CN1245877C - 用于控制动物害虫的增效农药混合物 - Google Patents
用于控制动物害虫的增效农药混合物 Download PDFInfo
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- CN1245877C CN1245877C CNB028039289A CN02803928A CN1245877C CN 1245877 C CN1245877 C CN 1245877C CN B028039289 A CNB028039289 A CN B028039289A CN 02803928 A CN02803928 A CN 02803928A CN 1245877 C CN1245877 C CN 1245877C
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- 239000011787 zinc oxide Substances 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明涉及增效混合物,其包括一种或多种钠离子通道效应物和化合物(Z)-3-(6-氯-3-吡啶甲基)-1,3-噻唑烷-2-亚基氨腈或化合物(E)-1-(2-氯-1,3-噻唑-5-基甲基)-3-甲基-2-硝基胍或化合物1-[(6-氯-3-吡啶基)甲基]-N-硝基-2-咪唑烷亚胺以及这些混合物防治害虫的用途。
Description
本发明涉及增效混合物,其包括一种或多种钠离子通道效应物和化合物(Z)-3-(6-氯-3-吡啶甲基)-1,3-噻唑烷-2-亚基氨腈或化合物(E)-1-(2-氯-1,3-噻唑-5-基甲基)-3-甲基-2-硝基胍或化合物1-[(6-氯-3-吡啶基)甲基]-N-硝基-2-咪唑烷亚胺以及这些混合物防治害虫的用途。
钠离子通道拮抗剂与选自乙酰胆碱受体调控剂的某些化合物的混合物已为公众所知(WO 00/54591,Research Disclosure May1997,No.39786)。然而,在实际应用中,上述已知混合物并不总能令人满意,原因或者是由于对某些昆虫的杀虫效果不佳或由于所需施用量非常高。
现已发现包括一种或多种钠离子通道效应物和化合物(Z)-3-(6-氯-3-吡啶甲基)-1,3-噻唑烷-2-亚基氨腈(Thiacloprid)或化合物(E)-1-(2-氯-1,3-噻唑-5-基甲基)-3-甲基-2-硝基胍(Chlothianidin)或化合物1-[(6-氯-3-吡啶基)甲基]-N-硝基-2-咪唑烷亚胺(吡虫啉)的混合物具有增效活性并适于防治害虫。由于上述增效作用,可以显著降低活性化合物的用量,即该混合物的活性大于各组分活性。
术语钠离子通道效应物是指可阻止钠离子通过神经细胞的细胞膜运输的化合物。上述化合物以及它们的作用方式已经公开在,例如“Pesticide Biochemistry and Physiology,60:177-185”和“Archives of Insect Biochemistry and Physiology,37:91-103”中。钠离子通道抑制剂已经公开在,例如美国专利US5,543,573;US5,708,170;US5,324,837和US5,462,938中。作为实例,列举下列结构式的化合物:
其中
A代表CR4R5或NR6,
W代表O或S,
X,Y,Z,X’,Y’和Z’各自独立地代表H,卤素,OH,CN,NO2,
代表任选被下列基团一或多取代的C1-C6-烷基:卤素,C1-C3-烷氧基,C1-C3-卤代烷氧基,C3-C6-环烷基,C2-C6-烯氧基或磺酰氧基,
代表任选被下列基团一或多取代的C1-C6-烷氧基:卤素,C1-C3-烷氧基或C3-C6-环烷基,
代表C1-C6-烷氧基羰基,代表C3-C6-环烷基羰氧基,代表任选被下列基团一或多取代的苯基:卤素,C1-C4-烷基或C1-C4-烷氧基,代表任选被C1-C3-烷基一或二取代的氨基羰氧基,
代表C1-C6-烷氧基羰氧基,代表C1-C6-烷基磺酰氧基,代表C2-C6-烯基或代表NR12R13,
m,p和q各自独立地代表1,2,3,4或5,
n代表0,1或2,
r代表1或2,
t代表1,2,3或4,
R,R1,R2,R3,R4和R5各自独立地代表H或C1-C4-烷基,
R6代表H,C1-C6-烷基,C1-C6-卤代烷基,C1-C6-烷氧基烷基,C1-C6-烷氧基,C1-C6-卤代烷氧基,C2-C6-烯基,C2-C6-炔基,C1-C6-烷基羰基,C1-C6-烷氧基羰基,C1-C6-烷硫基或C1-C6-卤代烷硫基,
R7和R8各自独立地代表H,卤素,C1-C6-烷基,C1-C6-烷基羰氧基或代表任选被下列基团一或多取代的苯基:卤素,CN,NO2,C1-C6-烷基,C1-C6-卤代烷基,C1-C6-烷氧基或C1-C6-卤代烷氧基,
R9和R10各自独立地代表H或C1-C4-烷基,
R11代表H,C1-C6-烷基,C1-C6-卤代烷基,C1-C4-烷基羰基,C1-C6-烷氧基羰基或C1-C6-卤代烷氧基羰基,
R12和R13各自独立地代表H或C1-C6-烷基,
G代表H,
代表任选被下列基团一或多取代的C1-C6-烷基:卤素,C1-C4-
烷氧基,C1-C6-卤代烷氧基,CN,NO2,S(O)nR14,COR15,CO2R16,苯基或
C3-C6-环烷基,
代表C1-C6-烷氧基,C1-C6-卤代烷氧基,CN,NO2,
S(O)nR17,COR18,CO2R19,
代表任选被下列基团一或多取代的苯基:卤素,CN,C1-C3-卤代
烷基或C1-C3-卤代烷氧基,
代表C3-C6-环烷基或苯硫基,
Q代表任选被下列基团一或多取代的苯基:卤素,CN,SCN,NO2,S(O)nR20,C1-C4-烷基,C1-C4-卤代烷基,C1-C4-烷氧基烷基,C1-C6-烷氧基,C1-C6-卤代烷氧基或NR21R22,
n代表0,1或2,
R14,R15,R16,R18,R19,R21和R22各自独立地代表H或C1-C6-烷基,
R17和R20各自独立地代表C1-C6-烷基或C1-C6-卤代烷基,
R33代表CO2R34,
R34代表H,C1-C6-烷基,C1-C6-卤代烷基,苯基或卤代苯基以及基团
代表C-N或,特别是,代表C=N。
还优选式(III)钠离子通道效应物,特别是其中
代表C=N的那些化合物。
优选的式(I)化合物,其中
Xm代表4-OCF3或4-SCF3,
Yp代表3-Cl,3-CF3,3-CN,4-Cl,4-CF3或4-CN以及
Zq代表3-Cl,3-CF3,3-CN,4-Cl,4-CF3或4-CN。
可提及下式化合物
优选下述式(II)化合物,其中
Y’p代表4-OCF3或4-SCF3,
