CN113336699A - 杀虫化合物 - Google Patents
杀虫化合物 Download PDFInfo
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- CN113336699A CN113336699A CN202110609728.4A CN202110609728A CN113336699A CN 113336699 A CN113336699 A CN 113336699A CN 202110609728 A CN202110609728 A CN 202110609728A CN 113336699 A CN113336699 A CN 113336699A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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Abstract
Description
本申请是母案为中国发明专利申请201480019539.X的分案申请。
本发明涉及双酰胺衍生物,涉及用于制备它们的工艺和中间体,涉及使用它们来控制昆虫、螨类、线虫和软体动物有害生物的方法,并且涉及包含它们的杀昆虫、杀螨、杀线虫和杀软体动物的组合物。
具有杀虫特性的化合物披露于EP 1714958、JP 2006306771、WO 2006137376、EP1916236、WO 2007017075、WO 2008000438、WO 2008/074427、WO 2009049845以及WO2010127928中。对于控制有害生物的替代方法存在需要。优选地,新型化合物可以拥有改进的杀虫特性,如改进的功效、改进的选择性、降低的毒性、产生耐药性的更低倾向、或针对更宽范围有害生物的活性。化合物可以更有利地被配制或在作用位点提供更有效的递送和保留,或者可以更容易生物降解。
出人意料地,已经发现某些被一种芳基全氟烷基基团以及4-吡啶基或1-氧化吡啶-1-鎓-4-基基团取代的双酰胺衍生物具有有益的特性,这使得它们尤其适合用作杀虫剂。
本发明因此提供了一种具有化学式(I)的化合物
其中
Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;
Q2是一个具有化学式(II)的部分
其中
Y1选自Cl、Br、I、甲基、乙基、环丙基、甲氧基、二氟甲氧基、三氟甲氧基、或甲氧基甲基
Y5选自Cl、Br、I、甲基、乙基
Y3是七氟丙-2-基或九氟丁-2-基
X是氢或F
R1选自C1-C8烷基、C2-C8烯基、C2-C8炔基、C1-C8烷基羰基、C1-C8烷氧基羰基、羟基、和C1-C8烷氧基;
R2选自氢、C1-C8烷基、C2-C8烯基、C2-C8炔基、C1-C8烷基羰基、C1-C8烷氧基羰基、羟基、C1-C8烷氧基、和氨甲酰基-C1-C4亚烷基;并且
G1和G2都是氧;
或其农业化学上可接受的盐。
具有化学式(I)的化合物能以不同的几何或光学异构体(对映体和/或非对映异构体)或者互变异构体的形式存在。本发明涵盖了所有的此类异构体以及互变异构体以及它们的处于所有比例的混合物,连同同位素形式,诸如氘化的化合物。
每个烷基部分单独的或者作为一个大的基团的一部分(例如烷氧基、烷氧基羰基、烷基羰基、烷氨基羰基、二烷氨基羰基)是直链的或支链的,并且是例如甲基、乙基、正丙基、正丁基、异丙基、正丁基、仲丁基、异丁基或叔丁基。这些烷基基团优选是C1至C6烷基基团,更优选是C1-C4并且最优选是C1-C3烷基基团。
优选地本发明提供了一种具有化学式(I)的化合物,其中
Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;
Y1选自Cl、Br、I、甲基、乙基、甲氧基、二氟甲氧基、三氟甲氧基、或甲氧基甲基
Y5选自Cl、Br、I、乙基
Y3是七氟丙-2-基或九氟丁-2-基
X是氢或F
R1选自C1-C8烷基、C2-C8烯基;
R2选自氢、C1-C8烷基、C2-C8烯基;并且
G1和G2都是氧;
更优选地本发明提供了一种具有化学式(I)的化合物,其中
Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;
Y1选自Cl、Br、I、甲基、乙基;
Y5选自Cl、Br、I、乙基;
Y3是七氟丙-2-基
X是氢或F
R1选自C2-C4烷基;
R2选自氢、C1-C4烷基;并且
G1和G2都是氧;
甚至更优选地本发明提供了一种具有化学式(I)的化合物,其中
Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;
Y1选自Cl、Br、甲基、乙基;
Y5选自Cl、Br、乙基;
Y3是七氟丙-2-基
X是氢或F
R1选自C2-C4烷基;
R2选自氢、C1-C4烷基;并且
G1和G2都是氧;
最优选地本发明提供了一种具有化学式(I)的化合物,其中
Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;
Y1选自Cl、Br、甲基、乙基;
Y5选自Cl、Br、乙基;
Y3是七氟丙-2-基
X是F
R1是乙基;
R2选自氢、甲基、乙基;并且
G1和G2都是氧;
R1、R2、Y1和Y5的进一步优选的值是以任意组合如以下对于本发明的不同实施例所列出的,并且G1和G2都是氧,Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;Q2是一个具有化学式(II)的部分
并且Y3是七氟丙-2-基或九氟丁-2-基。
优选地Y1选自Cl、Br、I、甲基、乙基;
更优选地Y1选自Cl、Br、乙基;
甚至更优选地Y1选自Cl、Br;
优选地Y5选自Cl、Br、I、乙基;
更优选地Y5选自Cl、Br、乙基;
甚至更优选地Y5选自Cl、Br;
优选地R1选自甲基、乙基、丙基、异丙基、烯丙基:
更优选地R1选自甲基、乙基;
甚至更优选地R1是乙基;
优选地R2选自氢、甲基、乙基、丙基、异丙基、烯丙基、氨基羰基-亚乙基;
更优选地R2选自氢、甲基、乙基;
甚至更优选地R2是氢;
在一个实施例(A)中本发明提供了具有化学式(I)的化合物,其中
Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;
Q2是一个具有化学式(II)的部分
Y1选自Cl、Br、I、甲基、乙基;
Y5选自Cl、Br、I、乙基;
Y3是七氟丙-2-基或九氟丁-2-基
X是氢或F
R1选自甲基、乙基、丙基、异丙基、烯丙基;
R2选自氢、甲基、乙基、丙基、异丙基、氨基羰基-亚乙基;并且
G1和G2都是氧;
或其农业化学上可接受的盐。
在一个优选的实施例(A)中本发明提供了具有化学式(I)的化合物,其中
Y1选自Cl、Br、甲基、乙基;
Y5选自Cl、Br、乙基;
Y3是七氟丙-2-基
X是氢或F
R1选自甲基、乙基;
R2选自氢、甲基、乙基;并且
G1和G2都是氧;
并且其他的取代基具有如在上文实施例(A)的之一中所列出的含义。
更优选地,在实施例(A)中的取代基如下
Y1选自Cl、Br、甲基;
Y5选自Cl、Br、乙基;
Y3是七氟丙-2-基
X是氢或F
R1选自甲基、乙基;
R2选自氢、甲基、乙基;并且
G1和G2都是氧;
并且其他的取代基具有如在上文实施例(A)的之一中所列出的含义。
甚至更优选地,在实施例(A)中的取代基如下
Y1选自Cl、Br;
Y5选自Cl、Br;
Y3是七氟丙-2-基
X是氢或F
R1选自甲基、乙基,优选地乙基;
R2选自氢、甲基、乙基;并且
G1和G2都是氧;
并且其他的取代基具有如在上文实施例(A)的之一中所列出的含义。
最优选地,在实施例(A)中的取代基如下
Y1是Cl;
Y5是Br;
Y3是七氟丙-2-基
X是F
R1选自甲基、乙基;
R2是氢;并且
G1和G2都是氧;
并且其他的取代基具有如在上文实施例(A)的之一中所列出的含义。
在一个实施例(B)中本发明提供了具有化学式(I)的化合物,其中
Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;
Q2是一个具有化学式(II)的部分
Y1选自Cl、Br、I、甲基、乙基;
Y5选自Cl、Br、I、乙基;
Y3是七氟丙-2-基或九氟丁-2-基
X是氢或F
R1选自乙基、丙基、异丙基、烯丙基;
R2选自氢、甲基、乙基、丙基、异丙基、氨基羰基-亚乙基;并且
G1和G2都是氧;
或其农业化学上可接受的盐。
在一个优选的实施例(B)中本发明提供了具有化学式(I)的化合物,其中
Y1选自Cl、Br、甲基、乙基;
Y5选自Cl、Br、乙基;
Y3是七氟丙-2-基或九氟丁-2-基
X是氢或F
R1是乙基;
R2选自氢、甲基、乙基;并且
G1和G2都是氧;
并且其他的取代基具有如在上文实施例(B)的之一中列出的含义。
更优选地,在实施例(B)中的取代基如下
Y1选自Cl、Br、甲基;
Y5选自Cl、Br、乙基;
Y3是七氟丙-2-基
X是氢或F
R1是乙基;
R2选自氢、甲基、乙基;并且
G1和G2都是氧;
并且其他的取代基具有如在上文实施例(B)的之一中列出的含义。
甚至更优选地,在实施例(B)中的取代基如下
Y1是Cl;
Y5是Br;
Y3是七氟丙-2-基
X是F
R1是乙基;
R2是氢;并且
G1和G2都是氧;
并且其他的取代基具有如在上文实施例(B)的之一中列出的含义。
本发明进一步涉及根据化学式(V)的化合物
其中
R选自OH、C1-C6烷氧基、F、Cl或Br;
Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;
并且X和R1的值如以上对于本发明的不同实施例所列出的,或其一种盐。
本发明进一步涉及一种用于生产根据化学式(I)的化合物或其一种农业化学上可接受的盐的工艺,其特征在于使根据化学式(V)的化合物
其中
R选自OH、C1-C6烷氧基、Cl、F或Br
并且X和R1的值如以上对于本发明的不同实施例所列出的,并且Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基
与一种具有化学式NHR2Q2的胺反应
其中
Q2是一个具有化学式(II)的部分
并且Y3是七氟丙-2-基或九氟丁-2-基
R2、Y1和Y5是以任意组合如以上对于本发明的不同实施例所列出的。
本发明进一步涉及根据化学式(V)的化合物的使用方法
用于生产根据化学式(III)的化合物
其中
X是氢或F,
R选自OH、C1-C6烷氧基、Cl、F或Br
并且Q1、Q2、R1、R2、Y1和Y5的值如以上对于本发明的不同实施例所列出的,或其一种盐。
本发明进一步涉及根据化学式(IV)的化合物
其中X是氢或F,并且R1是选自甲基、乙基、正丙基和正丁基,优选地正丁基,
R选自羟基、卤素、C1-C6-烷基-C(O)O-、苯基-C(O)O-、C1-C6-烷氧基-C(O)O-、苯氧基-C(O)O-、苄氧基-C(O)O-和咪唑-1-基,优选地OH、C1-C6烷氧基、Cl、F或Br,更优选地C1-C6烷氧基,
或其一种盐。
因此,本发明涉及根据化学式(IV-a)、(IV-b)、(IV-c)和(IV-d)的化合物
本发明进一步涉及根据化学式(IV)的化合物的使用方法
用于生产根据化学式(V)的化合物
其中X和R1具有如以上对于本发明的不同实施例所列出的含义并且优选地R1选自甲基、乙基、正丙基和正丁基,
R选自羟基、卤素、C1-C6-烷基-C(O)O-、苯基-C(O)O-、C1-C6-烷氧基-C(O)O-、苯氧基-C(O)O-、苄氧基-C(O)O-和咪唑-1-基,优选地OH、C1-C6烷氧基、Cl、F或Br,更优选地C1-C6烷氧基,
并且Q1是4-吡啶基或1-氧化吡啶-1-鎓-4-基;
或其一种盐。
在下表1至4中和在实例中的这些化合物展示了本发明的化合物,但是并不限制本发明。
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率下更大的疗效,这可以由本领域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。
表1:
表1提供了具有化学式(III)的112种化合物,其中Q1是4-吡啶基,并且Q2、R1和R2具有在下表中列出的值。
表2:
表2提供了具有化学式(III)的112种化合物,其中Q1是1-氧化吡啶-1-鎓-4-基,并且Q2、R1和R2具有在下表中列出的值。
表3:
表3提供了具有化学式(V)的30种化合物,其中Q1是4-吡啶基,并且R1和R具有在下表中列出的值。化合物3.1至3.3以及3.16至3.18并不根据本发明。
表4:
表4提供了具有化学式(V)的30种化合物,其中Q1是1-氧化吡啶-1-鎓-4-基,并且R1和R具有在下表中列出的值。化合物4.1至4.3以及4.16至4.18并不根据本发明。
本发明的化合物可以通过多种方法来制造,例如,在WO 08/000438或者WO 2010/127928中披露的方法。
1)具有化学式(III)的化合物可以通过用一种具有化学式NHR2Q2的胺对具有化学式(V)的化合物(其中R为OH、C1-C6烷氧基、Cl,F或Br)进行处理而制造。当R是OH时,此类反应可以是在偶联剂(例如DCC(N,N’-二环己基碳二亚胺),EDC(1-乙基-3-[3-二甲基氨基-丙基]碳二亚胺盐酸盐)或BOP-Cl(双(2-氧代-3-噁唑烷基)膦酰氯))存在下,在碱(例如吡啶、三乙胺、4-(二甲氨基)吡啶或二异丙基乙胺)存在下,以及任选地在亲核性催化剂(例如羟基苯并三唑)存在下进行。当R是Cl时,此类反应可以在碱性条件下,例如,在吡啶、三乙胺、4-(二甲氨基)吡啶或者二异丙基乙胺的存在下,以及可任选地在亲核性催化剂的存在下进行。可替代地,该反应可以在一个两相系统(包括一种有机溶剂,优选地乙酸乙酯,以及一种水溶剂,优选一种碳酸氢钠的溶液)中进行。当R是C1-C6烷氧基时,可以通过在一个热过程中将酯和胺一起加热而将酯直接转化为酰胺。
2)具有化学式(V)的酰基卤(其中R为Cl、F或Br)可以从具有化学式(V)的羧酸(其中R为OH),通过用亚硫酰二氯或者草酰氯进行处理而制造。
3)具有化学式(V)的羧酸(其中R为OH)可以从具有化学式(V)的酯(其中R为C1-C6烷氧基),通过用一种碱性氢氧化物(如氢氧化钠)在一种溶剂(如乙醇)中对该酯进行处理而形成。
4)具有化学式(V)的酯(其中R为C1-C6烷氧基)可以在如1)中所描述的标准条件下,通过将具有化学式(IV)的化合物(其中R为C1-C6烷氧基)用一种具有化学式Q1-COOH的羧酸或者一种具有化学式Q1-COHal(其中Hal为Cl、F或Br)的酰基卤进行酰化的处理而制造。
5)具有化学式(IV)的化合物(其中R为C1-C6烷氧基),可以从具有化学式(VI)的化合物,通过在酸性条件下用一种醇R-OH相继处理,并且然后形成N-R1键进行制造。例如,可以通过用一种醛或酮以及一种还原剂如氰基硼氢化钠对胺进行处理从而实现还原氨化。可替代地,可任选地在碱的存在下,可以通过用一种烷化剂如卤代烷对胺进行处理从而实现烷化。可替代地,在一种合适的催化剂/配体系统、常常是一种钯(0)络合物的存在下,可以通过用一种芳基的卤化物或磺酸盐对胺进行处理从而实现芳基化。
6)可替代地,具有化学式(IV)的化合物(其中,R为C1-C6烷氧基),可以从具有化学式(VII)的化合物(其中,R为C1-C6烷氧基并且LG是离去基团如溴、氯或磺酸盐),通过由一种具有化学式R1-NH2的胺或者其他的亚胺类似物置换该离去基团,随后通过用一种金属催化剂水解而制造。参见,例如:化学通讯(Chemical Communications)(2009),(14),1891-1893或者有机化学杂志(Journal of Organic Chemistry)(2000),65(8),2612-2614。
具有化学式(VII)的化合物以及具有化学式R1-NH2的胺是已知的化合物或者可以通过本领域普通技术人员已知的方法来制造。
6a)可替代地,具有化学式(IV)的化合物(其中R为C1-C6烷氧基),可以从具有化学式XV的化合物(其中R是C1-C6烷氧基),经由在一种金属催化剂以及两种合适的碳结构单元(例如乙醛或乙腈)存在下的还原来制造。参见例如:有机化学杂志(J.Org.Chem.)2007,72,9815或有机通讯(Org.Lett.)2005,7,471
7)可替代地,具有化学式(III)的化合物可以在如1)中所描述的标准条件下,通过用一种具有化学式Q1-COOH的羧酸或者一种具有化学式Q1-COHal(其中Hal为Cl、F或Br)的酰基卤对具有化学式(IX)的化合物进行处理而制造。
8)具有化学式(IX)的化合物可以从具有化学式(VIII)的化合物(其中P为一种合适的保护基团并且R为OH、Cl或C1-C6烷氧基),通过在如1)中所描述的标准条件下,与一种具有化学式NHR2Q2的胺形成酰胺键,随后通过在标准条件下去除保护基团P*而形成。
9)具有化学式(VIII)的化合物(其中R为OH或C1-C6烷氧基)可以通过对具有化学式(IV)的化合物(其中R为OH或C1-C6烷氧基)中的胺官能度进行保护来制造。合适的保护基团包括氨基甲酸酯(如叔丁氧羰基、烯丙氧羰基以及苄氧基羰基)、三烷基甲硅烷基基团(如叔丁基二甲基甲硅烷基)以及酰基(如乙酰基)。
10)对于具有化学式(VIII)的化合物以及具有化学式(IV)的化合物,可以将酯类(其中R为C1-C6烷氧基)通过在一种溶剂如乙醇中用一种碱性氢氧化物如氢氧化钠进行处理而将其水解为酸(其中R为OH)。通过用如在2)和3)中描述的亚硫酰二氯或草酰氯进行处理,这些酸可以被转化为酰基氯(其中R为Cl)。
11)可替代地,具有化学式(IV)的化合物(其中,R为OH、Cl、F、Br或C1-C6烷氧基)可以在如1)中所描述的标准条件下,通过与一种具有化学式NHR2Q2的胺形成酰胺键而直接被转化为具有化学式(IX)的化合物。
12)可替代地,具有化学式(IX)的化合物可以从具有化学式(XI)的化合物(其中,LG是离去基团,如碘、溴、氯或磺酸盐),通过用一种具有化学式R1-NH2的化合物或者其他的亚胺类似物置换该离去基团,随后通过用一种金属催化剂进行水解而制造。参见,例如:化学通讯(Chemical Communications)(2009),(14),1891-1893或者有机化学杂志(Journalof Organic Chemistry)(2000),65(8),2612-2614。
13)具有化学式(XI)的化合物可以从具有化学式(X)的化合物(其中,R为Cl或OH并且LG是如在12)中所描述的离去基团),在如在1)中所描述的标准条件下,通过形成酰胺键进行制造。具有化学式(X)以及化学式(IV)的化合物是已知的化合物或者可以通过本领域普通技术人员已知的方法来制造。
14)具有化学式(IX)的化合物(其中R1是氢)的一种可替代的合成法可以通过将具有化学式(XIII)的硝基化合物进行还原(如通过在酸性条件下用氯化锡进行处理,或者通过一种贵金属如钯碳所催化的氢化作用)来实现。
Y是LG或F或H
15)具有化学式(XIII)的化合物可以从具有化学式(XII)的化合物(其中,R为OH、Cl或C1-C6烷氧基),在如在1)中所描述的标准条件下,经由与一种具有化学式NHR2Q2的胺的酰化作用得到。
16)对于具有化学式(XII)的化合物,可以通过在一种溶剂如在3)中描述的乙醇中将酯类(其中R为C1-C6烷氧基)用一种碱性氢氧化物如氢氧化钠进行处理,从而水解成酸(其中R为OH)。通过用如在2)中描述的亚硫酰二氯或草酰氯进行处理,这些酸可以被转化为酰基氯(其中R为Cl)。具有化学式(XII)的化合物是已知的或者可以通过本领域普通技术人员已知的方法来制造。
17)具有化学式(XII)的化合物可以从具有化学式(XIV)的化合物(其中LG是离去基团,如重氮基或氯),通过与氟化物(如KF)反应进行制造。
使用一种氟化物亲核体对卤素的置换也可以在具有化学式(XIII)的中间体上进行。
18)具有化学式(XIII)的化合物(其中R2选自C1-C8烷基、C2-C8烯基、C2-C8炔基)可以从具有化学式(XIII)的化合物(其中R2是氢)通过用一种碱,随后用一种合适的亲电子试剂处理它们而进行制备。碱的实例可以是金属氢化物如氢化钠、氢化钾或氢化钙,或金属醇盐如叔丁醇钾,或有机金属如甲基锂、丁基锂、烷基镁化卤,金属氨化物如二异丙氨基锂,或六甲基二硅基氨基锂,或者碱性盐如碳酸钾。可以使用一种溶剂。它可以是,例如,一种极性无质子溶剂如DMF,或者一种醚如THF,或者二甲氧基乙烷。该反应可以在0℃以下或者80℃以上进行,但是优选地在DMF中0℃和25℃之间。该亲电子试剂是R2-X’,其中R2是选自C1-C8烷基、C2-C8烯基、C2-C8炔基,并且X’是离去基团,像溴、氯、碘、甲磺酸根、三氟甲磺酸根、甲苯磺酸根以及类似物。该碱,连同亲电子试剂可以过量使用,但是优选地,该碱以与该亲电试剂相等的量值使用。
19)具有化学式(III)的化合物(其中Q1和Q2如在说明书中定义,R1不同于氢并且R2选自C1-C8烷基、C2-C8烯基、C2-C8炔基)可以从具有化学式(III)的化合物(其中Q1和Q2如在说明书中定义,R1不同于氢并且R2是氢),通过用一种碱,随后用一种合适的亲电子试剂处理它而进行制备。碱的实例可以是金属氢化物如氢化钠、氢化钾或氢化钙,或金属醇盐如叔丁醇钾,或有机金属如甲基锂、丁基锂、烷基镁化卤,金属氨化物如二异丙氨基锂或六甲基二硅基氨基锂,或者碱性盐如碳酸钾。可以使用一种溶剂。它可以是,例如,一种极性无质子溶剂如DMF,或者一种醚如THF,或者二甲氧基乙烷。该反应可以在0℃以下或者80℃以上进行,但是优选地在DMF中0℃和25℃之间。该亲电子试剂是R2-X’,其中R2是选自C1-C8烷基、C2-C8烯基、C2-C8炔基,并且X’是离去基团,像溴、氯、碘、甲磺酸根、三氟甲磺酸根、甲苯磺酸根以及类似物。该碱,连同亲电子试剂可以过量使用,但是优选地,该碱以与该亲电试剂相等的量值使用。优选的条件是在0℃和25℃之间,在DMF中的氢化钠。
20)具有化学式(III)的化合物(其中Q1和Q2如在说明书中定义,R1选自C1-C8烷基、C2-C8烯基、C2-C8炔基并且R2不同于氢)可以从具有化学式(III)的化合物(其中Q1和Q2如在说明书中定义,R1是氢并且R2不同于氢),通过用一种碱,随后用一种合适的亲电子试剂处理它而进行制备。碱的实例可以是金属氢化物如氢化钠、氢化钾或氢化钙,或金属醇盐如叔丁醇钾,或有机金属如甲基锂、丁基锂、烷基镁化卤,金属氨化物如二异丙氨基锂,或六甲基二硅基氨基锂,或者碱性盐如碳酸钾。可以使用一种溶剂。它可以是,例如,一种极性无质子溶剂如DMF,或者一种醚如THF,或者二甲氧基乙烷。该反应可以在0℃以下或者80℃以上进行,但是优选地在DMF中0℃和25℃之间。该亲电子试剂是R1-X’,其中R1是选自C1-C8烷基、C2-C8烯基、C2-C8炔基,并且X’是离去基团,像溴、氯、碘、甲磺酸根、三氟甲磺酸根、甲苯磺酸根以及类似物。该碱,连同亲电子试剂可以过量使用,但是优选地,该碱以与该亲电试剂相等的量值使用。优选的条件是在0℃和25℃之间,在DMF中的氢化钠。
具有式(I)的化合物可以用来对抗并且控制昆虫有害生物(例如鳞翅目、双翅目、半翅目、缨翅目、直翅目、网翅目、鞘翅目、蚤目、膜翅目和等翅目)以及其他的无脊椎动物的有害生物(例如,螨、线虫以及软体动物有害生物)的侵染。昆虫、螨、线虫以及软体动物在下文中总称为有害生物。这些可通过使用本发明化合物对抗并且控制的有害生物包括那些与农业(该术语包括食物和纤维产物的农作物的培育)、园艺和畜牧、宠物、林业和蔬菜源(例如果实,谷粒和木材)的产物的储存有关的有害生物;那些与人造结构的损害及人和动物的疾病传播有关的有害生物;以及公害有害生物(例如苍蝇)。
上述动物有害生物的实例是:
来自蜱螨目,例如,
下毛瘿螨属、针刺瘿螨属、窄瘿螨属、瘤瘿螨属、粗脚粉螨、钝眼蜱属、锐缘蜱属、牛蜱属、短须螨属、苔螨属、上三节瘿螨属、皮螨属、鸡皮刺螨、表皮螨属、始叶螨属、瘿螨属、半跗线螨属、璃眼蜱属、硬蜱属、小爪螨属(Olygonychus spp.)、钝缘蜱属、侧多食附线螨(Polyphagotarsone latus)、全爪螨属、桔芸锈螨、植食螨、跗线螨属、痒螨属、扇头蜱属、根嗜螨属、疥螨属、狭跗线螨属、跗线属、和叶螨属;
来自虱目(Anoplura),例如,
血虱属、长颚虱属、虱属、瘿绵蚜属和根瘤蚜属;
来自鞘翅目,例如,
