷(0.89g),然后逐滴地添加30%过氧化氢溶液(1.33g)。
将反应混合物与60g的水混合并用甲基叔丁基醚(30mL)萃取。将萃取液用水(20mL)洗涤,然后用盐水洗涤并蒸发以给出油状物。
将粗产物通过快速色谱法(二氧化硅,环己烷/乙酸乙酯=9:1)纯化以得到白色结晶材料。
1H NMR(400MHz,CDCl3)δppm 3.84(s,3H),5.62(br s,1H),7.74(s,1H),7.80(s,1H)。
19F NMR(376MHz,CDCl3)δppm-185.58(s,1F),-75.76(s,6F)。
LC-MS(方法A):tR=1.02min,m/z=409[M-1],411[M+1]。
d)5-(4-溴吡唑-1-基)-4-(二氟甲氧基)-1-甲基-3-[1,2,2,2-四氟-1-(三氟甲 基)乙基]吡唑的制备
向冷却至-78℃的5-(4-溴吡唑-1-基)-1-甲基-3-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-4-醇(0.12g)和氢氧化钾(0.33g)于乙腈/水=1:1的混合物(3mL)中的搅拌溶液中添加(溴二氟甲基)膦酸二乙酯(0.16g)。允许反应混合物升温至室温并且然后将其在此温度下搅拌15h。将反应混合物用乙酸乙酯稀释,并且然后依次用水和盐水洗涤。将有机层经硫酸镁干燥,过滤并在真空下蒸发,以得到标题化合物,所述标题化合物未进一步纯化即用于下一个步骤中。
1H NMR(400MHz,CDCl3)δppm 3.87(s,3H),6.25(t,J=73.2Hz,1H),7.80(s,1H),7.82(s,1H)。
19F NMR(376MHz,CDCl3)δppm-186.61(s,1F),-82.66(s,2F),-75.65(s,6F)。
LC-MS(方法A):tR=1.16min,m/z=459[M-1],461[M+1]。
e)2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基] 吡唑-3-基]吡唑-4-基]苯甲酸甲酯的制备
向微波管中装入5-(4-溴吡唑-1-基)-4-(二氟甲氧基)-1-甲基-3-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑(0.130g)、(4-氯-3-甲氧基羰基-苯基)硼酸(0.067g)、Pd(dppf)2Cl2(4.2mg)、无水氟化铯(0.094g)和无水二噁烷(1mL)。将管用氩气吹扫、密封并且在微波反应器中加热至120℃持续30min。将反应混合物用水稀释并且用乙酸乙酯萃取。将有机层依次用水和盐水洗涤,经硫酸镁干燥并蒸发。将粗产物通过快速色谱法(二氧化硅,环己烷/乙酸乙酯梯度为从0至10%)进行纯化。
LC-MS(方法A):tR=1.22min,m/z=549[M-1],551[M+1]。
f)2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基] 吡唑-3-基]吡唑-4-基]苯甲酸的制备
将2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酸甲酯(0.076mg)、氢氧化锂一水合物(0.0116mg)、四氢呋喃(1.7mL)和水(0.4mL)的混合物在室温下搅拌5h。将混合物用1N HCl酸化并且将产物用二氯甲烷萃取。将萃取液经硫酸镁干燥并蒸发,以得到黄色固体。
LC-MS(方法A):tR=1.11min,m/z=535[M-1],537[M+1]。
g)实例1:2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2- 四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰胺的制备
在室温下向2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酸(0.074g)在干燥的二氯甲烷(1.4mL)中的搅拌溶液中添加一滴干燥的二甲基甲酰胺,然后添加草酰氯(0.0357g)。将反应混合物在室温下搅拌30min并然后在40℃下搅拌10min。冷却至室温后,将反应混合物蒸发至干燥。将剩余的酰基氯溶解于干燥的吡啶(1.4mL)中,然后添加1-氨基-1-氰基-环丙烷盐酸盐(0.0245g)。将反应混合物在室温下搅拌1h,然后蒸发至干燥。将残余物通过快速色谱法(二氧化硅,环己烷/乙酸乙酯梯度为从0至40%)进行纯化。
1H NMR(400MHz,CDCl3)δppm 1.44(m,2H),1.71(m,2H),3.93(s,3H),6.27(t,J=73.2Hz,1H),6.90(br s,1H),7.46(d,J=8.4Hz,1H)7.58(dd,J=8.4,2.2Hz,1H),7.96(d,J=2.2Hz,1H),8.06(s,1H),8.14(s,1H)。
19F NMR(376MHz,CDCl3)δppm-186.44(s,1F),-82.48(s,2F),-75.63(s,6F)。
LC-MS(方法A):tR=1.11min,m/z=599[M-1],601[M+1]。
h)实例10:2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2, 2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(乙氧基甲基)苯甲酰胺的制备
在室温下向NaH(24mg,60%在油中)在THF(0.2mL)中的搅拌溶液中添加2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰胺(实例1,600mg)在THF(1.0mL)中的溶液,并且将混合物搅拌30min。将氯甲基乙基醚(37mg)在THF(0.2mL)中的溶液添加到此混合物中,并将整体进一步搅拌30min。将反应混合物用水性氯化铵淬灭,并且将有机相用乙酸乙酯萃取三次。将合并的有机层经硫酸钠干燥,并且将残余物通过硅胶色谱法进行纯化,以得到100mg的呈白色固体的标题产物。
1H NMR(400MHz,CDCl3)δppm 1.09-1.35(m,3H)1.37-1.93(m,4H)3.37(br s,1H)3.75(br s,1H)3.94(d,3H)4.64(br s,1H)4.92-5.39(m,1H)6.27(t,1H)7.45(d,0.5H)7.51-7.65(m,2H)7.79(s,0.5H)7.99-8.23(m,2H)
19F NMR(376MHz,氯仿-d)δppm-186.49(s,1f)-82.55(s,2F)-75.64(s,6F)
LC-MS(方法A):tR=1.20min,m/z=659[M+1]。
与实例1和实例10类似地制备表1中的以下化合物。
表1:式(I)的化合物的实例
配制品实例(%=重量百分比)
蓖麻油聚乙烯
乙二醇醚(36mol的EO) 5% - -
三丁基苯氧基聚乙二醇
任何所希望浓度的乳液可以从这些浓缩物通过用水稀释来制备。
乙二醇单甲
醚 20% - - -
聚乙二醇
石油醚
(沸程:160℃-190℃) - - 94% -
这些溶液适合以微滴的形式使用。
将该活性成分溶解于二氯甲烷中,将该溶液喷雾在一种或多种载体上并且随后将溶剂在真空下进行蒸发。
通过将载体与活性成分均匀混合获得即用型尘剂。
二异丁基-
萘磺酸钠 - 6% 10%
辛基苯氧基聚乙二醇
将活性成分与添加剂混合并且在合适的研磨机中充分地研磨该混合物。这给出了可湿性粉剂,这些可湿性粉剂可以用水进行稀释以给出任何所希望浓度的悬浮液。
实例F6:挤出机颗粒
将活性成分与添加剂混合,并且研磨该混合物,用水湿润,挤出,粒化并在空气流中干燥。
实例F7:包衣颗粒剂
活性成分 3%
聚乙二醇(MW 200) 3%
高岭土 94%
在混合器中,将精细研磨的活性成分均匀地施用到已经用聚乙二醇湿润的高岭土上。这给出了无尘的包衣颗粒。
实例F8:悬浮液浓缩物
将精细研磨的活性成分与添加剂密切混合。任何所希望的浓度的悬浮液可以通过用水稀释从由此产生的悬浮液浓缩物制备。
将该组合与佐剂充分混合并且将该混合物在适合的研磨机中充分研磨,从而获得可以直接用于种子处理的粉剂。
实例F10:可乳化浓缩物
活性成分 10%
辛基酚聚乙二醇醚 3%
(4-5mol的环氧乙烷)
在植物保护中可以使用的具有任何所要求的稀释的乳液可以通过用水稀释从这种浓缩物中获得。
实例F11:种子处理用的可流动性浓缩物
将精细地研磨的组合与佐剂紧密地混合,得到悬浮液浓缩物,从该悬浮液浓缩液可以通过用水稀释获得任何所希望的稀释度的悬浮液。使用此类稀释物,可以对活的植物连同植物繁殖材料进行处理并且对其针对微生物侵染通过喷雾、浇灌或浸渍进行保护。
通过添加其他杀昆虫、杀螨和/或杀真菌活性的成分,根据本发明的组合物的活性可以显著地加宽,并且适合于普遍情况。根据实施例1至5中任一项所述的化合物与其他具有杀昆虫、杀螨和/或杀真菌活性的成分的混合物还可以具有另外出人意料的优点,这些优点还可以在更宽的意义上描述为协同活性。例如,植物的更好的耐受性、降低的植物毒性、昆虫可以在它们的不同发育阶段得到控制、或者在它们的生产期间(例如,在研磨或者混合期间,在它们的储存期间或它们的使用期间)的更好的行为。
在这里,适当添加的活性成分是例如以下类别的活性成分的代表:有机磷化合物、硝基苯酚衍生物、硫脲、保幼激素、甲脒、二苯甲酮衍生物、脲类、吡咯衍生物、氨基甲酸酯、拟除虫菊酯、氯化烃、酰基脲、吡啶基亚甲基氨基衍生物、大环内酯类、新烟碱以及苏芸金芽孢杆菌制剂。
以下根据实施例1至5中任一项所述的化合物与活性成分的混合物是优选的(缩写“TX”意为选自根据实施例1至5中任一项所述的化合物、优选来自实施例5的化合物):
辅助剂,该辅助剂选自由以下组成的物质组:石油(别名)(628)+TX,