X’m代表3-Cl,3-CF3,3-CN,4-Cl,4-CF3或4-CN,
R7代表H和
R8代表被下述基团取代的苯基:3-Cl,3-CF3,3-CN,4-Cl,4-CF3或4-CN。
可提及的下式化合物
优选下述式(III)化合物,其中
Cl代表被4-OCF3或4-SCF3取代的苯基,
G代表H,CO2CH3或CO2C2H5,
R33代表CO2CH3或CO2C2H5和
Z’t代表3-Cl,3-CF3,3-CN,4-Cl,4-CF3或4-CN。
可提及的下式化合物
噁二唑虫
US5,116,850和US5,304,573中还公开了其它钠离子通道抑制剂。作为实例,列出了下述结构式代表的化合物
其中
W代表氧或硫,
X”和Y”各自独立地代表H,CN,SCN,
代表任选被下列基团一或多取代的C1-C6-烷基:卤素,NO2,CN,C1-C4-烷氧基,C1-C4-烷硫基,苯基,卤代苯基,C1-C4-烷基磺酰基或C1-C4-烷氧基羰基,
代表C2-C4-烯基,C2-C4-卤代烯基,C2-C4-炔基,C2-C4-卤代炔基,C3-C6-环烷基,C3-C6-卤代环烷基,
代表任选被下列基团一或多取代的苯基:卤素,CN,NO2,C1-C4-烷基,C1-C4-卤代烷基,C1-C4-烷氧基,C1-C4-卤代烷氧基,C1-C4-烷硫基,C1-C4-烷基磺酰基或C1-C4-卤代烷基磺酰基,
代表含有一或两个杂原子的六元芳环,其中所述杂原子选自由0或1个氧原子,0或1个硫原子和0,1或2个氮原子组成的一组杂原子以及其中该杂芳环通过碳原子连接并且它任选被在X”中提及的基团一或多取代,
Q’代表H,
代表任选被下列基团一或多取代的C1-C6-烷基:卤素,CN,C1-C3-烷氧基,C1-C6-烷氧基羰基或苯基,其中苯基本身还可被下列基团一或多取代:卤素,CN,NO2,C1-C4-烷基,C1-C4-卤代烷基,C1-C4-烷基磺酰基和C1-C4-烷基亚磺酰基,
代表C2-C6-烯基,C2-C6-炔基或
代表C1-C4-烷基羰基,C1-C4-卤代烷基羰基或代表NR28R29,
或
代表含有一个或两个杂原子的五或六元杂芳环(例如吡啶基),其中所述杂原子选自由0或1个氧原子,0或1个硫原子和0,1或2个氮原子组成的一组杂原子以及其中该杂芳环通过碳原子连接并任选被在X”中提及的基团一或多取代,
m代表0,1,2,3,4或5,
G’代表任选被在X”中提及的基团一或多取代的苯基,
代表含有一个或两个杂原子的五或六元杂芳环(例如吡啶基),其中所述杂原子选自由0或1个氧原子,0或1个硫原子和0,1或2个氮原子组成的一组杂原子以及该杂芳环通过碳原子连接并且它任选被在X”中提及的基团一或多取代,
R23,R24,R25,R26,R27,R28和R29各自独立地代表H或C1-C4-烷基和基团,
优选下述式(IV)化合物,其中
X”m代表4-OCF3或4-SCF3,
G’代表被下述基团取代的苯基:3-Cl,3-CF3,3-CN,4-Cl,4-CF3或4-CN和
Q’代表被Cl或CF3取代的杂环,例如4-Cl-2-吡啶基。
作为实例,可提及下列化合物:
优选下述式(V)化合物,其中
Y”m代表4-OCF3或4-SCF3。
作为实例,可提及下列化合物:
其它钠离子通道效应物是二苯甲酮-腙,例如公开在EP-O-0 742202,JP-1000 14 69,WO 96/33 168,WP-O-647 622,WO 97/11 050和WO 97/38 973中。它们包括式(VI)的二苯甲酮-腙
其中
R30代表H,C1-C6-烷基或C1-C6-烷氧基羰基,特别是H或COCH3,
R31代表C1-C6-烷基,特别是甲基或乙基,
R32代表卤素,特别是氯,和
R33代表O-SO2-C1-C6-烷基或O-SO2-C1-C6-卤代烷基,特别是O-SO2CH3或O-SO2-CF3,或
代表CH2-S(O)y-C1-C6-烷基或CH2-S(O)y-C1-C6-卤代烷基,其中
y代表0,1或2,
代表特别是(CH2)S(O)yCH3,CH2-S(O)yC2H5或CH2-S(O)yCH2CF3,特别优选CH2-S-CH3。
特别优选下列化合物:
(Et=乙基)
另一组已知的钠离子通道抑制剂是双-芳基-甲基哌啶,例如公开在WO 95/23507,US 5,569,664,WO 96/36228,WO 97/26252,WO 98/00015,WO 99/14 193和WO 00/01838中。上述抑制剂包括式(VII)化合物
其中
R34代表H或OH,
R35和R36各自独立地代表卤素,C1-C6-卤代烷基,卤代烷硫基或C1-C6-卤代烷氧基,特别是CF3,OCF3和SCF3,
R37代表H,C1-C6-烷基,C1-C6-卤代烷基,C1-C6-烷氧基,C1-C6-卤代烷氧基,C1-C6-烷氧基羰基,NH-CO2-C1-C6-烷基或CH=N-O-C1-C6-烷基,
A代表CH或N和
B代表N或N_-O_。
特别优选下列化合物:
另一组钠离子通道效应物是噁二嗪,其例如公开在WO 96/36618,WO 99/41 245,US 5,536,720和WO 98/33 794中。
它们包括式(VIII)化合物
其中
R38代表H,C1-C6-烷基,C1-C6-烷基羰基或C1-C6-烷基羰氧基,特别是H,
R39代表C1-C6-烷基或C1-C6-烷氧基,
R40代表卤素,C1-C6-卤代烷基,C1-C6-卤代烷氧基或C1-C6-卤代烷硫基,特别是氯,CF3,OCF3或SCF3,和
Ar代表任选被下列基团一或多取代的苯基:卤素,CN,C1-C6-烷基或C1-C6-卤代烷基,特别是代表4-氯苯基,4-氰基苯基,4-三氟甲基苯基,3-氯苯基,3-氰基苯基或3-三氟甲基苯基,或
代表各自带有O,S或N原子的5或6元杂芳基,特别是噻吩基,呋喃基或吡啶基,它们任选被下列基团一或多取代:卤素,CN,C1-C6-烷基或C1-C6-卤代烷基。
作为实例可提及的下列化合物:
除了上述的选自钠离子通道效应物的一种或多种化合物外,本发明混合物中还包括至少一种下列式(IX),(X)和(XI)的化合物
Thiacloprid
Clothianidin
吡虫啉
化合物(IX)是已知的,公开在US 4,849,432中。
化合物(X)是已知的,公开在EP-0-375 907-A1中。
化合物(XI)是已知的,公开在EP-0-192 060中。
混合物中Na离子通道效应物与式(IX)-(XI)化合物的比例(以重量份计)通常为1∶0.1-1∶100,优选1∶1-1∶50。
特别优选本发明混合物中包括下式的活性化合物噁二唑虫
和式(X)的Clothianidin
还特别优选本发明混合物中包括下式的活性化合物噁二唑虫
和式(IX)的Thiacloprid
还特别优选本发明混合物中包括下式的活性化合物噁二唑虫
和式(XI)的吡虫啉