缺隆叩甲属、欧洲鳃角金龟、东方异丽金龟、花象属、蜉金龟属、玉米拟花萤、金龟属(Ataenius spp.)、甜菜隐食甲、甜菜胫跳甲、萤叶甲属、宽胸叩头虫属(Conoderusspp.)、根颈象属、绿金龟、象虫属、圆头犀金龟属、皮蠹属、根萤叶甲属、阿根廷兜虫、食植瓢虫属、Eremnus spp.、黑异爪蔗金龟、咖啡果小蠹、Lagria vilosa、马铃薯叶甲、稻水象属、Liogenys spp.、Maecolaspis spp.、栗色绒金龟、美洲叶甲属(Megascelis spp.)、油菜花露尾甲(Melighetes aeneus)、鳃金龟属、Myochrous armatus、锯谷盗属(Orycaephilusspp.)、耳喙象属(Otiorhynchus spp.)、鳃角金龟属、斑象属、弧丽金龟属、跳甲属、Rhyssomatus aubtilis、劫根蠹属、金龟子科、象虫属、麦蛾属、伪切根虫属(Somaticusspp.)、尖隐喙象属、大豆茎象、拟步行虫属、拟谷盗属、和斑皮蠹属;
来自双翅目,例如,
伊蚊属、疟蚊属、高粱芒蚊、橄榄果实蝇、花园毛蚊、迟眼蕈蚊属、红头丽蝇、蜡实蝇属、金蝇属、家蚊属、黄蝇属、寡鬃实蝇属、地种蝇属、黑腹果蝇、厕蝇属、胃蝇属、Geomyzatripunctata、舌蝇属、皮蝇属、虱蝇属(Hyppoboscaspp.)、斑潜蝇属、绿蝇属、黑潜蝇属、库蝇属、狂蝇属、瘿蚊属、瑞典麦秆蝇、藜泉蝇、草种蝇属、绕实蝇属、Riveliaquadrifasciata、Scatella spp.、蕈蚊属、刺蝇属、虻属、绦虫属、和大蚊属;
来自半翅目,例如,
瘤缘蝽(Acanthocoris scabrator)、绿蝽属、苜蓿盲蝽、果子斑点臭虫(Amblypelta nitida)、海虾盾缘蝽、土长蝽属、臭虫属、竹卵圆蝽属蝽(Clavigrallatomentosicollis)、淡盲蝽属(Creontiades spp.)、可可瘤盲蝽、Dichelops furcatus、棉红蝽属、Edessa spp.、美洲蝽属、六斑菜蝽、扁盾蝽属、茶翅蝽、具凹巨股长蝽(Horciasnobilellus)、稻缘蝽属、草盲蝽属、珠蚧属、卷心菜斑色蝽、Neomegalotomus spp.、烟盲蝽、绿蝽属、拟长蝽、海岛蝽象、皮蝽属、壁蝽属、红猎蝽属、可可盲蝽象、Scaptocoriscastanea、黑蝽属、Thyanta spp.、锥鼻虫属、木薯网蝽;
无网长管蚜(Acyrthosium pisum)、Adalges spp.、Agalliana ensigera、Agonoscena targionii、盘粉虱属、剌粉虱属、甘蔗穴粉虱、软毛粉虱、菜粉虱、棉叶蝉、檬果长突叶蝉、肾圆盾介壳虫属、蚜科、蚜属、薄圆盾介壳虫属、茄沟无网蚜、马铃薯木虱、伯粉虱属、舌尾蚜属、甘蓝蚜、喀木虱属、双尾蚜、蜡蚧属、黑褐圆盾蚧、橙褐圆盾蚧、大叶蝉属、大白叶蝉、隐瘤蚜属、叶蝉属、褐软蚧、玉米黄翅叶蝉、裸粉虱属、柑橘木虱、麦双尾蚜、西圆尾蚜属、小绿叶蝉属、苹果棉蚜、葡萄斑叶蝉属、蜡蛤属(Gascardia spp.)、赤桉木虱、菜缢管蚜(Hyadaphis pseudobrassicae)、大尾蚜属、超瘤蚜种(Hyperomyzus pallidus)、檬果绿叶蝉、Jacobiasca lybica、灰飞虱属、水土坚蚧、蛎盾蚧属、萝卜蚜、Lyogenys maidis、长管蚜属、Mahanarva spp.、蛾蜡蝉科、麦无网蚜、麦蜡蝉、瘤蚜属、新声蚜属、黑尾叶蝉属、褐飞虱属、梨绿蚜、狗牙根草芥壳虫、甘蔗棉蚜、杨梅缘粉虱、考氏木虱、片盾蚧属、瘿绵蚜属、玉米蜡蝉、扁角飞虱属、忽布疣额蚜、根瘤蚜属、臀纹粉蚧属、拟白轮盾介壳虫属、粉蚧属、棉跳盲蝽、木虱属、棉蚧(Pulvinaria aethiopica)、齿盾蚧属、Quesada gigas、电光叶蝉、缢管蚜属、黑盔蚧属、带叶蝉属、二叉蚜属、芒蚜属、白背飞虱、苜蓿膜翅角蝉、条斑飞虱、桔蚜属、粉虱属、Tridiscus sporoboli、葵粉蚧属、非洲木虱、尖盾蚧、Zygina flammigera、Zyginidiascutellaris;
来自膜翅目,例如,
顶切叶蚁属、三节叶蜂属(Arge spp.)、布切叶白蚁属、茎叶蜂属、松叶蜂属、锯角叶蜂科、松叶蜂(Gilpinia polytoma)、梨实蜂属(Hoplocampa spp.)、毛蚁属、小黄家蚁、新松叶蜂属、农蚁属、Slenopsis invicta、水蚁属以及胡蜂属;
来自等翅目,例如,
家白蚁属、白蚁(Corniternes cumulans)、楹白蚁属、大白蚁属、澳白蚁属、小白蚁属、散白蚁属;热带火蚁
来自鳞翅目,例如,
长翅卷蛾属、褐带卷蛾属、透翅蛾属、地夜蛾属、棉叶虫、Amylois属、黎豆夜蛾、黄卷蛾属、银蛾属(Argyresthia spp.)、带卷蛾属、丫纹夜蛾属、棉潜蛾、玉米楷夜蛾、粉斑螟蛾、桃蛀果蛾、禾草螟属、卷叶蛾属、越蔓桔草螟(Chrysoteuchia topiaria)、葡萄果蠹蛾(Clysia ambiguella)、卷叶螟属、云卷蛾属、纹卷蛾属、鞘蛾属、磷翅目粉蝶、Cosmophilaflava、草螟属、大菜螟、苹果异形小卷蛾、黄杨木蛾、小卷蛾属、黄杨绢野螟、杆草螟属、苏丹棉铃虫、金刚钻属、非洲茎螟、粉螟属、叶小卷蛾属(Epinotia spp.)、细斑灯蛾、豆荚螟(Etiella zinckinella)、花小卷蛾属、环针单纹蛾、黄毒蛾属、切根虫属、Feltiajaculiferia、小食心虫属(Grapholita spp.)、绿青虫蛾、实夜蛾属、菜螟、切叶野螟属(Herpetogramma spp.)、美国白蛾、番茄蠹蛾、小玉米螟(Lasmopalpus lignosellus)、旋纹潜叶蛾、潜叶细蛾属、葡萄花翅小卷蛾、Loxostege bifidalis、毒蛾属、潜蛾属(Lyonetiaspp.)、幕枯叶蛾属、甘蓝夜蛾、烟草天蛾、秘夜蛾属(Mythimna spp.)、夜蛾属、秋尺蛾属、Orniodes indica、欧洲玉米螟、超小卷蛾属、褐卷蛾属、小眼夜蛾、蛀茎夜蛾、棉红铃虫(Pectinophora gossypiela)、咖啡潜叶蛾、一星黏虫、马铃薯麦蛾、菜粉蝶、粉蝶属、小菜蛾、芽蛾属、尺叶蛾属、薄荷灰夜蛾、西方豆地香(Richia albicosta)、白禾螟属(Scirpophaga spp.)、蛀茎夜蛾属、长须卷蛾属、灰翅夜蛾属、棉大卷叶螟、兴透翅蛾属、异舟蛾属、卷叶蛾属、粉纹夜蛾、番茄斑潜蝇、以及巢蛾属;
来自食毛目(Mallophaga),例如,
畜虱属(Damalinea spp.)和啮毛虱属;
来自直翅目,例如,
蠊属、小蠊属、蝼蛄属、马德拉蜚蠊、飞蝗属、北痣蟋蟀、大蠊属、痣蟋蟀属以及沙漠蝗属;
来自啮虫目(Psocoptera),例如,
虱啮属(Liposcelis spp);
来自蚤目,例如,
角叶蚤属、栉头蚤属和印鼠客蚤;
来自缨翅目,例如,
Calliothrips phaseoli、花蓟马属、阳蓟马属、褐带蓟马属、单亲蓟马属(Parthenothrips spp.)、南非柑桔蓟马、大豆蓟马、带蓟马属、蓟马属;
来自缨尾目(Thysanura),例如,
衣鱼(Lepisma saccharina)。
根据本发明的活性成分可以用于控制,即限制或毁灭,出现在特别是在植物上,尤其是在农业、园艺和森林中的有用植物和观赏植物上,或在这样的植物的器官如果实、花、叶、秆、根茎或根上的上述类型的有害生物,并且在某些情况下,甚至在较晚的时间点形成的植物器官上仍然针对这些有害生物的保护。
合适的目标作物具体是谷物,例如小麦、大麦、黑麦、燕麦、水稻、玉米或高粱;甜菜,例如糖用甜菜或饲料甜菜;水果,例如苹果类水果、核果类水果或无核水果,例如苹果、梨、李子、桃、杏仁、樱桃或浆果,例如草莓、覆盆子或黑莓;豆科作物,例如蚕豆、小扁豆、豌豆或大豆;油料作物,例如油菜、芥菜、罂粟、橄榄、向日葵、椰子、蓖麻、可可或落花生;葫芦,例如南瓜、黄瓜或甜瓜;纤维植物,例如棉花、亚麻、大麻或黄麻;柑桔类水果,例如橙子、柠檬、葡萄柚或橘子;蔬菜,例如菠菜、莴苣、芦笋、甘蓝、胡萝卜、洋葱、蕃茄、马铃薯或铃状椒;樟科植物,例如鳄梨、肉桂或樟脑;以及还有烟草、坚果、咖啡、茄子、甘蔗、茶叶、胡椒、葡萄树、蛇麻子、车前科、产胶植物以及观赏植物。
因此,本发明提供了一种用于对抗和控制昆虫、螨、线虫或软体动物的方法,该方法包括将杀昆虫、杀螨、杀线虫或杀软体动物有效量的具有化学式(I)的化合物,或一种含化学式(I)的化合物的组合物施用到有害生物,有害生物场所,优选地一种植物,或易受有害生物攻击的植物上,具有化学式(I)的这些化合物优选地用于针对昆虫、螨或线虫。
对于螨,例如,朱砂叶螨、二点叶螨、桔全爪螨、桔刺皮节蜱、跗线属。
对于线虫,例如,南方根结线虫、松材线虫、水稻干尖线虫、大豆胞囊线虫、短体线虫属。
另外,这些化合物可以用于控制动物有害生物,特别是昆虫、蜘蛛、蠕虫、线虫以及软体动物,在农业、园艺、兽医医药领域、森林、园林以及娱乐消遣设施、存储产物和材料的保护以及卫生学领域中会遇到它们。这些化合物优选地可以用作植物保护剂。它们可以有效地针对普通敏感的和抗性的种类并且针对所有或一些发育阶段。
这些有害生物尤其包括:
来自虱目(毛虱目),例如,牛羽虱属、血虱属、毛虱属、虱属、啮毛虱属。
来自蛛形纲,例如:粗脚粉螨、柑橘癌瘿螨、刺皮瘿螨属、针刺瘿螨属、钝眼蜱属、锐缘蜱属、牛蜱属、短须螨属、苜蓿苔螨、皮螨属、鸡皮刺螨、始叶螨属、梨上瘿螨、真叶螨属、瘿螨属、半跗线螨属、璃眼蜱属、硬蜱属、黑寡妇、后红叶螨属(Metatetranychus spp.)、小爪螨属、钝缘蜱属、全爪螨属、桔芸锈螨、侧多食跗线螨、痒螨属、扇头蜱属、根嗜螨属、疥螨属、中东金蝎、狭趺线螨属(Stenotarsonemus spp.)、跗线属、叶螨属、番茄斜背瘤瘿螨(Vasates lycopersici)。
来自双壳纲,例如,饰贝属。
来自唇足纲的目,例如,地蜈蚣属、蚰蜒属。
来自鞘翅目,例如,菜豆象、喙丽金龟属、杨树萤叶甲、叩甲属、马铃薯鳃角金龟、家具窃蠹、星天牛属、花象属、圆皮蠹属、阿鳃金龟属、隐翅甲属(Atomaria spp.)、毛皮蠹属、恶条豆象、豆象属、龟象属、门拟卡司方喙象(Cleonus mendicus)、宽胸叩头虫属、根颈象属、褐新西兰肋翅鳃角金龟、象虫属、杨干隐喙象、皮蠹属、根萤叶甲属、食植瓢虫属、蛀茎象甲、裸蛛甲、黑异爪蔗金龟、Hylamorpha elegans、北美家天牛、紫苜蓿叶象、咪小蠹属、甘蔗大褐齿爪鳃金龟、马铃薯甲虫、稻水象甲、筒喙象属、粉蠹属、油菜花露尾甲、西方五月鳃角金龟、天牛属(Migdolus spp.)、墨天牛属、黄缘象甲(Naupactus xanthographus)、黄蛛甲、犀角金龟、锯谷盗、黑葡萄耳象、小青花金龟、辣根猿叶甲、鳃角金龟属、日本金龟子、安第斯马铃薯象属、油菜金头跳甲、蛛甲属、暗色瓢虫、谷蠹、米象属、尖隐喙象属、茎干象属、Symphyletes spp.、黄粉虫、拟谷盗属、斑皮蠹属、籽象属、脊虎天牛属、距步甲属。
来自弹尾目,例如,武装棘跳虫。
来自革翅目,例如,欧洲球螋。
来自倍足纲的目,例如,千足虫(Blaniulus guttulatus)。
来自双翅目,例如,伊蚊属、按蚊属、花园毛蚊、红头丽蝇、地中海蜡实蝇、金蝇属、锥蝇属、嗜人瘤蝇、库蚊属、黄蝇属、橄榄大实蝇、人肤蝇、果蝇属、厕蝇属、胃蝇属、黑蝇属、虱蝇属(Hyppobosca spp.)、皮蝇属、斑潜蝇属、绿蝇属、家蝇属、绿蝽属、狂蝇属、瑞典麦秆蝇、藜泉蝇、草种蝇属、刺蝇属、虻属、绦虫属(Tannia spp.)、欧洲大蚊、污蝇属。
来自腹足纲,例如阿勇蛞蝓属(Arion spp.)、扁卷螺属、小泡螺属、蜡项蛞蝓属、土蜗属、椎实螺属、钉螺属、琥珀螺属。
来自蠕虫纲,例如,十二指肠钩口线虫、锡兰钩口线虫、巴西钩口线虫、钩口线虫属、似引蛔线虫、蛔虫属、马来丝虫、帝汶布鲁丝虫、仰口线虫属、夏氏线虫属、支睾吸虫属、古柏线虫属、双腔吸虫属、丝圆线虫、阔节裂头绦虫、麦地那龙线虫、细粒棘球绦虫、多房棘球绦虫、蛲虫、片吸虫属、血毛线虫属、异刺属、短膜壳绦虫、猪圆线虫属、非洲眼线虫、细颈属、结节线虫属、后睾吸虫属、旋盘尾丝虫、胃线虫属、并殖吸虫属、血吸虫属、费氏类圆线虫、粪类圆线虫、粪圆线虫属、牛肉绦虫、猪肉绦虫、旋毛虫、本地毛形线虫、株布氏旋毛虫、纳氏旋毛虫、伪旋毛虫、毛圆线虫属、毛首鞭形线虫、斑氏线虫。
它此外还可能去控制原生动物,例如艾美球虫属。
来自半翅目,例如,南瓜缘蝽、拟丽蝽属、土长蝽属、俊盲蝽属、斑腿微刺盲蝽、异背长蝽属、臭虫属、绿盲蝽、胡椒缘蝽、Dichelops furcatus、厚氏长棒网蝽、棉红蝽属、美洲蝽属、扁盾蝽属、角盲蝽属、具凹巨股长蝽(Horcias nobilellus)、稻缘蝽属、叶喙缘蝽、草盲蝽属、蔴漂长蝽(Macropes excavatus)、盲蝽科、绿蝽属、稻蝽属(Oebalus spp.)、蝽科、方背皮蝽、壁蝽属、棉伪斑腿盲蝽、Pseudacysta persea、红猎蝽属、可可盲蝽象、黑蝽属、梨冠网蝽、Tibraca spp.、锥蝽属。
来自同翅目例如无网长管蚜属、Aeneolamiaspp.、隆脉木虱属、小白蛾属(Aleurodes spp.)、甘蔗穴粉虱、须粉虱属(Aleurothrixus spp.)、杜果叶蝉属、李薊圓尾蚜、肾圆盾蚧属、梨矮蚜、蚜属、葡萄叶蝉、小圆盾蚧属、圆盾蚧属、桤木属、茄沟无网蚜、小粉虱属、李短尾蚜、微管蚜属(Brachycolus spp.)、甘蓝蚜、小褐稻虱、红头大叶蝉、甘蔗粉角蚜、沫蝉科、蜡蚧属、草莓钉蚜、蔗黄雪盾蚧、茶绿叶蝉、核桃黑斑蚜、黑褐圆盾蚧、玉米叶蝉、霍氏长盾蚧、软蚧属、茶蔗隐瘤蚜、黄翅叶蝉属(Dalbulus spp.)、裸粉虱属、呆木虱属、白背盾蚧属、Doralisspp.、履绵蚧属、西圆尾蚜属、灰粉蚧属、小绿叶蝉属、绵蚜属、葡萄斑叶蝉属、具二叶殃叶蝉(Euscelis bilobatus)、咖啡地粉蚧、假桃病毒叶蝉、梅大尾蚜、吹绵蚧属、片角叶蝉属、扁喙叶蝉属、灰飞虱、褐球蚧属(Lecanium spp.)、蛎盾蚧属、萝卜蚜、长管蚜属、毛缘沫蝉(Mahanarva fimbriolata)、高粱蚜、Metcalfiella spp.、麦无网蚜、黑缘平翅斑蚜、Monelliopsis pecanis、瘤蚜属、莴苣蚜、黑尾叶蝉属、稻褐飞虱、Oncometopiaspp.、普来隆旌蚧(Orthezia praelonga)、杨梅缘粉虱、枸杞木虱属、片盾蚧属、瘿绵蚜属、玉米蜡蝉、绵粉蚧属、杨平翅绵蚜、忽布疣蚜、根瘤蚜属、苏铁褐点并盾蚧、动性球菌属、梨形原绵蚧、桑白盾蚧、粉蚧属、木虱属、金小蜂属、Pyrillaspp.、笠圆盾蚧属、Quesada gigas、平刺粉蚧属、缢管蚜属、黑盔蚧属、Scaphoides titanus、麦二叉蚜、苏铁刺圆盾蚧、长唇基飞虱属、白背飞虱、稻飞虱属(Sogatodes spp.)、费斯提纳形角蝉(Stictocephala festina)、Tenalaphara malayensis、胡桃黑蚜、广胸沫蝉属、声蚜属、温室粉虱、个木虱属、小叶蝉属、矢尖蚧属、葡萄根瘤蚜。
来自膜翅目,例如松叶蜂属、实叶蜂属、毛蚁属、小黄家蚁、胡蜂属。
来自等足目,例如,鼠妇、栉水虱、球鼠妇。
来自等翅目,例如,散白蚁属、土白蚁属。
来自鳞翅目,例如,桑剑纹夜蛾、烦夜蛾、地老虎属、棉叶波纹夜蛾、干煞夜蛾属、甘蓝夜蛾、棉潜蛾、松尺蠖、亚麻黄卷蛾、棉褐带卷娥、苹果小卷蛾、冬尺蛾、禾草螟属、云杉色卷蛾、葡萄果蠹蛾、Cnaphalocerusspp.、埃及金刚钻、地中海粉斑螟、褐尾蠹、切根虫属、脏切夜蛾属、大蜡螟、铃夜蛾属、实夜蛾属、褐织蛾、茶长卷蛾、苹果巢蛾、贪夜蛾属、苹细蛾、绿果冬夜蛾、豆白隆切根虫、毒蛾属、黄褐天幕毛虫、甘蓝夜蛾、稻毛胫夜蛾、东方粘虫、巫夜蛾属、水稻负泥虫、小眼夜蛾、红铃麦蛾、桔潜蛾、菜粉蝶属、菜蛾、斜纹夜蛾属、拟粘液蛾属、大豆夜蛾、玉米螟、灰翅夜蛾属、Thermesia gemmatalis、袋谷蛾、幕谷蛾、栎绿卷蛾、粉夜蛾属。
来自直翅目,例如家蟋、东方蛮蠊、德国小蠊、蝼蛄属、马德拉蜚蠊、飞蝗属、黑蝗属、美洲大蠊、沙漠蝗。
来自蚤目,例如,角叶属、印鼠客蚤。
来自综合目(Symphyla),例如,白松虫(Scutigerella immaculata)。
来自缨翅目,例如,稻蓟马、Enneothrips flavens、花蓟马属、阳蓟马属、温室条篱蓟马、卡蓟马属、葡萄蓟马、硬蓟马属、小豆蔻带蓟马(Taeniothrips cardamoni)、蓟马属。
来自缨尾目,例如,西洋衣鱼(Lepisma saccharina)。
这些植物寄生线虫包括例如鳗属、滑刃线虫属、刺线虫属、伞滑刃线虫属、鳞球茎茎线虫、球异皮线虫属、螺旋线虫属、异皮线虫属、长针线虫属、根结线虫属、短体线虫属、香蕉穿孔线虫、小盘旋线虫属、毛刺线虫属、矮化线虫属、小垫刃线虫属、半穿刺线虫、剑线虫属。
此外,兽医医药领域内,本发明的这些新颖的化合物可以有效地用以抵抗各种有害的动物寄生有害生物(体内寄生虫以及体外寄生虫),例如,昆虫和蠕虫。
这类动物寄生有害生物的实例包括以下描述的有害生物。
昆虫的实例包括胃蝇属、刺蝇属、啮毛虱属、红猎蝽属、犬栉头蚤、温带臭虫、猫栉头蚤、铜绿蝇等。
螨的实例包括钝缘蜱属、硬蜱属、牛蜱属,等。
在兽医领域内,例如在兽医医药领域内,根据本发明的活性化合物是有效地抵抗动物寄生虫,特别是体内寄生虫或体外寄生虫。
术语体内寄生虫特别包括蠕虫,例如绦虫、线虫或吸虫,以及原生动物,例如球虫亚纲。
体外寄生虫典型地并且优选地是节肢动物,特别是昆虫例如苍蝇(叮和舔),寄生的蝇幼虫、虱、毛发虱、鸟虱、蚤以及类似物;或螨(acarids),例如蜱,例如硬蜱或软蜱,或螨虫(mites),例如疥螨、秋螨、鸟螨以及类似物。
这些寄生虫包括:
来自虱目,例如血虱属、毛虱属、虱属、阴虱属、盲虱属;具体实例是:棘颚虱、牛颚虱、绵羊颚虱、卵形颚虱(Linognathus oviformis)、足颚虱、山羊颚虱、巨头驴血虱、牛血虱、猪血虱、人头虱、人体虱、葡萄根瘤蚜、阴虱、水牛盲虱;来自食毛目和钝角亚目和细角亚目,例如毛羽虱属、禽虱属、巨羽虱属、牛羽虱属、Werneckiella spp.、Lepikentron spp.、畜虱属、啮毛虱属、猫羽虱属;具体实例是:牛羽虱、羊毛虱、具边毛虱、牛畜虱、犬啮毛虱、猫羽虱、山羊毛虱、Lepikentron ovis、咬虱;来自双翅目和长角亚目和短角亚目,例如伊蚊属、疟蚊属、库蚊属、蚋属、真蚋属、白蛉属、罗蛉属、库蠓属、斑虻属、短蚋亚属、维蚋属、瘤虻属、黄虻属、虻属、麻虻属、Philipomyia属、蜂虱蝇属、苍蝇属、齿骨蝇属、蝇属、黑角蝇属、Morellia spp.、厕蝇属、舌蝇属、丽蝇属、绿蝇属、金蝇属、污蝇属、麻蝇属、牛虻属、皮蝇属、胃蝇属、虱蝇属、羊虱蝇属(Lipoptena spp.)、蜱蝇属、鼻狂蝇属、大蚊属;具体实例是:埃及伊蚊、白纹伊蚊、带喙伊蚊、冈比亚按蚊、五斑按蚊、红头丽蝇、高额麻虻、五带淡色库蚊、尖音库蚊、环跗库蚊、黄腹厕蝇、肉蝇、厩螫蝇、欧洲大蚊、铜绿蝇、丝光绿蝇、爬蚋、静食白蛉、长须白蛉、华丽短蚋、马尾维蚋、红头厌蚋、多声虻、夜蛾虻、北美黑虻、卷虻(Tabanussudeticus)、古氏瘤虻、盲斑虻、黄缘斑虻、高额麻虻、意大利麻虻(Haematopota italica)、秋家蝇、家蝇、角蝇、水牛蝇、刺扰血蝇、刺激齿股蝇(Hydrotaea irritans)、白斑齿股蝇、黄绿金蝇(Chrysomya chloropyga)、蛆症金蝇、羊狂蝇、牛皮蝇、纹皮蝇、山羊牛蝇、人肤蝇、绵羊虱蝇、卡氏羊虱蝇(Lipoptena capreoli)、鹿羊虱蝇(Lipoptena cervi)、杂色虱蝇(Hippobosca variegata)、马虱蝇、肠胃蝇、赤尾胃蝇、裸节胃蝇、鼻胃蝇、黑角胃蝇、黑腹胃蝇、蜂虱蝇;来自蚤目例如蚤属、栉头蚤属、潜蚤属、客蚤属、角叶蚤属;具体实例是:犬栉头蚤、猫栉头蚤、人蚤、穿皮潜蚤、印鼠客蚤;来自异翅目,例如,臭虫属、锥鼻虫属属、红猎蝽属、锥蝽属。
来自蜚蠊目,例如东方蛮蠊、美洲大蠊、德国小蠊、夏柏拉蟑螂属(例如褐帶蠊);
来自蜱螨亚纲(螨科)和后气门目与中气门目,例如锐缘蜱属、钝缘蜱属、耳蜱属、硬蜱属(Ixodes spp.)、钝眼蜱属、扇头蜱属(牛蜱属)、革蜱属、血蜱属、璃眼蜱属、皮刺螨属、扇头蜱属(多宿主蜱的原始属)、禽刺螨属、肺刺螨属、刺利螨属、肺刺螨属、胸孔螨属、瓦螨属、蜂盾螨属;具体实例是:波斯锐缘蜱、鸽锐缘蜱、非洲钝缘蜱、刺耳扁虱、微小扇头蜱(微小牛蜱)、消色扇头蜱(消色牛蜱)、具环扇头蜱(具环牛蜱)、有矩扇头蜱(有矩牛蜱)、三宿璃眼蜱、埃及璃眼蜱、边缘璃眼蜱、长喙璃眼蜱、外翻扇头蜱、蓖子硬蜱、六角形硬蜱、犬硬蜱、多毛硬蜱、浅红硬蜱、肩突硬蜱、全环硬蜱、嗜群血蜱、长棘血蜱、朱红血蜱、鼠耳血蜱、犬血蜱、长角血蜱、边缘革蜱、网纹革蜱、饰纹矩头蜱、棕色蜱、安德逊氏革蜱、变异革蜱、毛里求斯璃眼蜱、血红扇头蜱、囊状扇头蜱、具尾扇头蜱、好望角扇头蜱、图兰扇头蜱、赞比亚扇头蜱、美洲钝眼蜱、彩饰钝眼蜱、斑点钝眼蜱、希伯来钝眼蜱、卡延钝眼蜱、鸡皮刺螨、囊形刺脂螨、北方刺脂螨、大蜂螨;来自轴螨目(前气门亚目)和粉螨目(无气门亚目),例如蜂盾螨属、姬螯属、禽螯螨属、肉螨属、疮螨属、蠕形螨属、恙螨属、牦螨属、粉螨属、食酪螨属、嗜木螨属、颈下螨属、翅螨属、痒螨属、皮螨属、耳疥螨属、疥螨属、耳螨属、鸟疥螨属、胞螨属、鸡雏螨属;具体实例是:牙氏姬螯螨、布氏姬螯螨、犬脂螨、牛蠕形螨、绵羊蠕形螨、山羊蠕形螨、马脂螨、马蠕形螨、猪蠕形螨、秋收恙螨、迪萨得芮新恙螨(Neotrombicula desaleri)、Neoschongastia xerothermobia、红恙螨、狗耳螨、猫耳螨、犬疥螨、牛疥螨、羊疥螨、山羊疥螨(S.caprae)、马疥螨、猪疥螨、羊痒螨、免痒螨、马痒螨、牛痒螨、绵羊痒螨、Pneumonyssoidic mange、犬鼻疥虫、伍氏蜂跗线螨。
根据本发明的活性化合物还适合于控制侵袭动物的节肢动物、蠕虫以及原生动物。
动物包括农业牲畜例如像牛、绵羊、山羊、马、猪、驴、骆驼、水牛、兔、鸡、火鸡、鸭、鹅、养殖鱼、蜜蜂。
而且,动物包括家畜—还指宠物—例如像狗、猫、笼鸟、观赏鱼以及已知为试验动物的那些,例如像仓鼠、豚鼠、大鼠以及小鼠。
通过控制这些节肢动物、蠕虫和/或原生动物,旨在降低死亡并且提高性能(在肉、乳、羊毛、生皮、蛋、蜜等方面)以及宿主动物的健康,这样使得通过根据本发明的活性化合物的使用使更经济的和更简单的动物照管成为可能。
例如,可能希望的是预防或阻止这些寄生虫从这些宿主吸取血液。
还有,控制这些寄生虫可以帮助预防传染源的传播。
如在此关于兽医领域所使用的,术语“控制”指这些活性化合物将受这类寄生虫感染的动物中的相应寄生虫的发生率有效地降低到无害水平。
更具体地,如在此使用的,“控制”指这些活性化合物在杀死相应寄生虫、抑制它的生长或抑制它的繁殖方面是有效的。一般地,当用于动物的处理时,根据本发明的活性化合物可以直接施用。
优选地,它们是作为药物组合物施用,这些药物组合物可以包含药学上可接受的赋形剂和/或本领域内知晓的助剂。
在兽医领域和在动物照管方面,这些活性化合物以已知的方式(通过以例如片剂、胶囊、饮品、灌服、颗粒剂、糊剂、大丸剂、馈入方法(feed-through method)、栓剂形式肠内给予;通过肠胃外给予,例如像通过注射(包括肌内、皮下、静脉内、腹膜内等)、植入,通过搐鼻法,通过以例如淋浴或浸渍、喷雾、倾倒和沾滴(spotting-on)、洗涤、撒粉的形式以及在包含活性化合物的成型物品(例如,辊环、耳标、尾标、肢体带、缰绳、制造装置以及类似物)的帮助下的皮肤施用)来进行应用(例如给予)。
这些活性化合物可以配制为洗发剂或在气溶胶、非增压喷雾(例如泵式喷雾以及喷嘴喷雾)中可用的合适的配制品。
当用于牲畜、家禽、家畜等时,根据本发明的活性化合物可以作为配制品(例如粉剂、可湿性粉剂[“WP”]、乳液、可乳化性浓缩物[“EC”]、流动物、均匀溶液以及悬浮浓缩物[“SC”],它们按重量计直接地或在稀释之后(例如100到10000倍稀释)包括按重量计从1%到80%的量的活性化合物),或者作为一种化学浴来施用。
当在兽医领域使用时,根据本发明的活性化合物可以与合适的增效剂或其他活性化合物(例如像杀螨剂、杀昆虫剂、驱蠕虫药、抗原生动物药)组合使用。
在本发明中,一种具有针对有害生物(包括所有这些有害生物)的杀虫作用的物质称作一种杀虫剂。
当本发明的一种活性化合物用作一种杀虫剂时它能以常规配制品形式制备。
配制品形式的实例包括溶液、乳液、可湿性粉剂、可水分散的颗粒、悬浮液、粉剂、泡沫、糊剂、片剂、颗粒、气溶胶、活性化合物渗入的天然及合成材料、微囊剂、种衣(seedcoating)剂、与一种燃烧装置一起使用的配制品(例如,熏蒸和烟熏药筒、罐、盘管或作为燃烧装置的类似物)、ULV(冷雾、暖雾),等。
这些配制品可以通过本身已知的多种方法来生产。