杀螨剂,该杀螨剂选自由以下组成的物质组:1,1-双(4-氯苯基)-2-乙氧基乙醇(IUPAC名称)(910)+TX、2,4-二氯苯基苯磺酸酯(IUPAC/化学文摘名)(1059)+TX、2-氟-N-甲基-N-1-萘乙酰胺(IUPAC名称)(1295)+TX、4-氯苯基苯基砜(IUPAC名称)(981)+TX、阿巴美丁(1)+TX、灭螨醌(3)+TX、乙酰虫腈[CCN]+TX、氟丙菊酯(9)+TX、涕灭威(16)+TX、涕灭砜威(863)+TX、α-氯氰菊酯(202)+TX、赛硫磷(870)+TX、磺胺螨酯[CCN]+TX、氨基硫代盐(872)+TX、胺吸磷(875)+TX、胺吸磷草酸氢盐(875)+TX、双甲脒(24)+TX、杀螨特(881)+TX、三氧化二砷(882)+TX、AVI 382(化合物代码)+TX、AZ 60541(化合物代码)+TX、益棉磷(44)+TX、保棉磷(azinphos-methyl)(45)+TX、偶氮苯(IUPAC名称)(888)+TX、三唑锡(azacyclotin)(46)+TX、偶氮磷(azothoate)(889)+TX、苯菌灵(62)+TX、苯诺沙磷(benoxafos)(别名)[CCN]+TX、苯螨特(benzoximate)(71)+TX、苯甲酸苄酯(IUPAC名称)[CCN]+TX、联苯肼酯(74)+TX、氟氯菊酯(76)+TX、乐杀螨(907)+TX、溴灭菊酯(别名)+TX、溴烯杀(bromocyclene)(918)+TX、溴硫磷(920)+TX、乙基溴硫磷(921)+TX、溴螨酯(bromopropylate)(94)+TX、噻嗪酮(99)+TX、丁酮威(103)+TX、丁酮砜威(104)+TX、丁基哒螨灵(butylpyridaben)(别名)+TX、石硫合剂(calcium polysulfide)(IUPAC名称)(111)+TX、毒杀芬(campheechlor)(941)+TX、氯灭杀威(carbanolate)(943)+TX、甲萘威(115)+TX、克百威(carbofuran)(118)+TX、卡波硫磷(947)+TX、CGA 50’439(研究代码)(125)+TX、灭螨猛(chinomethionat)(126)+TX、杀螨醚(chlorbenside)(959)+TX、杀虫脒(964)+TX、杀虫脒盐酸盐(964)+TX、溴虫腈(130)+TX、敌螨(968)+TX、杀螨酯(chlorfenson)(970)+TX、敌螨特(chlorfensulfide)(971)+TX、氯芬磷(131)+TX、乙酯杀螨醇(chlorobenzilate)(975)+TX、伊托明(chloromebuform)(977)+TX、灭虫脲(chloromethiuron)(978)+TX、丙酯杀螨醇(chloropropylate)(983)+TX、毒死蜱(145)+TX、甲基毒死蜱(146)+TX、虫螨磷(chlorthiophos)(994)+TX、瓜菊酯(cinerin)I(696)+TX、瓜菊酯II(696)+TX、瓜菊酯类(cinerins)(696)+TX、四螨嗪(158)+TX、氯氰碘柳胺(别名)[CCN]+TX、库马磷(174)+TX、克罗米通(别名)[CCN]+TX、巴毒磷(crotoxyphos)(1010)+TX、硫杂灵(1013)+TX、果虫磷(cyanthoate)(1020)+TX、丁氟螨酯(CAS登记号:400882-07-7)+TX、三氯氟氰菊酯(196)+TX、三环锡(199)+TX、氯氰菊酯(201)+TX、DCPM(1032)+TX、DDT(219)+TX、田乐磷(demephion)(1037)+TX、田乐磷-O(1037)+TX、田乐磷-S(1037)+TX、内吸磷(demeton)(1038)+TX、甲基内吸磷(224)+TX、内吸磷-O(1038)+TX、甲基内吸磷-O(224)+TX、内吸磷-S(1038)+TX、甲基内吸磷-S(224)+TX、磺吸磷(demeton-S-methylsulfon)(1039)+TX、杀螨隆(226)+TX、氯亚胺硫磷(dialifos)(1042)+TX、二嗪磷(227)+TX、苯氟磺胺(230)+TX、敌敌畏(236)+TX、甲氟磷(dicliphos)(别名)+TX、开乐散(242)+TX、百治磷(243)+TX、遍地克(1071)+TX、甲氟磷(dimefox)(1081)+TX、乐果(262)+TX、二甲杀螨霉素(dinacti)(别名)(653)+TX、消螨酚(dinex)(1089)+TX、消螨酚(dinex-diclexine)(1089)+TX、消螨通(dinobuton)(269)+TX、敌螨普(dinocap)(270)+TX、敌螨普-4[CCN]+TX、敌螨普-6[CCN]+TX、二硝酯(1090)+TX、硝戊酯(dinopenton)(1092)+TX、硝辛酯(dinosulfon)(1097)+TX、硝丁酯(dinoterbon)(1098)+TX、敌恶磷(1102)+TX、二苯砜(IUPAC名称)(1103)+TX、双硫仑(别名)[CCN]+TX、乙拌磷(278)+TX、DNOC(282)+TX、苯氧炔螨(dofenapyn)(1113)+TX、多拉克汀(别名)[CCN]+TX、硫丹(294)+TX、因毒磷(endothion)(1121)+TX、EPN(297)+TX、依立诺克丁(别名)[CCN]+TX、乙硫磷(309)+TX、益硫磷(ethoate-methyl)(1134)+TX、乙螨唑(etoxazole)(320)+TX、乙嘧硫磷(etrimfos)(1142)+TX、抗螨唑(fenazaflor)(1147)+TX、喹螨醚(328)+TX、苯丁锡(fenbutatin oxide)(330)+TX、苯硫威(fenothiocarb)(337)+TX、甲氰菊酯(342)+TX、吡螨胺(fenpyrad)(别名)+TX、唑螨酯(fenpyroximate)(345)+TX、芬螨酯(fenson)(1157)+TX、氟硝二苯胺(fentrifanil)(1161)+TX、氰戊菊酯(349)+TX、氟虫腈(354)+TX、嘧螨酯(fluacrypyrim)(360)+TX、氟佐隆(1166)+TX、氟螨噻(flubenzimine)(1167)+TX、氟螨脲(366)+TX、氟氰戊菊酯(flucythrinate)(367)+TX、联氟螨(fluenetil)(1169)+TX、氟虫脲(370)+TX、氟氯苯菊酯(flumethrin)(372)+TX、氟杀螨(fluorbenside)(1174)+TX、氟胺氰菊酯(fluvalinate)(1184)+TX、FMC 1137(研究代码)(1185)+TX、抗螨脒(405)+TX、抗螨脒盐酸盐(405)+TX、安硫磷(formothion)(1192)+TX、胺甲威(formparanate)(1193)+TX、γ-HCH(430)+TX、果绿啶(glyodin)(1205)+TX、苄螨醚(halfenprox)(424)+TX、庚烯醚(heptenophos)(432)+TX、十六碳烷基环丙烷甲酸酯(IUPAC/化学文摘名)(1216)+TX、噻螨酮(441)+TX、碘甲烷(IUPAC名称)(542)+TX、水胺硫磷(isocarbophos)(别名)(473)+TX、异丙基O-(甲氧基氨基硫代磷酰基)水杨酸酯(IUPAC名称)(473)+TX、伊维菌素(别名)[CCN]+TX、茉莉菊酯(jasmolin)I(696)+TX、茉莉菊酯II(696)+TX、碘硫磷(jodfenphos)(1248)+TX、林丹(430)+TX、虱螨脲(490)+TX、马拉硫磷(492)+TX、丙螨氰(malonoben)(1254)+TX、灭蚜磷(mecarbam)(502)+TX、地安磷(mephosfolan)(1261)+TX、甲硫芬(别名)[CCN]+TX、虫螨畏(methacrifos)(1266)+TX、甲胺磷(527)+TX、杀扑磷(529)+TX、灭虫威(530)+TX、灭多虫(531)+TX、溴甲烷(537)+TX、速灭威(metolcarb)(550)+TX、速灭磷(556)+TX、自克威(mexacarbate)(1290)+TX、米尔螨素(557)+TX、米尔贝肟(milbemycin oxime)(别名)[CCN]+TX、丙胺氟磷(mipafox)(1293)+TX、久效磷(561)+TX、茂硫磷(morphothion)(1300)+TX、莫昔克丁(别名)[CCN]+TX、二溴磷(naled)(567)+TX、NC-184(化合物代码)+TX、NC-512(化合物代码)+TX、氟蚊灵(nifluridide)(1309)+TX、尼柯霉素(别名)[CCN]+TX、戊氰威(nitrilacarb)(1313)+TX、戊氰威(nitrilacarb)1:1氯化锌络合物(1313)+TX、NNI-0101(化合物代码)+TX、NNI-0250(化合物代码)+TX、氧乐果(omethoate)(594)+TX、杀线威(602)+TX、亚异砜磷(oxydeprofos)(1324)+TX、砜拌磷(oxydisulfoton)(1325)+TX、pp’-DDT(219)+TX、对硫磷(615)+TX、氯菊酯(626)+TX、石油油料(别名)(628)+TX、芬硫磷(1330)+TX、稻丰散(631)+TX、甲拌磷(636)+TX、伏杀硫磷(637)+TX、硫环磷(phosfolan)(1338)+TX、亚胺硫磷(638)+TX、磷胺(639)+TX、辛硫磷(642)+TX、甲基嘧啶磷(652)+TX、氯化松节油(polychloroterpenes)(传统名称)(1347)+TX、杀螨霉素(polynactins)(别名)(653)+TX、丙氯诺(1350)+TX、丙溴磷(662)+TX、蜱虱威(promacyl)(1354)+TX、克螨特(671)+TX、胺丙畏(propetamphos)(673)+TX、残杀威(678)+TX、乙噻唑磷(prothidathion)(1360)+TX、发硫磷(prothoate)(1362)+TX、除虫菊酯I(696)+TX、除虫菊酯II(696)+TX、除虫菊素(pyrethrins)(696)+TX、哒螨灵(699)+TX、哒嗪硫磷(pyridaphenthion)(701)+TX、嘧螨醚(pyrimidifen)(706)+TX、嘧硫磷(1370)+TX、喹硫磷(quinalphos)(711)+TX、喹硫磷(quintiofos)(1381)+TX、R-1492(研究代码)(1382)+TX、RA-17(研究代码)(1383)+TX、鱼藤酮(722)+TX、八甲磷(schradan)(1389)+TX、硫线磷(sebufos)(别名)+TX、塞拉菌素(selamectin)(别名)[CCN]+TX、SI-0009(化合物代码)+TX、苏硫磷(sophamide)(1402)+TX、季酮螨酯(738)+TX、螺甲螨酯(739)+TX、SSI-121(研究代码)(1404)+TX、舒非仑(别名)[CCN]+TX、氟虫胺(sulfluramid)(750)+TX、治螟磷(sulfotep)(753)+TX、硫黄(754)+TX、SZI-121(研究代码)(757)+TX、τ-氟胺氰菊酯(398)+TX、吡螨胺(763)+TX、TEPP(1417)+TX、叔丁威(terbam)(别名)+TX、司替罗磷(777)+TX、三氯杀螨砜(tetradifon)(786)+TX、杀螨霉素(tetranactin)(别名)(653)+TX、杀螨硫醚(tetrasul)(1425)+TX、久效威(thiafenox)(别名)+TX、抗虫威(thiocarboxime)(1431)+TX、久效威(thiofanox)(800)+TX、甲基乙拌磷(thiometon)(801)+TX、克杀螨(1436)+TX、苏力菌素(thuringiensin)(别名)[CCN]+TX、威菌磷(triamiphos)(1441)+TX、苯噻螨(triarathene)(1443)+TX、三唑磷(820)+TX、唑呀威(triazuron)(别名)+TX、敌百虫(824)+TX、氯苯乙丙磷(trifenofos)(1455)+TX、甲杀螨霉素(trinactin)(别名)(653)+TX、蚜灭多(847)+TX、氟吡唑虫(vaniliprole)[CCN]和YI-5302(化合物代码)+TX,
杀藻剂,该杀藻剂选自由以下组成的物质组:百杀辛(bethoxazin)[CCN]+TX、二辛酸铜(IUPAC名称)(170)+TX、硫酸铜(172)+TX、cybutryne[CCN]+TX、二氯萘醌(dichlone)(1052)+TX、双氯酚(232)+TX、茵多酸(295)+TX、三苯锡(fentin)(347)+TX、熟石灰[CCN]+TX、代森钠(nabam)(566)+TX、灭藻醌(quinoclamine)(714)+TX、醌萍胺(quinonamid)(1379)+TX、西玛津(730)+TX、三苯基乙酸锡(IUPAC名称)(347)和三苯基氢氧化锡(IUPAC名称)(347)+TX,