本发明的活性化合物混剂(混合物)适合于防治动物害虫,特别是在农业、林业、储藏产品和材料的保护以及卫生领域中发生的昆虫,螨类和线虫,同时具有很好的植物耐受性以及对温血动物的有利的毒性。它们可优选用作植物保护剂。它们对普通敏感和抗性种类以及对所有或各发育阶段都具有活性。上述害虫包括:
等足目:例如,潮虫(Oniscus asellus)、平甲虫、鼠妇。
倍足目:例如,具斑马陆。
唇足目:例如,食果地蜈蚣、蚰蜒属。
综合目:例如,庭园么蚰。
缨尾目:例如,台湾衣鱼。
弹尾目:例如,武装棘跳虫。
直翅目:例如,家蟋蟀、蝼蛄属、非洲飞蝗、黑蝗属、沙漠蝗。
蜚蠊目:例如,东方蜚蠊、美洲大蠊、马得拉蜚蠊、德国小蠊。
革翅目:例如,欧洲球螋。
等翅目:例如,散白蚁属。
虱目:例如,体虱、血虱属、颚虱属、嚼虱属、畜虱属。
缨翅目:例如,温室条蓟马、烟蓟马、棕榈蓟马、苜蓿蓟马。
异翅亚目:例如,扁盾蝽属、棉红蝽(Dysdercus intermedius)、方背皮蝽、温带臭虫、长红猎蝽、椎猎蝽属。
同翅目:例如,甘蓝粉虱、甘薯粉虱、温室白粉虱、棉蚜、甘蓝蚜、茶隐瘤蚜、豆卫矛蚜、苹果蚜、苹果绵蚜、桃大尾蚜、葡萄根瘤蚜、瘿绵蚜属、麦长管蚜、瘤蚜属、忽布疣蚜、禾谷缢管蚜、绿小叶蝉属、殃叶蝉(Euscelis bilobatus)、黑尾叶蝉、欧果坚球蚧、榄珠蜡蚧、灰飞虱、褐飞虱、红肾圆盾蚧、常春藤圆盾蚧、粉蚧属、木虱属。
鳞翅目:例如,棉红铃虫、松粉蝶尺蛾、果园秋尺蛾、潜叶细蛾(lithocolletis blancardella)、苹果巢蛾、小菜蛾、黄褐天幕毛虫、黄毒蛾、毒蛾属、棉潜蛾(Bucculatrix thurberiella)、柑橘潜叶蛾、地夜蛾属、切夜蛾属、脏切夜蛾、埃及钻夜蛾、实夜蛾属、甘蓝夜蛾、小眼夜蛾、灰翅夜蛾属、粉纹夜蛾、苹果蠹蛾、粉蝶属、禾草螟属、玉米螟、地中海粉斑螟、蜡螟、幕谷蛾、袋谷蛾、褐织蛾、黄尾卷叶蛾、烟卷蛾(Capua reticulana)、云杉色卷蛾、葡萄果蠹蛾、茶长卷蛾、栎绿卷蛾、Cnaphalocerus属、水稻负泥虫。
鞘翅目:例如,家具窃蠹、谷蠹、豆象(Bruchidius obtectus)、菜豆象、北美家天牛、蓝毛臀萤叶甲、马铃薯叶甲、辣根猿叶甲、条叶甲属、油菜金头跳甲、墨西哥豆瓢虫、隐食甲属、锯谷盗、花象属、米象属、葡萄黑耳喙象、香蕉根颈象、种子象、紫苜蓿叶象、皮蠹属、斑皮蠹属、圆皮蠹属、毛皮蠹属、粉蠹属、油菜花露尾甲、蛛甲属、黄蛛甲、麦蛛甲、拟谷盗属、黄粉甲、叩甲属、宽胸叩甲属、五月鳃金龟、马铃薯鳃金龟、褐新西兰肋翅鳃角金龟、稻水象。
膜翅目:例如,松叶蜂属、实叶蜂属、毛蚁属、小家蚁、胡蜂属。
双翅目:例如,伊蚊属、按蚊属、库蚊属、黄猩猩果蝇、家蝇属、厕蝇属、红头丽蝇、绿蝇属、金蝇属、疽蝇属、胃蝇属、虱蝇属、螫蝇属、狂蝇属、皮蝇属、虻属、螗蜩属(Tannia spp.)、花园毛蚊、瑞典麦杆蝇、草种蝇属、菠菜泉蝇、地中海实蝇、油橄榄果实蝇、沼泽大蚊、种蝇属、斑潜蝇属。
蚤目:例如,印鼠客蚤、角叶蚤属。
蛛形纲:例如,蝎(Scorpio maurus)、红斑蛛、粗脚粉螨、锐缘蜱属、纯缘蜱属、鸡皮刺螨、兔瘿螨、柑橘皱叶刺瘿螨、牛蜱属、扇头蜱属、花蜱属、璃眼蜱属、硬蜱属、瘙螨属、痒螨属、疥螨属、跗线螨属、苜蓿苔螨、全爪螨属、叶螨属、半跗线螨属、短须螨属。
植物寄生线虫包括,例如短体线虫属、相似穿孔线虫、起绒草茎线虫、半穿刺线虫、异皮属、球异皮属、根结属、滑刃线虫属、长针线虫属、剑线属、毛刺属、伞滑刃线虫属。
根据本发明,可以处理所有植物和植物各部分。此处植物可以理解为表示所有植物以及植物群落,例如需要和不需要的野生植物或作物(包括自然长出的作物)。作物可以是通过常规育种和优化方法或通过生物技术和遗传工程方法或上述方法的结合获得的植物,包括转基因植物以及包括获得或没有获得植物育种权(Sortenschutzrechte)保护的植物栽培品种。植物的各部分可理解为表示所有地上和地下部分以及植物器官,如茎、叶、花和根,可提及的实例为叶片、针叶、枝条、树干、花、子实体、果实和种子以及根、块茎和根状茎。植物各部分还包括收获的植物和植物营养体以及有性繁殖材料,例如种苗、块茎、根状经、插条和种子。
采用活性化合物混合物进行本发明植物和植物各部分的处理是通过常规处理方法直接施用或作用于它们的环境、生境或贮藏区进行处理,例如通过浸渍、喷雾、熏蒸、弥雾、撒播、刷涂以及在繁殖材料特别是种子的情况下还可以进行一层或多层包衣处理。
本发明活性化合物混合物可被加工成常规制剂,如液剂,乳剂,可湿性粉剂,悬浮剂,粉剂,细粉剂,糊剂,可溶粉剂,颗粒剂,浓悬浮乳剂,用活性化合物浸渍的天然和合成材料,以及聚合物包封的微胶囊。
这些制剂是通过已知方法制备的,例如通过将活性化合物与填充剂,即液体溶剂和/或固体载体混合而生产,制剂中任选加入表面活性剂,即乳化剂和/或分散剂,和/或发泡剂。
使用水作为填充剂的情况下,例如,还可使用有机溶剂作为助溶剂。适当的液体溶剂主要有:芳香烃类,如二甲苯,甲苯或烷基萘,氯代芳烃类和氯代脂肪烃类,如氯苯,二氯乙烷(Chlorethylene)或二氯甲烷,脂肪烃类,如环己烷或链烷烃,例如石油馏份,矿物油和植物油,醇类,如丁醇或乙二醇及其醚和酯,酮类,如丙酮,甲基乙基酮,甲基异丁基酮或环己酮,强极性溶剂,如二甲基甲酰胺和二甲基亚砜,以及水。
适当的固体载体有:
例如铵盐和天然矿物粉末,如高岭土,粘土,滑石,白垩,石英,硅镁土,蒙脱土或硅藻土,和合成矿物粉末,如高分散二氧化硅,氧化铝和硅酸盐;适合颗粒剂的固体载体有:例如,粉碎和分级的天然岩石,如方解石,大理石,浮石,海泡石和白云石,以及无机和有机粉末的合成颗粒,以及有机材料的颗粒,如锯末,坚果壳,玉米穗茎和烟草茎;适当的乳化剂和/或发泡剂有:例如非离子和阴离子乳化剂,如聚氧乙烯脂肪酸酯,聚氧乙烯脂肪醇醚,例如烷芳基聚乙二醇醚,烷基磺酸盐,烷基硫酸盐,芳基磺酸盐以及蛋白水解产物;适合的分散剂有:例如木素亚硫酸废液和甲基纤维素。
制剂中还可使用粘着剂,如羧甲基纤维素和粉末、颗粒或胶乳状天然或合成聚合物,如阿拉伯树胶,聚乙烯醇和聚乙酸乙烯酯,以及天然磷脂,如脑磷脂和卵磷脂,和合成磷脂。其它添加剂可以是矿物油和植物油。
还可以使用着色剂,如无机颜料,例如氧化铁,氧化钛和普鲁士兰,以及有机染料,如茜素染料,偶氮染料和金属酞菁染料,和痕量营养物,如铁、锰、硼、铜、钴、钼和锌的盐。
制剂中通常含有0.1-95%重量,优选0.5-90%重量的活性化合物。
本发明活性化合物还可通过其市售制剂以及由上述制剂制备的、与其它活性化合物制成混合物的应用形式存在,其它活性化合物如杀虫剂、引诱剂、消毒剂、杀细菌剂、杀螨剂、杀线虫剂、杀真菌剂、植物生长调节剂或除草剂。杀虫剂包括,例如磷酸酯、氨基甲酸酯、羧酸酯、卤代烃类、苯基脲类和由微生物制备的物质等。