例如,一种配制品可以通过将该活性化合物与一种展开剂(developer)(就是,一种液体稀释剂或载体;一种液化的气体稀释剂或载体;一种固体稀释剂或载体),以及可任选地与一种表面活性剂(就是,一种乳化剂和/或分散剂和/或发泡剂)混合来生产。
在水被用作展开剂的情况下,例如还可以将一种有机溶剂用作一种助溶剂。
液体稀释剂或载体的实例包括芳香族烃(例如,二甲苯、甲苯、烷基萘及其类似物)、氯代芳烃或氯代脂肪烃(例如氯苯、氯化乙烯、二氯甲烷)、脂肪烃(例如环己烷)、石蜡(例如矿物油馏分)、醇(例如丁醇、乙二醇及它们的醚、酯以及类似物)、酮(例如丙酮、甲基乙基酮、甲基异丁基甲酮、环己酮以及类似物)、强极性溶剂(例如二甲基甲酰胺、二甲亚砜以及类似物)、水以及类似物。该液化的气体稀释剂或载体可以是在标准温度与标准压力下是气态的那些,例如气溶胶喷射剂例如丁烷、丙烷、氮气、二氧化碳以及卤代烃。该固体稀释剂的实例包括粉碎的的天然矿物质(例如高岭土、粘土、滑石、白垩、石英、凹凸棒石、蒙脱石、硅藻土,以及类似物)、粉碎的合成矿物质(例如高度分散的硅酸、氧化铝、硅酸盐以及类似物)、以及类似物。用于颗粒剂的固体载体的实例包括粉碎的并且筛选的岩石(例如方解石、大理石、浮石、海泡石、白云石以及类似物)、无机与有机粉末合成的颗粒、有机材料的精细颗粒(例如锯屑、椰壳、玉米芯、烟草杆以及类似物)、以及类似物。该乳化剂和/或发泡剂的实例包括非离子和阴离子乳化剂[例如,聚氧化乙烯脂肪酸酯、聚氧乙烯脂肪酸醇醚(例如烷芳基聚乙二醇醚)、烷基磺酸盐、烷基硫酸盐、芳基磺酸盐以及类似物]、白蛋白水解物,以及类似物。该分散剂的实例包括木质素亚硫酸废液以及甲基纤维素。
固定剂也可以用在这些配制品(粉剂、颗粒剂、乳液)中,并且该固定剂的实例包括羧甲基纤维素、天然的和合成的聚合物(例如阿拉伯树胶、聚乙烯醇、聚乙酸乙烯酯,以及类似物)以及类似物。也可以使用着色剂,并且这些着色剂的实例包括无机颜料(例如氧化铁、氧化钛、普鲁土蓝以及类似物)、有机染料(例如茜素染料、偶氮染料或金属酞菁染料)、以及另外地,微量元素例如铁、锰、硼、铜、钴、钼以及锌的盐。这些配制品总体上可以按重量计包含范围从0.1%至95%(并且优选按重量计0.5%至90%)的量的该活性成分。根据本发明的化合物还可以作为与其他活性化合物(例如,杀昆虫剂、毒饵、杀细菌剂、杀螨剂、杀线虫剂、杀真菌剂、生长调节剂、除草剂以及类似物)的混合物,以它们商业上有用的配制品形式以及以从那些配制品制备的施用形式而存在。
根据本发明的以一种商业上有用的施用形式的化合物的含量可以在一个广泛范围内变化。
根据本发明的活性化合物在实际使用中的浓度可以例如按重量计处于0.0000001%至100%的范围,并且优选按重量计处于0.00001%至1%的范围内。
根据本发明的化合物可以通过适合于该使用形式的常规方法来使用。
本发明的活性化合物当针对卫生有害生物以及与储存产物相关的有害生物使用时,具有对于石灰材料上的碱有效的稳定性,并且还在木材和土壤中显示出优异的残效性。本发明的化合物对于施用量、残余配制品、选择性、毒性、生产方法、高活性、宽的控制谱、安全性、抗性生物(例如对有机磷试剂和/或氨基甲酸酯试剂有抗性的有害生物)的控制具有有利的特性。
本发明的进一步实施例如下所述。
具有式(I)的化合物可以用来对抗并且控制昆虫有害生物(例如鳞翅目、双翅目、半翅目、缨翅目、直翅目、网翅目、鞘翅目、蚤目、膜翅目和等翅目)以及其他的无脊椎动物的有害生物(例如,螨、线虫以及软体动物有害生物)的侵染。昆虫、螨、线虫以及软体动物在下文中总称为有害生物。这些可通过使用本发明化合物对抗并且控制的有害生物包括那些与农业(该术语包括食物和纤维产物的农作物的培育)、园艺和畜牧、宠物、林业和蔬菜源(例如果实,谷粒和木材)的产物的储存有关的有害生物;那些与人造结构的损害及人和动物的疾病传播有关的有害生物;以及公害有害生物(例如苍蝇)。
本发明的化合物可用于例如草坪,观赏植物例如花卉、灌木、阔叶树木或常绿植物,如松类,以及树木注入,有害生物管理等。
本发明的这些化合物可以用于控制动物家居有害生物,包括:蚂蚁、臭虫(成虫)、蜜蜂、甲虫、梣叶槭蝽、竹蜂、皮蠹、蜈蚣、烟草、甲虫、苜蓿苔螨、蟑螂、杂拟谷盗、蟋蟀、蠷螋、家衣鱼、跳蚤、蝇类、谷蠹、千足虫、蚊、赤拟谷盗、稻象虫、锯谷盗、蠹虫、栉水虱、蜘蛛、白蚁、蜱、黄蜂、蟑螂、蟋蟀、蝇类、小甲虫(例如拟步甲、白腹皮蠹和葬甲)、蚊类、鼠妇虫、蝎子、蜘蛛、红蜘蛛(二斑红蜘蛛、云杉红蜘蛛)、蜱。
本发明的化合物可以用以控制观赏植物有害生物,包括:蚂蚁(包括外引红火蚁)、粘虫、杜鹃花毛虫、蚜虫、结草虫、葡萄黑象甲(成虫)、梣叶槭蝽、食心虫、加利福尼亚州橡木虫、尺蠖、蟑螂、蟋蟀、地老虎、东方天幕毛虫、榆树叶甲虫、欧洲叶蜂、美国白蛾、跳甲、森林天幕毛虫、舞毒蛾幼虫、日本丽金龟(成虫)、六月甲虫(成虫)、网蝽、食叶毛虫、叶蝉、潜叶虫(成虫)、卷叶蛾类、雕叶虫、蠓、蚊、夹竹桃蛾幼虫、鼠妇虫、松锯锋、松纵坑切梢小蠹、松树梢果蛾类、盲蝽、根叶甲、锯锋、介壳虫(爬虫)、蜘蛛、沫蝉、斑纹甲虫、斑纹橡木虫、蓟马、梢果蛾、丛蛾幼虫、黄蜂、茶细螨、褐蜡蚧、加利福尼亚州红蚌质蚧(爬虫)、苜蓿苔螨、粉蚧、松针介壳虫(爬虫)、红蜘蛛、粉虱。
本发明的化合物可以用以控制草皮有害生物,包括:蚂蚁(包括外引红火蚁)、粘虫、蜈蚣、蟋蟀、地老虎、蠷螋、跳蚤(成虫)、蚱蜢、日本丽金龟(成虫)、千足虫、螨、蚊(成虫)、鼠妇虫、草地螟、潮虫、蜱(包括传播莱姆病的种类)、早熟禾谷象(成虫)、草坪草黑金龟(成虫)、恙螨、跳蚤(成虫)、蛴螬(抑制)、阿根廷茎象甲(成虫)、蝼蛄(若虫和幼成虫)、蝼蛄(成熟成虫)、麦长蝽。
可以通过具有化学式(I)的化合物控制的有害生物种类实例包括:桃蚜(蚜虫)、棉蚜(蚜虫)、黑豆蚜(蚜虫)、草盲蝽属(盲蝽)、棉红蝽属(盲蝽)、稻褐飞虱(飞虱)、黑尾叶蝉(叶蝉)、绿蝽属(臭蝽)、美洲蝽属(臭蝽)、稻缘蝽属(臭蝽)、西花蓟马(蓟马)、蓟马属(蓟马)、马铃薯甲虫(马铃薯甲虫)、墨西哥棉铃象(棉铃象甲)、肾圆盾蚧属(介壳虫)、粉虱属(粉虱)、烟粉虱(粉虱)、欧洲玉米螟(欧洲玉米螟)、海灰翅夜蛾(棉树叶虫)、烟芽夜蛾(烟夜蛾)、棉铃虫(棉铃虫)、谷实夜蛾(棉铃虫)、棉大卷叶螟(棉卷叶螟)、大菜粉蝶(粉蝶)、小菜蛾(小菜蛾)、地老虎属(地老虎)、二化螟(二化螟)、非洲飞蝗(蝗虫)、澳大利亚瘟疫蝗虫(蝗虫)、根萤叶甲属(根虫)、苹果全爪螨(苹果红蜘蛛)、桔全爪螨(柑橘红蜘蛛)、二点叶蹒(二斑叶蹒)、朱砂叶螨(红蜘蛛)、桔芸锈螨(柑橘锈螨)、侧多食跗线螨(茶细螨)、短-须螨属(葡萄短须螨)、微小牛蜱(具环牛蜱)、变异革蜱(美洲犬蜱)、猫栉头蚤(猫蚤)、斑潜蝇属(潜叶虫)、家蝇(家蝇)、埃及伊蚊(蚊)、按蚊属(蚊)、库蚊属(蚊)、绿蝇属(丽蝇)、德国小蠊(蟑螂)、美洲大蠊(蟑螂)、东方蛮蠊(蟑螂)、澳白蚁科的白蚁(例如澳白蚁属)、木白蚁科(例如新白蚁属)、犀白蚁科(例如台湾家白蚁、黄肢散白蚁、黄胸散白蚁、南方散白蚁、西方散白蚁和桑特散白蚁)以及白蚁科(例如黄球白蚁(Globitermes sulphureus))、热带火蚁(火蚁)、小黄家蚁(法老蚁)、畜虱属和毛虱属(咬虱和吸吮虱)、根结线虫属(根结线虫)、球异皮线虫属和异皮线虫属(胞囊线虫)、短体线虫属(腐线虫)、粉褶辈属(香蕉穿孔线虫)、小垫刃线虫属(柑橘线虫)、捻转血矛线虫(捻转胃虫)、秀丽隐杆线虫(醋线虫)、毛圆线虫属(胃肠线虫)和网纹野蛞蝓(蛞蝓)。
本发明的化合物可以用于对不同植物的有害生物控制,包括大豆(例如在某些情况下10g/ha-70g/ha)、玉米(例如在某些情况下10g/ha-70g/ha)、甘蔗(例如在某些情况下20g/ha-200g/ha)、苜蓿(例如在某些情况下10g/ha-70g/ha)、芸薹(例如在某些情况下10g/ha-50g/ha)、油菜(例如卡罗拉(canola))(例如在某些情况下20g/ha-70g/ha)、马铃薯(包括甘薯)(例如在某些情况下10g/ha-70g/ha)、棉花(例如在某些情况下10g/ha-70g/ha)、水稻(例如在某些情况下10g/ha-70g/ha)、咖啡(例如在某些情况下30g/ha-150g/ha)、柑橘(例如在某些情况下60g/ha-200g/ha)、扁桃(例如在某些情况下40g/ha-180g/ha)、果实类蔬菜(例如番茄、胡椒、番椒、茄子、黄瓜、南瓜、等)(例如在某些情况下10g/ha-80g/ha)、茶(例如在某些情况下20g/ha-150g/ha)、鳞茎类蔬菜(例如洋葱、韭等)(例如在某些情况下30g/ha-90g/ha)、葡萄(例如在某些情况下30g/ha-180g/ha)、梨果(例如苹果、梨等)(例如在某些情况下30g/ha-180g/ha)以及核果(例如梨、李子等)(例如在某些情况下30g/ha-180g/ha)。
本发明的化合物可以用于大豆以控制例如南美玉米苗斑螟、阿根廷兜虫、南美叶甲、大豆茎象、蚁科、小地老虎、马陆(Julusspp.)、黎豆夜蛾、美洲叶甲亚属(Megascelisspp.)、安第斯马铃薯象属、蝼蛄科、南方绿椿象、壁蝽属、绿蝽属、新长缘蝽属(Neomegalotomus spp.)、菜豆莹叶甲、日本金龟子、Edessa spp.、丽金龟(Liogenysfuscus)、英雄美洲蝽、普通蛀茎夜蛾、栗土蝽(Scaptocoris castanea)、鳃角金龟属、大豆夜蛾、灰翅夜蛾属、烟粉虱、缺隆叩甲属,本发明的化合物优选地用于大豆以控制阿根廷兜虫、南美叶甲、南方绿椿象、壁蝽属、绿蝽属、菜豆莹叶甲、日本金龟子、英雄美洲蝽、鳃角金龟属、缺隆叩甲属。
本发明的化合物可以用于玉米以控制例如英雄美洲蝽、Dichelops furcatus、阿根廷兜虫、南美玉米苗斑螟、草地贪夜蛾、南方绿椿象、菜豆莹叶甲、日本金龟子、小地老虎、南美叶甲、半翅目、安第斯马铃薯象属、栗土蝽(Scaptocoris castanea)、蚁科、马陆属、玉米黄翅叶蝉、玉米根萤叶甲、南美毛胫夜蛾、烟粉虱、实夜蛾属、叶螨属、蓟马属、鳃角金龟属、土蝽属、丽金龟、灰翅夜蛾属、玉米螟属、蛀茎夜蛾属、缺隆叩甲属。本发明的化合物优选地用于玉米以控制英雄美洲蝽、Dichelops furcatus、阿根廷兜虫、南方绿椿象、菜豆莹叶甲、日本金龟子、南美叶甲、玉米根萤叶甲、叶螨属、蓟马属、鳃角金龟属、土蝽属、缺隆叩甲属。
本发明的化合物可以用于甘蔗以控制例如,尖隐喙象属、白蚁、沫蝉属。本发明的化合物优选地用于甘蔗以控制白蚁、Mahanarvaspp.。
本发明的化合物可以用于苜蓿以控制,例如,虫象鼻虫、紫苜蓿叶象、纹黄豆粉蝶、Collopsspp.、索拉纳小绿叶蝉(Empoasca solana)、跳甲属、大眼长蝽属、豆荚盲蝽、美国牧草盲蝽、膜翅角蝉属、灰翅夜蛾属、粉纹夜蛾。本发明的化合物优选地用于苜蓿以控制虫象鼻虫、紫苜蓿叶象、索拉纳小绿叶蝉、跳甲属、大眼长蝽属、美国牧草盲蝽、粉纹夜蛾。
本发明的化合物可以用于芸薹以控制,例如,菜蛾、菜粉蝶属、甘蓝夜蛾属、金翅夜蛾属、粉纹夜蛾、条跳甲属、灰翅夜蛾属、索拉纳小绿叶蝉、蓟马属、灰翅夜蛾属、地种蝇属。本发明的化合物优选地用于芸薹以控制小菜蛾、粉蝶属、金翅夜蛾属、粉纹夜蛾、条跳甲属、蓟马属。
本发明的化合物可以用于油菜(例如卡罗拉)以控制例如,露尾甲属、白菜象鼻虫、油菜蚤跳甲属。
本发明的化合物可以用于马铃薯(包括甘薯)以控制例如,小绿叶蝉属、马铃薯叶甲属、南美叶甲、茄麦蛾属、枸杞木虱属、玛绢金龟、缺隆叩甲属。本发明的化合物优选地用于马铃薯(包括甘薯)以控制小绿叶蝉属、马铃薯叶甲属、南美叶甲、茄麦蛾属、准个木虱属、缺隆叩甲属。
本发明的化合物可以用于棉花以控制,例如,墨西哥棉铃象、红铃虫属、实夜蛾属、灰翅夜蛾属、叶螨属、小绿叶蝉属、蓟马属、烟粉虱、草盲蝽属、鳃角金龟属、土蝽属。本发明的化合物优选地用于棉花以控制墨西哥棉铃象、叶螨属、小绿叶蝉属、蓟马属、草盲蝽属、鳃角金龟属、土蝽属。
本发明的化合物可以用于水稻以控制,例如,稻缘蝽属、纵卷叶野螟属、禾草螟属、白禾螟属、稻水象属、美洲稻蝽。本发明的化合物优选地用于水稻以控制稻缘蝽属、稻水象属、美洲稻蝽。
本发明的化合物可以用于咖啡以控制,例如,咖啡果小蠹、咖啡潜叶蛾、叶螨属。本发明的化合物优选地用于咖啡以控制咖啡果小蠹、咖啡潜叶蛾。
本发明的化合物可以用于柑橘以控制,例如,桔全爪螨、桔芸锈螨、短须螨属、柑橘木虱、硬蓟马属、蓟马属、矢尖蚧属、地中海蜡实蝇、叶潜蛾属。本发明的化合物优选地用于柑橘以控制桔全爪螨、桔芸锈螨、短须螨属、柑橘木虱、硬蓟马属、蓟马属、叶潜蛾属。
本发明的化合物可以用于扁桃以控制,例如,脐橙螟蛾、叶螨属。
本发明的化合物可以用于果实类蔬菜包括番茄、胡椒、辣椒、茄子、黄瓜、南瓜等以控制蓟马属、叶螨属、跗线螨属、刺皮瘿螨属、小绿叶蝉属、灰翅夜蛾属、实夜蛾属、番茄斑潜蝇、斑潜蝇属、烟粉虱、粉虱属、木虱属、西花蓟马、花蓟马属、花象属、条跳甲属、杜果叶蝉属、食植瓢虫属、翅蝽属、硬蓟马属、白翅野螟属、新白翅野螟属(Neoleucinodes spp.)。本发明的化合物优选地用于果实类蔬菜包括番茄、胡椒、辣椒、茄子、黄瓜、南瓜等以控制例如蓟马属、叶螨属、跗线螨属、刺皮瘿螨属、小绿叶蝉属、灰翅夜蛾属、实夜蛾属、番茄斑潜蝇、斑潜蝇属、枸杞木虱属、西花蓟马、花蓟马属、杜果叶蝉属、硬蓟马属、白翅野螟属、新白翅野螟属。
本发明的化合物可以用于茶以控制,例如,白盾蚧属、小绿叶蝉属、硬蓟马属、茶细蛾。本发明的化合物优选地用于茶以控制小绿叶蝉属、硬蓟马属。
本发明的化合物可以用于鳞茎类蔬菜(包括洋葱、韭等)以控制,例如,蓟马属、灰翅夜蛾属、实夜蛾属。本发明的化合物优选地用于鳞茎类蔬菜(包括洋葱、韭等)以控制例如蓟马属。
本发明的化合物可以用于葡萄以控制,例如,小绿叶蝉属、花翅小卷蛾属、花蓟马属、蓟马属、叶螨属、葡萄蓟马、魏始叶螨、葡萄叶蝉、斑硕叶蚤属。本发明的化合物优选地用于葡萄以控制花蓟马属、蓟马属、叶螨属、葡萄蓟马、斑硕叶蚤属。
本发明的化合物可以用于梨果(包括苹果、梨等)以控制,例如,喀木虱属、木虱属、苹果全爪螨、苹果蠹蛾。本发明的化合物优选地用于梨果(包括苹果、梨等)以控制喀木虱属、木虱属、苹果全爪螨。
本发明的化合物可以用于核果以控制,例如,梨小食心虫、硬蓟马属、蓟马属、花蓟马属、叶螨属。本发明的化合物优选地用于核果以控制硬蓟马属、蓟马属、花蓟马属、叶螨属。因此,本发明提供了一种用于对抗和/或控制动物有害生物(例如一种无脊椎动物有害生物)的方法,该方法包括向该有害生物、该有害生物的场所、或易受有害生物攻击的植物施用杀有害生物有效量的一种具有式(I)的化合物。具体地,本发明提供了一种用于对抗和/或控制昆虫、螨、线虫或软体动物的方法,该方法包括将杀昆虫、杀螨、杀线虫或杀软体动物有效量的一种具有式(I)的化合物,或一种包含具有式(I)的一种化合物的组合物施用到有害生物,有害生物场所,优选地一种植物,或易受有害生物攻击的植物,具有式(I)的这些化合物优选地用于针对昆虫、螨或线虫。
如在此使用的术语“植物”包括幼苗、灌木以及树木。作物应被理解为还包括已经通过常规的育种或通过基因工程的方法被赋予对除草剂或多种类别的除草剂(例如ALS-、GS-、EPSPS-、PPO-以及HPPD-抑制剂)耐受性的那些作物。通过常规的育种方法已经赋予其对咪唑啉酮类(例如,甲氧咪草烟)的耐受性的作物的一个实例是克利尔菲 夏季油菜(卡罗拉(canola))。通过基因工程方法而赋予对除草剂的耐受性的作物的实例包括例如草甘膦和草丁膦抗性的玉米品种,这些玉米品种在和商标名下是可商购的。
作物还应理解为是已经通过基因工程方法赋予对有害昆虫的抗性的那些,例如Bt玉米(抗欧洲玉米螟)、Bt棉花(抗棉铃象虫甲)并且还有Bt马铃薯(抗科罗拉多甲虫)。Bt玉米的实例是的Bt 176玉米杂交体(先正达种子公司(Syngenta Seeds))。包含有一个或多个编码杀虫剂抗性和表达一种或多种毒素的基因的转基因植物的实例是(玉米)、Yield(玉米)、(棉花)、(棉花)、(马铃薯)、和其植物作物或种子材料均可以是抗除草剂的并且同时是抗昆虫摄食的(“叠加的”转基因结果)。例如,种子可以在具有表达杀虫的Cry3蛋白的能力的同时是耐草甘膦的。
作物还应理解为是通过常规的育种方法或基因工程获得并且包括所谓的输出型(output)性状(例如改进的存储能力、更高的营养价值以及改进的香味)。
为了将具有式(I)的化合物应用为对于有害生物、有害生物场所或易受有害生物侵袭的植物的杀昆虫剂、杀螨剂、杀线虫剂或杀软体动物剂,通常将具有式(I)的化合物配制成一种组合物,该组合物包括除了具有式(I)的化合物之外的一种合适的惰性稀释剂或载体以及任选地一种表面活性剂(SFA)。SFA是能够通过降低界面张力修改界面(例如液/固、液/气或液/液界面)特性并且由此引起其他特性(例如分散、乳化以及湿润)变化的化学品。优选地,所有的组合物(固体以及液体配制品两者)包括按重量计0.0001%至95%,更优选地1%至85%,例如5%至60%的具有式(I)的化合物。该组合物总体上被用于控制有害生物,这样使得具有式(I)的化合物以从0.1g至10kg/公顷,优选地从1g至6kg/公顷,更优选地从1g至1kg/公顷的比率施用。
当在一种拌种剂中使用时,具有式(I)的化合物总体上以每千克种子0.0001g至10g(例如0.001g或0.05g),优选地0.005g至10g,更优选地0.005g至4g的比率使用。
在另一个方面,本发明提供了包含杀有害生物有效量的具有式(I)的一种化合物的组合物,特别是以下一种杀昆虫的、杀螨的、杀线虫的、或杀软体动物的组合物:该组合物包括一种杀昆虫的、杀螨的、杀线虫的、或杀软体动物的有效量的具有式(I)的化合物以及其一种合适的载体或稀释剂。该组合物优选地是一种杀昆虫的、杀螨的、杀线虫的或杀软体动物的组合物。
这些组合物可以选自多种配制品类型,包括可尘化粉剂(DP)、可溶性粉剂(SP)、水溶性颗粒剂(SG)、水可分散性颗粒剂(WG)、可湿性粉剂(WP)、颗粒剂(GR)(慢或快释的)、可溶性浓缩物(SL)、油易混合的液体(OL)、超低体积液体(UL)、可乳化性浓缩物(EC)、可分散性浓缩物(DC)、乳液(水包油(EW)和油包水(EO)两者)、微乳液(ME)、悬浮浓缩物(SC)、气溶胶、雾/烟配制品、胶囊悬浮液(CS)以及种子处理配制品。在任何情况下,所选择的配制品类型将取决于所设想的具体目的以及具有化学式(I)的化合物的物理、化学和生物特性。
可尘化粉剂(DP)可以通过将具有式(I)的化合物与一种或多种固体稀释剂(例如,天然粘土、高岭土、叶蜡石、膨润土、氧化铝、蒙脱石、硅藻土(kieselguhr)、白垩土、硅藻土(diatomaceous earths)、磷酸钙、碳酸钙和碳酸镁、硫、石灰、面粉、滑石和其他有机和无机的固体载体)混合并将该混合物机械地碾磨成细粉末来制备。
可溶性粉剂(SP)可以通过将具有化学式(I)的化合物与一种或多种水溶性无机盐(例如碳酸氢钠、碳酸钠或硫酸镁)或一种或多种水溶性有机固体(例如多糖)以及可任选地的一种或多种润湿剂、一种或多种分散剂或所述试剂的混合物进行混合来制备以改进水分散性/水溶性。然后将该混合物研磨成细粉末。也可以将类似的组合物颗粒化以形成水溶性颗粒剂(SG)。
可湿性粉剂(WP)可以通过将具有式(I)的化合物与一种或多种固体稀释剂或载体、一种或多种湿润剂以及优选地,一种或多种分散剂,以及可任选地,一种或多种的悬浮剂混合来制备以促进在液体中的分散。然后将该混合物研磨成细粉末。也可以将类似的组合物颗粒化以形成水可分散性颗粒剂(WG)。
可以这样形成颗粒剂(GR):通过将具有式(I)的化合物与一种或多种粉状固体稀释剂或载体的混合物造粒来形成,或者通过将具有式(I)的化合物(或其在一种适宜试剂中的溶液)吸收进多孔颗粒材料(例如浮石、凹凸棒石粘土、漂白土、硅藻土(kieselguhr)、硅藻土(diatomaceous earths)或玉米芯粉),或通过将具有式(I)的化合物(或其在适宜试剂中的溶液)吸附到硬芯材料(例如沙、硅酸盐、矿物碳酸盐、硫酸盐或磷酸盐)上并且如果必要的话,进行干燥来由预成型的空白颗粒形成。普遍用来帮助吸收或吸附的试剂包括溶剂(诸如脂肪族和芳香族的石油溶剂、醇、醚、酮和酯)以及粘着剂(诸如聚乙酸乙烯酯、聚乙烯醇、糊精、糖和植物油)。也可以在颗粒中包括一种或多种其他添加剂(例如乳化剂、湿润剂或分散剂)。
可分散的浓缩物(DC)可以通过将具有化学式(I)的化合物溶于水或一种有机溶剂(如酮、醇或乙二醇醚)中来制备。这些溶剂可以包含表面活性剂(例如用来在喷雾槽中改进水稀释性或防止结晶)。
可乳化性浓缩物(EC)或水包油乳液(EW)可以通过将具有式(I)的化合物溶于有机溶剂(可任选地包含一种或多种湿润剂、一种或多种乳化剂或者所述试剂的混合物)中来制备。在EC中使用的适合的有机溶剂包括芳族烃(例如烷基苯或烷基萘,例如SOLVESSO 100、SOLVESSO 150和SOLVESSO 200;SOLVESSO是注册商标)、酮(例如环己酮或甲基环己酮)和醇(例如苯甲醇、糠醇或丁醇)、N-烷基吡咯烷酮(例如N-甲基吡咯烷酮或N-辛基吡咯烷酮)、脂肪酸的二甲基酰胺(例如C8-C10脂肪酸二甲基酰胺)以及氯化烃。EC产物可以在添加至水中时自发地乳化,产生具有足够稳定性以便允许通过适当设备喷洒施用的乳液。EW的制备包括获得液体(如果其在室温不是液体,其可以在典型地低于70℃的合理温度下被熔化)或溶液(通过将其溶于合适的溶剂)形式的具有式(I)化合物,然后在高剪切下将所得液体或溶液乳化进包含一种或多种SFA的水中,以产生乳液。在EW中使用的适合的溶剂包括植物油、氯化烃(诸如氯苯)、芳香族溶剂(诸如烷基苯或烷基萘)以及其他在水中具有低溶解度的适当的有机溶剂。
微乳液(ME)可以通过将水与一种或多种溶剂和一种或多种SFA的掺合物混合来制备,以自发地产生一种热力学稳定的各向同性的液体配制品。具有式(I)的化合物一开始就存在于水中或溶剂/SFA掺合物中。适用于ME的溶剂包括以上所述用于EC或EW中的那些。ME可以是水包油体系或油包水体系(存在哪种体系可以通过电导率测量来确定)并且可以适合用于在相同配制品中混合水溶性的和油溶性的杀有害生物剂。ME适合用于稀释进入水中,保持为微乳液或形成常规的水包油乳液。
悬浮浓缩物(SC)可以包含具有式(I)的化合物的精细分散的不溶固体颗粒的水性或非水性悬浮液。SC可以通过将具有式(I)的固体化合物可任选地与一种或多种分散剂在适宜介质中球磨或珠磨来制备,以产生该化合物的细颗粒悬浮液。在该组合物中可以包括一种或多种湿润剂,并且可以包括悬浮剂以降低颗粒的沉降速度。可替代地,可以将具有式(I)的化合物干磨并将其加入包含以上所述试剂的水中,以产生所希望的最终产物。
气溶胶配制品包括具有化学式(I)的化合物和适宜的推进剂(例如,正丁烷)。也可将具有化学式(I)的化合物溶于或分散于适宜的介质(例如水或可与水混溶的液体,如正丙醇)中以提供在不加压的手动喷雾泵中使用的组合物。
可以将具有式(I)的化合物在干态下与烟火混合物混合以形成一种组合物,该组合物适合于在一个封闭空间内产生含有该化合物的烟。
胶囊悬浮液(CS)可以通过以与制备EW配制品类似的方式来制备,除了附加的聚合步骤之外,这样使得获得油滴的水分散体,其中每个油滴都被聚合物外壳包裹并且含具有式(I)的一种化合物以及其可任选的一种载体或稀释剂。该聚合物壳可以通过界面缩聚反应或通过凝聚程序来生产。这些组合物可以提供具有式(I)的化合物的受控释放并且它们可以用于种子处理。具有式(I)的化合物也可以被配制在可生物降解的聚合物基质中,以提供该化合物的缓慢的受控释放。
组合物可以包括一种或多种添加剂以改进该组合物的生物学性能(例如通过改进表面上的湿润性、保留或分布;处理过的表面上的防雨性;或具有式(I)的化合物的吸收或迁移性)。这样的添加剂包括表面活性剂、基于油的喷雾添加剂,例如某些矿物油或天然植物油(例如大豆和油菜籽油),以及这些与其他生物增强佐剂(可帮助或修饰具有式(I)的化合物的作用的成分)的掺合物。
具有式(I)的化合物还可以被配制以作为种子处理而使用,例如作为粉末组合物,包括用于干的种子处理的粉末(DS)、水溶性的粉末(SS)、或用于浆料处理的水可分散的粉末(WS)、或作为一种液体组合物,包括可流动的浓缩物(FS)、一种溶液(LS)或一种胶囊悬浮液(CS)。DS、SS、WS、FS和LS组合物的制备分别与以上描述的DP、SP、WP、SC和DC组合物的那些非常类似。用于处理种子的组合物可以包括一种用于协助该组合物附着到种子上的试剂(例如一种矿物油或一种成膜阻挡物)。
湿润剂、分散剂和乳化剂可以是阳离子、阴离子、两性的或非-离子类型的表面SFA。
适合的阳离子型SFA包括季铵化合物(例如十六烷基三甲基溴化铵)、咪唑啉以及胺盐。