驱蠕虫剂,该驱蠕虫剂选自由以下组成的物质组:阿巴美丁(1)+TX、克芦磷酯(1011)+TX、多拉克汀(别名)[CCN]+TX、埃玛菌素(291)+TX、埃玛菌素苯甲酸酯(291)+TX、依立诺克丁(别名)[CCN]+TX、伊维菌素(别名)[CCN]+TX、米尔贝肟(别名)[CCN]+TX、莫昔克丁(别名)[CCN]+TX、哌嗪[CCN]+TX、司拉克丁(selamectin)(别名)[CCN]+TX、多杀菌素(737)和托布津(thiophanate)(1435)+TX,
杀鸟剂,该杀鸟剂选自由以下组成的物质组:氯醛糖(127)+TX、异狄氏剂(1122)+TX、倍硫磷(346)+TX、吡啶-4-胺(IUPAC名称)(23)和士的宁(745)+TX,
杀细菌剂,该杀细菌剂选自由以下组成的物质组:1-羟基-1H-吡啶-2-硫酮(IUPAC名称)(1222)+TX、4-(喹喔啉-2-基氨基)苯磺酰胺(IUPAC名称)(748)+TX、8-羟基喹啉硫酸盐(446)+TX、溴硝醇(97)+TX、二辛酸铜(IUPAC名称)(170)+TX、氢氧化铜(IUPAC名称)(169)+TX、甲酚[CCN]+TX、双氯酚(232)+TX、双吡硫翁(1105)+TX、多地辛(1112)+TX、敌磺钠(fenaminosulf)(1144)+TX、甲醛(404)+TX、汞加芬(别名)[CCN]+TX、春雷霉素(483)+TX、春雷霉素盐酸盐水合物(483)+TX、二(二甲基二硫代氨基甲酸)镍(IUPAC名称)(1308)+TX、三氯甲基吡啶(nitrapyrin)(580)+TX、辛噻酮(octhilinone)(590)+TX、奥索利酸(606)+TX、土霉素(611)+TX、羟基喹啉硫酸钾(446)+TX、噻菌灵(probenazole)(658)+TX、链霉素(744)+TX、链霉素倍半硫酸盐(744)+TX、叶枯酞(766)+TX、和硫柳汞(别名)[CCN]+TX,
生物试剂,该生物试剂选自由以下组成的物质组:棉褐带卷蛾GV(别名)(12)+TX、放射形土壤杆菌(别名)(13)+TX、钝绥螨属物种(Amblyseius spp.)(别名)(19)+TX、芹菜夜蛾NPV(别名)(28)+TX、原樱翅缨小蜂(Anagrus atomus)(别名)(29)+TX、短距蚜小蜂(Aphelinus abdominalis)(别名)(33)+TX、棉蚜寄生蜂(Aphidius colemani)(别名)(34)+TX、食蚜瘿蚊(Aphidoletes aphidimyza)(别名)(35)+TX、苜蓿银纹夜蛾NPV(别名)(38)+TX、坚强芽孢杆菌(Bacillus firmus)(别名)(48)+TX、球形芽孢杆菌(Bacillussphaericus Neide)(学名)(49)+TX、苏云金芽孢杆菌(Bacillus thuringiensisBerliner)(学名)(51)+TX、苏云金芽孢杆菌鲇泽亚种(Bacillus thuringiensissubsp.aizawai)(学名)(51)+TX、苏云金芽孢杆菌以色列亚种(Bacillus thuringiensissubsp.israelensis)(学名)(51)+TX、苏云金芽孢杆菌日本亚种(Bacillus thuringiensissubsp.japonensis)(学名)(51)+TX、苏云金芽孢杆菌库尔斯塔克亚种(Bacillusthuringiensis subsp.kurstaki)(学名)(51)+TX、苏云金芽孢杆菌拟步行甲亚种(Bacillus thuringiensis subsp.tenebrionis)(学名)(51)+TX、球孢白僵菌(Beauveriabassiana)(别名)(53)+TX、布氏白僵菌(Beauveria brongniartii)(别名)(54)+TX、普通草蛉(Chrysoperla carnea)(别名)(151)+TX、孟氏隐唇瓢虫(Cryptolaemus montrouzieri)(别名)(178)+TX、苹果蠹蛾GV(别名)(191)+TX、西伯利亚离颚茧蜂(Dacnusa sibirica)(别名)(212)+TX、豌豆潜叶蝇姬小蜂(Diglyphus isaea)(别名)(254)+TX、丽蚜小蜂(Encarsiaformosa)(学名)(293)+TX、桨角蚜小蜂(Eretmocerus eremicus)(别名)(300)+TX、谷实夜蛾NPV(别名)(431)+TX、嗜菌异小杆线虫(Heterorhabditis bacteriophora)和大异小杆线虫(H.megidis)(别名)(433)+TX、斑长足瓢虫(Hippodamia convergens)(别名)(442)+TX、橘粉介壳虫寄生蜂(Leptomastix dactylopii)(别名)(488)+TX、盲蝽(Macrolophuscaliginosus)(别名)(491)+TX、甘蓝夜蛾NPV(别名)(494)+TX、黄阔柄跳小蜂(Metaphycushelvolus)(别名)(522)+TX、黄绿绿僵菌(Metarhizium anisopliae var.acridum)(学名)(523)+TX、金龟子绿僵菌小孢变种(Metarhizium anisopliae var.anisopliae)(学名)(523)+TX、欧洲新松叶蜂(Neodiprion sertifer)NPV和红头新松叶蜂(N.lecontei)NPV(别名)(575)+TX、小花蝽属物种(别名)(596)+TX、玫烟色拟青霉(Paecilomycesfumosoroseus)(别名)(613)+TX、智利小植绥螨(Phytoseiulus persimilis)(别名)(644)+TX、甜菜夜蛾核多角体病毒(Spodoptera exigua multicapsid nuclear polyhedrosisvirus)(学名)(741)+TX、毛蚊线虫(Steinernema bibionis)(别名)(742)+TX、小卷蛾斯氏线虫(Steinernema carpocapsae)(别名)(742)+TX、夜蛾斯氏线虫(别名)(742)+TX、格氏线虫(Steinernema glaseri)(别名)(742)+TX、锐比斯氏线虫(Steinernema riobrave)(别名)(742)+TX、Steinernema riobravis(别名)(742)+TX、蝼蛄斯氏线虫(Steinernemascapterisci)(别名)(742)+TX、斯氏线虫属物种(Steinernema spp.)(别名)(742)+TX、赤眼蜂属物种(别名)(826)+TX、西方盲走螨(Typhlodromus occidentalis)(别名)(844)和蜡蚧轮枝菌(Verticillium lecanii)(别名)(848)+TX,
土壤消毒剂,该土壤消毒剂选自由以下组成的物质组:碘甲烷(IUPAC名称)(542)和溴甲烷(537)+TX,
化学不育剂,该化学不育剂选自由以下组成的物质组:唑磷嗪(apholate)[CCN]+TX、双(氮丙啶)甲氨基膦硫化物(bisazir)(别名)[CCN]+TX、白消安(别名)[CCN]+TX、除虫脲(250)+TX、迪麦替夫(dimatif)(别名)[CCN]+TX、六甲蜜胺(hemel)[CCN]+TX、六甲磷(hempa)[CCN]+TX、甲基涕巴(metepa)[CCN]+TX、甲硫涕巴(methiotepa)[CCN]+TX、甲基唑磷嗪(methyl apholate)[CCN]+TX、不孕啶(morzid)[CCN]+TX、氟幼脲(penfluron)(别名)[CCN]+TX、涕巴(tepa)[CCN]+TX、硫代六甲磷(thiohempa)(别名)[CCN]+TX、硫涕巴(别名)[CCN]+TX、曲他胺(别名)[CCN]和尿烷亚胺(别名)[CCN]+TX,
昆虫信息素,该昆虫信息素选自由以下组成的物质组:(E)-癸-5-烯-1-基乙酸酯与(E)-癸-5-烯-1-醇(IUPAC名称)(222)+TX、(E)-十三碳-4-烯-1-基乙酸酯(IUPAC名称)(829)+TX、(E)-6-甲基庚-2-烯-4-醇(IUPAC名称)(541)+TX、(E,Z)-十四碳-4,10-二烯-1-基乙酸酯(IUPAC名称)(779)+TX、(Z)-十二碳-7-烯-1-基乙酸酯(IUPAC名称)(285)+TX、(Z)-十六碳-11-烯醛(IUPAC名称)(436)+TX、(Z)-十六碳-11-烯-1-基乙酸酯(IUPAC名称)(437)+TX、(Z)-十六碳-13-烯-11-炔-1-基乙酸酯(IUPAC名称)(438)+TX、(Z)-二十-13-烯-10-酮(IUPAC名称)(448)+TX、(Z)-十四碳-7-烯-1-醛(IUPAC名称)(782)+TX、(Z)-十四碳-9-烯-1-醇(IUPAC名称)(783)+TX、(Z)-十四碳-9-烯-1-基乙酸酯(IUPAC名称)(784)+TX、(7E,9Z)-十二碳-7,9-二烯-1-基乙酸酯(IUPAC名称)(283)+TX、(9Z,11E)-十四碳-9,11-二烯-1-基乙酸酯(IUPAC名称)(780)+TX、(9Z,12E)-十四碳-9,12-二烯-1-基乙酸酯(IUPAC名称)(781)+TX、14-甲基十八碳-1-烯(IUPAC名称)(545)+TX、4-甲基壬-5-醇与4-甲基壬-5-酮(IUPAC名称)(544)+TX、α-多纹素(alpha-multistriatin)(别名)[CCN]+TX、西部松小蠹集合信息素(brevicomin)(别名)[CCN]+TX、十二碳二烯醇(codlelure)(别名)[CCN]+TX、可得蒙(codlemone)(别名)(167)+TX、诱蝇酮(cuelure)(别名)(179)+TX、环氧十九烷(disparlure)(277)+TX、十二碳-8-烯-1-基乙酸酯(IUPAC名称)(286)+TX、十二碳-9-烯-1-基乙酸酯(IUPAC名称)(287)+TX、十二碳-8+TX、10-二烯-1-基乙酸酯(IUPAC名称)(284)+TX、dominicalure(别名)[CCN]+TX、4-甲基辛酸乙酯(IUPAC名称)(317)+TX、丁香酚(别名)[CCN]+TX、南部松小蠹集合信息素(frontalin)(别名)[CCN]+TX、诱虫十六酯(gossyplure)(别名)(420)+TX、诱杀烯混剂(grandlure)(421)+TX、诱杀烯混剂I(别名)(421)+TX、诱杀烯混剂II(别名)(421)+TX、诱杀烯混剂III(别名)(421)+TX、诱杀烯混剂IV(别名)(421)+TX、己诱剂(hexalure)[CCN]+TX、齿小蠹二烯醇(ipsdienol)(别名)[CCN]+TX、小蠢烯醇(ipsenol)(别名)[CCN]+TX、金龟子性诱剂(japonilure)(别名)(481)+TX、三甲基二氧三环壬烷(lineatin)(别名)[CCN]+TX、litlure(别名)[CCN]+TX、粉纹夜蛾性诱剂(looplure)(别名)[CCN]+TX、诱杀酯(medlure)[CCN]+TX、megatomoic acid(别名)[CCN]+TX、诱虫醚(methyl eugenol)(别名)(540)+TX、诱虫烯(muscalure)(563)+TX、十八碳-2,13-二烯-1-基乙酸酯(IUPAC名称)(588)+TX、十八碳-3,13-二烯-1-基乙酸酯(IUPAC名称)(589)+TX、贺康彼(orfralure)(别名)[CCN]+TX、椰蛀犀金龟聚集信息素(oryctalure)(别名)(317)+TX、非乐康(ostramone)(别名)[CCN]+TX、诱虫环(siglure)[CCN]+TX、sordidin(别名)(736)+TX、食菌甲诱醇(sulcatol)(别名)[CCN]+TX、十四碳-11-烯-1-基乙酸酯(IUPAC名称)(785)+TX、地中海实蝇引诱剂(839)+TX、地中海实蝇引诱剂A(别名)(839)+TX、地中海实蝇引诱剂B1(别名)(839)+TX、地中海实蝇引诱剂B2(别名)(839)+TX、地中海实蝇引诱剂C(别名)(839)和trunc-call(别名)[CCN]+TX,