特别优选的共组分是,例如下述物质:
杀真菌剂:
Aldimorph,氨丙膦酸,氨丙膦酸钾盐,Andoprim,敌菌灵,氧环唑,腈嘧菌酯,
苯霜灵,麦锈灵,苯菌灵,苄烯酸,苄烯酸异丁酯,双丙氨膦,乐杀螨,联苯,联苯三唑醇,灭瘟素,糠菌唑,乙嘧酚磺酸酯,丁硫啶,
石硫合剂,Capsimycin,敌菌丹,克菌丹,多菌灵,萎锈灵,Carvon,灭螨锰,灭瘟唑,苯咪唑菌,地茂散,氯化苦,百菌清,乙菌利,Clozylacon,硫杂灵,霜脲氰,环丙唑醇,嘧菌环胺,酯菌胺,
咪菌威,双氯酚,苄氯三唑醇,Diclofluanid,哒菌酮,氯硝胺,乙霉威,苯醚甲环唑,二甲嘧酚,烯酰吗啉,烯唑醇,烯唑醇-M,敌螨普,二苯胺,吡菌硫,灭菌磷,二氰蒽醌,十二环吗啉,多果定,敌菌酮,
敌瘟磷,氧唑菌,乙环唑,乙嘧酚,土菌灵,
噁唑酮菌,咪菌腈,氯苯嘧啶醇,腈苯唑,呋菌胺,种衣酯,拌种咯,苯锈啶,丁苯吗啉,醋酸三苯锡,羟基三苯锡,福美铁,嘧菌腙,氟啶胺,氟联苯菌,氟氯菌核利,氟喹唑,呋嘧醇,氟硅唑,磺菌胺,氟酰胺,粉唑醇,灭菌丹,三乙膦酸铝,三乙膦酸钠,四氯苯酞,麦穗宁,呋霜灵,呋吡唑灵,灭菌胺,呋菌唑,呋醚唑,拌种胺,
双胍盐,六氯苯,己唑醇,恶霉灵,
抑霉唑,亚胺唑,双胍辛,双八胍盐,双胍辛醋酸盐,Iodocarb,种菌唑,异稻瘟净,异菌脲,Irumamycin,稻瘟灵,氯苯咪菌酮,
春雷霉素,亚胺菌,含铜杀菌剂如:氢氧化铜,环烷酸铜,王铜,硫酸铜,氧化铜,喹啉铜和波尔多液,
代森锰铜,代森锰锌,代森锰,Meferimzone,嘧菌胺,灭锈胺,甲霜灵,叶菌唑,磺菌威,呋菌胺,代森联,苯吡咯菌,噻菌胺,米多霉素,腈菌唑,甲菌利,
福镁镍,异丙消,氟苯嘧啶醇,
呋酰胺,恶霜灵,Oxamocarb,喹菌酮,氧化萎锈灵,Oxyfenthiin,
多效唑,稻瘟酯,戊菌唑,戊菌隆,氯瘟磷,多马霉素,哌丙灵,多抗霉素,Polyoxorim,烯丙苯噻唑,咪鲜胺,腐霉利,霜霉威,Propanosine-sodium,丙环唑,丙森锌,吡菌磷,啶斑肟,嘧霉胺,咯喹酮,氯吡呋醚,
Quinconazole,五氯硝基苯,
硫和硫制剂,
戊唑醇,叶枯酞,四氯硝基苯,四环唑,四氟醚唑,噻菌灵,噻菌腈,溴氟唑菌,甲基硫菌灵,福美双,硫氰苯甲酰胺,甲基立枯磷,甲苯氟磺胺,三唑酮,三唑醇,叶锈特,咪唑嗪,水杨菌胺,三环唑,十三吗啉,氟菌唑,嗪胺灵,灭菌唑,
烯效唑,
有效霉素A,乙烯菌核利,烯霜苄唑,
氰菌胺,代森锌,福美锌,以及
咪草酯(Dagger G)
OK-8705,OK-8801,
α-(1,1-二甲基乙基)-β-(2-苯氧基乙基)-1H-1,2,4-三唑-1-乙醇,
α-(2,4-二氯苯基)-β-氟-b-丙基-1H-1,2,4-三唑-1-乙醇,
α-(2,4-二氯苯基)-β-甲氧基-a-甲基-1H-1,2,4-三唑-1-乙醇,
α-(5-甲基-1,3-二噁烷-5-基)-β-[[4-(三氟甲基)-苯基]-亚甲基]-1H-1,2,4-三唑-1-乙醇,
(5RS,6RS)-6-羟基-2,2,7,7-四甲基-5-(1H-1,2,4-三唑-1-基)-3-辛酮,
(E)-a-(甲氧基亚氨基)-N-甲基-2-苯氧基-苯基乙酰胺,
1-异丙基{2-甲基-1-[[[1-(4-甲基苯基)-乙基]-氨基]-羰基]-丙基}-氨基甲酸酯,
1-(2,4-二氯苯基)-2-(1H-1,2,4-三唑-1-基)-乙酮-O-(苯基甲基)-肟,
1-(2-甲基-1-萘基)-1H-吡咯-2,5-二酮,
1-(3,5-二氯苯基)-3-(2-丙烯基)-2,5-吡咯烷二酮,
1-[(二碘甲基)-磺酰基]-4-甲基-苯,
1-[[2-(2,4-二氯苯基)-1,3-二氧戊环-2-基]-甲基]-1H-咪唑,
1-[[2-(4-氯苯基)-3-苯基环氧乙烷基]-甲基]-1H-1,2,4-三唑,
1-[1-[2-[(2,4-二氯苯基)-甲氧基]-苯基]-乙烯基]-1H-咪唑,
1-甲基-5-壬基-2-(苯基甲基)-3-吡咯烷醇,
2’,6’-二溴-2-甲基-4’-三氟甲氧基-4’-三氟-甲基-1,3-噻唑-5-甲酰苯胺,
2,2-二氯-N-[1-(4-氯苯基)-乙基]-1-乙基-3-甲基-环丙烷甲酰胺,
2,6-二氯-5-(甲硫基)-4-嘧啶基-硫氰酸酯,
2,6-二氯-N-(4-三氟甲基苄基)-苯甲酰胺,
2,6-二氯-N-[[4-(三氟甲基)-苯基]-甲基]-苯甲酰胺,
2-(2,3,3-三碘-2-丙烯基)-2H-四唑,
2-[(1-甲基乙基)-磺酰基]-5-(三氯甲基)-1,3,4-噻二唑,
2-[[6-脱氧-4-O-(4-O-甲基-β-D-吡喃葡糖基)-a-D-吡喃葡萄糖基]-氨基]-4-甲氧基-1H-吡咯并[2,3-d]嘧啶-5-腈,
2-氨基丁烷,
2-溴-2-(溴甲基)-戊二腈,
2-氯-N-(2,3-二氢-1,1,3-三甲基-1H-茚-4-基)-3-吡啶甲酰胺,
2-氯-N-(2,6-二甲基苯基)-N-(异硫氰酸根合甲基)-乙酰胺,
2-苯基苯酚(OPP),
3,4-二氯-1-[4-(二氟甲氧基)-苯基]-1H-吡咯-2,5-二酮,
3,5-二氯-N-[氰基[(1-甲基-2-丙炔基)-氧基]-甲基]-苯甲酰胺,
3-(1,1-二甲基丙基-1-氧代-1H-茚-2-腈,
3-[2-(4-氯苯基)-5-乙氧基-3-异噁唑烷基]-吡啶,
4-氯-2-氰基-N,N-二甲基-5-(4-甲基苯基)-1H-咪唑-1-磺酰胺,
4-甲基-四唑并[1,5-a]喹唑啉-5(4H)-酮,
8-(1,1-二甲基乙基)-N-乙基-N-丙基-1,4-二氧杂螺[4.5]癸烷-2-甲胺,
8-羟基喹啉硫酸盐(sulfat),
9H-咕吨-2-[(苯基氨基)-羰基]-9-甲酰肼,
双-(1-甲基乙基)-3-甲基-4-[(3-甲基苯甲酰基)-氧基]-2,5-噻吩二甲酯,
顺式-1-(4-氯苯基)-2-(1H-1,2,4-三唑-1-基)-环庚醇,
顺式-4-[3-[4-(1,1-二甲基丙基)-苯基-2-甲基丙基]-2,6-二甲基-吗啉盐酸盐,
[(4-氯苯基)-偶氮]-氰基乙酸乙酯,
碳酸氢钾,
甲四硫醇钠盐,
1-(2,3-二氢-2,2-二甲基-1H-茚-1-基)-1H-咪唑-5-羧酸甲酯,
N-(2,6-二甲基苯基)-N-(5-异噁唑基羰基)-DL-丙氨酸甲酯,
N-(氯乙酰基)-N-(2,6-二甲基苯基)-DL-丙氨酸甲酯,
N-(2,3-二氯-4-羟基苯基)-1-甲基-环己烷甲酰胺,
N-(2,6-二甲基苯基)-2-甲氧基-N-(四氢-2-氧代-3-呋喃基)-乙酰胺,
N-(2,6-二甲基苯基)-2-甲氧基-N-(四氢-2-氧代-3-噻吩基)-乙酰胺,
N-(2-氯-4-硝基苯基)-4-甲基-3-硝基-苯磺酰胺,
N-(4-环己基苯基)-1,4,5,6-四氢-2-嘧啶胺,