合适的阴离子的SFA包括脂肪酸的碱金属盐、硫酸脂肪族单酯的盐(例如,月桂基硫酸钠)、磺化的芳香族化合物的盐(例如,十二烷基苯磺酸钠、十二烷基苯磺酸钙、丁基萘磺酸盐以及二异丙基萘磺酸钠和三异丙基萘磺酸钠的混合物)、醚硫酸盐、醇醚硫酸盐(例如,月桂醇聚醚-3-硫酸钠)、醚羧酸盐(例如月桂醇聚醚-3-羧酸钠)、磷酸酯(一种或多种脂肪醇与磷酸(主要是单酯)或五氧化二磷(主要是二酯)反应的产物,例如月桂基醇与四磷酸之间的反应;此外这些产物可以是乙氧基化的)、磺基琥珀酰胺酸盐、石蜡或链烯烃磺酸盐、牛磺酸盐以及木素磺酸盐。
适合的两性类型的SFA包括甜菜碱、丙酸盐和甘氨酸盐。
适合的该非-离子类型的SFA包括环氧烷类(诸如环氧乙烷、环氧丙烷、环氧丁烷或其混合物)与脂肪醇类(诸如油醇或鲸蜡醇)或与烷基酚类(诸如辛基酚、壬基酚或辛基甲酚)的缩合产物;衍生自长链脂肪酸或己糖醇酐的偏酯;所述偏酯与环氧乙烷的缩合产物;嵌段聚合物(包含环氧乙烷和环氧丙烷);烷醇酰胺;单酯(例如脂肪酸聚乙二醇酯);氧化胺(例如月桂基二甲基氧化胺);以及卵磷脂。
适合的悬浮剂包括亲水性胶体(诸如多糖、聚乙烯吡咯烷酮或羧甲基纤维素钠)和膨胀性粘土(诸如膨润土或凹凸棒石)。
具有式(I)化合物可以通过任何已知的施用杀有害生物化合物的方法来施用。例如,它可以(配制的或未配制的)直接地施用于这些有害生物或这些有害生物的所在场所(例如这些有害生物的栖息地,或易受有害生物侵染的种植植物),或施用于植物的任何部分,包括叶、茎、枝或根,施用于种植前的种子,或施用至植物正在生长或将被种植的其他介质(例如根周的土壤,普通土壤,稻田水或水栽的种植体系),或它可以喷雾、撒粉、通过浸渍施用,作为乳脂或糊剂配制品施用,作为蒸气施用或通过将组合物(例如颗粒组合物或包在水溶袋中的组合物)分布或并入土中或水环境中来施用。
具有式(I)的化合物还可以被注射到植物中或使用电动喷雾技术或其他低容量法喷雾到植物上,或者通过陆地或空中灌溉系统施用。
用作水性制剂(水溶液或分散体)的组合物总体上以含高比例的活性成分的浓缩物的形式来提供,该浓缩物在使用之前加入到水中。这些浓缩物(可以包括DC、SC、EC、EW、ME、SG、SP、WP、WG和CS)经常被要求经受长期的存储并且在此种存储之后能够加入到水中以形成水性制剂,该制剂保持均质状态足够长的时间以使它们能通过常规的喷雾设备施用。此种水性制剂可以包含变化量的具有式(I)的化合物(例如,按重量计0.0001%至10%),这取决于它们所为之使用的目的。
具有化学式(I)的化合物能与肥料(例如含氮-、钾-、或磷-的肥料)混合使用。合适的配制品类型包括肥料颗粒。这些混合物优选地包含高达按重量计25%的具有式(I)的化合物。
因此,本发明还提供了一种包括一种肥料与一种具有式(I)的化合物的肥料组合物。
本发明的组合物可以包含其他的具有生物活性的化合物,例如微量营养素,或具有杀真菌活性的化合物,或具有调节植物生长、除草、杀昆虫、杀线虫或杀螨活性的化合物。
具有化学式(I)的化合物可以是该组合物的单独的活性成分或者它可以与一种或多种另外的活性成分,例如杀有害生物剂,例如杀虫剂、杀真菌剂或除草剂,或在合适的情况下与增效剂或植物生长剂进行混合。另外的活性成分可以提供在一个场所具有更宽的活性谱或增加的保留时间的一种组合物;增效或补充这种具有化学式(I)的化合物的活性(例如通过增加作用速度或克服排斥性);或者帮助克服或预防对单个组分的抗性的发展。具体的另外的活性成分将取决于该组合物的所预期的应用。
本发明化合物还用于动物健康领域,例如它们可用于对抗寄生无脊椎动物有害生物,更优选用于对抗在动物体内或动物体表的寄生无脊椎动物有害生物。有害生物的实例包括线虫、吸虫、绦虫、苍蝇、螨、壁虱(tricks)、虱子、跳蚤、蝽以及蛆。该动物可为非人类动物,例如与农业有关的动物,例如牛、猪、绵羊、山羊、马或驴,或宠物动物,例如狗或猫。
在另外一个方面,本发明提供了一种在医疗处理方法中使用的本发明的化合物。
在另外一个方面,本发明涉及一种用于控制动物体内或动物体表的寄生无脊椎动物有害生物的方法,该方法包括给予杀有害生物有效量的本发明的一种化合物。该给予例如可为口服给予、非消化道给予或外部给予,例如至动物身体表面。在另外一个方面,本发明涉及用于控制动物体内或动物体表的寄生无脊椎动物有害生物的本发明的化合物。在另一方面,本发明涉及在制备一种药剂以控制动物体内或动物体表的寄生无脊椎动物有害生物中本发明的化合物的用途
在另外一个方面,本发明涉及一种控制寄生无脊椎动物有害生物的方法,该方法包括将杀有害生物有效量的本发明的化合物给至动物所栖息的环境。
在另外一个方面,本发明涉及一种保护动物免受寄生无脊椎动物有害生物之害的方法,该方法包括给予该动物杀有害生物有效量的本发明的化合物。在另外一个方面,本发明涉及用以在保护动物免受寄生无脊椎动物有害生物之害中使用的本发明的化合物。在另外一个方面,本发明涉及在制备一种药剂以保护动物免受寄生无脊椎动物有害生物之害中本发明的化合物的用途。
在另外一个方面,本发明提供了一种处理受寄生无脊椎动物有害生物之害的动物的方法,该方法包括给予该动物杀有害生物有效量的本发明的化合物。在另外一个方面,本发明涉及用以在处理受寄生无脊椎动物有害生物之害的动物中使用的本发明的化合物。在另外一个方面,本发明涉及在制备一种药剂以处理受寄生无脊椎动物有害生物之害的动物中本发明的化合物的用途。
在另外一个方面,本发明提供了一种药物组合物,该组合物包括本发明的化合物以及药学上合适的赋形剂。
本发明的化合物可单独使用或者与一种或多种其他生物活性成分组合使用。
在一个方面,本发明提供了一种组合产物,该组合产物包括杀有害生物有效量的一种组分A以及杀有害生物有效量的一种组分B,其中组分A为本发明的一种化合物并且化合物B为以下所述的一种化合物。
本发明的化合物可与驱蠕虫药剂组合使用。此类驱蠕虫药剂包括选自大环内酯类化合物的化合物,例如伊维菌素、阿维菌素、阿维菌素、依马克丁、依立诺克丁、多拉克汀、司拉克丁、莫昔克丁、奈马克丁以及米尔倍霉素衍生物,如在EP-357460、EP-444964以及EP-594291中所述。其他驱蠕虫药剂包括半合成及生物合成阿维菌素/米尔倍霉素类衍生物,例如在US-5015630、WO-9415944以及WO-9522552中所述的那些。其他驱蠕虫药剂包括苯并咪唑类,例如阿苯达唑、坎苯达唑、芬苯达唑、氟苯达唑、甲苯达唑、奥芬达唑、奥苯达唑、帕苯达唑、以及其他该类别的成员。其他驱蠕虫药剂包括咪唑并噻唑类以及四氢嘧啶类,例如四咪唑、左旋咪唑、噻嘧啶扑酸酯、奥克太尔或莫仑太尔。其他驱蠕虫药剂包括杀吸虫剂,例如三氯苯达唑和氯舒隆,以及杀绦虫剂,例如吡喹酮以及依西太尔。
本发明的化合物可以与帕拉合胺副梅花状青霉酰胺/吗克福丁(marcfortine)类驱蠕虫药剂的衍生物及类似物以及抗寄生虫噁唑啉(例如在US-5478855、US-4639771以及DE-19520936中所披露的)组合使用。
本发明的化合物可以与如WO-9615121中所述的一般种类二氧吗啉抗寄生虫剂的衍生物及类似物以及还与驱蠕虫活性的环状缩酚肽(例如WO-9611945、WO-9319053、WO-9325543、EP-626375、EP-382173、WO-9419334、EP-382173、以及EP-503538中所述的那些)组合使用。
本发明的化合物可以与其他杀体外寄生虫药组合使用;例如氟虫腈;拟除虫菊酯;有机磷酸酯;昆虫生长调节剂(例如虱螨脲);蜕皮激素促效剂(例如虫酰肼及其类似物);新烟碱(例如吡虫啉及其类似物)。
本发明的化合物可以与萜烯生物碱类组合使用,例如国际专利申请公开案第WO95/19363号或第WO 04/72086号中所述的那些,特别是其中所披露的化合物。
可以与本发明的化合物组合使用的此类生物活性化合物的其他实例包括(但不局限于)以下:
有机磷酸酯:乙酰甲胺磷、甲基吡噁磷、乙基谷硫磷、甲基谷硫磷、溴硫磷、乙基溴硫磷、硫线磷、四氯乙磷(chlorethoxyphos)、毒死蜱、氯芬磷、氯甲磷、内吸磷、内吸磷-S-甲基、内吸磷-S-甲基砜、氯亚胺硫磷、二嗪磷、敌敌畏、百治磷、乐果、乙拌磷、乙硫磷、灭线磷、氧嘧啶磷、伐灭磷、苯线磷、杀螟硫磷、丰索磷、倍硫磷、吡氟硫磷、地虫磷、安果、噻唑磷、庚烯磷、氯唑磷、异丙磷、异噁唑磷、马拉硫磷、虫螨畏、甲胺磷、杀扑磷、甲基对硫磷、速灭磷、久效磷、二溴磷、氧乐果、甲基氧代内吸磷、对氧磷、对硫磷、甲基对硫磷、稻丰散、伏杀硫磷、硫环磷、磷克、亚胺硫磷、磷胺、甲拌磷、肟硫磷、虫螨磷、虫螨磷-甲基、丙溴磷、丙虫磷、普乙塔磷斯(proetamphos)、丙硫磷、吡唑硫磷、哒嗪硫磷、喹硫磷、硫灭克磷、替美磷、特丁磷、丁基嘧啶磷、司替罗磷、西美东(thimeton)、三唑磷、敌百虫、灭蚜硫磷。
氨基甲酸酯:棉铃威、涕灭威、2-仲丁苯基甲基氨基甲酸酯、丙硫克百威、甲萘威、克百威、丁硫克百威、地虫威、乙硫苯威、苯氧威、芬硫克、呋线威、HCN-801、异丙威、茚虫威、灭虫威、灭多虫、5-甲基-间-异丙苯基丁炔基(甲基)氨基甲酸酯、杀线威、抗蚜威、残杀威、硫双威、久效威、唑蚜威、UC-51717。
拟除虫菊酯:氟丙菊酯、烯丙菊酯、α-氯氰菊酯(alphametrin)、5-苄基-3-呋喃基甲基(E)-
(1R)-顺式-2,2-二甲基-3-(2-氧硫杂环戊-3-亚基甲基)环丙烷羧酸酯、联苯菊酯、β-氟氯氰菊酯、氟氯氰菊酯、α-氯氰菊酯(α-cypermethrin)、β-氯氰菊酯、生物烯丙菊酯、生物烯丙菊酯((S)-环戊基异构体)、生物苄呋菊酯、联苯菊酯、NCI-85193、乙氰菊酯、氯氟氰菊酯、cythithrin、苯醚氰菊酯、溴氰菊酯、炔戊菊酯、高氰戊菊酯、醚菊酯、五氟苯菊酯、甲氰菊酯、氰戊菊酯、氟氰菊酯、氟氯苯菊酯、氟胺氰菊酯(D异构体)、炔咪菊酯、氯氟氰菊酯、λ-氯氟氰菊酯、氯菊酯、苯醚菊酯、炔丙菊酯、除虫菊酯(天然产物)、苄呋菊酯、胺菊酯、四氟苯菊酯、θ-氯氰菊酯、氟硅菊酯、t-氟胺氰菊酯、七氟菊酯、四溴菊酯、ζ-氯氰菊酯。
节肢动物生长调节剂:a)甲壳质合成抑制剂:苯甲酰脲:定虫隆、除虫脲、氟佐隆、氟螨脲、氟虫脲、氟铃脲、虱螨脲、双苯氟脲、伏虫脲、杀虫脲、噻嗪酮、苯虫醚、噻螨酮、乙螨唑、四螨嗪(clofentazin);b)蜕皮激素拮抗剂:氯虫酰肼、甲氧虫酰肼、虫酰肼;c)保幼激素类似物:吡丙醚、烯虫酯(包括S-烯虫酯)、苯氧威;d)脂质生物合成抑制剂:螺螨酯。
其他抗寄生虫药:灭螨醌、双甲脒、AKD-1022、ANS-118、印楝素、苏云金芽孢杆菌、杀虫磺、联苯肼酯、乐杀螨、溴螨酯、BTG-504、BTG-505、毒杀芬、杀螟丹、敌螨酯、杀虫脒、溴虫腈、环虫酰肼、噻虫胺、赛灭净、敌克隆登(diacloden)、杀螨隆、DBI-3204、二活菌素、二羥基甲基二羥基吡咯烷、敌螨通、敌螨普、硫丹、乙虫腈、醚菊酯、喹螨醚、氟螨嗪(flumite)、MTI-800、唑螨酯、嘧螨酯、氟螨噻、溴氟菊酯、氟螨嗪、三氟醚、苄螨醚(fluproxyfen)、苄螨醚(halofenprox)、氟蚁腙、IKI-220、水硅钠石、NC-196、印度薄荷草(neem guard)、尼敌诺特呋喃(nidinorterfuran)、烯啶虫胺、SD-35651、WL-108477、啶虫丙醚、克螨特、普罗芬布特(protrifenbute)、吡蚜酮、哒螨酮、嘧螨醚、NC-1111、R-195、RH-0345、RH-2485、RYI-210、S-1283、S-1833、SI-8601、氟硅菊酯、硅罗玛汀(silomadine)、多杀菌素、吡螨胺、三氯杀螨砜、四抗菌素、噻虫啉、杀虫环、噻虫嗪、唑虫酰胺、唑蚜威、三乙多杀菌素、三活菌素、增效炔醚、波塔雷克(vertalec)、YI-5301。
杀真菌剂:活化酯、4-十二烷基-2,6-二甲基吗啉、1-氨基丙基磷酸、胺扑灭、阿扎康唑、嘧菌酯、苯霜灵、苯菌灵、双丙氨磷、杀稻瘟菌素-S、波尔多液、糠菌唑、乙嘧酚磺酸酯、环丙酰菌胺、敌菌丹、克菌丹、多菌灵、氯芬唑(chlorfenazole)、地茂散、氯化苦、百菌清、乙菌利、碱式氯化铜、铜盐、环氟菌胺、霜脲氰、环唑醇、嘧菌环胺、酯菌胺、RH-7281、双氯氰菌胺、苄氯三唑醇、哒菌酮、氯硝胺、苯醚甲环唑、RP-407213、烯酰吗啉、醚菌胺、烯唑醇、烯唑醇-M、多果定、克瘟散、氧唑菌、恶唑菌酮、咪唑菌酮、氯苯嘧啶醇、腈苯唑、芬卡咪(fencaramid)、拌种咯、苯锈啶、丁苯吗啉、乙酸三苯锡、氟啶胺、咯菌腈、氟美托、氟吗啉(flumorf/flumorlin)、毒菌锡、氟嘧菌酯、氟喹唑、氟硅唑、氟酰胺、粉唑醇、灭菌丹、磷乙铝、呋霜灵、福拉比、己唑醇、种菌唑、异稻瘟净、异菌脲、稻瘟灵、春雷霉素、醚菌酯、代森锰锌、代森锰、精甲霜灵、灭锈胺、甲霜灵、叶菌唑、苯氧菌胺(metominostrobin/fenominostrobin)、苯菌酮、腈菌唑、甲胂铁铵、啶酰菌胺、肟醚菌胺、噁霜灵、戊菌唑、戊菌隆、烯丙苯噻唑、丙氯灵、霜霉威、丙环唑、丙氧喹啉、丙硫菌唑、啶斑肟、唑菌胺酯、嘧霉胺、咯喹酮、喹氧灵、螺环菌胺、硫、戊唑醇、氟醚唑、噻苯达唑、噻呋菌胺、甲基硫菌灵、塞仑、噻酰菌胺、三唑酮、三唑醇、三环唑、肟菌酯、灭菌唑、井冈霉素、乙烯菌核利。
生物剂:苏云金杆菌亚莎华亚种(Bacillus thuringiensis ssp aizawai)、苏云金杆菌库斯塔克亚种(kurstaki)、苏云金杆菌δ内毒素、杆状病毒、昆虫病原细菌、病毒以及真菌。
杀细菌剂:金霉素、土霉素、链霉素。
其他生物剂:恩氟沙星、非班太尔、喷沙西林、美洛昔康、头孢氨苄、卡那霉素、匹莫苯、克仑特罗、奥美拉唑、硫姆林、贝那普利、皮瑞普(pyriprole)、头孢喹肟、氟苯尼考、布舍瑞林、头孢维星、托拉菌素、头孢噻呋、卡洛芬、美氟腙、吡喹酮、三氯苯达唑。
当与其他活性成分组合使用时,本发明的化合物优选地是与以下组合使用(其中“Tx”指具有化学式(I)的化合物,并且具体地是一种选自表1的特定化合物(化合物1.1至1.112),或一种选自表2的特定化合物(化合物2.1至2.112),或一种选自表A的特定化合物(化合物1至5),该化合物与该给定的活性成分一起可以导致一种协同性的组合):吡虫啉+Tx、恩氟沙星+Tx、吡喹酮+Tx、双羟萘酸噻嘧啶+Tx、非班太尔+Tx、喷沙西林+Tx、美洛昔康+Tx、头孢氨苄+Tx、卡那霉素+Tx、匹莫苯+Tx、克仑特罗+Tx、氟虫腈+Tx、伊维菌素+Tx、奥美拉唑+Tx、硫姆林+Tx、贝那普利+Tx、米尔倍霉素+Tx、赛灭净+Tx、噻虫嗪+Tx、皮瑞普+Tx、溴氰菊酯+Tx、头孢喹肟+Tx、氟苯尼考+Tx、布舍瑞林+Tx、头孢维星+Tx、托拉菌素+Tx、头孢噻呋+Tx、司拉克丁+Tx、卡洛芬+Tx、美氟腙+Tx、莫昔克丁+Tx、烯虫酯(包括S-烯虫酯)+Tx、氯舒隆+Tx、噻嘧啶+Tx、双甲脒+Tx、三氯苯达唑+Tx、阿维菌素+Tx、阿维菌素+Tx、依马克丁+Tx、依立诺克丁+Tx、多拉克汀+Tx、司拉克丁+Tx、奈马克丁+Tx、阿苯达唑+Tx、坎苯达唑+Tx、芬苯达唑+Tx、氟苯达唑+Tx、甲苯达唑+Tx、奥芬达唑+Tx、奥苯达唑+Tx、帕苯达唑+Tx、四咪唑+Tx、左旋咪唑+Tx、噻烯氢嘧啶+Tx、奥克太尔+Tx、莫仑太尔+Tx、三氯苯达唑+Tx、依西太尔+Tx、氟虫腈+Tx、虱螨脲+Tx、蜕皮激素+Tx或虫酰肼+Tx;更优选地:恩氟沙星+Tx、吡喹酮+Tx、双羟萘酸噻嘧啶+Tx、非班太尔+Tx、喷沙西林+Tx、美洛昔康+Tx、头孢氨苄+Tx、卡那霉素+Tx、匹莫苯+Tx、克仑特罗+Tx、奥美拉唑+Tx、硫姆林+Tx、贝那普利+Tx、皮瑞普+Tx、头孢喹肟+Tx、氟苯尼考+Tx、布舍瑞林+Tx、头孢维星+Tx、托拉菌素+Tx、头孢噻呋+Tx、司拉克丁+Tx、卡洛芬+Tx、莫昔克丁+Tx、氯舒隆+Tx、噻嘧啶+Tx、依立诺克丁+Tx、多拉克汀+Tx、司拉克丁+Tx、奈马克丁+Tx、阿苯达唑+Tx、坎苯达唑+Tx、芬苯达唑+Tx、氟苯达唑+Tx、甲苯达唑+Tx、奥芬达唑+Tx、奥苯达唑+Tx、帕苯达唑+Tx、四咪唑+Tx、左旋咪唑+Tx、噻烯氢嘧啶+Tx、奥克太尔+Tx、莫仑太尔+Tx、三氯苯达唑+Tx、依西太尔+Tx、虱螨脲+Tx或蜕皮激素+Tx;甚至更优选地:恩氟沙星+Tx、吡喹酮+Tx、双羟萘酸噻嘧啶+Tx、非班太尔+Tx、喷沙西林+Tx、美洛昔康+Tx、头孢氨苄+Tx、卡那霉素+Tx、匹莫苯+Tx、克仑特罗+Tx、奥美拉唑+Tx、硫姆林+Tx、贝那普利+Tx、皮瑞普+Tx、头孢喹肟+Tx、氟苯尼考+Tx、布舍瑞林+Tx、头孢维星+Tx、托拉菌素+Tx、头孢噻呋+Tx、司拉克丁+Tx、卡洛芬+Tx、莫昔克丁+Tx、氯舒隆+Tx或噻嘧啶+Tx。
比率的实例包括100:1至1:6000、50:1至1:50、20:1至1:20,甚至尤其是从10:1至1:10、5:1至1:5、2:1至1:2、4:1至2:1、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。那些混合比率被理解为包括,一方面是重量比,并且还有另一方面是摩尔比。
一种组合特别值得注意,其中该另外的活性成分具有与具有式I的化合物不同的作用部位。在某些情况下,与至少一种具有类似控制范围但具有不同作用部位的其他寄生无脊椎有害生物控制活性成分的组合将特别有利于抗性管理。因此,本发明的组合产物可以包括杀有害生物有效量的具有式I的化合物以及杀有害生物有效量的至少一种其他的寄生无脊椎有害生物控制活性成分,该寄生无脊椎有害生物控制活性成分具有类似控制范围但具有不同作用部位。
本领域普通技术人员认识到由于在环境中及在生理条件下化合物的盐与其相应非盐形式处于平衡状态,所以盐也具有非盐形式的生物学效用。
因此,本发明的化合物(以及与本发明的活性成分组合使用的活性成分)的多种盐可用于控制无脊椎有害生物以及动物寄生虫。盐包括与以下无机酸或有机酸形成的酸加成盐,例如氢溴酸、盐酸、硝酸、磷酸、硫酸、乙酸、丁酸、富马酸、乳酸、马来酸、丙二酸、草酸、丙酸、水杨酸、酒石酸、4-甲苯磺酸或戊酸。本发明的化合物还包括N-氧化物。相应地,本发明包括本发明的化合物(包括其N-氧化物以及盐)与其他活性成分(包括其N-氧化物以及盐)的组合。
用于动物健康的组合物也可以包含本领域普通技术人员已知作为配制品辅助的配制助剂及添加剂(其中一些可视为还充当固体稀释剂、液体稀释剂或表面活性剂)。这类配制品助剂以及添加剂可控制:pH值(缓冲剂)、加工期间的起泡(消泡剂如聚有机硅氧烷)、活性成分的沉降(悬浮剂)、黏度(触变增稠剂)、容器内微生物生长(抗微生物剂)、产物冷冻(抗冻剂)、颜色(染料/颜料分散体)、洗脱性(成膜剂或黏着剂)、蒸发(蒸发延迟剂)以及其他配制品特性。成膜剂包括,例如聚乙酸乙烯酯、聚乙酸乙烯酯共聚物、聚乙烯吡咯烷酮-乙酸乙烯酯共聚物、聚乙烯醇、聚乙烯醇共聚物以及蜡。制剂助剂和添加剂的实例包McCutcheon的部门,糖果制造出版公司(The Manufacturing Confectioner PublishingCo.)出版的McCutcheon的卷2功能材料(functional Materials)(北美和国际年鉴版);和PCT公布WO 03/024222中列出的那些。
本发明的化合物可以在不含其他佐剂的情况下施用,但最常施用将是这样一种配制品,该配制品包括一种或多种活性成分连同合适的载体、稀释剂及表面活性剂并且视预期的最终用途可能与食物组合。一种施用方法涉及喷雾这些组合产物的水分散体或精炼油溶液。具有喷雾油、喷雾油浓缩物、黏展剂(spreader sticker)、佐剂、其他溶剂、以及增效剂(例如胡椒基丁醚)的组合物常常增强了化合物功效。此种喷雾可由喷雾容器(例如罐、瓶或其他容器)借助于泵或通过由加压容器(例如加压气雾剂喷雾罐)释放来施用。此类喷雾组合物可采用多种形式,例如喷雾、雾状物、泡沫、烟或雾。此类喷雾组合物因此视具体情况而定可进一步包含推进剂、发泡剂等。值得注意的是一种喷雾组合物,该组合物包含杀有害生物有效量的本发明的一种化合物以及一种载体。此喷雾组合物的一个实施例包含杀有害生物有效量的本发明的一种化合物以及一种推进剂。代表性的推进剂包括(但不局限于)甲烷、乙烷、丙烷、丁烷、异丁烷、丁烯、戊烷、异戊烷、新戊烷、戊烯、氢氟碳、氯氟碳、二甲醚、以及上述物的混合物。值得注意的是一种喷雾组合物(以及一种利用由喷雾容器分配的这样一种喷雾组合物的方法),它是用于控制至少一种选自下组的寄生无脊椎有害生物,该组由以下各项组成:蚊子、黑蝇、厩螯蝇、鹿蝇、马蝇、黄蜂、小黄蜂、大黄蜂、蜱、蜘蛛、蚂蚁、蚋及其类似物,包括单独或组合形式。
控制动物寄生虫包括控制寄生于宿主动物体表(例如肩、腋窝、腹部、大腿内部)的外寄生虫以及寄生于宿主动物体内(例如胃、肠、肺、静脉、皮下、淋巴组织)的内寄生虫。外寄生或疾病传播有害生物包括,例如恙螨、蜱、虱、蚊子、苍蝇、螨以及跳蚤。内寄生虫包括犬心丝虫、钩虫以及蠕虫。本发明的化合物可尤其适于对抗外寄生有害生物。本发明的化合物可适于对动物全身和/或非全身控制寄生虫的侵染或感染。
本发明的化合物可适于对抗侵染动物受试者的寄生无脊椎有害生物,这些动物包括野生动物、家畜及农业劳作动物中的那些。家畜为用于指(单数或复数)有意在农业环境中饲养的用于出产例如食物或纤维、或其劳动力的家养动物的术语;家畜的实例包括牛、绵羊、山羊、马、猪、驴、骆驼、水牛、兔、母鸡、火鸡、鸭及鹅(例如为肉、乳、黄油、蛋、毛皮、皮革、羽毛和/或羊毛而养殖)。通过对抗寄生虫,致死率以及效能(就肉、乳、羊毛、皮、蛋等而言)降低得以减少,因此施用本发明的化合物允许动物饲养业更经济且简单。
本发明的化合物可适于对抗侵染伴侣动物及宠物(例如狗、猫、宠物鸟及观赏鱼)、研究及实验动物(例如仓鼠、豚鼠、大鼠及小鼠)为/在动物园、野生栖息地和/或马戏团养殖的动物的寄生无脊椎有害生物。
在本发明的一个实施例中,该动物优选为一种脊椎动物并且更优选为一种哺乳动物、鸟类或鱼类。在一个特别实施例中,动物受试者为一种哺乳动物(包括大型猿,例如人类)。其他哺乳动物受试者包括灵长类(例如猴)、牛科(例如牛或乳牛)、猪科(例如家猪或猪)、羊科(例如山羊或绵羊)、马科(例如马)、犬科(例如狗)、猫科(例如家猫)、骆驼、鹿、驴、水牛、羚羊、兔及啮齿动物(例如豚鼠、松鼠、大鼠、小鼠、沙鼠、以及仓鼠)。鸟类包括鸭科(天鹅、鸭及鹅)、鸠鸽科(例如鸠及鸽子)、雉科(例如鹧鸪、松鸡及火鸡)、走禽科(Thesienidae)(例如家养鸡)、鹦鹉科(Psittacines)(例如长尾鹦鹉、金刚鹦鹉、以及鹦鹉)、猎禽及平胸类鸟(例如鸵鸟)。
由本发明的化合物所处理或保护的鸟可与商业性或非商业性鸟类饲养有关。这些鸟类尤其包括为宠物市场或收集市场养殖的鸭科,例如天鹅、鹅及鸭;鸠鸽科,例如鸠及家鸽;雉科,例如鹧鸪、松鸡及火鸡;走禽科,例如家养鸡;以及鹦鹉科,例如长尾鹦鹉、金刚鹦鹉及鹦鹉。
为了本发明的目的,术语“鱼类”理解为包括(不限于)真骨鱼类,即硬骨鱼。鲑目(包括鲑科)以及鲈形目(包括棘臀鱼科)均包含于真骨鱼类中。潜在鱼类受体的实例尤其包括鲑科、鮨科、鲷科、丽鱼科、以及棘臀鱼科。
预期其他动物也受益于本发明的方法,包括有袋动物(例如袋鼠)、爬行动物(例如养殖龟)、以及其他有重要经济价值的家畜,对于这些动物而言,本发明的方法安全且有效处理或预防了寄生虫感染或侵染。
通过向有待保护的动物给予杀有害生物有效量的本发明的化合物所控制的寄生无脊椎有害生物的实例包括体外寄生虫(节肢动物、螨等)以及体内寄生虫(蠕虫,例如线虫、吸虫、绦虫、棘头虫等)。
通常描述为蠕虫病的疾病或疾病组是由于动物宿主受到被称为蠕虫的寄生虫的感染。术语‘蠕虫’旨在包括线虫、吸虫、绦虫以及棘头虫。蠕虫病是关于家养动物(例如猪、绵羊、马、牛、山羊、犬、猫及家禽)的普遍并且严重的经济问题。
蠕虫中描述为线虫的蠕虫类别在多种动物物种中造成普遍并且有时严重的感染。
预期由本发明化合物处理的线虫包括(但不局限于)以下属:棘唇线虫属、猫圆线虫属、钩口线虫属、血管圆线虫属、禽蛔虫属、蛔虫属、布鲁格氏丝虫属、仰口线虫属、毛细线虫属、夏氏线虫属、古柏线虫属、环棘属、网尾线虫属、膨结线虫属、棘唇属、裂头属、恶丝虫属、龙线虫属、蛲虫属、类丝线虫属、血矛线虫属、异刺线虫属、兔唇蛔虫属、罗阿丝虫属、曼森氏线虫属、缪勒线虫属、板口线虫属、细颈线虫属、结节线虫属、胃线虫属、尖尾线虫属、副丝虫属、副蛔虫属、泡翼线虫属、原圆线虫属、鬃丝虫属、尾旋属、冠丝虫属、类圆线虫属、圆线虫属、吸吮线虫属、弓蛔线虫属、弓蛔虫属、旋毛虫属、毛线线虫属、毛圆线虫属、鞭虫属、钩虫属和吴策线虫属。
在上述内容中,在感染上述这些动物的线虫中最常见的属是血矛线虫属、毛圆线虫属、胃线虫属、细颈线虫属、古柏线虫属、蛔虫属、仰口线虫属、结节线虫属、夏氏线虫属、鞭虫属、圆线虫属、毛线线虫属、网尾线虫属、毛细线虫属、异刺线虫属、弓蛔虫属、禽蛔虫属、尖尾线虫属、钩口线虫属、钩虫属、弓蛔线虫属以及副蛔虫属。这些属中的某些属如细颈线虫属、古柏线虫属和结节线虫属主要攻击肠道,而其他属如血矛线虫属和胃线虫属更盛行于胃部,还有其他属如网尾线虫属存在于肺中。另外其他寄生虫可位于其他组织中,例如心脏及血管、皮下及淋巴组织及其类似组织。