昆虫驱避剂,该昆虫驱避剂选自由以下组成的物质组:2-(辛基硫代)乙醇(IUPAC名称)(591)+TX、避蚊酮(butopyronoxyl)(933)+TX、丁氧基(聚丙二醇)(936)+TX、己二酸二丁酯(IUPAC名称)(1046)+TX、邻苯二甲酸二丁酯(1047)+TX、丁二酸二丁酯(IUPAC名称)(1048)+TX、避蚊胺[CCN]+TX、驱蚊灵(dimethyl carbate)[CCN]+TX、邻苯二甲酸二甲酯[CCN]+TX、乙基己二醇(1137)+TX、己脲[CCN]+TX、甲喹丁(methoquin-butyl)(1276)+TX、甲基新癸酰胺[CCN]+TX、草氨酸盐(oxamate)[CCN]和派卡瑞丁[CCN]+TX,
杀昆虫剂,该杀昆虫剂选自由以下组成的物质组:1-二氯-1-硝基乙烷(IUPAC/化学文摘名称)(1058)+TX、1,1-二氯-2,2-二(4-乙基苯基)乙烷(IUPAC名称)(1056)+TX、1,2-二氯丙烷(IUPAC/化学文摘名称)(1062)+TX、带有1,3-二氯丙烯的1,2-二氯丙烷(IUPAC名称)(1063)+TX、1-溴-2-氯乙烷(IUPAC/化学文摘名称)(916)+TX、乙酸2,2,2-三氯-1-(3,4-二氯苯基)乙基酯(IUPAC名称)(1451)+TX、2,2-二氯乙烯基2-乙基亚磺酰基乙基甲基磷酸酯(IUPAC名称)(1066)+TX、二甲基氨基甲酸2-(1,3-二硫杂环戊烷-2-基)苯基酯(IUPAC/化学文摘名称)(1109)+TX、硫氰酸2-(2-丁氧基乙氧基)乙基酯(IUPAC/化学文摘名称)(935)+TX、甲基氨基甲酸2-(4,5-二甲基-1,3-二氧环戊烷-2-基)苯基酯(IUPAC/化学文摘名称)(1084)+TX、2-(4-氯-3,5-二甲苯基氧基)乙醇(IUPAC名称)(986)+TX、2-氯乙烯基二乙基磷酸酯(IUPAC名称)(984)+TX、2-咪唑啉酮(IUPAC名称)(1225)+TX、2-异戊酰基茚满-1,3-二酮(IUPAC名称)(1246)+TX、甲基氨基甲酸2-甲基(丙-2-炔基)氨基苯基酯(IUPAC名称)(1284)+TX、月桂酸2-硫氰基乙基酯(IUPAC名称)(1433)+TX、3-溴-1-氯丙-1-烯(IUPAC名称)(917)+TX、二甲基氨基甲酸3-甲基-1-苯基吡唑-5-基酯(IUPAC名称)(1283)+TX、甲基氨基甲酸4-甲基(丙-2-炔基)氨基-3,5-二甲苯基酯(IUPAC名称)(1285)+TX、二甲基氨基甲酸5,5-二甲基-3-氧代环己-1-烯基酯(IUPAC名称)(1085)+TX、阿巴美丁(1)+TX、乙酰甲胺磷(2)+TX、啶虫脒(4)+TX、家蝇磷(别名)[CCN]+TX、乙酰虫腈[CCN]+TX、氟丙菊酯(9)+TX、丙烯腈(IUPAC名称)(861)+TX、棉铃威(15)+TX、涕灭威(16)+TX、涕灭砜威(863)+TX、氯甲桥萘(864)+TX、烯丙菊酯(17)+TX、阿洛氨菌素(别名)[CCN]+TX、除害威(866)+TX、α-氯氰菊酯(202)+TX、α-蜕皮激素(别名)[CCN]+TX、磷化铝(640)+TX、赛硫磷(870)+TX、硫代酰胺(872)+TX、灭害威(873)+TX、胺吸磷(875)+TX、胺吸磷草酸氢盐(875)+TX、双甲脒(24)+TX、新烟碱(877)+TX、乙基杀扑磷(883)+TX、AVI 382(化合物代码)+TX、AZ 60541(化合物代码)+TX、印楝素(别名)(41)+TX、甲基吡啶磷(42)+TX、谷硫磷-乙基(44)+TX、谷硫磷-甲基(45)+TX、偶氮磷(889)+TX、苏云金芽孢杆菌δ内毒素类(别名)(52)+TX、六氟硅酸钡(别名)[CCN]+TX、多硫化钡(IUPAC/化学文摘名称)(892)+TX、熏菊酯[CCN]+TX、Bayer 22/190(研究代码)(893)+TX、Bayer22408(研究代码)(894)+TX、噁虫威(58)+TX、丙硫克百威(60)+TX、杀虫磺(66)+TX、β-氟氯氰菊酯(194)+TX、β-氯氰菊酯(203)+TX、联苯菊酯(76)+TX、生物烯丙菊酯(78)+TX、生物烯丙菊酯S-环戊烯基异构体(别名)(79)+TX、戊环苄呋菊酯(bioethanomethrin)[CCN]+TX、生物氯菊酯(908)+TX、除虫菊酯(80)+TX、二(2-氯乙基)醚(IUPAC名称)(909)+TX、双三氟虫脲(83)+TX、硼砂(86)+TX、溴灭菊酯(别名)+TX、溴苯烯磷(914)+TX、溴杀烯(918)+TX、溴-DDT(别名)[CCN]+TX、溴硫磷(920)+TX、溴硫磷-乙基(921)+TX、合杀威(924)+TX、噻嗪酮(99)+TX、畜虫威(926)+TX、脱甲基丁嘧啶磷(butathiofos)(927)+TX、丁酮威(103)+TX、丁酯膦(932)+TX、丁酮砜威(104)+TX、丁基哒螨灵(别名)+TX、硫线磷(109)+TX、砷酸钙[CCN]+TX、氰化钙(444)+TX、多硫化钙(IUPAC名称)(111)+TX、毒杀芬(941)+TX、氯灭杀威(943)+TX、甲萘威(115)+TX、克百威(118)+TX、二硫化碳(IUPAC/化学文摘名称)(945)+TX、四氯化碳(IUPAC名称)(946)+TX、三硫磷(947)+TX、丁硫克百成(119)+TX、杀螟丹(123)+TX、杀螟丹盐酸盐(123)+TX、西伐丁(别名)(725)+TX、冰片丹(960)+TX、氯丹(128)+TX、开蓬(963)+TX、杀虫脒(964)+TX、杀虫脒盐酸盐(964)+TX、氯氧磷(129)+TX、溴虫腈(130)+TX、毒虫畏(131)+TX、定虫隆(132)+TX、氯甲磷(136)+TX、氯仿[CCN]+TX、三氯硝基甲烷(141)+TX、氯辛硫磷(989)+TX、灭虫吡啶(990)+TX、毒死蜱(145)+TX、毒死蜱-甲基(146)+TX、虫螨磷(994)+TX、环虫酰肼(150)+TX、灰菊素I(696)+TX、灰菊素II(696)+TX、灰菊素类(696)+TX、顺式苄呋菊酯(cis-resmethrin)(别名)+TX、顺式苄呋菊酯(cismethrin)(80)+TX、功夫菊酯(别名)+TX、除线威(999)+TX、氯氰碘柳胺(别名)[CCN]+TX、噻虫胺(165)+TX、乙酰亚砷酸铜[CCN]+TX、砷酸铜[CCN]+TX、油酸铜[CCN]+TX、蝇毒磷(174)+TX、畜虫磷(1006)+TX、克罗米通(别名)[CCN]+TX、巴毒磷(1010)+TX、克芦磷酯(1011)+TX、冰晶石(别名)(177)+TX、CS708(研究代码)(1012)+TX、苯腈膦(1019)+TX、杀螟睛(184)+TX、果虫磷(1020)+TX、环虫菊酯[CCN]+TX、乙氰菊酯(188)+TX、氟氯氰菊酯(193)+TX、三氯氟氰菊酯(196)+TX、氯氰菊酯(201)+TX、苯氰菊酯(206)+TX、环丙马秦(209)+TX、畜蜱磷(别名)[CCN]+TX、d-柠檬烯(别名)[CCN]+TX、d-四甲菊酯(别名)(788)+TX、DAEP(1031)+TX、棉隆(216)+TX、DDT(219)+TX、单甲基克百威(decarbofuran)(1034)+TX、溴氰菊酯(223)+TX、田乐磷(1037)+TX、田乐磷-O(1037)+TX、田乐磷-S(1037)+TX、内吸磷(1038)+TX、内吸磷-甲基(224)+TX、内吸磷-O(1038)+TX、内吸磷-O-甲基(224)+TX、内吸磷-S(1038)+TX、内吸磷-S-甲基(224)+TX、磺吸磷(demeton-S-methylsulphon)(1039)+TX、丁醚脲(226)+TX、氯亚胺硫磷(1042)+TX、二胺磷(1044)+TX、二嗪磷(227)+TX、异氯磷(1050)+TX、除线磷(1051)+TX、敌敌畏(236)+TX、迪克力弗斯(dicliphos)(别名)+TX、迪克莱赛尔(dicresyl)(别名)[CCN]+TX、百治磷(243)+TX、地昔尼尔(244)+TX、狄氏刑(1070)+TX、二乙基5-甲基吡唑-3-基磷酸酯(IUPAC名称)(1076)+TX、除虫脲(250)+TX、二羟丙茶碱(dilor)(别名)[CCN]+TX、四氟甲醚菊酯[CCN]+TX、甲氟磷(1081)+TX、地麦威(1085)+TX、乐果(262)+TX、苄菊酯(1083)+TX、甲基毒虫畏(265)+TX、敌蝇威(1086)+TX、消螨酚(1089)+TX、消螨酚(dinex-diclexine)(1089)+TX、丙硝酚(1093)+TX、戊硝酚(1094)+TX、达诺杀(1095)+TX、呋虫胺(271)+TX、苯虫醚(1099)+TX、蔬果磷(1100)+TX、二氧威(1101)+TX、敌恶磷(1102)+TX、乙拌磷(278)+TX、苯噻乙双硫磷(dithicrofos)(1108)+TX、DNOC(282)+TX、多拉克汀(别名)[CCN]+TX、DSP(1115)+TX、蜕皮激素(别名)[CCN]+TX、EI 1642(研究代码)(1118)+TX、依马克丁(291)+TX、依马克丁苯甲酸酯(291)+TX、EMPC(1120)+TX、烯炔菊酯(292)+TX、硫丹(294)+TX、因毒磷(1121)+TX、异狄氏剂(1122)+TX、EPBP(1123)+TX、EPN(297)+TX、保幼醚(1124)+TX、依立诺克丁(别名)[CCN]+TX、高氰戊菊酯(302)+TX、牛津郡丙硫磷(etaphos)(别名)[CCN]+TX、乙硫苯威(308)+TX、乙硫磷(309)+TX、乙虫腈(310)+TX、益硫磷-甲基(1134)+TX、灭线磷(312)+TX、甲酸乙酯(IUPAC名称)[CCN]+TX、乙基-DDD(别名)(1056)+TX、二溴化乙烯(316)+TX、二氯化乙烯(化学名称)(1136)+TX、环氧乙烷[CCN]+TX、醚菊酯(319)+TX、乙嘧硫磷(1142)+TX、EXD(1143)+TX、氨磺磷(323)+TX、苯线磷(326)+TX、抗螨唑(1147)+TX、皮蝇磷(1148)+TX、苯硫威(1149)+TX、芬氟司林(1150)+TX、杀螟硫磷(335)+TX、丁苯威(336)+TX、嘧酰虫胺(fenoxacrim)(1153)+TX、苯氧威(340)+TX、吡氯氰菊酯(1155)+TX、甲氰菊酯(342)+TX、吡螨胺(fenpyrad)(别名)+TX、丰索磷(1158)+TX、倍硫磷(346)+TX、倍硫磷-乙基[CCN]+TX、氰戊菊酯(349)+TX、氟虫腈(354)+TX、氟啶虫酰胺(358)+TX、氟虫酰胺(CAS登记号:272451-65-7)+TX、氟氯双苯隆(flucofuron)(1168)+TX、氟环脲(366)+TX、氟氰戊菊酯(367)+TX、联氟螨(1169)+TX、嘧虫胺[CCN]+TX、氟虫脲(370)+TX、三氟醚菊酯(1171)+TX、氟氯苯菊酯(372)+TX、氟胺氰菊酯(1184)+TX、FMC 