N-(4-己基苯基)-1,4,5,6-四氢-2-嘧啶胺,
N-(5-氯-2-甲基苯基)-2-甲氧基-N-(2-氧代-3-唑烷基)-乙酰胺,
N-(6-甲氧基)-3-吡啶基)-环丙烷甲酰胺,
N-[2,2,2-三氯-1-[(氯乙酰基)-氨基]-乙基]-苯甲酰胺,
N-[3-氯-4,5-双-(2-丙炔氧基)-苯基]-N’-甲氧基-甲亚氨酰胺(methanimidamid),
N-甲酰基-N-羟基-DL-丙氨酸钠盐,
[2-(二丙基氨基)-2-氧代乙基]-乙基硫代氨基磷酸O,O-二乙酯,
苯基丙基硫代氨基磷酸O-甲基S-苯基酯,
1,2,3-苯并噻二唑-7-硫代羟酸S-甲酯,
螺[2H]-1-苯并吡喃-2,1’(3’H)-异苯并呋喃]-3’-酮,
杀细菌剂:
溴硝丙二醇、双氯酚、三氯甲基吡啶、福美镍、春雷霉素、辛噻酮、呋喃羧酸、土霉素、烯丙苯噻唑、链霉素、叶枯酞、硫酸铜和其它铜制剂。
杀虫剂/杀螨剂/杀线虫剂:
阿维菌素、乙酰甲胺磷、啶虫脒、氟丙菊酯、棉铃成、涕灭成、砜灭威、顺式氯氰菊酯、甲体氯氰菊酯、双甲脒、齐墩螨素、AZ 60541、艾扎丁、甲基吡恶磷、乙基谷硫磷、谷硫磷、三唑锡,
日本甲虫芽孢杆菌、球形芽孢杆菌、枯草芽孢杆菌、苏云金芽孢杆菌、Baculoviruses、蚕白僵菌、纤细白僵菌、恶虫威、丙硫克百威、杀虫磺、苯螨特、高效氟氯氰菊酯、联苯肼酯、联苯菊酯、Bioethanomethrin、生物氯菊酯、仲丁威、溴硫磷A、合杀威、噻嗪酮、特嘧硫磷、丁酮威、Butylpyridaben
硫线磷、甲萘威、克百威、三硫磷、丁硫克百威、杀螟丹、Chloethocarb、氯氧磷、氟唑虫清、毒虫畏、氟啶脲、氯甲磷、毒死蜱、甲基毒死蜱、Chlovaporthrin、顺式苄呋菊酯、顺式氯菊酯、Clocythrin、除线威、四螨嗪、杀螟腈、Cycloprene、乙氰菊酯、氟氯氰菊酯、氯氟氰菊酯、三环锡、氯氰菊酯、灭蝇胺
溴氰菊酯、甲基内吸磷、内吸磷硫赶式异构体、甲基内吸磷硫赶式异构体、丁醚脲、二嗪磷、敌敌畏、除虫脲、乐果、甲基毒虫畏、苯虫醚、乙拌磷、碘酰丁二辛、苯氧炔螨
Efusilanate、Emamectin、右旋烯炔菊酯、硫丹、虫霉属、Eprinomectin、S-氰戊聚酯、乙硫苯威、乙硫磷、灭线磷、醚菊酯、特苯噁唑、乙嘧硫磷
苯线磷、喹螨醚、苯丁锡、杀螟硫磷、苯硫威、Fenoxacrim、苯氧威、甲氰菊酯、Fenpyrad、Fenpyrithrin、唑螨酯、氰戊菊酯、氟虫腈、氟啶胺、啶蜱脲、溴氟菊酯、氟环脲、氟氰戊菊酯、氟虫脲、Flutenzine、氟胺氰菊酯、地虫硫磷、丁苯硫磷、噻唑磷、Fubfenprox、呋线成
颗粒体病毒
特丁苯酰肼、六六六、庚烯磷、氟铃脲、噻螨酮、烯虫乙酯、吡虫啉、氯唑磷、异柳磷、噁唑磷、齐墩螨素
核多角体病毒
高效氯氟氰菊酯、氟丙氧脲
马拉硫磷、灭蚜磷、四聚乙醛、甲胺磷、Metharhiziumanisopliae、Metharhizium flavoviride、杀扑磷、甲硫威、灭多威、甲氧苯酰肼、速灭威、恶虫酮、速灭磷、米尔螨素、久效磷
二溴磷、烯啶虫胺、硝虫噻嗪、双苯氟脲
氧乐果、杀线威、亚砜磷
玫烟色拟青霉、对硫磷A、甲基对硫磷、氯菊酯、稻丰散、甲拌磷、伏杀硫磷、亚胺硫磷、磷胺、辛硫磷、抗蚜威、乙基嘧啶磷、甲基嘧啶磷、丙溴磷、猛杀威、残杀威、丙硫磷、发硫磷、吡蚜酮、吡唑硫磷、反灭虫菊、除虫菊素、哒螨灵、Pyridathion、嘧螨醚、蚊蝇醚
喹硫磷
Ribavirin
杀抗松、硫线磷、Selamectin、氟硅菊酯、艾克敌105、Sulfotep、硫丙磷
氟胺氰菊酯、虫酰肼、吡螨胺、嘧丙磷、氟苯脲、七氟菊酯、双硫磷、灭虫畏、特丁硫磷、杀虫畏、辛体氯氰菊酯、Thiamethoxam、噻丙腈、Thiatriphos、硫环杀、硫双威、久效威、敌贝特、溴氯氰菊酯、四溴菊酯、苯螨噻、唑蚜威、三唑磷、Thiazuron、氯咪唑、敌百虫、杀铃脲、混杀成
蚜灭多、氟吡唑虫、麦柯特尔
YI 5302
己体氯氰菊酯、zolaprofos
(1R-顺)-[5-(苯基甲基)-3-呋喃基]-甲基-3-[(二氢-2-氧代-3(2H)-亚呋喃基)-甲基]-2,2-二甲基环丙烷羧酸酯
(3-苯氧基苯基)-甲基-2,2,3,3-四甲基环丙烷羧酸酯
1-[(2-氯-5-噻唑基)甲基]四氢-3,5-二甲基-N-硝基-1,3,5-三嗪-2(1H)-亚胺
2-(2-氯-6-氟苯基)-4-[4-(1,1-二甲基乙基)苯基]-4,5-二氢-噁唑
2-(乙酰氧基)-3-十二烷基-1,4-萘二酮
2-氯N-[[[4-(1-苯基乙氧基)-苯基]-氨基]-羰基]-苯甲酰胺
2-氯-N-[[[4-(2,2-二氯-1,1-二氟乙氧基)-苯基]-氨基]-羰基]-苯甲酰胺
3-甲基苯基-丙基氨基甲酸酯
4-[4-(4-乙氧基苯基)-4-甲基戊基]-1-氟-2-苯氧基-苯
4-氯-2-(1,1-二甲基乙基)-5-[[2-(2,6-二甲基-4-苯氧基苯氧基)乙基]硫代]-3(2H)-哒嗪酮
4-氯-2-(2-氯-2-甲基丙基)-5-[(6-碘-3-吡啶基)甲氧基]-3(2H)-哒嗪酮
4-氯-5-[(6-氯-3-吡啶基)甲氧基]-2-(3,4-二氯苯基)-3(2H)-哒嗪酮
苏云金芽孢杆菌EG-2348株系
2-苯甲酰基-1-(1,1-二甲基乙基)-肼基苯甲酸,
2,2-二甲基-3-(2,4-二氯苯基)-2-氧代-1-氧杂螺[4,5]癸-3-烯-4-基丁酸酯
[3-[(6-氯-3-吡啶基)甲基]-2-亚噻唑烷基]-氨腈
二氢-2-(硝基亚甲基)-2H-1,3-噻嗪-3(4H)-甲醛
[2-[[1,6-二氢-6-氧代-1-(苯基甲基)-4-哒嗪基]氧基]乙基]-氨基甲酸乙酯
N-(3,4,4-三氟-1-氧代-3-丁烯基)-甘氨酸
N-(4-氯苯基)-3-[4-(二氟甲氧基)苯基]-4,5-二氢-4-苯基-1H-吡唑-1-甲酰胺
N-[(2-氯-5-噻唑基)甲基]-N’-甲基-N”-硝基-胍
N-甲基-N’-(1-甲基-2-丙烯基)-1,2-肼二硫代甲酰胺
N-甲基-N’-2-丙烯基-1,2-肼二硫代甲酰胺
[2-(二丙基氨基)-2-氧代乙基]-乙基硫代氨基磷酸O,O-二乙酯
还可与其它已知活性化合物,如除草剂或与肥料和生长调节剂混合。
当用作杀虫剂时,本发明活性化合物混剂还可以市售制剂和由上述制剂制备的与增效剂混合的应用形式存在。增效剂是能够提高活性化合物活性的化合物,但加入的增效剂本身不必须是具有活性的。
由市售制剂制备的应用形式中活性化合物的含量可在宽的范围内变化。应用形式中活性化合物的浓度为0.0000001至95%重量活性化合物,优选0.0001至1%重量。
以适用于应用形式的常规方法施用。
当用于防治卫生害虫和储藏物品中的害虫时,活性化合物混合物具有优异的木材和粘土残留活性和对石灰化底物上的碱具有很好的稳定性。