预期由本发明及本发明方法处理的吸虫包括(不限于)以下各属:重翼吸虫属(Alaria)、片吸虫属、侏形吸虫属、后睾吸虫属、并殖吸虫属以及血吸虫属。
设想到用本发明和本发明的方法处理的绦虫包括但不限于以下各属:裂头属、复孔绦虫属、迭宫绦虫属及绦虫属。
人类胃肠道中最常见的寄生虫属为
钩口线虫属、板口线虫属、蛔虫属、类圆线虫属、毛形线虫属、毛细线虫属、鞭虫属及蛲虫属。其他存在于血液或胃肠道外其他组织和器官中的具有医学重要性的寄生虫属是丝虫如吴策线虫属、布鲁格氏丝虫属、旋盘尾丝虫和罗阿丝虫属以及龙线虫属丝虫,还有圆线虫属和旋毛虫属肠道蛔虫的肠外阶段。
许多其他蠕虫属与种为本领域所已知,并且也预期由本发明的化合物所处理。这些被极为详细地列举于兽医临床寄生学教科书(Textbook of Veterinary ClinicalParasitology)(第1卷,蠕虫(Helminths),E.J.L.索尔斯比(Soulsby),F.A.戴维斯(Davis)公司,美国宾夕法尼亚州费城);蠕虫、节肢动物和原生动物(Helminths,Arthropods andProtozoa)(门尼格的兽医寄生虫学和昆虫学第6版(6thMonnig’s VeterinaryHelminthology and Entomology))(E.J.L.索尔斯比(Soulsby),威廉斯(Williams)和威尔金斯(Wilkins)公司,美国马里兰州巴尔的摩)中。
本发明的化合物可以有效地抵抗一些动物体外寄生虫(例如,哺乳动物或鸟类的节肢动物体外寄生虫)。
昆虫及螨有害生物包括,例如咀嚼虫(例如苍蝇及蚊子)、螨虫、蜱、虱、跳蚤、蝽虫、寄生蝇及其类似物。
成蝇包括例如角蝇或扰血蝇、马蝇或虻属、厩螫蝇(the stable fly)或厩螫蝇(Stomoxys calcitrans)、黑蝇或蚋属、鹿蝇或斑虻属、虱蝇或绵羊虱蝇、及采采蝇或(舌蝇属)。寄生蝇蛆包括,例如肤蝇(羊狂蝇及黄蝇属)、丽蝇或绿蝇属、螺旋蛆或锥形蛆蝇、纹皮蝇或皮蝇属、羊毛虫以及马胃蝇。蚊包括例如库蚊属、疟蚊属及伊蚊属。
螨虫包括中气门目属,例如,巨刺螨属,比如鸡螨虫、鸡皮刺螨;疥螨虫或痒螨虫,例如疥螨科,比如Salpharcoptes scalphabiei;兽疥螨虫,比如痒螨属,包括牛痒螨及羊痒螨;恙螨,例如恙螨属,例如北美恙螨、阿氏真恙螨。
蜱包括例如软体蜱,包括软蜱属,例如锐缘蜱属及钝缘蜱属;硬件蜱,包括硬蜱属,例如血红扇头蜱、美洲狗蜱、安氏革蜱、美洲花蜱、肩突硬蜱及其他扇头蜱属(包括先前的牛蜱)。
虱包括,例如(吸吮虱),例如,禽虱属。
以及牛羽虱属;咬虱,例如血虱属、毛虱属及盲虱属。
跳蚤包括例如栉头蚤属,诸如犬蚤(犬栉头蚤)及猫蚤(猫栉头蚤);客蚤属,诸如东方鼠蚤(印鼠客蚤);以及蚤属,诸如人蚤(致痒蚤)。
蝽虫包括例如臭虫科或例如普通床虱蝽(温带臭虫);锥猎蝽属,包括锥猎蝽,亦称为猎蝽;例如长红锥蝽及锥蝽属。
通常,苍蝇、跳蚤、虱、蚊子、蚋、螨虫、蜱及蠕虫对家畜及伴侣动物领域造成巨大损失。节肢动物寄生虫还是人类公害并且可在人类及动物中作为致病生物的载体。
许多其他寄生无脊椎有害生物为本领域中已知,并且也预期由本发明的化合物所处理。这些非常详细地列举于医学和兽医昆虫学(Medical and Veterinary Entomology)(纽约和多伦多,约翰威立出版社(John Wiley AND Sons),D.S.科特尔(D.S.Kettle));家畜的节肢动物有害生物控制:技术综述(Control of Arthropod Pests of Livestock:AReview of Technology)(美国佛罗里达州布卡拉顿(Boca Raton,FIa),CRC出版社(CRCPress),R.O.德鲁曼(R.O.Drummand)、J.E.乔治(J.E.George)及S.E.昆兹(S.E.Kunz))中。
本发明的化合物还可以有效地抵抗体外寄生虫,包括:蝇比如扰血蝇(扰角蝇)骚扰血蝇(角蝇)、蚋属(黑蝇)、舌蝇属(采采蝇)、刺激齿股蝇(头蝇)、秋家蝇(秋家蝇)、家蝇(居家蝇)、简莫蝇(汗蝇)、虻属(马蝇)、牛皮蝇、纹皮蝇、丝光绿蝇、铜绿蝇(绿丽蝇)、丽蝇属(丽蝇)、原伏蝇属、羊狂蝇(鼻狂蝇)、库蠓属(蠓)、马虱蝇、肠胃蝇、赤尾胃蝇以及鼻胃蝇;虱比如牛毛虱(牛畜虱)、马毛虱、驴血虱、铲吻猫羽虱、具刺袋鼠虱(Heterodoxus spiniger)、棘颚虱以及犬啮毛虱;羊蜱蝇比如绵羊虱蝇;以及螨比如痒螨属、人疥螨、牛痒螨、马脂螨、姬螯螨属、猫耳螨、恙螨属以及耳疥虫(耳螨)。
本发明的处理通过已知的方式,例如通过以例如片剂、胶囊、饮品、浸润制剂、颗粒剂、糊剂、大丸药、馈入方法(feed-through procedures)或栓剂形式的肠内给予;或例如通过注射(包括肌内、皮下、静脉内、腹膜内)或植入的肠胃外给予;或通过鼻腔给予。
当本发明的化合物与其他生物学活性成分组合施用时,它们可例如以独立组合物形式单独给予。在此情况下,这些生物学活性成分可同时或顺序给予。可替代地,这些生物学活性成分可以是一种组合物的组分。
本发明的化合物能以受控释放形式给予,例如以皮下或经口给予的缓释配制品形式给予。
典型地,根据本发明的杀虫组合物包含本发明的化合物,可任选地与其他生物学活性成分或其N-氧化物或盐、一种或多种医药学上或兽医学上可接受的载体组合,这些载体包含关于所预期的给予途径(例如经口或肠胃外给予,例如注射)并且根据标准规范所选择的赋形剂及助剂。另外,合适载体是基于与组合物中一种或多种活性成分的相容性来选择,包括例如相对于pH值及水分含量的稳定性考虑。因此,值得注意地是保护动物免受寄生无脊椎动物有害生物侵害的本发明的多种化合物,这些化合物包括一种杀寄生虫有效量的本发明的化合物,该化合物可任选地与其他生物学活性成分以及至少一种载体组合。
对于包括静脉内、肌内及皮下注射的肠胃外给予而言,本发明的化合物能以悬浮液、溶液或乳液形式配制于油性或水性媒介物中,并且可包含例如悬浮剂、稳定剂和/或分散剂的佐剂。
本发明的化合物还可以配制为用于弹丸注射或持续输注。用于注射的药物组合物包括水溶性形式活性成分(例如活性化合物的盐)的水溶液,优选于包含如药物配制品领域内已知的其他赋形剂或助剂的生理学上兼容的缓冲液中。另外,这些活性化合物的悬浮液可在亲脂性媒介物中制备。合适的亲脂性媒介物包括脂肪油(例如芝麻油)、合成脂肪酸酯(例如油酸乙酯以及甘油三酸酯)或材料(例如脂质体)。
水性注射悬浮液可包含增加该悬浮液黏度的物质,例如羧甲基纤维素钠、山梨糖醇、或葡聚糖。用于注射的配制品可以单位剂型(例如于安瓿或多剂量容器中)呈现。可替代地,该活性成分在使用前可处于粉末形式以与合适的媒介物(例如无菌无热原质水)组构。
除前述配制品之外,本发明的化合物还可配制为长效制剂。此类长效配制品可通过植入(例如皮下或肌内)或通过肌内或皮下注射给予。
本发明的化合物可与合适的聚合物或疏水性材料(例如以具有药理学上可接受的油的乳液形式)、与离子交换树脂,或以略微可溶的衍生物(例如(不限于)微溶性盐)形式经配制用于此给予途径。
对于吸入给予而言,本发明的化合物可使用加压包装或雾化器及合适推进剂,例如(不限于)二氯二氟甲烷、三氯氟甲烷、二氯四氟乙烷或二氧化碳,以气雾剂喷雾形式来递送。在加压气雾剂情况下,剂量单位可通过提供一种阀来传递经计量的量而得到控制。
用于在吸入器或吹入器中使用的例如明胶构成的胶囊及筒可配制为包含该化合物与合适粉剂基料(例如乳糖或淀粉)的粉末混合物。
本发明的化合物可具有有利的药物代谢动力学及药效学特性,由经口给予以及摄取而提供全身可用性。因此,在有待保护的动物摄取后,本发明的化合物在血流中的杀寄生虫有效浓度可保护所治疗的动物免受吸血有害生物(例如跳蚤、蜱以及虱)的侵害。因此,以经口给予形式(即除杀寄生虫有效量的本发明化合物之外,包含一种或多种选自黏合剂及适于经口给予的填充剂以及浓缩饲料载体)保护动物免受寄生无脊椎有害生物侵害的组合物是值得注意的。
对于溶液(最易于吸收的可用形式)、乳液、悬浮液、糊剂、凝胶、胶囊、片剂、大丸剂、粉剂、颗粒剂、瘤胃滞留(rumen-retention)及饲料/水/舔块形式的经口给予,本发明的化合物可与本领域中已知的适于经口给予组合物的黏合剂/填充剂一起配制,例如糖及糖衍生物(例如乳糖、蔗糖、甘露醇、山梨糖醇)、淀粉(例如玉米淀粉、小麦淀粉、米淀粉、马铃薯淀粉)、纤维素及衍生物(例如甲基纤维素、羧甲基纤维素、乙基羟基纤维素)、蛋白质衍生物(例如玉米素、明胶)及合成聚合物(例如聚乙烯醇、聚乙烯吡咯烷酮)。如果希望的话,可添加润滑剂(例如硬脂酸镁)、崩解剂(例如交联聚乙烯吡咯烷酮、琼脂、海藻酸)以及染料或颜料。糊剂及凝胶通常也包含胶黏剂(例如阿拉伯胶、海藻酸、膨润土、纤维素、黄原胶、胶状硅酸镁铝)以帮助使该组合物与口腔保持接触而非容易喷出。
在一个实施例中,本发明的组合物经配制成为可咀嚼和/或可食用的产物(例如可咀嚼治疗剂或可食用片剂)。该产物将理想地具有所保护的动物所喜爱的口味、质地和/或香味,以便易于经口给予本发明的化合物。
若这些杀虫组合物呈浓缩饲料形式,则该载体典型地选自高性能饲料、饲料用谷物或蛋白浓缩物。
此类含有浓缩饲料的组合物除杀寄生虫活性成分之外,还可包含促进动物健康或生长、改善用于屠宰或以其他方式对畜牧业有用的动物的肉类质量的添加剂。
这些添加剂可包括,例如维生素、抗生素、化疗剂、抑细菌剂、抑真菌剂、球虫抑制剂以及激素。
本发明的化合物还可使用例如常规的栓剂基质(例如可可脂或其他甘油酯)配制成直肠组合物(例如栓剂或保留灌肠剂)。
用于本发明方法的配制品可以包括一种抗氧化剂,例如BHT(丁基化羟基甲苯)。该抗氧化剂总体上以0.1百分比-5百分比(wt/vol)的量存在。一些配制品要求一种增溶剂(例如油酸)以溶解该活性试剂,特别是若包括多杀菌素时。用于这些倾倒配制品中的常见铺展剂包括十四烷酸异丙酯、棕榈酸异丙酯、饱和C12-C18脂肪醇的辛酸/癸酸酯、油酸、油醇酯、油酸乙酯、甘油三酯、硅油以及二丙二醇甲基醚。用于本发明方法的倾倒配制品是根据已知技术制备的。当这种倾倒物为溶液时,使杀寄生虫药/杀昆虫剂与载体或媒介物混合,若需要时使用加热以及搅拌。助剂或其他成分可添加到活性剂与载体的混合物中,或它们可在添加该载体之前与该活性剂混合。处于乳液或悬浮液形式的倾倒配制品类似地使用已知技术来制备。
可以采用针对相对疏水性药物化合物的其他传递系统。脂质体及乳液是疏水性药物所用的传递媒介物或载体的熟知实例。另外,若需要,则可使用有机溶剂,例如二甲亚砜。
有效控制寄生无脊椎有害生物所需的施用率(例如“杀有害生物有效量”)将取决于以下因素:有待控制的寄生无脊椎动物有害生物的物种、有害生物的生命周期、生命阶段、其大小、场所、季节(time of year)、宿主作物或动物、摄食行为、交配行为、环境湿度、温度及其类似因素。本领域普通技术人员可容易地确定所希望的寄生无脊椎有害生物控制程度所需的杀有害生物有效量。
总体上对于兽医学用途而言,本发明的化合物以杀有害生物有效量给予有待保护而免受寄生无脊椎有害生物侵害的动物,特别是恒温动物。
杀有害生物有效量是实现可观测程度的减低目标寄生无脊椎有害生物出现率或活力的效果所需的活性成分的量值。本领域普通技术人员应了解杀有害生物有效量可关于对本发明的方法有用的多种化合物及组合物、所希望的杀有害生物效果及持续时间、目标寄生无脊椎有害生物物种、有待保护的动物、施用模式及其类似物而变化,并且实现特定结果所需的量可经由简单实验来确定。
对于经口或肠胃外为动物给予,以合适时间间隔给予的本发明组合物的剂量典型地在约0.01mg/kg至约100mg/kg并且优选约0.01mg/kg至约30mg/kg动物体重的范围内。
本发明的组合物给予动物的合适时间间隔范围为约每日一次至约每年一次。范围为约每周一次至约每6个月一次的给予时间间隔是值得注意的。每月一次的给予时间间隔(即每月向动物给予化合物一次)是特别值得注意的。
本发明还提供了一种用于控制害虫((如蚊科和其他的疾病媒介物)的方法;还参见http://www.who.int/malaria/vector_control/irs/en/)。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,向该目标有害生物、它们的场所或表面或基质施用本发明的组合物。通过举例,通过本发明的方法预期了一种表面(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一种基质,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)。
在一个实施例中,用于控制此类有害生物的方法包括向该目标有害生物、它们的场所或表面或基质施用一种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。此类施用可以通过涂刷、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,本发明的方法预期了一种表面(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,预期了施用此类组合物以用于在一种基质上的有害生物的滞留的控制,该基质是例如处于网织品、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使用)的织物材料。
有待处理的基质(包含无纺物、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。纺织品处理的方法已知于例如,手工纺织整理:第1卷:设备,第2卷:颜色,第3卷:涂料,第4卷:环境;(Handbuch Textilveredlung:Band 1:Ausrüstung、Band 2:Farbgebung、Band 3:Beschichtung、Band 4:Umwelttechnik);发布者:德国专业出版商,版次:15,修订版(Verlag:Deutscher Fachverlag;Auflage:15.,überarbeiteteAusgabe)(2006年4月17日);ISBN-10:3866410123;ISBN-13:978-3866410121,特别参见第1卷:设备(Band 1:Ausrüstung),27-198页,更优选118页;或WO 2008151984或WO2003034823或US 5631072或WO 200564072或WO 2006128870或EP 1724392或WO2005064072或WO 2005113886或WO 2007090739。
如在此使用的术语“植物”包括幼苗、灌木以及树木。
术语“作物”或“植物”应理解为还包括通过使用重组DNA技术转化的作物植物,这些作物植物能够合成一种或多种选择性地作用毒素,例如已知,来自产毒素的细菌,尤其是芽胞杆菌属的那些。
可通过所述转基因植物表达的毒素包括,例如杀虫蛋白质,例如来自于枯草芽孢杆菌或日本甲虫芽孢杆菌的杀虫蛋白质;或来自于苏云金芽孢杆菌的杀虫蛋白质,例如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;或线虫寄生性细菌的杀虫蛋白质,例如光杆状茵属或致病杆菌属,例如发光光杆状茵、嗜线虫致病杆菌;由动物产生的毒素,例如蝎毒素、蜘蛛毒素、黄蜂毒素和其他昆虫特异性神经毒素;由真菌产生的毒素,例如链霉菌毒素;植物凝集素,例如豌豆凝集素、大麦凝集素或雪花莲凝集素;凝集素类;蛋白酶抑制剂,例如胰蛋白酶抑制剂、丝氨酸蛋白酶抑制剂、马铃薯贮存蛋白(patatin)、半胱氨酸蛋白酶抑制剂、木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),例如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽毒蛋白、皂草毒素蛋白或异株泻根毒蛋白;类固醇代谢酶,例如3-羟基类固醇氧化酶、蜕皮类固醇-UDP-糖基-转移酶、胆固醇氧化酶、蜕皮激素抑制剂、HMG-COA-还原酶,离子通道阻断剂,例如钠通道或钙通道阻断剂,保幼激素酯酶,利尿激素受体、茋合酶、联苄合酶、几丁酶和葡聚糖酶。
在本发明背景下,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区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。在经修饰毒素的情况下,天然产生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,例如在Cry3A055的情况下,一种组织蛋白酶-G-识别序列被插入Cry3A毒素(参见WO 03/018810)。
这样的毒素或能够合成这样的毒素的转基因植物的实例披露于例如EP-A-0 374753、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工艺对于本领域普通技术人员是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-0367 474、EP-A-0 401 979以及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。这些昆虫可以存在于任何昆虫分类群,但尤其是通常在甲虫(鞘翅目)、双翅昆虫(双翅目)以及蝴蝶(鳞翅目)中发现。
包括一种或多种编码杀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。这样的植物的实例是: (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以及Cry3Bb1毒素);(玉米品种,表达Cry9C毒素);Herculex(玉米品种,表达Cry1Fa2毒素以及实现对除草剂草丁膦铵的耐受性的酶膦丝菌素N-乙酰转移酶(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
此类转基因作物的其他实例是:
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,注册号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玉米还转基因地表达PAT酶以达到对除草剂草丁膦铵盐的耐受性。
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,注册号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玉米还转基因地表达PAT酶以达到对除草剂草丁膦铵盐的耐受性。
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,注册号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(Brussels),比利时,注册号C/DE/02/9。MON863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,B-1150布鲁塞尔,比利时,注册号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,注册号C/NL/00/10。遗传修饰的玉米,表达蛋白质Cry1F以实现对某些鳞翅目昆虫的抗性和表达PAT蛋白质以实现对除草剂草丁膦铵盐的耐受性。
7.NK603×MON 810玉米,来自孟山都欧洲公司(Monsanto Europe S.A.),270-272德特文瑞大街,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×MON 810玉米转基因表达由土壤杆菌属菌株CP4获得的CP4 EPSPS蛋白质,使之耐除草剂(含有草甘膦),以及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。
通过添加其他有杀昆虫、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,并且适合于当时的环境。具有化学式I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进一步地、意料之外的优点,这些优点还可以在更宽的含义上描述为协同活性。例如,植物对其更好的耐受性、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,在研磨或者混合过程中,在它们的储藏或它们的使用过程中)更好的行为。
在这里,合适的活性成分的添加物是,例如,下面类别的活性成分的代表物: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、新烟碱以及苏云金芽孢杆菌制剂。
以下具有化学式I的化合物与活性成分的混合物是优选的(缩写“TX”意为“本发明的选自表1(化合物1.1至1.112)的一种特定化合物,或选自表2(化合物2.1至2.112)的一种特定化合物,或选自表A(化合物1至5)的一种特定化合物”):
一种佐剂,该佐剂选自由石油(别名(628)+TX)组成的组的物质,