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60-38(研究代码)(1328)+TX、芬硫磷(1330)+TX、苯醚菊酯(630)+TX、稻丰散(631)+TX、甲拌磷(636)+TX、伏杀硫磷(637)+TX、硫环磷(1338)+TX、亚胺硫磷(638)+TX、对氯硫磷(1339)+TX、磷胺(639)+TX、磷化氢(IUPAC名称)(640)+TX、辛硫磷(642)+TX、辛硫磷-甲基(1340)+TX、甲胺嘧磷(pirimetaphos)(1344)+TX、抗蚜威(651)+TX、乙基嘧啶磷(1345)+TX、甲基嘧啶磷(652)+TX、聚氯二环戊二烯异构体类(IUPAC名称)(1346)+TX、聚氯萜类(传统名称)(1347)+TX、亚砷酸钾[CCN]+TX、硫氰酸钾[CCN]+TX、丙炔菊酯(655)+TX、早熟素I(别名)[CCN]+TX、早熟素II(别名)[CCN]+TX、早熟素III(别名)[CCN]+TX、乙酰嘧啶磷(primidophos)(1349)+TX、丙溴磷(662)+TX、丙氟菊酯[CCN]+TX、蜱虱威(1354)+TX、猛杀威(1355)+TX、丙虫磷(1356)+TX、胺丙畏(673)+TX、残杀威(678)+TX、乙噻唑磷(1360)+TX、丙硫磷(686)+TX、发硫磷(1362)+TX、丙苯烃菊酯(protrifenbute)[CCN]+TX、吡蚜酮(688)+TX、吡唑硫磷(689)+TX、定菌磷(693)+TX、苄呋菊酯(pyresmethrin)(1367)+TX、除虫菊酯I(696)+TX、除虫菊酯II(696)+TX、除虫菊酯类(696)+TX、哒螨灵(699)+TX、啶虫丙醚(700)+TX、哒嗪硫磷(701)+TX、嘧螨醚(706)+TX、嘧硫磷(1370)+TX、吡丙醚(708)+TX、苦木提取物(quassia)(别名)[CCN]+TX、喹硫磷(quinalphos)(711)+TX、喹硫磷-甲基(1376)+TX、畜宁磷(1380)+TX、喹硫磷(quintiofos)(1381)+TX、R-1492(研究代码)(1382)+TX、雷复尼特(别名)[CCN]+TX、苄呋菊酯(719)+TX、鱼藤酮(722)+TX、RU 15525(研究代码)(723)+TX、RU 25475(研究代码)(1386)+TX、尼亚那(ryania)(别名)(1387)+TX、利阿诺定(传统名称)(1387)+TX、沙巴藜芦(别名)(725)+TX、八甲磷(1389)+TX、硫线磷(别名)+TX、塞拉菌素(别名)[CCN]+TX、SI-0009(化合物代码)+TX、SI-0205(化合物代码)+TX、SI-0404(化合物代码)+TX、SI-0405(化合物代码)+TX、氟硅菊酯(728)+TX、SN72129(研究代码)(1397)+TX、亚砷酸钠[CCN]+TX、氰化钠(444)+TX、氟化钠(IUPAC/化学文摘名称)(1399)+TX、六氟硅酸钠(1400)+TX、五氯酚钠(623)+TX、硒酸钠(IUPAC名称)(1401)+TX、硫氰酸钠[CCN]+TX、苏硫磷(1402)+TX、多杀菌素(737)+TX、螺甲螨酯(739)+TX、螺虫乙酯(CCN)+TX、萨尔科福隆(sulcofuron)(746)+TX、萨尔科福隆钠(sulcofuron-sodium)(746)+TX、氟虫胺(750)+TX、治螟磷(753)+TX、磺酰氟(756)+TX、硫丙磷(1408)+TX、焦油(别名)(758)+TX、τ-氟胺氰菊酯(398)+TX、噻螨威(1412)+TX、TDE(1414)+TX、虫酰肼(762)+TX、吡螨胺(763)+TX、丁基嘧啶磷(764)+TX、氟苯脲(768)+TX、七氟菊酯(769)+TX、双硫磷(770)+TX、TEPP(1417)+TX、环戊烯丙菊酯(1418)+TX、叔丁威(terbam)(别名)+TX、特丁硫磷(773)+TX、四氯乙烷[CCN]+TX、杀虫畏(777)+TX、四甲菊酯(787)+TX、θ氯氰菊酯(204)+TX、噻虫啉(791)+TX、塞芬诺克斯(thiafenox)(别名)+TX、噻虫嗪(792)+TX、苯噻硫磷(thicrofos)(1428)+TX、克虫威(1431)+TX、杀虫环(798)+TX、杀虫环草酸氢盐(798)+TX、硫双威(799)+TX、久效威(800)+TX、甲基乙拌磷(801)+TX、虫线磷(1434)+TX、杀虫单(thiosultap)(803)+TX、杀虫双(thiosultap-sodium)(803)+TX、苏云金素(别名)[CCN]+TX、唑虫酰胺(809)+TX、四溴菊酯(812)+TX、四氟苯菊酯(813)+TX、反式苄氯菊酯(transpermethrin)(1440)+TX、威菌磷(1441)+TX、唑蚜威(818)+TX、三唑磷(820)+TX、唑呀威(别名)+TX、敌百虫(824)+TX、三氯偏磷酸-3(trichlormetaphos-3)(别名)[CCN]+TX、毒壤膦(1452)+TX、三氯丙氧磷(1455)+TX、杀铃脲(835)+TX、混杀威(840)+TX、烯虫硫酯(1459)+TX、蚜灭磷(847)+TX、甲烯氟虫腈(vaniliprole)[CCN]+TX、藜芦定(别名)(725)+TX、藜芦碱(别名)(725)+TX、XMC(853)+TX、灭杀威(854)+TX、YI-5302(化合物代码)+TX、ζ-氯氰菊酯(205)+TX、泽塔米林(zetamethrin)(别名)+TX、磷化锌(640)+TX、丙硫恶唑磷(zolaprofos)(1469)以及ZXI8901(研究代码)(858)+TX、氰虫酰胺[736994-63-19]+TX、氯虫酰胺[500008-45-7]+TX、唑螨氰(cyenopyrafen)[560121-52-0]+TX、丁氟螨酯[400882-07-7]+TX、氟虫吡喹(pyrifluquinazon)[337458-27-2]+TX、乙基多杀菌素(spinetoram)[187166-40-1+187166-15-0]+TX、螺虫乙酯[203313-25-1]+TX、砜虫啶(sulfoxaflor)[946578-00-3]+TX、丁虫腈(flufiprole)[704886-18-0]+TX、氯氟醚菊酯[915288-13-0]+TX、四氟醚菊酯(tetramethylfluthrin)[84937-88-2]+TX、三氟苯嘧啶(triflumezopyrim)(披露于WO2012/092115中)+TX,
杀软体动物剂,该杀软体动物剂选自由以下组成的物质组:二(三丁基锡)氧化物(IUPAC名称)(913)+TX、溴乙酰胺[CCN]+TX、砷酸钙[CCN]+TX、除线威(cloethocarb)(999)+TX、乙酰亚砷酸铜[CCN]+TX、硫酸铜(172)+TX、三苯锡(347)+TX、磷酸铁(IUPAC名称)(352)+TX、四聚乙醛(518)+TX、灭虫威(530)+TX、氯硝柳胺(576)+TX、氯硝柳胺-乙醇胺(576)+TX、五氯酚(623)+TX、五氯苯氧化钠(623)+TX、噻螨威(tazimcarb)(1412)+TX、硫双威(799)+TX、三丁基氧化锡(913)+TX、蜗螺杀(trifenmorph)(1454)+TX、混杀威(trimethacarb)(840)+TX、三苯基乙酸锡(IUPAC名称)(347)和三苯基氢氧化锡(IUPAC名称)(347)+TX、吡唑虫啶(pyriprole)[394730-71-3]+TX,
杀线虫剂,该杀线虫剂选自由以下各项组成的物质组:AKD-3088(化合物代码)+TX、1,2-二溴-3-氯丙烷(IUPAC/化学文摘名称)(1045)+TX、1,2-二氯丙烷(IUPAC/化学文摘名称)(1062)+TX、1,2-二氯丙烷与1,3-二氯丙烯(IUPAC名称)(1063)+TX、1,3-二氯丙烯(233)+TX、3,4-二氯四氢噻吩1,1-二氧化物(IUPAC/化学文摘名称)(1065)+TX、3-(4-氯苯基)-5-甲基罗丹宁(IUPAC名称)(980)+TX、5-甲基-6-硫代-1,3,5-噻二嗪-3-基乙酸(IUPAC名称)(1286)+TX、6-异戊烯基氨基嘌呤(别名)(210)+TX、阿维菌素(1)+TX、乙酰虫腈[CCN]+TX、棉铃威(15)+TX、涕灭威(aldicarb)(16)+TX、涕灭砜威(863)+TX、AZ 60541(化合物代码)+TX、苯氯噻(benclothiaz)[CCN]+TX、苯菌灵(62)+TX、丁基哒螨灵(别名)+TX、克线丹(109)+TX、克百威(carbofuran)(118)+TX、二硫化碳(945)+TX、丁硫克百威(119)+TX、氯化苦(141)+TX、毒死蜱(145)+TX、除线威(999)+TX、细胞分裂素(别名)(210)+TX、棉隆(216)+TX、DBCP(1045)+TX、DCIP(218)+TX、除线特(diamidafos)(1044)+TX、除线磷(1051)+TX、二克磷(dicliphos)(别名)+TX、乐果(262)+TX、多拉克汀(别名)[CCN]+TX、埃玛菌素(291)+TX、埃玛菌素苯甲酸酯(291)+TX、依立诺克丁(别名)[CCN]+TX、灭线磷(312)+TX、二溴乙烷(316)+TX、苯线磷(326)+TX、fenpyrad(别名)+TX、丰索磷(1158)+TX、噻唑磷(408)+TX、丁硫环磷(1196)+TX、糠醛(别名)[CCN]+TX、GY-81(研究代码)(423)+TX、速杀硫磷[CCN]+TX、碘甲烷(IUPAC名称)(542)+TX、异酰胺磷(isamidofos)(1230)+TX、氯唑磷(1231)+TX、伊维菌素(别名)[CCN]+TX、激动素(别名)(210)+TX、甲基减蚜磷(1258)+TX、威百亩(519)+TX、威百亩钾盐(别名)(519)+TX、威百亩钠盐(519)+TX、溴甲烷(537)+TX、异硫氰酸甲酯(543)+TX、米尔贝肟(别名)[CCN]+TX、莫昔克丁(别名)[CCN]+TX、疣孢漆斑菌(Myrotheciumverrucaria)组合物(别名)(565)+TX、NC-184(化合物代码)+TX、杀线威(602)+TX、甲拌磷(636)+TX、磷胺(639)+TX、磷虫威[CCN]+TX、克线丹(别名)+TX、司拉克丁(别名)[CCN]+TX、多杀菌素(737)+TX、叔丁威(别名)+TX、特丁磷(773)+TX、四氯噻吩(IUPAC/化学文摘名称)(1422)+TX、thiafenox(别名)+TX、虫线磷(1434)+TX、三唑磷(820)+TX、唑蚜威(triazuron)(别名)+TX、二甲苯酚[CCN]+TX、YI-5302(化合物代码)和玉米素(别名)(210)+TX、氟噻虫砜(fluensulfone)[318290-98-1]+TX,
硝化抑制剂,该硝化抑制剂选自由以下组成的物质组:乙基黄原酸钾[CCN]以及氯啶(nitrapyrin)(580)+TX,
植物激活剂,该植物激活剂选自由以下各项组成的物质组:阿拉酸式苯(acibenzolar)(6)+TX、阿拉酸式苯-S-甲基(6)+TX、噻菌灵(658)和大虎杖(Reynoutriasachalinensis)提取物(别名)(720)+TX,