本发明活性化合物混剂不仅对植物害虫、卫生害虫和储藏物品中的害虫具有活性,而且在兽医领域,对防治动物寄生虫(外寄生虫),例如硬蜱、软蜱、兽疥癣螨、叶螨、蝇(叮咬和吸食)、寄生性蝇幼虫、虱、头虱、羽虱和跳蚤也有活性。这些寄生虫包括:
虱目,例如,血虱属、颚虱属、虱属、Pthirus spp.、管虱属;
食毛目以及钝角亚目和细角亚目,例如,毛羽虱属、Menoponspp.、巨毛虱属、羽虱属、Werneckiella spp.、Lepikentron spp.、畜虱属、嚼虱属、猫羽虱属;
双翅目以及长角亚目和短角亚目,例如,伊蚊属、按蚊属、库蚊属、蚋属、真蚋属、白蛉属、Lutzomyia spp.、库蠓属、斑虻属、瘤虻属、黄虻属、虻属、麻翅虻属、Philipomyia spp.、蜂虱蝇属.、家蝇属、齿股蝇属、螫蝇属、角蝇属、莫蝇属、厕蝇属、舌蝇属、丽蝇属、绿蝇属、金蝇属、Wohlfahrtia spp.、麻蝇属、狂蝇属、皮蝇属、胃蝇属、虱蝇属、Lipoptena spp.、蜱蝇属
蚤目,例如,蚤属、栉首蚤属、印鼠客蚤属、角叶蚤属
异翅亚目,例如,臭虫属、椎猎蝽属、红腹猎蝽属、全圆蝽属
蜚蠊目,例如,东方蜚蠊,美洲大蠊,德国小蠊、蜚蠊属
蜱螨目以及后气门亚目和中气门亚目,例如,锐缘蜱属、纯缘蜱属、残喙蜱属、硬蜱属、花蜱属、牛蜱属、革蜱属、Haemophysalis spp.、璃眼蜱属、扇头蜱属、皮刺螨属、刺利螨属、肺刺螨属、胸孔螨属、瓦螨属
辐螨亚目(前气门亚目)和粉螨目(无气门亚目),例如,蜂跗线螨属、姬螫螨属、禽螫厘螨属、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、瘙螨属、痒螨属、耳螨属、疥螨属、痂螨属、疙螨属、胞螨属、皮膜螨属。
本发明活性化合物混剂也适用于防治侵扰农业家畜的节肢动物,农业家畜如牛、绵羊、山羊、马、猪、驴、骆驼、水牛、兔、鸡、火鸡、鸭、鹅、蜜蜂,其它家养动物,例如狗、猫、笼养鸟、水族馆的鱼以及所谓的试验动物,例如田鼠、豚鼠、大鼠和小鼠。通过防治上述节肢动物,旨在减少动物死亡和减产(肉、奶、毛、皮、蛋、蜜等),因此,通过使用本发明活性化合物混剂可以使动物饲养更经济、更简单。
应用于兽医领域时,本发明活性化合物混剂可通过已知方法经肠给药,例如以片剂、胶囊剂、饮剂、灌药剂、颗粒剂、膏剂、大丸剂、喂食过程和栓剂形式进行;非经肠给药,例如通过注射(肌肉注射、皮下注射、静脉注射、腹膜内注射等),植入法;经鼻给药;经皮肤给药,例如以浸泡或洗浴、喷雾、泼上或擦上、洗涤和撒粉方式进行,也可借助于含有活性化合物的成型制品,例如项圈、耳饰物、尾饰物、肢环(带)、笼头、装饰器具等。
当用于家畜,家禽,宠物等时,活性化合物混剂可使用制剂形式(例如粉剂,乳剂,流动剂),其中包括1-80%重量的活性化合物,直接使用或100-10000倍稀释后使用,或用作药浴。
另外,已发现本发明活性化合物混剂还对损坏工业材料的昆虫具有很强的杀虫活性。
作为实例并优选列出下述昆虫,但并不限于这些:
鞘翅目昆虫,如
北美家天牛、绿虎天牛(Chlorophorus pilosis)、家具窃蠹、报死材窃蠹、类翼窃蠹、Dendrobium pertinex、松芽枝窃蠹、松产品窃蠹(Priobium carpini)、褐粉蠹、粉蠹(Lyctus africanus)、南方粉蠹、栎粉蠹、粉蠹(Lyctus pubescens)、胸粉蠹(Trogoxylonaequale)、鳞毛粉蠹、材小蠹属、条木小蠹属、咖啡黑长蠹、Bostrychuscapucins、褐异翅长蠹、棘长蠹属、竹竿粉长蠹
革翅目,例如
蓝黑树蜂、云杉大树蜂、泰加大树蜂、大树蜂(Urocerus augur)
白蚁,例如
木白蚁(Kalotermes flavicollis)、麻头堆砂白蚁、印巴结构木异白蚁、欧美散白蚁、散白蚁(Reticulitermes santonensis)、散白蚁(Reticulitermes lucifugus)、达尔文澳白蚁、内华达古白蚁、台湾乳白蚁
缨尾目,例如台湾衣鱼
本发明中工业材料可以理解为表示非生活(nicht-lebende)用品,例如优选塑料、粘合剂、胶、纸和板、皮革、木材、(加工后)木制品和涂料。
木材和木制品是特别需要优选保护使其免受昆虫侵袭的材料。
通过使用本发明组合物或含有它的混合物可以保护的木材和木制品可以理解为表示,例如:
建筑用木材、木梁、铁路轨枕、桥梁组件、船头、木制交通工具、箱子、货架、集装箱、电杆、木镶板、木窗和木门、胶合板、粗纸板、在房屋建筑或建筑细木工行业中常用的细木工或木制品。
活性化合物可直接,或以浓缩形式或常规制剂,如粉剂,颗粒剂,溶液,悬浮剂,乳剂或糊剂方式使用。
上述制剂可以已知方法制备,例如通过将活性化合物与至少一种溶剂或稀释剂,乳化剂,分散剂和/或粘合剂或固定剂,抗水剂混合,以及如需要加入催干剂和UV稳定剂以及如需要加入染料和颜料以及其它加工助剂。
用于保护木材和木制品的杀虫组合物或浓缩物包括0.0001至95%重量,特别是0.001至60%重量浓度的本发明活性化合物。
组合物或浓缩物的使用量是根据昆虫种类和发生情况和介质而确定的。最佳施用量各自可通过施用中的系列试验确定。然而,基于需保护的材料,一般,使用0.0001至20%重量,优选0.001至10%重量的活性化合物是足够的。
适合的溶剂和/或稀释剂是有机化学溶剂或溶剂混合物和/或低挥发性的油性或油类有机溶剂或溶剂混合物和/或极性有机溶剂或溶剂混合物和/或水,如需要可加入乳化剂和/或湿润剂。
优选使用的有机溶剂是油性或油类溶剂,蒸发值大于35以及闪点大于30℃,并优选大于45℃。上述的不溶于水和低挥发度的油性或油类溶剂是适合的矿物油或它们的芳族馏分或含有矿物油的溶剂混合物,优选石油溶剂,石油和/或烷基苯。
优选使用沸程为170-220℃的矿物油,沸程为170-220℃的石油溶剂,沸程为250-350℃的锭子油,沸程为160-280℃的石油和芳烃,松节油等。
在优选实施方案中,使用沸程为180-210℃的液体脂族烃或沸程为180-220℃的芳族和脂族烃的高沸程混合物和/或锭子油和/或一氯代萘,优选α-一氯代萘。
蒸发值大于35以及闪点大于30℃并优选大于45℃的低挥发度的有机油性或油类溶剂可用高或中挥发度的有机溶剂部分替换,条件是溶剂混合物的蒸发值同样大于35以及闪点大于30℃并优选大于45℃,以及杀虫剂-杀真菌剂-混合物可溶或可乳化于该溶剂混合物中。
优选实施方案中,某些有机溶剂或溶剂混合物用脂族极性有机溶剂或溶剂混合物替代。优选使用含有羟基和/或酯和/或醚基的脂族有机溶剂,例如乙二醇醚,酯等。