一种杀螨剂,该杀螨剂选自以下物质组成的组:1,1-二(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/化学文摘名称)(1059)+TX、2-氟-N-甲基-N-1-萘乙酰胺(IUPAC名称)(1295)+TX、4-氯苯基苯砜(IUPAC名称)(981)+TX、阿维菌素(1)+TX、灭螨醌(3)+TX、乙酰虫腈[CCN]+TX、氟丙菊酯(9)+TX、涕灭威(16)+TX、涕灭氧威(863)+TX、α-氯氰菊酯(202)+TX、赛硫磷(870)+TX、磺胺螨酯[CCN]+TX、逐磷酰胺(872)+TX、胺吸磷(875)+TX、草酸氢胺吸磷(875)+TX、双甲脒(24)+TX、杀螨特(881)+TX、氧化亚砷(882)+TX、AVI382(化合物代码)+TX、AZ60541(化合物代码)+TX、乙基谷硫磷(44)+TX、谷硫磷(45)+TX、偶氮苯(IUPAC名称)(888)+TX、三唑锡(46)+TX、偶氮磷(889)+TX、苯来特(62)+TX、苯噁磷(别名)[CCN]+TX、苯螨特(71)+TX、苯甲酸苄酯(IUPAC名称)[CCN]+TX、联苯肼酯(74)+TX、联苯菊酯(76)+TX、乐杀螨(907)+TX、溴灭菊酯(别名)+TX、溴烯杀(918)+TX、溴硫磷(920)+TX、乙基溴硫磷(921)+TX、溴螨酯(94)+TX、噻嗪酮(99)+TX、丁酮威(103)+TX、丁酮氧威(104)+TX、butylpyridaben(别名)+TX、多硫化钙(IUPAC名称)(111)+TX、毒杀芬(941)+TX、氯灭杀威(943)+TX、西维因(115)+TX、卡巴呋喃(118)+TX、卡波硫磷(947)+TX、CGA50’439(研究代码)(125)+TX、灭螨猛(126)+TX、氯杀螨(959)+TX、杀虫脒(964)+TX、杀虫眯盐酸盐(964)+TX、溴虫腈(130)+TX、杀螨醇(968)+TX、杀螨酯(970)+TX、敌螨特(971)+TX、毒虫畏(131)+TX、克氯苯(975)+TX、丁甲虫脒(977)+TX、灭虫脲(978)+TX、丙酯杀螨醇(983)+TX、毒死蜱(145)+TX、甲基毒死蜱(146)+TX、虫螨磷(994)+TX、瓜菊酯I(696)+TX、瓜菊酯II(696)+TX、多种瓜菊酯(696)+TX、四螨嗪(158)+TX、克罗散泰(别名)[CCN]+TX、蝇毒磷(174)+TX、克罗米通(别名)[CCN]+TX、巴毒磷(1010)+TX、硫杂灵(1013)+TX、果虫磷(1020)+TX、丁氟螨酯(CAS注册号.:400882-07-7)+TX、三氟氯氰菊酯(196)+TX、三环锡(199)+TX、氯氰菊酯(201)+TX、DCPM(1032)+TX、DDT(219)+TX、田乐磷(1037)+TX、田乐磷-O(1037)+TX、田乐磷-S(1037)+TX、内吸磷(1038)+TX、甲基内吸磷(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、内吸磷-S-甲砜(1039)+TX、丁醚脲(226)+TX、氯亚磷(1042)+TX、二嗪农(227)+TX、抑菌灵(230)+TX、敌敌畏(236)+TX、dicliphos(别名)+TX、三氯杀螨醇(242)+TX、百治磷(243)+TX、除螨灵(1071)+TX、甲氟磷(1081)+TX、乐果(262)+TX、二活菌素(别名)(653)+TX、消螨酚(1089)+TX、消螨酚-diclexine(1089)+TX、消螨通(269)+TX、消螨普(270)+TX、消螨普-4[CCN]+TX、消螨普-6[CCN]+TX、邻敌螨消(1090)+TX、dinopentonpenton(1092)+TX、硝辛酯(1097)+TX、硝丁酯(1098)+TX、敌杀磷(1102)+TX、二苯基砜(IUPAC名称)(1103)+TX、戒酒硫(别名)[CCN]+TX、乙拌磷(278)+TX、DNOC(282)+TX、dofenapyn(1113)+TX、多拉克汀(别名)[CCN]+TX、硫丹(294)+TX、因毒磷(1121)+TX、EPN(297)+TX、依立诺克丁(别名)[CCN]+TX、乙硫磷(309)+TX、益硫磷(1134)+TX、乙螨唑(320)+TX、乙嘧硫磷(1142)+TX、抗螨唑(1147)+TX、喹螨醚(328)+TX、苯丁锡(330)+TX、苯硫威(337)+TX、甲氰菊酯(342)+TX、fenpyrad(别名)+TX、唑螨酯(345)+TX、除螨酯(1157)+TX、fentrifanil(1161)+TX、氰戊菊酯(349)+TX、氟虫腈(354)+TX、嘧螨酯(360)+TX、吡虫隆(1166)+TX、氟螨噻(1167)+TX、氟环脲(366)+TX、氟氰戊菊酯(367)+TX、联氟螨(1169)+TX、氟虫脲(370)+TX、氟氯苯菊酯(372)+TX、氟杀螨(1174)+TX、氟胺氰菊酯(1184)+TX、FMC1137(研究代码)(1185)+TX、伐虫脒(405)+TX、伐虫脒盐酸盐(405)+TX、安果(1192)+TX、胺甲威(1193)+TX、γ-HCH(430)+TX、果绿定(1205)+TX、苄螨醚(424)+TX、庚烯磷(432)+TX、十六烷基环丙甲酸酯(IUPAC/化学文摘名称)(1216)+TX、噻螨酮(441)+TX、碘甲烷(IUPAC名称)(542)+TX、水胺硫磷(别名)(473)+TX、异丙基O-(甲氧基氨基硫磷酰)水杨酸酯(IUPAC名称)(473)+TX、伊维菌素(别名)[CCN]+TX、茉莉菊酯I(696)+TX、茉莉菊酯II(696)+TX、碘硫磷(1248)+TX、林旦(430)+TX、虱螨脲(490)+TX、马拉松(492)+TX、丙螨氰(1254)+TX、灭蚜磷(502)+TX、地胺磷(1261)+TX、甲硫芬(别名)[CCN]+TX、虫螨畏(1266)+TX、甲胺磷(527)+TX、杀扑磷(529)+TX、灭虫威(530)+TX、灭多威(531)+TX、甲基溴(537)+TX、速灭威(550)+TX、速灭磷(556)+TX、自克威(1290)+TX、密灭汀(557)+TX、米尔倍霉素(别名)[CCN]+TX、丙胺氟(1293)+TX、久效磷(561)+TX、茂果(1300)+TX、莫昔克丁(别名)[CCN]+TX、二溴磷(567)+TX、NC-184(化合物代码)+TX、NC-512(化合物代码)+TX、氟蚁灵(1309)+TX、尼可霉素(别名)[CCN]+TX、戊氰威(1313)+TX、戊氰威1:1氯化锌复合物(1313)+TX、NNI-0101(化合物代码)+TX、NNI-0250(化合物代码)+TX、氧化乐果(594)+TX、杀线威(602)+TX、异亚砜磷(1324)+TX、砜拌磷(1325)+TX、pp’-DDT(219)+TX、对硫磷(615)+TX、苄氯菊酯(626)+TX、石油(别名)(628)+TX、芬硫磷(1330)+TX、稻丰散(631)+TX、甲拌磷(636)+TX、伏杀磷(637)+TX、硫环磷(1338)+TX、亚胺硫磷(638)+TX、磷胺(639)+TX、辛硫磷(642)+TX、甲基嘧啶磷(652)+TX、多氯萜烯(传统名称)(1347)+TX、杀螨素(别名)(653)+TX、丙氯醇(1350)+TX、丙溴磷(662)+TX、蜱虱威(1354)+TX、克螨特(671)+TX、胺丙畏(673)+TX、残杀威(678)+TX、乙噻唑磷(1360)+TX、发硫磷(1362)+TX、除虫菊酯I(696)+TX、除虫菊酯II(696)+TX、多种除虫菊酯(696)+TX、哒螨灵(699)+TX、哒嗪硫磷(701)+TX、嘧螨醚(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(1389)+TX、克线丹(别名)+TX、塞拉菌素(别名)[CCN]+TX、SI-0009(化合物代码)+TX、苏硫磷(1402)+TX、螺螨酯(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(750)+TX、治螟磷(753)+TX、硫磺(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(别名)+TX、杀虫畏(777)+TX、四氯杀螨砜(786)+TX、四抗菌素(别名)(653)+TX、杀螨好(1425)+TX、thiafenox(别名)+TX、抗虫威(1431)+TX、久效威(800)+TX、甲基乙拌磷(801)+TX、克杀螨(1436)+TX、苏云金素(别名)[CCN]+TX、威菌磷(1441)+TX、苯螨噻(1443)+TX、三唑磷(820)+TX、唑呀威(别名)+TX、敌百虫(824)+TX、三氯丙氧磷(1455)+TX、三活菌素(别名)(653)+TX、蚜灭多(847)+TX、vaniliprole[CCN]和YI-5302(化合物代码)+TX,
一种杀藻剂,该杀藻剂选自由以下物质组成的组:3-苯并[b]噻吩-2-基-5,6-二氢-1,4,2-噁噻嗪-4-氧化物[CCN]+TX、二辛酸铜(IUPAC名称)(170)+TX、硫酸铜(172)+TX、cybutryne[CCN]+TX、二氢萘醌(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、三苯锡乙酸盐(IUPAC名称)(347)和氢氧化三苯锡(IUPAC名称)(347)+TX,
一种驱蠕虫剂,该驱蠕虫剂选自由以下物质组成的组:阿维菌素(1)+TX、克芦磷酯(1011)+TX、多拉克汀(别名)[CCN]+TX、依马克丁(291)+TX、依马克丁苯甲酸酯(291)+TX、依立诺克丁(别名)[CCN]+TX、伊维菌素(别名)[CCN]+TX、米尔倍霉素(别名)[CCN]+TX、莫昔克丁(别名)[CCN]+TX、哌嗪[CCN]+TX、塞拉菌素(selamectin)(别名)[CCN]+TX、多杀菌素(737)和硫菌灵(thiophanate)(1435)+TX,
一种杀鸟剂,该杀鸟剂选自由以下物质组成的组: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,
一种杀细菌剂,该杀细菌剂选自由以下物质组成的组: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盐)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、烯丙苯噻唑(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,
一种生物试剂,该生物试剂选自由以下物质构成的组:棉褐带卷蛾颗粒体病毒(Adoxophyes orana GV)(别名)(12)+TX、放射形土壤杆菌(别名)(13)+TX、捕食螨(Amblyseius spp.)(别名)(19)+TX、芹菜夜蛾核多角体病毒(Anagrapha falcifera NPV)(别名)(28)+TX、Anagrus atomus(别名)(29)+TX、蚜虫寄生蜂(Aphelinus abdominalis)(别名)(33)+TX、棉蚜寄生蜂(Aphidius colemani)(别名)(34)+TX、食蚜瘿蚊(Autographacalifornica NPV)(别名)(35)+TX、苜蓿银纹夜蛾核多角体病毒(Bacillus firmus)(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.I(Bacillus thuringiensis subsp.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k.(Bacillus thuringiensissubsp.kurstaki)(学名)(51)+TX、苏云金芽孢杆菌t.(Bacillus thuringiensissubsp.tenebrionis)(学名)(51)+TX、球孢白僵茵(Beauveria bassiana)(别名)(53)+TX,布氏白僵茵(Beauveria brongniartii)(别名)(54)+TX、草蜻蛉(Chrysoperla carnea)(别名)(151)+TX、孟氏隐唇瓢虫(Cryptolaemus montrouzieri)(别名)(178)+TX、苹果蠹蛾颗粒体病毒(Cydia pomonella 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(Encarsia formosa)(学名)(293)+TX、桨角蚜小蜂(Eretmocerus eremicus)(别名)(300)+TX、玉米穗夜蛾核多角体病毒(Helicoverpa zea NPV)(别名)(431)+TX、嗜茵异小杆线虫(Heterorhabditis bacteriophora)和H.megidis(别名)(433)+TX、会聚长足瓢虫(Hippodamia convergens)(别名)(442)+TX、橘粉介壳虫寄生蜂(Leptomastixdactylopii)(别名)(488)+TX、盲蝽(Macrolophus caliginosus)(别名)(491)+TX,甘蓝夜蛾核多角体病毒(Mamestra brassicae NPV)(别名)(494)+TX、Metaphycus helvolus(别名)(522)+TX、黄绿绿僵茵(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、松黄叶蜂(Neodiprion sertifer)核多角体病毒和红头松树叶蜂(N.lecontei)核多角体病毒(别名)(575)+TX、小花蝽(别名)(596)+TX、玫烟色拟青霉(Paecilomyces fumosoroseus)(别名)(613)+TX、智利捕植螨(Phytoseiulus persimilis)(别名)(644)+TX、甜菜夜蛾(Spodoptera exigua multicapsid)多核衣壳核多角体病毒(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、Steinernema glaseri(别名)(742)+TX、Steinernema riobrave(另名)(742)+TX、Steinernema riobravis(别名)(742)+TX、Steinernema scapterisci(别名)(742)+TX、斯氏线虫属(Steinernema spp.)(别名)(742)+TX、赤眼蜂属(别名)(826)+TX、西方盲走螨(Typhlodromus occidentalis)(别名)(844)和蜡蚧轮枝茵(Verticillium lecanii)(别名)(848)+TX,
一种土壤消毒剂,该土壤消毒剂选自由以下物质组成的组:碘甲烷(IUPAC名称)(542)和甲基溴(537)+TX,
一种化学不育剂,该化学不育剂选自由以下物质组成的组:唑磷嗪(apholate)[CCN]+TX、双(氮丙啶)甲氨基膦硫化物(bisazir)(替代名称)[CCN]+TX、白消安(替代名称)[CCN]+TX、除虫脲(250)+TX、迪麦替夫(dimatif)(替代名称)[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、不育特(methyl apholate)[CCN]+TX、不孕啶(morzid)[CCN]+TX、氟幼脲(penfluron)(替代名称)[CCN]+TX、涕巴(tepa)[CCN]+TX、硫代六甲磷(thiohempa)(替代名称)[CCN]+TX、硫涕巴(替代名称)[CCN]+TX、曲他胺(替代名称)[CCN]和尿烷亚胺(替代名称)[CCN]+TX,
一种昆虫信息素,该昆虫信息素选自由以下物质组成的组:(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-甲基十八-1-烯(IUPAC名称)(545)+TX、4-甲基壬醛-5-醇与4-甲基壬醛-5-酮(IUPAC名称)(544)+TX、α-多纹素(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、十二碳二烯醇(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、醋酸十六烯酯(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、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、十八-2,13-二烯-1-基乙酸酯(IUPAC名称)(588)+TX、十八-3,13-二烯-1-基乙酸酯(IUPAC名称)(589)+TX、贺康彼(orfralure)(别名)[CCN]+TX、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、十四-11-烯-1-基乙酸酯(IUPAC名称)(785)+TX、特诱酮(839)+TX、特诱酮A(别岩)(839)+TX、特诱酮B1(别名)(839)+TX、特诱酮B2(别名)(839)+TX、特诱酮C(别名)(839)和trunc-call(别名)[CCN]+TX,
一种昆虫驱避剂,该昆虫驱避剂选自以下物质组成的组: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、避蚊胺[CCN]+TX、驱蚊酯(dimethyl carbate)[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、氨羰基甲酸酯(oxamate)[CCN]和羟哌酯[CCN]+TX,
一种杀昆虫剂,该杀昆虫剂选自以下物质组成的组: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、1,2-二氯丙烷与1,3-二氯丙烷一起(IUPAC名称)(1063)+TX、1-溴-2-氯乙烷(IUPAC/化学文摘名称)(916)+TX、2,2,2-三氯-1-(3,4-二氯苯基)乙酸乙酯(IUPAC名称)(1451)+TX、2,2-二氯乙烯基2-乙基亚硫酰基乙基-甲基-磷酸酯(IUPAC名称)(1066)+TX、2-(1,3-二硫杂环戊烷-2-基)苯基-二甲基氨基甲酸酯(IUPAC/化学文摘名称)(1109)+TX、2-(2-丁氧基乙氧基)乙基硫氰酸酯(IUPAC/化学文摘名称)(935)+TX、2-(4,5-二甲基-1,3-二氧戊环-2-基)苯基-甲基氨基甲酸酯(IUPAC/化学文摘名称)(1084)+TX、2-(4-氯-3,5-二甲基苯氧基)乙醇(IUPAC名称)(986)+TX、2-氯乙烯基-二甲基-磷酸酯(IUPAC名称)(984)+TX、2-咪唑烷酮(IUPAC名称)(1225)+TX、2-异戊基茚满-1,3-二酮(IUPAC名称)(1246)+TX、2-甲基(丙炔-2-基)氨基苯基-甲基氨基甲酸酯(IUPAC名称)(1284)+TX、2-硫氰酰乙基月桂酸酯(IUPAC名称)(1433)+TX、3-溴-1-氯丙-1-烯(IUPAC名称)(917)+TX、3-甲基-1-苯基吡唑-5-基-二甲基氨基甲酸酯(IUPAC名称)(1283)+TX、4-甲基(丙-2-炔基)氨基-3,5-二甲苯基-甲基氨基甲酸酯(IUPAC名称)(1285)+TX、5,5-二甲基-3-氧代环己-1-烯基-二甲基氨基甲酸酯(IUPAC名称)(1085)+TX、阿维菌素(1)+TX、高灭磷(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、艾氏剂(864)+TX、丙烯菊酯(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、逐磷酰胺(872)+TX、灭害威(873)+TX、胺吸磷(875)+TX、草酸氢胺吸磷(875)+TX、双甲脒(24)+TX、新烟碱(877)+TX、乙基杀扑磷(883)+TX、AVI382(化合物代码)+TX、AZ60541(化合物代码)+TX、印楝素(别名)(41)+TX、甲基吡啶磷(42)+TX、乙基谷硫磷(44)+TX、甲基谷硫磷(45)+TX、偶氮磷(889)+TX、苏云金芽孢杆菌δ-内毒素(别名)(52)+TX、六氟合硅酸钡(别名)[CCN]+TX、多硫化钡(IUPAC/化学文摘名称)(892)+TX、熏菊酯[CCN]+TX、拜耳22/190(研究代码)(893)+TX、拜耳22408(研究代码)(894)+TX、恶虫威(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、生物丙烯菊酯(78)+TX、生物丙烯菊酯S-环戊烯基异构体(别名)(79)+TX、bioethanomethrin[CCN]+TX、生物氯菊酯(908)+TX、生物苄呋菊酯(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、溴烯杀(918)+TX、溴-DDT(别名)[CCN]+TX、溴硫磷(920)+TX、乙基溴硫磷(921)+TX、合杀威(924)+TX、噻嗪酮(99)+TX、畜虫威(926)+TX、butathiofos(927)+TX、丁酮威(103)+TX、丁酯膦(932)+TX、丁酮砜威(104)+TX、butylpyridaben(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、西维因(115)+TX、卡巴呋喃(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、丁硫克百威(119)+TX、杀螟丹(123)+TX、杀螟丹盐酸盐(123)+TX、藜芦碱(别名)(725)+TX、冰片丹(960)+TX、氯丹(128)+TX、十氯酮(963)+TX、杀虫脒(964)+TX、杀虫眯盐酸盐(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、chlorprazophos(990)+TX、毒死蜱(145)+TX、甲基毒死蜱(146)+TX、虫螨磷(994)+TX、环虫酰肼(150)+TX、瓜菊酯I(696)+TX、瓜菊酯II(696)+TX、多种瓜菊酯(696)+TX、顺式苄呋菊酯(别名)+TX、cismethrin(80)+TX、氰菊酯(别名)+TX、地虫威(999)+TX、克罗散泰(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、杀螟腈(184)+TX、果虫磷(1020)+TX、环虫菊[CCN]+TX、乙氰菊酯(188)+TX、氟氯氰菊酯(193)+TX、三氟氯氰菊酯(196)+TX、氯氰菊酯(201)+TX、苯氰菊酯(206)+TX、灭蝇胺(209)+TX、畜蜱磷(别名)[CCN]+TX、右旋柠檬烯(别名)[CCN]+TX、右旋胺菊酯(别名)(788)+TX、DAEP(1031)+TX、棉隆(216)+TX、DDT(219)+TX、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、甲基内吸磷(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、内吸磷-S-甲基砜(1039)+TX、丁醚脲(226)+TX、氯亚磷(1042)+TX、diamidafos(1044)+TX、二嗪农(227)+TX、异氯磷(1050)+TX、除线磷(1051)+TX、敌敌畏(236)+TX、dicliphos(别名)+TX、dicresyl(别名)[CCN]+TX、百治磷(243)+TX、地昔尼尔(244)+TX、狄氏剂(1070)+TX、二乙基5-甲基吡唑-3-基磷酸酯(IUPAC名称)(1076)+TX、二氟脲(250)+TX、二羟丙茶碱(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、二甲基亚硝胺(265)+TX、敌蝇威(1086)+TX、消螨酚(1089)+TX、消螨酚-diclexine(1089)+TX、丙硝酚(1093)+TX、戊硝酚(1094)+TX、地乐酚(1095)+TX、呋虫胺(271)+TX、苯虫醚(1099)+TX、蔬果磷(1100)+TX、二氧威(1101)+TX、敌杀磷(1102)+TX、乙拌磷(278)+TX、dithicrofos(1108)+TX、DNOC(282)+TX、多拉克汀(别名)[CCN]+TX、DSP(1115)+TX、脱皮甾酮(别名)[CCN]+TX、EI1642(研究代码)(1118)+TX、依马克丁(291)+TX、依马克丁苯甲酸盐(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、etaphos(别名)[CCN]+TX、乙硫苯威(308)+TX、乙硫磷(309)+TX、乙虫腈(310)+TX、益硫磷(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、依芬普司(319)+TX、乙嘧硫磷(1142)+TX、EXD(1143)+TX、伐灭磷(323)+TX、克线磷(326)+TX、抗螨唑(1147)+TX、皮蝇磷(1148)+TX、双乙威(1149)+TX、五氟苯菊酯(1150)+TX、杀螟硫磷(335)+TX、仲丁威(336)+TX、fenoxacrim(1153)+TX、苯氧威(340)+TX、吡氯氰菊酯(1155)+TX、甲氰菊酯(342)+TX、fenpyrad(别名)+TX、丰索磷(1158)+TX、倍硫磷(346)+TX、乙基倍硫磷[CCN]+TX、氰戊菊酯(349)+TX、氟虫腈(354)+TX、氟啶虫酰胺(358)+TX、氟虫双酰胺(CAS注册号:272451-65-7)+TX、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、FMC1137(研究代码)(1185)+TX、地虫硫磷(1191)+TX、伐虫脒(405)+TX、伐虫脒盐酸盐(405)+TX、安果(1192)+TX、胺甲威(1193)+TX、丁苯硫磷(1194)+TX、福司吡酯(1195)+TX、噻唑膦(408)+TX、丁环硫磷(1196)+TX、呋线威(412)+TX、抗虫菊(1200)+TX、γ-三氟氯氰菊酯(197)+TX、γ-HCH(430)+TX、双胍盐(422)+TX、双胍醋酸盐(422)+TX、GY-81(研究代码)(423)+TX、苄螨醚(424)+TX、氯虫酰肼(425)+TX、HCH(430)+TX、HEOD(1070)+TX、七氯(1211)+TX、庚烯磷(432)+TX、速杀硫磷[CCN]+TX、氟铃脲(439)+TX、HHDN(864)+TX、氟蚁腙(443)+TX、氰化氢(444)+TX、烯虫乙酯(445)+TX、hyquincarb(1223)+TX、吡虫啉(458)+TX、炔咪菊酯(460)+TX、茚虫威(465)+TX、碘甲烷(IUPAC名称)(542)+TX、IPSP(1229)+TX、氯唑磷(1231)+TX、碳氯灵(1232)+TX、水胺硫磷(别名)(473)+TX、异艾氏剂(1235)+TX、异柳磷(1236)+TX、移栽灵(1237)+TX、异丙威(472)+TX、异丙基O-(甲氧基氨基硫磷酰)水杨酸酯(IUPAC名称)(473)+TX、稻瘟灵(474)+TX、异拌磷(1244)+TX、异恶唑硫磷(480)+TX、伊维菌素(别名)[CCN]+TX、茉莉菊酯I(696)+TX、茉莉菊酯II(696)+TX、碘硫磷(1248)+TX、保幼激素I(别名)[CCN]+TX、保幼激素II(别名)[CCN]+TX、保幼激素III(别名)[CCN]+TX、克来范(1249)+TX、烯虫炔酯(484)+TX、λ-三氟氯氰菊酯(198)+TX、砷酸铅[CCN]+TX、雷皮菌素(CCN)+TX、溴苯磷(1250)+TX、林旦(430)+TX、lirimfos(1251)+TX、虱螨脲(490)+TX、噻唑磷(1253)+TX、间位异丙苯基-甲基氨基甲酸酯(IUPAC名称)(1014)+TX、磷化镁(IUPAC名称)(640)+TX、马拉松(492)+TX、丙螨氰(1254)+TX、叠氮磷(1255)+TX、灭蚜磷(502)+TX、甲基减蚜磷(1258)+TX、灭蚜松(1260)+TX、地胺磷(1261)+TX、氯化亚汞(513)+TX、mesulfenfos(1263)+TX、氰氟虫腙(CCN)+TX、威百亩(519)+TX、威百亩-钾(别名)(519)+TX、威百亩-钠(519)+TX、虫螨畏(1266)+TX、甲胺磷(527)+TX、甲磺酰氟(IUPAC/化学文摘名称)(1268)+TX、杀扑磷(529)+TX、灭虫威(530)+TX、杀虫乙烯磷(1273)+TX、灭多威(531)+TX、甲氧普林(532)+TX、methoquin-butyl(1276)+TX、甲醚菊酯(别名)(533)+TX、甲氧氯(534)+TX、甲氧虫酰肼(535)+TX、甲基溴(537)+TX、异硫氰酸甲酯(543)+TX、甲基氯仿(别名)[CCN]+TX、二氯甲烷[CCN]+TX、甲氧苄氟菊酯[CCN]+TX、速灭威(550)+TX、恶虫酮(1288)+TX、速灭磷(556)+TX、自克威(1290)+TX、密灭汀(557)+TX、米尔倍霉素(别名)[CCN]+TX、丙胺氟(1293)+TX、灭蚁灵(1294)+TX、久效磷(561)+TX、茂果(1300)+TX、莫昔克丁(别名)[CCN]+TX、萘肽磷(别名)[CCN]+TX、二溴磷(567)+TX、萘(IUPAC/化学文摘名称)(1303)+TX、NC-170(研究代码)(1306)+TX、NC-184(化合物代码)+TX、烟碱(578)+TX、硫酸烟碱(578)+TX、氟蚁灵(1309)+TX、烯啶虫胺(579)+TX、硝乙脲噻唑(1311)+TX、戊氰威(1313)+TX、戊氰威1:1氯化锌复合物(1313)+TX、NNI-0101(化合物代码)+TX、NNI-0250(化合物代码)+TX、去甲烟碱(传统名称)(1319)+TX、双苯氟脲(585)+TX、多氟脲(586)+TX、O-5-二氯-4-碘苯基O-甲基-乙基硫代膦酸酯(IUPAC名称)(1057)+TX、O,O-二甲基O-4-甲基-2-氧代-2H-色烯-7-基硫代磷酸酯(IUPAC名称)(1074)+TX、O,O-二乙基O-6-甲基-2-丙基嘧啶-4-基硫代磷酸酯(IUPAC名称)(1075)+TX、O,O,O’,O’-四丙基二硫代焦磷酸酯(IUPAC名称)(1424)+TX、油酸(IUPAC名称)(593)+TX、氧化乐果(594)+TX、杀线威(602)+TX、亚砜磷(609)+TX、异亚砜磷(1324)+TX、砜拌磷(1325)+TX、pp’-DDT(219)+TX、对位-二氯苯[CCN]+TX、对硫磷(615)+TX、甲基对硫磷(616)+TX、氟幼脲(别名)[CCN]+TX、五氯苯酚(623)+TX、月桂酸五氯苯酯(IUPAC名称)(623)+TX、苄氯菊酯(626)+TX、石油(别名)(628)+TX、PH60-38(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、甲基辛硫磷(1340)+TX、pirimetaphos(1344)+TX、抗蚜威(651)+TX、乙基嘧啶磷(1345)+TX、甲基嘧啶磷(652)+TX、多氯二环戊二烯异构体(IUPAC名称)(1346)+TX、多氯萜烯(传统名称)(1347)+TX、亚砷酸钾[CCN]+TX、硫氰酸钾[CCN]+TX、炔丙菊酯(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、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[CCN]+TX、吡蚜酮(688)+TX、吡唑硫磷(689)+TX、吡菌磷(693)+TX、pyresmethrin(1367)+TX、除虫菊酯I(696)+TX、除虫菊酯II(696)+TX、多种除虫菊酯(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、苦木素(别名)[CCN]+TX、喹硫磷(quinalphos)(711)+TX、甲基喹硫磷(quinalphos)(1376)+TX、quinothion(1380)+TX、喹硫磷(quintiofos)(1381)+TX、R-1492(研究代码)(1382)+TX、雷复尼特(别名)[CCN]+TX、苄呋菊脂(719)+TX、鱼藤酮(722)+TX、RU15525(研究代码)(723)+TX、RU25475(研究代码)(1386)+TX、鱼尼丁(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、克线丹(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、spirotetrmat(CCN)+TX、sulcofuron(746)+TX、sulcofuron钠(746)+TX、氟虫胺(750)+TX、治螟磷(753)+TX、硫酰氟(756)+TX、硫丙磷(1408)+TX、焦油(别名)(758)+TX、σ-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(别名)+TX、特丁磷(773)+TX、四氯乙烷[CCN]+TX、杀虫畏(777)+TX、胺菊酯(787)+TX、θ-氯氰菊酯(204)+TX、噻虫啉(791)+TX、thiafenox(别名)+TX、噻虫嗪(792)+TX、thicrofos(1428)+TX、抗虫威(1431)+TX、杀虫环(798)+TX、杀虫环氢草酸(798)+TX、硫双威(799)+TX、久效威(800)+TX、甲基乙拌磷(801)+TX、硫磷嗪(1434)+TX、thiosultap(803)+TX、杀虫双(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(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、异皮蝇磷(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、蚜灭多(847)+TX、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、zetamethrin(别名)+TX、磷化锌(640)+TX、zolaprofos(1469)和ZXI8901(研究代码)(858)+TX、溴氰虫酰胺[736994-63-19]+TX、氯虫苯甲酰胺[500008-45-7]+TX、腈吡螨酯[560121-52-0]+TX、丁氟螨酯[400882-07-7]+TX、pyrifluquinazon[337458-27-2]+TX、乙基多杀菌素[187166-40-1+187166-15-0]+TX、螺虫乙酯[203313-25-1]+TX、砜虫啶[946578-00-3]+TX、丁烯氟虫腈[704886-18-0]+TX、氯氟醚菊酯[915288-13-0]+TX、四氟醚菊酯[84937-88-2]+TX,
一种杀软体动物剂,该杀软体动物剂选自由以下物质组成的组: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、氯硝柳胺乙醇胺盐(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、杀螺吗啉(trifenmorph)(1454)+TX、混杀威(trimethacarb)(840)+TX、乙酸三苯基锡(IUPAC名称)(347)和三苯基氢氧化锡(IUPAC名称)(347)+TX、皮瑞普(pyriprole)[394730-71-3]+TX,
一种杀线虫剂,该杀线虫剂选自由以下物质组成的组:AKD-3088(化合物代码)+TX、1,2-二溴-3-氯丙烷(IUPAC/化学文摘名)(1045)+TX、1,2-二氯丙烷(IUPAC/化学文摘名)(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)(1065)+TX、3-(4-氯苯基)-5-甲基绕丹宁(IUPAC名称)(980)+TX、5-甲基-6-硫代-1,3,5-噻二嗪烷-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(aldoxycarb)(863)+TX、AZ 60541(化合物代码)+TX、benclothiaz[CCN]+TX、苯茵灵(62)+TX、丁基哒螨酮(butylpyridaben)(别名)+TX、硫线磷(cadusafos)(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(cloethocarb)(999)+TX、细胞分裂素(cytokinins)(别名)(210)+TX,棉隆(216)+TX、DBCP(1045)+TX、DCIP(218)+TX、除线特(diamidafos)(1044)+TX、除线磷(dichlofenthion)(1051)+TX、二克磷(dicliphos)(别名)+TX、乐果(262)+TX、依马克丁(别名)[CCN]+TX、苯甲酸依马克丁(291)+TX、依立诺克丁(291)+TX、(别名)[CCN]+TX、灭线磷(312)+TX、二溴乙烷(316)+TX、苯线磷(fenamiphos)(326)+TX、吡螨胺(别名)+TX、丰索磷(fenpyrad)(1158)+TX、噻唑磷(fosthiazate)(408)+TX、丁硫环磷(fosthietan)(1196)+TX、糠醛(别名)[CCN]+TX、GY-81(研究代码)(423)+TX、速杀硫磷(heterophos)[CCN]+TX、碘甲烷(IUPAC名称)(542)+TX、isamidofos(1230)+TX、氯唑磷(isazofos)(1231)+TX、激动素(kinetin)(别名)[CCN]+TX、糠氨基嘌呤(mecarphon)(别名)(210)+TX、甲基灭蚜磷(mecarphon)(1258)+TX、威百亩(519)+TX、威百亩钾盐(别名)(519)+TX、威百亩钠盐(519)+TX、甲基溴(537)+TX、异硫氰酸甲酯(543)+TX、杀螨菌素肟(milbemycin oxime)(别名)[CCN]+TX、莫昔克丁(别名)[CCN]+TX、疣孢漆斑茵(Myrothecium verrucaria)组分(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(phosphocarb)[CCN]+TX、硫线磷(sebufos)(别名)+TX、塞拉菌素(selamectin)(别名)[CCN]+TX、多杀菌素(737)+TX、叔丁威(terbam)(别名)+TX、特丁磷(terbufos)(773)+TX、四氯噻吩(IUPAC/化学文摘名)(1422)+TX、thiafenox(别名)+TX、虫线磷(thionazin)(1434)+TX、三唑磷(triazophos)(820)+TX、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、fluensulfone[318290-98-1]+TX,
一种硝化作用抑制剂,该硝化作用抑制剂选自由以下物质组成的组:乙基黄原酸钾[CCN]以及氯啶(nitrapyrin)(580)+TX,
一种植物激活剂,该植物激活剂选自由以下物质组成的组:噻二唑素(acibenzolar)(6)+TX、噻二唑素-S-甲基(6)+TX、烯丙苯噻唑(probenazole)(658)和大虎杖(Reynoutria sachalinensis)提取物(别名)(720)+TX,
一种杀鼠剂,该杀鼠剂选自由以下物质组成的组: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、氮醛糖(127)+TX、氯鼠酮(140)+TX、维生素D3(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、敌鼠钠(273)+TX、维生素D2(301)+TX、氟鼠灵(357)+TX、氟乙酰胺(379)+TX、鼠朴定(1183)+TX、盐酸鼠朴定(1183)+TX、γ-HCH(430)+TX、HCH(430)+TX、氢氰酸(444)+TX、碘甲烷(IUPAC名称)(542)+TX、林旦(430)+TX、磷化镁(IUPAC名称)(640)+TX、甲基溴(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,
一种增效剂,该增效剂选自由以下物质组成的组:2-(2-丁氧基乙氧基)乙基胡椒基酯(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,
一种动物驱避剂,该动物驱避剂选自由以下物质组成的组: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、双胍盐(guazatine)(422)+TX、双胍醋酸盐(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,
一种杀病毒剂,该杀病毒剂选自由以下物质组成的组:衣马宁(imanin)(替代名称)[CCN]和利巴韦林(替代名称)[CCN]+TX,
一种创伤保护剂,该创伤保护剂选自由以下物质组成的组:氧化汞(512)+TX、辛噻酮(octhilinone)(590)和甲基硫茵灵(802)+TX,
以及生物活性的化合物,这些化合物选自以下物质组成的组: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、氟硅唑[35554-44-0]+TX、酰胺唑[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[88283-41-4]+TX、丙氯灵[67747-09-5]+TX、丙环唑[60207-90-1]+TX、硅氟唑[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、三唑醇[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、氟苯嘧啶醇[63284-71-9]+TX、乙嘧酚磺酸酯[41483-43-6]+TX、甲菌定[5221-53-4]+TX、乙嘧酚[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[53112-28-0]+TX、拌种咯[74738-17-3]+TX、咯菌腈[131341-86-1]+TX、苯霜灵[71626-11-4]+TX、呋霜灵[57646-30-7]+TX、甲霜灵[57837-19-1]+TX、Rmetalaxyl[70630-17-0]+TX、呋酰胺[58810-48-3]+TX、恶霜灵[77732-09-3]+TX、苯菌灵[17804-35-2]+TX、多菌灵[10605-21-7]+TX、乙氧咪[62732-91-6]+TX、麦穗宁[3878-19-1]+TX、噻苯达唑[148-79-8]+TX、乙菌利[84332-86-5]+TX、菌核利[24201-58-9]+TX、异菌脲[36734-19-7]+TX、myclozoline[54864-61-8]+TX、腐霉利[32809-16-8]+TX、乙烯菌核利[50471-44-8]+TX、啶酰菌胺[188425-85-6]+TX、萎锈灵[5234-68-4]+TX、甲呋酰胺[24691-80-3]+TX、氟酰胺[66332-96-5]+TX、灭锈胺[55814-41-0]+TX、氧化萎锈灵[5259-88-1]+TX、吡噻菌胺[183675-82-3]+TX、噻氟菌胺[130000-40-7]+TX、双胍盐[108173-90-6]+TX、多果定[2439-10-3][112-65-2](游离碱)+TX、双胍盐[13516-27-3]+TX、嘧菌酯[131860-33-8]+TX、醚菌胺[149961-52-4]+TX、烯肟菌酯{国际会议进展(Proc.BCPC,Int.Congr.),格拉斯哥,2003,1,93}+TX、氟嘧菌酯[361377-29-9]+TX、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、甲基代森锌[12071-83-9]+TX、福美双[137-26-8]+TX、代森锌[12122-67-7]+TX、福美锌[137-30-4]+TX、敌菌丹[2425-06-1]+TX、克菌丹[133-06-2]+TX、抑菌灵[1085-98-9]+TX、氟里醚[41205-21-4]+TX、灭菌丹[133-07-3]+TX、对甲抑菌灵[731-27-1]+TX、波尔多混合剂[8011-63-0]+TX、氢氧化铜[20427-59-2]+TX、氯氧化铜[1332-40-7]+TX、硫酸铜[7758-98-7]+TX、氧化铜[1317-39-1]+TX、代森锰铜[53988-93-5]+TX、喹啉铜[10380-28-6]+TX、消螨普[131-72-6]+TX、异丙消[10552-74-6]+TX、克瘟散[17109-49-8]+TX、异稻瘟净[26087-47-8]+TX、稻瘟灵[50512-35-1]+TX、氯瘟磷[36519-00-3]+TX、吡菌磷[13457-18-6]+TX、甲基立枯磷[57018-04-9]+TX、苯并噻二唑[135158-54-2]+TX、防霉灵[101-05-3]+TX、苯噻菌胺[413615-35-7]+TX、灭瘟素[2079-00-7]+TX、灭螨猛[2439-01-2]+TX、地茂散[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[117-80-6]+TX、双氯氰菌胺[139920-32-4]+TX、哒菌酮[62865-36-5]+TX、氯硝胺[99-30-9]+TX、乙霉威[87130-20-9]+TX、烯酰吗啉[110488-70-5]+TX、SYPLI90(氟吗啉)[211867-47-9]+TX、二噻农[3347-22-6]+TX、噻唑菌胺[162650-77-3]+TX、土菌灵[2593-15-9]+TX、恶唑菌酮[131807-57-3]+TX、咪唑菌酮[161326-34-7]+TX、氰菌胺[115852-48-7]+TX、三苯锡[668-34-8]+TX、嘧菌腙[89269-64-7]+TX、氟啶胺[79622-59-6]+TX、氟吡菌胺[239110-15-7]+TX、磺菌胺[106917-52-6]+TX、环酰菌胺[126833-17-8]+TX、三乙膦酸铝[39148-24-8]+TX、恶霉灵[10004-44-1]+TX、异丙菌胺[140923-17-7]+TX、IKF916(氰霜唑)[120116-88-3]+TX、春雷霉素[6980-18-3]+TX、磺菌威[66952-49-6]+TX、苯菌酮[220899-03-6]+TX、戊菌隆[66063-05-6]+TX、四氯苯酞[27355-22-2]+TX、多种多氧菌素[11113-80-7]+TX、烯丙苯噻唑[27605-76-1]+TX、霜霉威[25606-41-1]+TX、丙氧喹啉[189278-12-4]+TX、咯喹酮[57369-32-1]+TX、喹氧灵[124495-18-7]+TX、五氯硝基苯[82-68-8]+TX、硫磺[7704-34-9]+TX、噻酰菌胺[223580-51-6]+TX、咪唑嗪[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(RH7281)[156052-68-5]+TX、双炔酰菌胺[374726-62-2]+TX、吡唑萘菌胺[881685-58-1]+TX、氟唑环菌胺[874967-67-6]+TX、3-二氟甲基-1-甲基-1H-吡唑-4-羧酸(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)+TX、3-二氟甲基-1-甲基-1H-吡唑-4-羧酸[2-(2,4-二氯苯基)-2-甲氧基-1-甲基-乙基]-酰胺(披露于WO 2008/148570)+TX、1-[4-[4-[(5S)5-(2,6-二氟苯基)-4,5-二氢-1,2-噁唑-3-基]-1,3-噻唑-2-基]哌啶-1-基]-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮+TX、1-[4-[4-[5-(2,6-二氟苯基)-4,5-二氢-1,2-噁唑-3-基]-1,3-噻唑-2-基]哌啶-1-基]-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮[1003318-67-9],都披露于(WO 2010/123791、WO 2008/013925、WO 2008/013622和WO 2011/051243,20页)+TX、3-二氟甲基-1-甲基-1H-吡唑-4-羧酸(3’,4’,5’-三氟-联苯-2-基)-酰胺(披露于WO2006/087343)+TX、以及1-甲基-2-(2,4,5-三氯-噻吩-3-基)-乙基]+TX。
活性成分后的方括号中的参考文献,例如[3878-19-1]是指化学文摘注册号。以上描述的混合配对物是已知的。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13版;编著:C.D.S.汤姆林(TomLin);英国农作物保护委员会(The Pesticide Manual-AWorld Compendium;Thirteenth Edition;Editor:C.D.S.TomLin;The British CropProtection Council)]中时,它们在上文对于特定化合物在圆括号内给定的条目编号之下描述于该手册中;例如,化合物“阿维菌素”在条目编号(1)之下描述。当以上对具体的化合物加入“[CCN]”时,所讨论的化合物包括在“杀有害生物剂通用名纲要(Compendium ofPesticide Common Names)”中,该纲要在互联网上可得:[A.伍德(Wood);杀有害生物剂通用名纲要(Compendium of Pesticide Common Names),版权1995-2004];例如化合物“乙酰虫腈”在互联网址http://www.alanwood.net/pesticides/acetoprole.html下进行了描述。
上述的活性成分中大部分在上文是通过所谓的“通用名”、相关的“ISO通用名”或在个别情况下使用的另一个“通用名”来提及。如果其名称不是“通用名”,则对于特定化合物在圆括号内给出了作为代替而使用的该名称的性质;在这种情况下,使用IUPAC名称、IUPAC/化学文摘名称、“化学名称”、“传统名称”、“化合物名称”、或“研究代码”,或者如果既没有使用这些名称之一,也没有使用“通用名”,则使用的是“替代名称”。“CAS注册号”意指化学文摘注册号。
选自表P的具有化学式I的化合物与以上描述的活性成分的混合物包括选自表1(化合物1.1至1.112)的一种特定化合物,或选自表2(化合物2.1至2.112)的一种特定化合物,或选自表A(化合物1至5)的一种特定化合物和一种以上描述的活性成分,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,尤其优选项是从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,尤其是处于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。那些混合比率被理解为包括,一方面是重量比,并且还有另一方面是摩尔比。