杀鼠剂,该杀鼠剂选自由以下组成的物质组:2-异戊酰茚满-1,3-二酮(IUPAC名称)(1246)+TX、4-(喹喔啉-2-基氨基)苯磺酰胺(IUPAC名称)(748)+TX、α-氯代醇[CCN]+TX、磷化铝(640)+TX、安妥(880)+TX、三氧化二砷(882)+TX、碳酸钡(891)+TX、双鼠脲(912)+TX、溴鼠隆(89)+TX、溴敌隆(91)+TX、溴鼠胺(92)+TX、氰化钙(444)+TX、氯醛糖(127)+TX、氯鼠酮(140)+TX、胆钙化醇(别名)(850)+TX、氯灭鼠灵(1004)+TX、克灭鼠(1005)+TX、杀鼠萘(175)+TX、杀鼠嘧啶(1009)+TX、鼠得克(246)+TX、噻鼠灵(249)+TX、敌鼠(273)+TX、钙化醇(301)+TX、氟鼠灵(357)+TX、氟乙酰胺(379)+TX、氟鼠啶(1183)+TX、氟鼠啶盐酸盐(1183)+TX、γ-HCH(430)+TX、HCH(430)+TX、氰化氢(444)+TX、碘甲烷(IUPAC名称)(542)+TX、林旦(430)+TX、磷化镁(IUPAC名称)(640)+TX、溴甲烷(537)+TX、鼠特灵(1318)+TX、毒鼠磷(1336)+TX、磷化氢(IUPAC名称)(640)+TX、磷[CCN]+TX、杀鼠酮(1341)+TX、亚砷酸钾[CCN]+TX、灭鼠优(1371)+TX、海葱糖苷(1390)+TX、亚砷酸钠[CCN]+TX、氰化钠(444)+TX、氟乙酸钠(735)+TX、士的宁(745)+TX、硫酸铊[CCN]+TX、杀鼠灵(851)以及磷化锌(640)+TX,
增效剂,该增效剂选自由以下组成的物质组:2-(2-丁氧基乙氧基)乙基胡椒酸酯(IUPAC名称)(934)+TX、5-(1,3-苯并二氧杂环戊烯-5-基)-3-己基环己-2-烯酮(IUPAC名称)(903)+TX、具有橙花叔醇的法呢醇(别名)(324)+TX、MB-599(研究代码)(498)+TX、MGK264(研究代码)(296)+TX、增效醚(piperonyl butoxide)(649)+TX、增效醛(piprotal)(1343)+TX、增效酯(propyl isomer)(1358)+TX、S421(研究代码)(724)+TX、增效散(sesamex)(1393)+TX、芝麻林素(sesasmolin)(1394)和亚砜(1406)+TX,
动物驱避剂,该动物驱避剂选自由以下组成的物质组:蒽醌(32)+TX、氯醛糖(127)+TX、环烷酸铜[CCN]+TX、王铜(171)+TX、二嗪磷(227)+TX、二环戊二烯(化学名称)(1069)+TX、双胍辛盐(guazatine)(422)+TX、双胍辛乙酸盐(422)+TX、灭虫威(530)+TX、吡啶-4-胺(IUPAC名称)(23)+TX、塞仑(804)+TX、混杀威(trimethacarb)(840)+TX、环烷酸锌[CCN]和福美锌(856)+TX,
杀病毒剂,所述杀病毒剂选自由以下组成的物质组:衣马宁(别名)[CCN]和利巴韦林(别名)[CCN]+TX,
创伤保护剂,该创伤保护剂选自由以下各项组成的物质组:氧化汞(512)+TX、辛噻酮(octhilinone)(590)和甲基托布津(802)+TX,
以及生物活性化合物,该生物活性化合物选自由以下组成的组:阿扎康唑[60207-31-0]+TX、联苯三唑醇[70585-36-3]+TX、糠菌唑[116255-48-2]+TX、环丙唑醇[94361-06-5]+TX、苯醚甲环唑[119446-68-3]+TX、烯唑醇[83657-24-3]+TX、氟环唑[106325-08-0]+TX、腈苯唑[114369-43-6]+TX、氟喹唑[136426-54-5]+TX、氟硅唑[85509-19-9]+TX、粉唑醇[76674-21-0]+TX、己唑醇[79983-71-4]+TX、抑霉唑[35554-44-0]+TX、亚胺唑[86598-92-7]+TX、种菌唑[125225-28-7]+TX、叶菌唑[125116-23-6]+TX、腈菌唑[88671-89-0]+TX、稻瘟酯[101903-30-4]+TX、戊菌唑[66246-88-6]+TX、丙硫菌唑[178928-70-6]+TX、啶斑肟(pyrifenox)[88283-41-4]+TX、咪鲜胺[67747-09-5]+TX、丙环唑[60207-90-1]+TX、硅氟唑(simeconazole)[149508-90-7]+TX、戊唑醇[107534-96-3]+TX、氟醚唑[112281-77-3]+TX、三唑酮[43121-43-3]+TX、三唑酮[55219-65-3]+TX、氟菌唑[99387-89-0]+TX、灭菌唑[131983-72-7]+TX、三环苯嘧醇[12771-68-5]+TX、氯苯嘧啶醇[60168-88-9]+TX、氟氯苯嘧啶醇[63284-71-9]+TX、乙嘧酚磺酸酯(bupirimate)[41483-43-6]+TX、甲菌定(dimethirimol)[5221-53-4]+TX、乙菌定(ethirimol)[23947-60-6]+TX、十二环吗啉[1593-77-7]+TX、苯锈啶[67306-00-7]+TX、丁苯吗啉[67564-91-4]+TX、螺环菌胺[118134-30-8]+TX、十三吗啉[81412-43-3]+TX、嘧菌环胺[121552-61-2]+TX、嘧菌胺[110235-47-7]+TX、嘧霉胺(pyrimethanil)[53112-28-0]+TX、拌种咯[74738-17-3]+TX、咯菌腈(fludioxonil)[131341-86-1]+TX、苯霜灵(benalaxyl)[71626-11-4]+TX、呋霜灵(furalaxyl)[57646-30-7]+TX、甲霜灵[57837-19-1]+TX、R-甲霜灵[70630-17-0]+TX、呋酰胺[58810-48-3]+TX、恶霜灵(Oxadixyl)[77732-09-3]+TX、苯菌灵[17804-35-2]+TX、多菌灵[10605-21-7]+TX、咪菌威(debacarb)[62732-91-6]+TX、麦穗宁[3878-19-1]+TX、噻苯达唑[148-79-8]+TX、乙菌利(chlozolinate)[84332-86-5]+TX、菌核利(dichlozoline)[24201-58-9]+TX、异菌脲(Iprodione)[36734-19-7]+TX、甲菌利(myclozoline)[54864-61-8]+TX、腐霉利(procymidone)[32809-16-8]+TX、乙烯菌核利(vinclozoline)[50471-44-8]+TX、啶酰菌胺(boscalid)[188425-85-6]+TX、萎锈灵[5234-68-4]+TX、甲呋酰胺[24691-80-3]+TX、福多宁(flutolanil)[66332-96-5]+TX、灭锈胺[55814-41-0]+TX、氧化萎锈灵[5259-88-1]+TX、吡噻菌胺(penthiopyrad)[183675-82-3]+TX、噻呋菌胺[130000-40-7]+TX、双胍盐[108173-90-6]+TX、多果定(dodine)[2439-10-3][112-65-2](游离碱)+TX、双胍辛胺(iminoctadine)[13516-27-3]+TX、嘧菌酯[131860-33-8]+TX、醚菌胺[149961-52-4]+TX、烯肟菌酯{Proc.BCPC,Int.Congr.,Glasgow.2003,1,93}+TX、氟嘧菌酯[361377-29-9]+TX、甲基醚菌酯[143390-89-0]+TX、苯氧菌胺[133408-50-1]+TX、肟菌酯[141517-21-7]+TX、肟醚菌胺[248593-16-0]+TX、啶氧菌酯[117428-22-5]+TX、唑菌胺酯[175013-18-0]+TX、福美铁[14484-64-1]+TX、代森锰锌[8018-01-7]+TX、代森锰[12427-38-2]+TX、代森联[9006-42-2]+TX、甲代森锌(propineb)[12071-83-9]+TX、塞仑[137-26-8]+TX、代森锌[12122-67-7]+TX、福美锌[137-30-4]+TX、敌菌丹(captafol)[2425-06-1]+TX、克菌丹[133-06-2]+TX、苯氟磺胺[1085-98-9]+TX、唑啶草(fluoroimide)[41205-21-4]+TX、灭菌丹[133-07-3]+TX、对甲抑菌灵[731-27-1]+TX、波尔多(bordeaux)混合物[8011-63-0]+TX、氢氧化铜(copperhydroxid)[20427-59-2]+TX、氯化铜(copperoxychlorid)[1332-40-7]+TX、硫酸铜(coppersulfat)[7758-98-7]+TX、氧化铜(copperoxid)[1317-39-1]+TX、代森锰铜(mancopper)[53988-93-5]+TX、喹啉铜(oxine-copper)[10380-28-6]+TX、敌螨普(dinocap)[131-72-6]+TX、酞菌酯(硝基thal-isopropyl)[10552-74-6]+TX、克瘟散[17109-49-8]+TX、异稻瘟净(iprobenphos)[26087-47-8]+TX、稻瘟灵(isoprothiolane)[50512-35-1]+TX、氯瘟磷(phosdiphen)[36519-00-3]+TX、克菌磷(pyrazophos)[13457-18-6]+TX、甲基立枯磷(tolclofos-methyl)[57018-04-9]+TX、活化酯-S-甲基(acibenzolar-S-methyl)[135158-54-2]+TX、敌菌灵[101-05-3]+TX、苯噻菌胺[413615-35-7]+TX、灭瘟素(blasticidin)-S[2079-00-7]+TX、灭螨猛(chinomethionat)[2439-01-2]+TX、地茂散(chloroneb)[2675-77-6]+TX、百菌清[1897-45-6]+TX、环氟菌胺[180409-60-3]+TX、霜脲氰[57966-95-7]+TX、二氯萘醌(dichlone)[117-80-6]+TX、双氯氰菌胺(diclocymet)[139920-32-4]+TX、哒菌酮(diclomezine)[62865-36-5]+TX、氯硝胺(dicloran)[99-30-9]+TX、乙霉威(diethofencarb)[87130-20-9]+TX、烯酰吗啉[110488-70-5]+TX、SYP-LI90(Flumorph)[211867-47-9]+TX、二噻农(dithianon)[3347-22-6]+TX、噻唑菌胺(ethaboxam)[162650-77-3]+TX、土菌灵(etridiazole)[2593-15-9]+TX、恶唑菌酮[131807-57-3]+TX、咪唑菌酮(fenamidone)[161326-34-7]+TX、稻瘟酰胺(Fenoxanil)[115852-48-7]+TX、三苯锡(fentin)[668-34-8]+TX、嘧菌腙(ferimzone)[89269-64-7]+TX、氟啶胺(fluazinam)[79622-59-6]+TX、氟吡菌胺(fluopicolide)[239110-15-7]+TX、磺菌胺(flusulfamide)[106917-52-6]+TX、环酰菌胺[126833-17-8]+TX、乙膦酸-铝[39148-24-8]+TX、恶霉灵(hymexazol)[10004-44-1]+TX、丙森锌[140923-17-7]+TX、IKF-916(氰霜唑(Cyazofamid))[120116-88-3]+TX、春雷霉素(kasugamycin)[6980-18-3]+TX、磺菌威(methasulfocarb)[66952-49-6]+TX、苯菌酮[220899-03-6]+TX、戊菌隆(pencycuron)[66063-05-6]+TX、稻瘟酞[27355-22-2]+TX、多氧霉素(polyoxins)[11113-80-7]+TX、噻菌灵(probenazole)[27605-76-1]+TX、霜霉威[25606-41-1]+TX、碘喹唑酮(proquinazid)[189278-12-4]+TX、咯喹酮(pyroquilon)[57369-32-1]+TX、喹氧灵[124495-18-7]+TX、五氯硝苯[82-68-8]+TX、硫[7704-34-9]+TX、噻酰菌胺[223580-51-6]+TX、咪唑嗪(triazoxide)[72459-58-6]+TX、三环唑[41814-78-2]+TX、嗪氨灵[26644-46-2]+TX、有效霉素[37248-47-8]+TX、苯酰菌胺(zoxamide)(RH7281)[156052-68-5]+TX、双炔酰菌胺(mandipropamid)[374726-62-2]+TX、吡唑萘菌胺(isopyrazam)[881685-58-1]+TX、氟唑环菌胺(sedaxane)[874967-67-6]+TX、3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(9-二氯亚甲基-1,2,3,4-四氢-1,4-桥亚甲基-萘-5-基)-酰胺(披露于WO 