本发明使用的有机化学粘合剂是本身已知的合成树脂和/或粘合干性油,它们可用水稀释和/或可溶解或分散或乳化于使用的机化学溶剂中,特别是由下列物质组成或含有下列物质的粘合剂:丙烯酸盐树脂(Acrylatharz),乙烯基树脂,例如聚乙酸乙烯酯,聚酯类树脂,缩聚或聚加成反应树脂,聚氨酯树脂,醇酸树脂或改性的醇酸树脂,酚醛树脂,烃类树脂,如茚/香豆酮树脂,有机硅树脂,干性植物油和/或干性油和/或基于天然和/或合成树脂的物理干性粘合剂。
用作粘合剂的合成树脂可以乳剂,分散剂或溶液形式使用。沥青或沥青状物质也可用作粘合剂,用量至多为10%重量。还可以使用本身已知的染料,颜料,防水剂,气味掩蔽剂以及抑制剂或防腐蚀剂等。
本发明组合物或浓缩物中优选包括作为有机化学粘合剂的至少一种醇酸树脂或改性醇酸树脂和/或干性植物油。本发明优选使用含油量大于45%重量,优选50-68%重量的醇酸树脂。
上述所有或某些粘合剂可用固定剂(混合物)或增塑剂(混合物)替代。加入这些添加剂的目的是防止活性化合物的蒸发以及结晶或沉淀。它们优选替代0.01至30%的粘合剂(以使用粘合剂的100%计)。
增塑剂得自邻苯二甲酸酯类的化学物质,如邻苯二甲酸二丁基酯,邻苯二甲酸二辛基酯或邻苯二甲酸苄基丁基酯,磷酸酯类,如磷酸三丁酯,己二酸酯,如二-(2-乙基己基)己二酸酯,硬脂酸酯,如硬脂酸丁酯或硬脂酸戊酯,油酸酯,如油酸丁酯,甘油醚或高分子量的乙二醇醚,甘油酯和对甲苯磺酸酯。
固定剂化学上基于聚乙烯烷基醚,如聚乙烯基甲基醚或酮,如二苯甲酮或亚乙基二苯甲酮。
其它适合的溶剂或稀释剂特别是水,如需要可与一种或多种上述有机化学溶剂或稀释剂,乳化剂和分散剂混合使用。
特别有效的木材保护方法是通过大批量浸渍方法,例如通过真空,双真空(Doppelvakuum)或加压方法进行。
现混现用组合物中如需要还可以包括其它杀虫剂,以及如需要还可以加入一种或多种杀真菌剂。
其它混合组分优选WO94/29268中所提及的那些杀虫剂和杀真菌剂。在该文献中所述化合物也明确作为本申请的组成部分。
可提及的特别优选的混合组分是杀虫剂,如毒死蜱、辛硫磷、氟硅菊酯、顺式氯氰菊酯、氟氯氰菊酯、氯氰菊酯、溴氰菊酯、氯菊酯、吡虫啉、啶虫脒、氟虫脲、氟铃脲、四氟菊酯、Thiacloprid、Methoxyphenoxid和杀铃脲,以及杀真菌剂,如氧唑菌、己唑醇、氧环唑、丙环唑、戊唑醇、环丙唑醇、叶菌唑、抑霉唑、抑菌灵、甲苯氟磺胺、3-碘-2-丙炔基-丁基氨基甲酸酯、N-辛基-异噻唑啉-3-酮和4,5-二氯-N-辛基异噻唑啉-3-酮。
本发明混合物还可用于保护各种物品免受动植物的定殖,特别是与海水或盐水接触的物体,如船壳、观测屏、网、船体结构、码头和信号系统。
由于定居性寡毛纲目,如龙介虫科以及甲壳类和Ledamorpha(茗荷儿)类,如各种茗荷属和铠茗荷属,或藤壶亚目(藤壶虫),如藤壶属或指茗荷属的定殖增加了船体的摩擦阻力并由于增加了能源消耗以及经常停留于干船坞,这样明显增加了运营成本。
此外定殖的还有海藻,例如水云属和仙菜属,特别重要是由定居性软甲亚纲(昆甲类)的附着侵染,该昆甲类属于蔓足纲(蔓足类甲壳动物)。
令人惊奇地,目前已发现本发明混合物单独使用或与其它活性化合物混合使用都具有显著的防污(抗定殖)作用。
通过使用本发明混合物,或单独使用或与其它活性化合物混合使用,可无需使用重金属,如,例如硫化二(三烷基锡)、月桂酸三正丁基锡、氯化三正丁基锡、氧化铜(I)、氯化三乙基锡、三正丁基(2-苯基-4-氯苯氧基)-锡、氧化三丁基锡、二硫化钼、氧化锑、聚合钛酸丁酯、三氯化苯基-(联吡啶)-铋、氟化三正丁基锡、亚乙基二硫代氨基甲酸锰、二甲基二硫代氨基甲酸锌、亚乙基双硫代氨基甲酸锌、2-吡啶硫醇1-氧化物的锌和铜盐、亚乙基双硫代氨基甲酸双二甲基二硫代氨基甲酰基锌、氧化锌、亚乙基双二硫代氨基甲酸铜(I)、硫氰酸铜、环烷酸铜和卤化三丁基锡,或显著降低这些化合物的使用浓度。
如适合,现混现用防污漆还可包括其它活性化合物,优选杀藻剂、杀真菌剂、除草剂、杀软体动物剂或其它防污活性化合物。
优选与本发明防污组合物混合的适合的组分是:
杀藻剂,如
2-叔丁基氨基-4-环丙基氨基-6-甲硫基-1,3,5-三嗪、双氯酚、敌草隆、菌多酸、醋酸三苯基锡、异丙隆、甲基苯噻隆、乙氧氟草醚、灭藻醌和特丁净,
杀真菌剂,如
苯并[b]噻吩羧酸环己酰胺S,S-二氧化物、抑菌灵、Fluorfolpet、3-碘-2-丙炔基丁基氨基甲酸酯、甲苯氟磺胺和唑类,如
氧环唑、环丙唑醇、氧唑菌、己唑醇、叶菌唑、丙环唑和戊唑醇;
杀软体动物剂,如
醋酸三苯基锡、四聚乙醛、甲硫威、杀螺胺、硫双威和混杀威;
或常用防污活性化合物,如
4,5-二氯-2-辛基-4-异噻唑啉-3-酮、二碘甲基paratryl砜、2-(N,N-二甲硫基氨基甲酰基硫代)-5-硝基噻唑基、2-吡啶硫醇1-氧化物的钾,铜,钠和锌盐、吡啶三苯基硼烷、四丁基二锡氧烷、2,3,5,6-四氯-4-(甲磺酰基)-吡啶、2,4,5,6-四氯间苯二腈、二硫化四甲基秋兰姆和2,4,6-三氯苯基马来酰亚胺。
使用的防污组合物中包括本发明混剂中的浓度为0.001至50%重量,特别是0.01至20%重量的本发明活性化合物。
而且,本发明防污组合物包括在下述文献中公开的常用组分,例如:Ungerer,Chem.Ind.1985,37,730-732和Williams,AntifoulingMarine Coatings,Noyes,Park Ridge,1973。
除了杀藻剂、杀真菌剂、杀软体动物剂和本发明的杀虫活性化合物外,防污涂料中还特别包括粘合剂。
公知的粘合剂的实例包括溶剂体系的聚氯乙烯、溶剂体系的氯化橡胶、溶剂体系特别是含水体系的丙烯酸类树脂、水分散体形式或有机溶剂体系形式的氯乙烯/醋酸乙烯酯共聚物体系、丁二烯/苯乙烯/丙烯腈橡胶、干性油,如亚麻子油,树脂酯或与焦油或沥青、柏油以及环氧化合物、少量的氯化橡胶、氯化聚丙烯和乙烯基树脂混合形成的改性硬树脂。
如需要,涂料中还包括优选不溶于盐水的无机颜料、有机颜料或染料。涂料还可包括如松香类物质,以使活性化合物可控制地释放。涂料中还可以包括增塑剂,影响流变性质的改性剂,以及其它常规组分。还可以将本发明化合物或上述混合物加入自抛光防污体系中。
活性化合物混合物还适于防治封闭空间,如公寓,厂房,办公室,车厢等空间中出现的害虫,特别是昆虫,蜘蛛和螨。它们可单独使用或与其它活性化合物以及家用杀虫制剂中的其它活性化合物和助剂混合使用以控制上述害虫。它们对敏感和抗性种群以及所有发育阶段都有杀虫活性。这些害虫包括:
蝎目,例如钳蝎(Buthus occitanus)。
蜱螨目,例如波斯锐缘蜱、翘缘锐缘蜱、苔螨属、鸡皮刺螨、家食甜螨、非洲钝缘蜱、血红扇头蜱、恙螨(Trombicula alfreddugesi)、Neutrombicula autumnalis、屋尘螨、粉尘螨。
蛛形目,例如鸟蛤蛛科、园蛛科。
盲蛛目,例如拟蝎类(Pseudoscorpiones chelifer)、Pseudoscorpiones cheiridium、Opiliones phalangium。