以上描述的混合物可以被用于控制有害生物的方法中,该方法包括将一种含如上描述的混合物的组合物施用于有害生物或其环境中,除了一种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。
包含本发明的具有化学式(I)的一种化合物或选自表1(化合物1.1至1.112)的一种特定化合物,或选自表2(化合物2.1至2.112)的一种特定化合物,或选自表A(化合物1至5)的一种特定化合物以及一种或多种如以上描述的活性成分的混合物可以例如以一种单一的“掺水即用”的形式施用,以组合的喷洒混合物(该混合物由这些单一活性成分的单独配制品构成)(例如一种“桶混制剂”(tank-mix))施用,并且当以一种顺序的方式(即,一个在另一个适当短的时期之后,例如几小时或几天)施用时组合使用这些单独活性成分来施用。具有化学式I的化合物或选自表1(化合物1.1至1.112)的一种特定化合物,或选自表2(化合物2.1至2.112)的一种特定化合物,或选自表A(化合物1至5)的一种特定化合物以及如以上描述的活性成分的施用的顺序对于实施本发明并不是至关重要的。
这些组合物还可以包含其他固体或液体助剂,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一种本身已知的方式,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;和在至少一种助剂存在下,例如通过紧密混合活性成分与一种或一些助剂和/或与一种或一些助剂一起研磨活性成分来制备。用于制备这些组合物的这些工艺和化合物I用于制备这些组合物的用途也是本发明的主题。
组合物的施用方法、也就是说控制以上提及的类型的有害生物的方法,例如喷洒、雾化、喷粉、涂刷、敷料、散射或浇注,选择这些方式以适合当时环境的既定目标;以及这些组合物用于控制以上提及的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,优选地在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1到2000g活性成分,尤其是10到1000g/ha,优选地10到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(叶施药),可能的是选择施用的频率和比率以符合所提及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,这是通过用一种液体组合物将这些植物的所在地浸透或者通过将固体形式的活性成分引入植物的所在地(例如引入土壤,例如以颗粒(土施)的形式)来实现的。在水稻作物的情况下,这样的颗粒剂可以被计量加入淹水的稻田中。
根据本发明的这些组合物还适于保护植物繁殖材料(例如种子,如果实、块茎或籽粒,或者苗圃植物)对抗上述类型的有害生物。该繁殖材料可以用这些组合物在种植前处理,例如种子可以在播种前处理。可替代地,这些组合物可以施用到种子仁(涂布),或者通过在液体组合物中浸泡这些仁或者通过涂一层固体组合物。当该繁殖材料被种植在施用地点时,还可能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因此处理的植物繁殖材料是本发明另外的主题。
根据本发明的具有化学式(I)的化合物也可以与安全剂组合使用。优选地,在这些混合物中,具有化学式(I)的化合物或选自表1(化合物1.1至1.112)的一种特定化合物,或选自表2(化合物2.1至2.112)的一种特定化合物,或选自表A(化合物1至5)的一种特定化合物。尤其考虑以下与安全剂的混合物:
具有化学式(I)的化合物+解毒喹(cloquintocet-mexyl)、具有化学式(I)的化合物+解毒喹酸(cloquintocet acid)和它的盐类、具有化学式(I)的化合物+解草唑(fenchlorazole-ethyl)、具有化学式(I)的化合物+解草唑酸(fenchlorazole acid)和它的盐类、具有化学式(I)的化合物+吡唑解草酯(mefenpyr-diethyl)、具有化学式(I)的化合物+吡唑解草酯二酸(mefenpyr diacid)、具有化学式(I)的化合物+双苯恶唑酸-乙基(isoxadifen-ethyl)、具有化学式(I)的化合物+双苯恶唑酸(isoxadifen acid)、具有化学式(I)的化合物+解草恶唑、具有化学式(I)的化合物+解草恶唑R异构体、具有化学式(I)的化合物+解草酮、具有化学式(I)的化合物+二氯丙烯胺、具有化学式(I)的化合物+AD-67、具有化学式(I)的化合物+解草腈、具有化学式(I)的化合物+解草胺腈、具有化学式(I)的化合物+解草胺腈Z-异构体、具有化学式(I)的化合物+解草啶、具有化学式(I)的化合物+环丙磺酰胺、具有化学式(I)的化合物+萘二甲酸酐、具有化学式(I)的化合物+解草安、具有化学式(I)的化合物+N-(2-甲氧基苯甲酰基)-4-[(甲基氨基羰基)氨基]苯磺酰胺、具有化学式(I)的化合物+CL 304,415、具有化学式(I)的化合物+dicyclonon、具有化学式(I)的化合物+肟草安、具有化学式(I)的化合物+DKA-24、具有化学式(I)的化合物+R-29148、以及化学式(I)的化合物+PPG-1292。对于具有化学式(I)的化合物+杀草隆,具有化学式(I)的化合物+MCPA,具有化学式(I)的化合物+二甲四氯丙酸以及具有化学式(I)的化合物+精二甲四氯丙酸的混合物,也可以观察到安全效果。
TX的这些混合配伍物也可以是酯类或盐类的形式,例如,在农药手册,第12版(BCPC),2000(The Pesticide Manual,12th Edition(BCPC),2000)中所提及的。
在以上待与TX混合的活性成分的不同清单中,具有化学式I的化合物优选是选自表1(化合物1.1至1.112)的一种特定化合物,或选自表2(化合物2.1至2.112)的一种特定化合物,或选自表A(化合物1至5)的一种特定化合物。
具有化学式I的化合物,特别是选自表1(化合物1.1至1.112)的一种特定化合物,或选自表2(化合物2.1至2.112)的一种特定化合物,或选自表A(化合物1至5)的一种特定化合物与其他杀虫剂、杀真菌剂、除草剂、安全剂、佐剂等的上述混合物中,混合比率可以在一个大的范围上变动,并且优选地是
100:1至1:6000、尤其是50:1至1:50、更尤其是20:1至1:20、甚至更尤其是10:1至1:10。那些混合比率被理解为包括,一方面是重量比,并且还有另一方面是摩尔比。
这些混合物可有利地用于上述配制品中,(其中“活性成分”涉及TX与对应的各混合配伍物的混合物)。
一些混合物可以包含具有显著不同的物理、化学或生物特性的活性成分以使得的其本身不易于适合相同的常规配制品类型。在这些情况下,可以制备其他的配制品类型。举例来说,当一种活性成分是水不溶性固体并且另一种是水不溶性液体时,仍然有可能通过以悬浮液形式分散固体活性成分(使用类似于SC的配制品的配制品)但以乳液形式分散液体活性成分(使用类似于EW的配制品的配制品)而将每一活性成分分散在同一连续水相中。所得组合物是一种悬乳剂(SE)配制品。
包含TX、选自表1(化合物1.1至1.112)的一种特定化合物,或选自表2(化合物2.1至2.112)的一种特定化合物,或选自表A(化合物1至5)的一种特定化合物以及一种或多种如以上描述的活性成分的混合物可以例如以一种单一的“掺水即用”的形式施用,以组合的喷洒混合物(该混合物由这些单一活性成分的单独配制品构成)(例如一种“桶混制剂”(tank-mix))施用,并且当以一种顺序的方式(即,一个在另一个适当短的时期之后,例如几小时或几天)施用时组合使用这些单独活性成分来施用。具有化学式I的化合物或选自表1(化合物1.1至1.112)的一种特定化合物,或选自表2(化合物2.1至2.112)的一种特定化合物,或选自表A(化合物1至5)的一种特定化合物以及如以上描述的活性成分的施用的顺序对于实施本发明并不是至关重要的。
具有化学式(I)的化合物可与土壤、泥煤或其他的生根介质混合用于保护植物抵抗种子生、土生-或叶真菌疾-病。
用于在这些组合物中使用的合适的增效剂的实例包括胡椒基丁醚、增效菊、丙基增效散和十二烷基咪唑。
用以包括在这些组合物中的合适的除草剂和植物生长调节剂将取决于所打算的目的以及所要求的效果。
可被包括的水稻选择性除草剂的实例为敌稗。用于在棉花中使用的植物生长调节剂的实例为PIXTM。
一些混合物可以包含具有显著不同的物理、化学或生物特性的活性成分以使得的其本身不易于适合相同的常规配制品类型。在这些情况下,可以制备其他的配制品类型。举例来说,当一种活性成分是水不溶性固体并且另一种是水不溶性液体时,仍然有可能通过以悬浮液形式分散固体活性成分(使用类似于SC的配制品的配制品)但以乳液形式分散液体活性成分(使用类似于EW的配制品的配制品)而将每一活性成分分散在同一连续水相中。所得组合物是一种悬乳剂(SE)配制品。
以下实例展示但不限制本发明。
制备实例
实例
本部分自始至终使用以下缩写:s=单峰;bs=宽的单峰d=二重峰dd=双二重峰;dt=双三重峰;t=三重峰;tt=三三重峰;q=四重峰,sept=七重峰;m=多重峰;Me=甲基;Et=乙基;Pr=丙基;Bu=丁基;M.p.=熔点。
实例I1.1:N-[2-溴-6-氯-4-(1,1,1,2,3,3,3-七氟-丙-2-基)苯基]-2-氟-3-硝
基-苯甲酰胺
在环境温度下,向2-氟-3-硝基苯甲酸(309g,1.67mol)在二氯乙烷(2090ml)中的悬浮液里添加N,N-二甲基甲酰胺(1.3ml,16.7mmol),随后缓慢添加草酰氯(150ml,1.69mol)。将该反应混合物搅拌并在50℃加热直至一种溶液形成。允许该反应混合物冷却至环境温度然后添加至2-溴-6-氯-4-[1,1,1,2,3,3,3-七氟-丙-2-基]苯胺(描述于WO/10127926中)(125g,334mmol)在二氯乙烷(477ml)中的溶液,随后添加三乙胺(564ml,4.01mol)。将反应混合物在回流下搅拌4小时。通过添加饱和水性碳酸氢钠(500ml)来淬灭该反应。将各层分离并将该有机层用水(500ml)进行洗涤。将这些合并的水层用二氯乙烷(2x500ml)萃取两次。将这些合并的有机萃取物用硫酸钠干燥并进行浓缩。将粗残余物溶解在THF中并添加1N的氢氧化钠(2当量)溶液。将该混合物在室温下进行搅拌直至双酰化产物消失。然后添加乙酸乙酯(1L)和饱和水性碳酸氢钠(1L)。将各层分离并且将该水层用乙酸乙酯(4x250ml)进行萃取。将该有机层浓缩,通过硅胶过滤,并再次浓缩。将该残余物(181g)直接用在下一步骤中。
1H NMR(CDCl3,400MHz):8.39(m,1H),8.21(m,1H),8.09(d,1H),7.78(s,1H),7.67(s,1H),7.43(t,1H)。
制备实例
实例
本部分自始至终使用以下缩写:s=单峰;bs=宽的单峰d=二重峰dd=双二重峰;dt=双三重峰;t=三重峰;tt=三三重峰;q=四重峰,sept=七重峰;m=多重峰;Me=甲基;Et=乙基;Pr=丙基;Bu=丁基;M.p.=熔点。
实例I1.1:N-[2-溴-6-氯-4-(1,1,1,2,3,3,3-七氟-丙-2-基)苯基]-2-氟-3-硝
基-苯甲酰胺
在环境温度下,向2-氟-3-硝基苯甲酸(309g,1.67mol)在二氯乙烷(2090ml)中的悬浮液里添加N,N--二甲基甲酰胺(1.3ml,16.7mmol),随后缓慢添加草酰氯(150ml,1.69mol)。将该反应混合物搅拌并在50℃加热直至一种溶液形成。允许该反应混合物冷却至环境温度然后添加至2-溴-6-氯-4-[1,1,1,2,3,3,3-七氟-丙-2-基]苯胺(描述于WO/10127926中)(125g,334mmol)在二氯乙烷(477ml)中的溶液,随后添加三乙胺(564ml,4.01mol)。将反应混合物在回流下搅拌4小时。通过添加饱和水性碳酸氢钠(500ml)来淬灭该反应。将各层分离并将该有机层用水(500ml)进行洗涤。将这些合并的水层用二氯乙烷(2x500ml)萃取两次。将这些合并的有机萃取物用硫酸钠干燥并进行浓缩。将粗残余物溶解在THF中并添加1N的氢氧化钠(2当量)溶液。将该混合物在室温下进行搅拌直至双酰化产物消失。然后添加乙酸乙酯(1L)和饱和水性碳酸氢钠(1L)。将各层分离并且将该水层用乙酸乙酯(4x250ml)进行萃取。将该有机层浓缩,通过硅胶过滤,并再次浓缩。将该残余物(181g)直接用在下一步骤中。
1H NMR(CDCl3,400MHz):8.39(m,1H),8.21(m,1H),8.09(d,1H),7.78(s,1H),7.67(s,1H),7.43(t,1H)。
实例I2.1:3-氨基-N-[2-溴-6-氯-4-(1,2,2,2,3,3,3-七氟-丙-2-基)-苯基]-2-
氟-苯甲酰胺
将N-[2-溴-6-氯-4-(1,2,2,2,3,3,3--七氟-丙-2-基)苯基]-2-氟-3-硝基-苯甲酰胺(实例I1.1)(2g,3.69mmol)溶解在THF(16.6ml)中。然后添加NaOH(9.2ml)、四丁基溴化铵(0.121g,0.369mmol)以及连二亚硫酸钠(2.27g,11.1mmol)。将该混合物在回流下加热1.5小时并且然后冷却至室温。将该反应混合物用乙酸乙酯稀释,添加水并且分离各相。水相用乙酸乙酯萃取两次。将合并的有机相用1N水性HCl洗涤,并且然后用碳酸氢钠水性溶液洗涤,用硫酸钠进行干燥,过滤并浓缩。快速层析法(洗脱液:环己烷/乙酸乙酯从100:0至0:100),给出3-氨基-N-[2-溴-6-氯-4-(1,2,2,2,3,3,3-七氟-丙-2-基)-苯基]-2-氟-苯甲酰胺(1.13g,57.6%的产率)。
1H NMR(400MHz,CDCl3):8.25(d,1H),7.85(s,1H),7.74(s,1H)7.52(td,1H),7.12(t,1H),7.03(td,1H),3.80(bs,2H)ppm。
实例I3.1:N-[2-溴-6-氯-4-(1,1,1,2,3,3,3-七氟-丙-2-基)-苯基]-3-乙氨基-2-氟-苯甲酰胺
将3-氨基-N-[2-溴-6-氯-4-(1,2,2,2,3,3,3-七氟-丙-2-基)-苯基]-2-氟-苯甲酰胺(实例I 2.1)(0.585g,1.14mmol)溶解在甲醇(8.2ml)中,并且添加乙醛(0.065ml,1.14mmol)和乙酸(0.07ml,1.26mmol)。然后添加氰基硼氢化物(0.083g,1.26mmol)。在室温下搅拌该反应混合物1小时。将溶剂蒸发后,添加乙酸乙酯以及水性氢氧化钠溶液(0.1M)。将各层分离并且将该水层用乙酸乙酯萃取两次。将合并的有机层用水洗涤,经硫酸镁干燥,进行过滤并浓缩。将该残余物通过快速层析法(洗脱液:环己烷/乙酸乙酯100:0=>50:50)进行纯化,以给出N-[2-溴-6-氯-4-(1,1,1,2,3,3,3-七氟-丙-2-基)-苯基]-3-乙氨基-2-氟-苯甲酰胺(0.418g,68%)。
1H NMR(400MHz,CDCl3):8.23(d,1H),7.85(s,1H),7.72(s,1H),7.40(td,1H),7.17(t,1H),6.92(td,1H),4.01(bs,1H),3.28(q,2H),1.36(t,3H)ppm。
实例P1.1:N’-[3-[[2-溴-6-氯-4-[1,1,1,2,3,3,3-七氟-丙-2-基]苯基]氨基甲
酰基]-2-氟-苯基]-N-乙基-吡啶-4-甲酰胺(表A的化合物编号1)
将N-[2-溴-6-氯-4-(1,1,1,2,3,3,3-七氟-丙-2-基)-苯基]-3-乙氨基-2-氟-苯甲酰胺(实例I 3.1)(418mg,0.775mmol)溶解在四氢呋喃(4.3ml)中。将吡啶(0.25ml,3.1mmol)以及异烟酰氯盐酸盐(290mg,1.55mol)加入并且将该反应混合物在环境温度下搅拌16小时。将反应混合物倒入水性碳酸氢钠中。水相用乙酸乙酯萃取两次。将这些合并的有机相用硫酸钠进行干燥,过滤并进行浓缩。将该残余物通过硅胶柱层析(洗脱液:乙酸乙酯/环己烷20/80=>0:100)进行纯化。合并这些包含所希望的产物的部分并蒸发溶剂以给出纯的表A的化合物编号1(500mg,定量的)。熔点99℃-101℃。
1H NMR(400MHz,CDCl3):8.51(bs,2H),7.90-8.15(m,2H),7.86(s,1H),7.72(s,1H),7.25-7.62(m,2H),7.20(bs,2H),3.60-4.18(m,2H),1.20-1.40(m,3H)ppm。
实例P1.2:N’-[3-[[2-溴-6-氯-4-[1,1,1,2,3,3,3-七氟-丙-2-基]苯基]氨基甲
酰基]-2-氟-苯基]-N-乙基-1-氧化-吡啶-1-鎓-4-甲酰胺(表A的化合物编号2)
将N’-[3-[[2-溴-6-氯-4-[1,1,1,2,3,3,3-七氟-丙-2-基]苯基]氨基甲酰基]-2-氟-苯基]-N-乙基-吡啶-4-甲酰胺(实例P1.1;表A的化合物编号1)(0.320g,0.496mmol)溶解在二氯甲烷(3ml)中,添加3-氯过氧苯甲酸(0.245g,0.993mmol)。在室温下搅拌1h后,将该混合物用水以及碳酸氢钠的水溶液稀释。分离各相,并且将水相用二氯甲烷萃取。将合并的有机相在硫酸镁上干燥、将其过滤并进行浓缩。将该残余物在硅胶上通过柱层析法(洗脱液:DCM/MeOH从100:0至85:15)进行纯化,以给出纯的表A的化合物编号2(304mg,93%的产率)。熔点115℃-117℃。1H NMR(400MHz,CDCl3):8.00-8.18(m,4H),7.84(s,1H),7.72(s,1H),7.40-7.52(m,1H)7.32-7.40(m,1H),7.19-7.30(m,2H),3.87-4.15(m,2H),1.28(t,3H)ppm。
LC-MS方法:ZCQ12、ZCQ13和OA_标准
来自沃特斯的ZQ质谱仪(单四极杆质谱仪)
仪器参数:
电离法:电喷射
极性:正离子和负离子
毛细管:3.00kV
锥孔:30V
提取器:2.00V
源温度:150℃,
去溶剂化温度:350C
锥孔反吹气流:50L/Hr
脱溶剂气流:400L/Hr
质量范围:100Da至900Da
来自沃特斯的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:沃特斯公司(Waters)UPLC HSS T3,1.8μm,30x2.1mm,
温度(℃)
DAD波长范围(nm):210到500
溶剂梯度:
A=H2O+5%MeOH+0.05%HCOOH
B=乙腈+0.05%HCOOH
LC-MS方法:ZDQ11
来自沃特斯的ZQ质谱仪(单四极杆质谱仪)
仪器参数:
电离法:电喷射
极性:正离子和负离子
毛细管:3.00kV
锥孔:30V
提取器:2.00V
源温度:150℃,
去溶剂化温度:350C
锥孔反吹气流:50L/Hr
脱溶剂气流:400L/Hr
质量范围:100Da至900Da
来自沃特斯的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:沃特斯公司(Waters)UPLC HSS T3,1.8μm,30x2.1mm,
温度(℃)
DAD波长范围(nm):210到500
溶剂梯度:
A=H2O+5%MeOH+0.05%HCOOH
B=乙腈+0.05%HCOOH
在表A中的化合物以如上文所描述的相同的或者类似的方法进行制备:
表A:
生物学实例
这些实例展示了具有化学式(I)的化合物的杀昆虫和杀螨特性。进行了如下试验:
海灰翅夜蛾(埃及棉树叶虫):
将棉花叶圆片置于24孔微量滴定板中的琼脂上并且以200ppm的施用率用试验溶液进行喷雾。在干燥之后,将叶圆片用5只L1期幼虫进行侵染。在经过处理之后(DAT)3天,针对死亡率、摄食行为和生长调节对样品进行检查。
下列化合物对海灰翅夜蛾给出至少80%的控制:1、2、3、4、6、7、8、9、10、11、12、13、14、15、16、17、18、19。
烟芽夜蛾(烟夜蛾):
将卵(0-24h大)置于具有人工饲料的24孔微量滴定板中并且通过移液管以200ppm(在孔中的浓度为18ppm)施用率用试验溶液进行处理。在孵育时间4天之后,针对卵死亡率、幼虫死亡率和生长调节检查样品。
下列化合物对烟芽夜蛾给出至少80%的控制:1、2、6、7、8、9、10、11、12、13、14、15、16、17。
小菜蛾(Plutella xylostella)(小菜蛾(Diamond back moth)):
对具有人工饲料的24孔微量滴定板(MTP)通过移液管以200ppm(在孔中的浓度为18ppm)的施用率用试验溶液进行处理。在干燥之后,用L2期幼虫对MTP进行侵染(7-12/孔)。在孵育6天时间之后,针对幼虫死亡率、以及生长调节对样品进行检查。
下列化合物给出至少80%小菜蛾的控制:1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19。
黄瓜条叶甲(玉米根虫):
对具有人工饲料的24孔微量滴定板(MTP)通过移液管以200ppm(在孔中的浓度为18ppm)的施用率用试验溶液进行处理。在干燥之后,用L2期幼虫对MTP进行侵染(6-10/孔)。在孵育5天时间之后,针对幼虫死亡率、以及生长调节对样品进行检查。
下列化合物对黄瓜条叶甲给出至少80%的控制:1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19。
烟蓟马(葱蓟马):
将向日葵叶圆片放置于24孔微量滴定板中的琼脂上并且以200ppm的施用率用试验溶液进行喷雾。在干燥之后,将这些叶圆片用混合年龄的蚜虫群体侵染。在孵育7天时间之后,针对死亡率对样品进行检查。
下列化合物给出至少80%烟蓟马的控制:1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19。
二点叶螨(二斑叶螨)
将在24孔微量滴定板中的琼脂上的豆叶圆片以200ppm的施用率用试验溶液进行喷雾。在干燥之后,将这些叶圆片用混合年龄的螨群侵染。8天之后,针对卵死亡率、幼虫死亡率和成虫死亡率对圆片进行检查。
下列化合物给出至少80%二点叶螨的控制:1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19。
桃蚜(绿色桃蚜虫):
将向日葵叶圆片放置于24孔微量滴定板中的琼脂上并且以200ppm的施用率用试验溶液进行喷雾。在干燥之后,将这些叶圆片用混合年龄的蚜虫群体侵染。在孵育6天时间之后,针对死亡率对样品进行检查。
下列化合物对桃蚜给出至少80%的控制:1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19。
Claims (10)
7.一种非治疗目的的控制昆虫、螨、线虫或软体动物的方法,该方法包括向有害生物、有害生物的场所、或易受有害生物攻击的植物施用一种杀昆虫、杀螨、杀线虫、或杀软体动物有效量的、如权利要求1中所定义的具有化学式(I)的化合物。
8.一种杀昆虫、杀螨、杀线虫或杀软体动物的组合物,该组合物包含杀昆虫、杀螨、杀线虫或杀软体动物有效量的如权利要求1所定义的具有化学式(I)的化合物连同一种农业化学上可接受的稀释剂或载体。
9.根据权利要求8所述的组合物,该组合物进一步包括一种或多种其他的杀昆虫、杀螨、杀线虫或杀软体动物的化合物。
10.一种保护有用植物免受昆虫、螨、线虫或软体动物之害的方法,该方法包括向所述植物、其场所、或其植物繁殖材料施用一种杀昆虫、杀螨、杀线虫或杀软体动物有效量的如权利要求1所定义的具有化学式(I)的化合物。
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CN115745878A (zh) * | 2022-12-02 | 2023-03-07 | 青岛科技大学 | 一种含氟吡啶双酰胺类杀虫杀螨剂 |
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JP6505080B2 (ja) | 2019-04-24 |
EP2981523A1 (en) | 2016-02-10 |
WO2014161849A1 (en) | 2014-10-09 |
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