2007/048556中)+TX、3-二氟甲基-1-甲基-1H-吡唑-4-甲酸(3',4',5'-三氟-联苯基-2-基)-酰胺(披露于WO 2006/087343中)+TX、[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(环丙基羰基)氧基]-1,3,4,4a,5,6,6a,12,12a,12b-十氢-6,12-二羟基-4,6a,12b-三甲基-11-氧代-9-(3-吡啶基)-2H,11H萘并[2,1-b]吡喃并[3,4-e]吡喃-4-基]甲基-
环丙甲酸酯[915972-17-7]+TX以及1,3,5-三甲基-N-(2-甲基-1-氧丙基)-N-[3-(2-甲基丙基)-4-[2,2,2-三氟-1-甲氧基-1-(三氟甲基)乙基]苯基]-1H-吡唑-4-甲酰胺[926914-55-8]+TX。
在活性成分之后的括号中的参考例如[3878-19-1]是指化学文摘的登记号。上文描述的混合配伍物是已知的。当活性成分包括在“杀有害生物剂手册(The PesticideManual)”[杀有害生物剂手册-全球概览(The Pesticide Manual-A World Compendium);第十三版;编著:编辑:C.D.S.TomLin;The British Crop Protection Coimcil[英国农作物保护委员会]]中,它们在其中以上文对于特定化合物的圆括号中所给出的条目编号来描述;例如化合物“阿巴美丁”以条目编号(1)来描述。其中“[CCN]”是对于上文的特定化合物来加上的,所述的化合物包括在“Compendium of Pesticide Common Names[农药通用名概要]”中,其可以在互联网[A.Wood;Compendium of Pesticide Common Names,Copyright1995-2004]上获得;例如,化合物“乙酰虫腈”描述于国际互联网地址http://www.alanwood.net/pesticides/acetoprole.html.
多数活性成分通过上文中所谓的“通用名”来表示,在不同的情形中使用相应的“ISO通用名”或其它“通用名”。若名称不是“通用名”,则所使用的名称种类以特定化合物的圆括号中所给出的名称来代替;在这种情况下,使用IUPAC名称、IUPAC/化学文摘名、“化学名称”、“惯用名”、“化合物名称”或“开发代码”,或若既不使用那些名称之一也不使用“通用名”,则使用“别名”。“CAS登记号”意指化学文摘登记号。
根据实施例1至5中任一项所述的化合物与上述活性成分的活性成分混合物包括根据实施例1至5中任一项所述的化合物和上述活性成分,优选地是处于从100:1至1:6000的混合比率,尤其是从50:1至1:50,更尤其是处于从20:1至1:20的比率,甚至更尤其从10:1至1:10,非常尤其是从5:1和1:5,尤其优选的是从2:1至1:2的比率给出的,并且从4:1至2:1的比率同样是优选的,特别是处于1:1,或5:1、或5:2、或5:3、或5:4、或4:1、或4:2、或4:3、或3:1、或3:2、或2:1、或1:5、或2:5、或3:5、或4:5、或1:4、或2:4、或3:4、或1:3、或2:3、或1:2、或1:600、或1:300、或1:150、或1:35、或2:35、或4:35、或1:75、或2:75、或4:75、或1:6000、或1:3000、或1:1500、或1:350、或2:350、或4:350、或1:750、或2:750、或4:750的比率。那些混合比率是按重量计的。
如上所述的混合物可以被用于控制有害生物的方法中,该方法包括将含如上文所述的混合物的组合物施用于有害生物或其环境中,通过手术或疗法用于处理人或动物体的方法以及在人或动物体上实施的诊断方法除外。
包含根据实施例1至5中任一项所述的化合物和如上所述的一种或多种活性成分的混合物可以例如按以下来施用:以单一“即混即用物”的形式、以由单一活性成分组分的单独配制品构成的组合喷雾混合物(诸如“桶混物”)、以及以在按顺序方式(即以合理的短时间段(诸如几小时或几天)一个接一个地)施用的情况下组合使用这些单一活性成分。施用根据实施例1至5中任一项所述的化合物和上述活性成分的顺序对于实施本发明并不是至关重要的。
根据本发明的组合物还可以包含其他固体或液体助剂,例如稳定剂,例如未环氧化的或环氧化的植物油(例如环氧化的椰子油、菜籽油或大豆油),消泡剂(例如硅酮油),防腐剂,粘度调节剂,粘合剂和/或增粘剂,肥料或其他用于获得特定效果的活性成分,例如杀细菌剂、杀真菌剂、杀线虫剂、植物活化剂、杀软体动物剂或除草剂。
根据本发明的组合物是以本身已知的方式,在不存在助剂的情况下,例如通过研磨、筛选和/或压缩固体活性成分;和在至少一种助剂的存在下,例如通过紧密混合活性成分与一种或多种助剂和/或将活性成分与一种或多种助剂一起研磨来制备。这些用于制备组合物的方法和化合物I用于制备这些组合物的用途也是本发明的主题。
这些组合物的施用方法,即控制上述类型的有害生物的方法,如喷雾、雾化、撒粉、刷涂、包衣、撒播或浇灌-它们被选择以适于普遍情况的预期目的-以及这些组合物用于控制上述类型的有害生物的用途是本发明的其他主题。典型的浓度比是在0.1与1000ppm之间、优选在0.1与500ppm之间的活性成分。每公项的施用量总体上是每公项1g至2000g活性成分、尤其是10g/ha至1000g/ha、优选地是10g/ha至600g/ha。
在作物保护领域中,优选的施用方法是施用至这些植物的叶(叶施用),可能的是选择施用的频率和比率以符合所讨论的有害生物的侵染风险。可替代地,该活性成分可以通过根系统(内吸作用)到达植物,这是通过用液体组合物将这些植物的场所浸透或者通过将呈固体形式的活性成分引入植物的场所(例如引入土壤,例如以颗粒的形式(土施))来实现的。在水稻作物的情况下,这样的颗粒剂可以被计量地加入淹水的稻田中。
本发明的所述化合物及其组合物还适合于植物繁殖材料的保护(例如种子,像果实、块茎或籽粒,或者苗圃植物),以对抗上述类型的有害生物。可以用该化合物在种植前对该繁殖材料进行处理,例如可以在播种前对种子进行处理。可替代地,该化合物可以施用至种子籽粒(包衣),这是通过将籽粒浸渍入液体组合物中或通过施用固体组合物层实现的。还可能在该繁殖材料被种植在施用处时施用这些组合物,例如在条播期间将这些组合物施入种子犁沟。这些用于植物繁殖材料的处理方法和如此处理的植物繁殖材料是本发明另外的主题。典型的处理比率将取决于有待控制的植物以及有害生物/真菌,并且通常在每100kg种子1克至200克之间、优选在每100kg种子5克至150克之间,如在每100kg种子10克至100克之间。
术语种子包括所有种类的种子以及植物繁殖体,包括但并不限于真正的种子、种子块、吸盘、谷粒、鳞球茎、果实、块茎、谷物、根茎、插条、切割枝条以及类似物并且在优选实施例中意指真正的种子。
本发明还包括经根据实施例1至5中任一项所述的化合物包衣或处理的或含有其的种子。尽管取决于施用的方法成分的更多或更少的部分可以渗透到该种子材料中,术语“包衣或处理和/或含有”通常表示在施用的时候,在大多数情况下,该活性成分在该种子的表面。当所述种子产品被(再)种植时,它可以吸收活性成分。在一个实施例中,本发明可提供其上附着有根据实施例1至5中任一项所述的植物繁殖材料。此外,由此可得包含用根据实施例1至5中任一项所述的化合物处理过的植物繁殖材料的组合物。
种子处理包括本领域中已知的所有适合的种子处理技术,如拌种、种子包衣、种子撒粉、浸种以及种子造粒。根据实施例1至5中任一项所述的化合物的种子处理应用可以通过任何已知的方法进行,例如在播种前或播种/种植种子期间对种子进行喷雾或撒粉。
根据实施例1至5中任一项所述的化合物的杀有害生物/杀昆虫特性可以经由以下试验说明:
黄瓜条叶甲(玉米根虫):
将24孔微量滴定板中的置于琼脂层上的玉米芽通过喷雾用从10’000ppm DMSO储备溶液制备的水性测试溶液进行处理。干燥之后,将板用L2期幼虫侵染(6至10只/孔)。侵染4天之后,针对死亡率对这些样品进行评估。以下化合物在200ppm施用率下产生至少80%的死亡率:1、3、4、12、18和19。
英雄美洲蝽(Euschistus heros)(新热带区褐蝽象)摄食/接触活性
将在24孔微量滴定板中的琼脂上的大豆叶片用从10'000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。干燥之后,用N2期若虫对叶片进行侵染。侵染5天之后,针对死亡率对这些样品进行评估。以下化合物在200ppm施用率下产生至少80%的死亡率:1、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28和29。
桃蚜(Myzus persicae)(绿桃蚜):摄食/接触活性
将向日葵叶圆片置于24孔微量滴定板中的琼脂上并且用从10’000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。在干燥之后,将这些叶圆片用混合年龄的蚜虫种群进行侵染。侵染6天之后,针对死亡率对这些样品进行评估。以下化合物在200ppm施用率下产生至少80%的死亡率:1、2、3、4、6、7、8、9、10、11、12、13、15、16、17、18、19、20、22、23、24、25、26、27、28和29
小菜蛾(Plutella xylostella)(小菜蛾(Diamond back moth)):摄食/接触活性
将具有人工饲料的24孔微量滴定板用从10’000ppm DMSO储备溶液制备的水性测试溶液通过移液进行处理。干燥之后,将板用L2期幼虫侵染(10至15只/孔)。侵染5天之后,针对死亡率对这些样品进行评估。以下化合物在200ppm施用率下产生至少80%的死亡率:1、2、3、4、6、7、8、9、10、11、12、13、15、16、17、18、19、20、22、23、24、25、26、27、28和29。
海灰翅夜蛾(埃及棉叶虫):摄食/接触活性
将棉花叶圆片置于24孔微量滴定板中的琼脂上并且用从10’000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。干燥之后,将叶圆片用五只L1期幼虫侵染。侵染3天之后,针对死亡率对这些样品进行评估。以下化合物在200ppm施用率下产生至少80%的死亡率:1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28和29。
二点叶螨(Tetranychus urticae)(二斑叶螨):摄食/接触活性
将24孔微量滴定板中的琼脂上的豆叶圆片用从10’000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。干燥之后,将叶圆片用混合年龄的螨群体进行侵染。在侵染之后8天后,针对混合群体(活动阶段)的死亡率对这些样品进行评估。以下化合物在200ppm施用率下产生至少80%的死亡率:1、2、3、4、6、7、8、9、10、11、12、13、15、16、17、18、19、22、23、24、25、26、27、28和29。
烟蓟马(葱蓟马):摄食/接触活性
将向日葵叶圆片置于24孔微量滴定板中的琼脂上并且用从10'000ppm DMSO储备溶液制备的水性测试溶液进行喷雾。在干燥之后,将叶圆片用混合年龄的蓟马群体进行侵染。侵染6天之后,针对死亡率对这些样品进行评估。以下化合物在200ppm施用率下产生至少80%的死亡率:1、3、4、12、18和19。
本发明的化合物与已知的化合物的区别可以在于在低施用量下更大的效力,这可以由本领域技术人员使用在实例中概述的实验程序,使用更低的施用量(如果必要的话)例如,50ppm、12.5ppm、6ppm、3ppm、1.5ppm、0.8ppm或0.2ppm来证实。
此外,除了杀昆虫特性,与现有技术化合物相比,根据实施例1至5中任一项所述的化合物出人意料地显示具有改进的降解特性。另外,与现有技术化合物相比,根据实施例1至5中任一项所述的化合物出人意料地显示出对环境(例如蜜蜂或水生生物)的毒性更低。
Claims (12)
1.一种式(I)的化合物,
其中
R1选自H、C1-C6-烷基、C2-C6烯基、C2-C6炔基、C3-C7环烷基、C3-C7环烷基-C1-C3-烷基、C1-C6-烷基羰基、C1-C6-烷氧基羰基、芳基(C0-C3)-烷基和杂芳基(C0-C3)-烷基,其中C1-C6-烷基、C3-C6烯基、C3-C6炔基、C3-C7环烷基、C3-C7环烷基-C1-C3-烷基、C1-C6-烷基羰基、C1-C6-烷氧基羰基、芳基(C0-C3)-烷基和杂芳基(C0-C3)-烷基中的每一个是未取代的或被1至5个独立地选自卤素、氰基、C1-C6-烷氧基和C1-C6-烷氧基羰基的取代基取代的;
Q是H或氰基;
A是CH或N;
或其农用化学上可接受的盐或N-氧化物。
2.根据权利要求1所述的化合物或盐,其中,R1选自H、异丁基、2,2,2-三氟乙基、-C(=O)CH3、-C(=O)CH2CH3、-C(=O)环丙基、-C(=O)OCH3、-C(=O)OCH2CH3、-C(=O)CH(CH3)(CH3)、-CH2-C-CH、-CH2CN、-CH2-O-CH3、-CH2-O-CH2-CH3、-CH2-环丙基、异丙氧基甲基、乙基、丙基、甲基、异丙基、甲氧基丙基、甲氧基乙基、乙氧基乙基、-C(=O)OCH(CH3)(CH3)、-C(=O)CH2OCH3、-C(=O)OCH(CH3)(CH3)和-C(=O)OCH2Cl。
3.根据权利要求1所述的化合物或盐,其中,R1选自H、异丁基、2,2,2-三氟乙基、环丙基甲基、-C(=O)CH3、-C(=O)CH2CH3、-C(=O)环丙基、-C(=O)OCH3、-C(=O)OCH2CH3、-C(=O)CH(CH3)(CH3)、-CH2-C-CH、-CH2CN、-CH2-O-CH3、-CH2-O-CH2-CH3和-CH2-环丙基。
4.根据权利要求1至3中任一项所述的化合物或盐,其中,R1选自H、异丁基、2,2,2-三氟乙基、环丙基甲基、-C(=O)CH3、-C(=O)OCH3、-C(=O)OCH2CH3、-C(=O)CH(CH3)(CH3)、-CH2-C-CH、-CH2CN和-CH2-O-CH3。
5.根据权利要求1至4中任一项所述的化合物或盐,其中,Q是氰基。
6.根据权利要求1至5中任一项所述的化合物或盐,其中,A是CH。
7.根据权利要求1所述的化合物或盐,其选自
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰胺;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(异丙氧基甲基)苯甲酰胺;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-乙基-苯甲酰胺;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-甲基-苯甲酰胺;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-异丙基-苯甲酰胺;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(3-甲氧基丙基)苯甲酰胺;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(2-甲氧基乙基)苯甲酰胺;
N-[2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰基]-N-(1-氰基环丙基)氨基甲酸乙酯;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(甲氧基甲基)苯甲酰胺;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(乙氧基甲基)苯甲酰胺;
2-氯-N-(1-氰基环丙基)-N-(氰基甲基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰胺;
N-乙酰基-2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰胺;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(2-乙氧基乙基)苯甲酰胺;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-丙基-苯甲酰胺;
N-[2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰基]-N-环丙基-氨基甲酸乙酯
2-氯-N-(氰基甲基)-N-环丙基-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰胺;
2-氯-N-环丙基-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰胺;
N-[2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰基]-N-(1-氰基环丙基)氨基甲酸甲酯;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]吡啶-3-甲酰胺;
N-[2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰基]-N-(1-氰基环丙基)氨基甲酸异丙酯;
2-氯-N-(1-氰基环丙基)-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-异丁基-苯甲酰胺;
2-氯-N-环丙基-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(2-甲氧基乙酰基)苯甲酰胺;
N-[2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰基]-N-环丙基-氨基甲酸甲酯;
N-[2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰基]-N-环丙基-氨基甲酸异丙酯;
2-氯-N-环丙基-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-甲基-苯甲酰胺
2-氯-N-环丙基-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-乙基-苯甲酰胺;
2-氯-N-环丙基-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(乙氧基甲基)苯甲酰胺
2-氯-N-环丙基-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]-N-(甲氧基甲基)苯甲酰胺;以及
N-[2-氯-5-[1-[4-(二氟甲氧基)-2-甲基-5-[1,2,2,2-四氟-1-(三氟甲基)乙基]吡唑-3-基]吡唑-4-基]苯甲酰基]-N-(1-氰基环丙基)氨基甲酸氯甲酯。
8.一种杀有害生物组合物,所述杀有害生物组合物包含作为活性成分的至少一种根据权利要求1至7中任一项所述的化合物或其农用化学上可接受的盐或N-氧化物,以及至少一种助剂。
9.根据权利要求7所述的组合物,所述组合物进一步包含一种或多种其他杀昆虫、杀螨、杀线虫和/或杀真菌活性剂。
10.一种用于控制有害生物的方法,所述方法包括将根据权利要求8或9所述的组合物施用于所述有害生物或其环境中,除了通过手术或疗法用于处理人或动物体的方法以及对于人或动物体实施的诊断方法之外。
11.一种用于保护植物繁殖材料免受有害生物攻击的方法,所述方法包括用根据权利要求8或9所述的组合物处理所述繁殖材料或种植所述繁殖材料的地点。
12.一种包衣的植物繁殖材料,其中所述植物繁殖材料的包衣包含根据权利要求1至7中任一项所述的化合物。
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- 2018-08-09 CN CN201880052290.0A patent/CN111050559B/zh not_active Expired - Fee Related
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WO2024131588A1 (zh) * | 2022-12-21 | 2024-06-27 | 顺毅股份有限公司 | 一种n-取代的苯基吡唑衍生物及其制备和应用 |
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US11365187B2 (en) | 2022-06-21 |
UY37838A (es) | 2019-03-29 |
WO2019030359A1 (en) | 2019-02-14 |
AR112673A1 (es) | 2019-11-27 |
BR112020002759A2 (pt) | 2020-07-28 |
US20200361907A1 (en) | 2020-11-19 |
JP2020530476A (ja) | 2020-10-22 |
EP3664611A1 (en) | 2020-06-17 |
CN111050559B (zh) | 2022-01-14 |
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