等足目,例如潮虫、鼠妇。
倍足目,例如具斑马陆、山蛩虫属。
唇足目,例如地蜈蚣属。
Zygentoma目,例如栉衣鱼属、台湾衣鱼、Lepismodesinquilinus。
蜚蠊目,例如东方蜚蠊、德国小蠊、小蠊属(Blattellaasahinai)、马得拉蜚蠊、角腹蠊属、木蠊属、澳洲大蠊、美洲大蠊、褐斑大蠊、黑胸大蠊、长须蜚蠊。
跳跃亚目,例如家蟀。
革翅目,例如欧洲球螋。
等翅目,例如木白蚁属、散白蚁属。
啮虫目,例如Lepinatus属、粉啮虫属。
鞘翅目,例如圆皮蠹属、毛皮蠹属、皮蠹属、长头谷蠹、隐跗郭公虫属、蛛甲属、谷蠹、谷象、米象、玉米象、药材甲。
双翅目,例如埃及伊蚊、白纹伊蚊、Aedes taeniorhynchus、按蚊属、红头丽蝇、高额麻虻、致倦库蚊、尖音库蚊、Culex tarsalis、果蝇属、夏厕蝇、家蝇、白蛉属、麻蝇(Sarcophaga carnaria)、蚋属、厩螫蝇、大蚊(Tipula paludosa)。
鳞翅目,例如小蜡螟、蜡螟、印度古斑螟、谷蛾、袋谷蛾、幕谷蛾。
蚤目,例如犬栉首蚤、猫栉首蚤指名亚种、人蚤、穿皮潜蚤、印鼠客蚤。
膜翅目,例如广布弓背蚁、亮毛蚁、黑毛蚁、Lasius umbratus、小家蚁、Paravespula属、铺道蚁。
虱目,例如头虱、体虱、阴虱。
异翅亚目,例如热带臭虫、温带臭虫、长红猎蝽、侵扰锥猎蝽。
在家用杀虫剂领域中,它们可单独使用或与其它适合的活性化合物,如磷酸酯类,氨基甲酸酯类,拟除虫菊酯类,生长调节剂或选自其它已知各类杀虫剂的活性化合物混合使用。
它们可以使用气溶胶形式,非增压喷雾产品,例如通过泵和喷雾器喷雾、自动化喷雾系统、烟雾发生器、泡沫、凝胶、带有纤维素或聚合物制成的汽化片的蒸发器、液体蒸发器、凝胶和薄膜蒸发器、推进式蒸发器、不需能量或被动式蒸发系统、防蛀纸、防蛀袋和防蛀胶,作为颗粒剂或粉剂撒布饵料中或饵料位置。
如上所述,根据本发明可以处理所有植物以及它们的各部分。在优选实施方案中,处理野生植物种类和植物栽培品种,或通过常规生物育种方法,如杂交或原生质体融合获得的植物种类和植物载培品种以及它们的各部分。在另一优选实施方案中,处理的植物是通过遗传工程,如需要结合常规育种方法(Genetic Modified Organisms)获得的转基因植物和植物栽培品种及它们的各部分。对于术语“各部分”或“植物的各部分”或“植物各部分”上面已进行了说明。
特别优选本发明处理的植物是那些各自市场上可以买得到的或通用的植物栽培品种。植物栽培品种可以理解为表示通过常规育种,诱变或重组DNA技术获得的具有某些特性(“性状”)的植物。它们可以是品种,生物-和地理型。
根据植物种或植物栽培品种,它们的生长场所和生长条件(土壤,气候,植物营养生长期,肥料),本发明处理方法还可以获得超加合(“增效”)效应。因此,例如,可以减少施用量和/或扩大活性谱和/或提高本发明使用的活性物质和组合物的活性,植物长势更佳,增强对高或低温的耐受性,提高对旱或涝或土壤含盐量的耐受能力,提高了开花率,更易收获,加速成熟,更高的产量,品质更优和/或收获产品具有更高的营养价值,更好的储藏稳定性和/或收获产品的加工性能更佳,上述这些方面都超出了实际预期的效果。
本发明将优选处理的转基因(即通过遗传工程获得的那些植物)植物或植物栽培品种包括在遗传修饰中获得遗传物质的所有植物,其中所述遗传物质赋予这些植物特别有用的性状。这类性状的实例包括植物的长势更好,提高了对高温或低温的耐受性,增强了对旱或涝或土壤含盐量的耐受能力,提高了开花率,更易收获,加速成熟,更高的产量,品质更优和/或收获产品具有更高的营养价值,更好的储藏稳定性和/或收获产品的加工性能更佳。另一些和特别优选的上述性状的实例是提高植物对动物以及微生物害虫的防御能力,如抗昆虫,螨,植物病原真菌,细菌和/或病毒,以及提高植物对某些除草活性化合物的耐受能力。可提及的转基因植物的实例包括重要的经济作物,如禾谷类(小麦,水稻),玉米,大豆,马铃薯,棉花,油菜以及果树(苹果,梨,柑桔类水果和葡萄),其中特别优选玉米,大豆,马铃薯,棉花和油菜。优选的性状特别是通过在植物体内生成毒素来提高植物对昆虫的防御能力,特别是通过来源于苏云金芽孢杆菌的遗传物质(例如通过基因CryIA(a),CryIA(b),CryIA(c),CryIIA,CryIIIA,CryIIIB2,Cry9c,Cry2Ab,Cry3Bb和CryIF及其组合)(下文称作“Bt植物”)在植物体内产生的那些毒素。还特别优选的性状是通过系统获得抗性(SAR),系统素,植物抗毒素,激卫素和抗性基因以及相应的表达蛋白和毒素提高植物对真菌,细菌和病毒的防御能力。另外特别优选的性状还包括提高植物对某些除草活性化合物,例如咪唑啉酮,磺酰脲,草甘膦或膦基麦黄酮的耐受性(例如“PAT”基因)。在转基因植物中,赋予上述所需性状的基因还可以互相组合。可提及的“Bt植物”的实例是市售的下列玉米品种,棉花品种,大豆品种和马铃薯品种,它们的商品名为YIELDGARD_(例如玉米,棉花,大豆),KnockOut_(例如玉米),StarLink_(例如玉米),Bollgard_(棉花),Nucotn_(棉花)和NewLeaf_(马铃薯)。可提及的耐除草剂植物的实例是市售的下述玉米品种,棉花品种和大豆品种,它们的商品名为Roundup Ready_(耐草甘膦,例如玉米,棉花,大豆),Liberty Link_(耐膦基麦黄酮,例如油菜),IMI_(耐咪唑啉酮)以及STS_(耐磺酰脲,例如玉米)。可提及的抗除草剂植物(通过用于除草剂耐受性的常规方法培育的植物)包括商品名为Clearfield_(例如玉米)的市售植物品种。当然,上面的描述也适用于具有这些遗传性状或具有仍需开发的遗传性状的那些植物栽培品种,未来将培育这些植物和/或市场化开发。
以特别有利的方式用本发明活性化合物混合物通过本发明方法处理上述植物。对于本发明活性化合物或混合物的上述优选范围同样适用于这些植物的处理。特别优选使用本文中特别提及的化合物或混合物处理植物。
应用实施例
用于评估来自两种活性化合物的混剂的杀伤率的计算公式
对所述两种活性化合物的混剂的预期活性可根据下述方法计算(参见Colby,S.R.,“Calculating Synergistic and AntagonisticResponses of Herbicide Combinations”,Weeds
15,P 20-22,1967):
如果
X 活性化合物A在
mppm施用量时的杀伤率,用未处理对照的百分率表示,
Y 活性化合物B在
nppm施用量时的杀伤率,用未处理对照的百分率表示,
E 活性化合物A和B在
m和
nppm施用量时的杀伤率,用未处理对照的百分率表示,
则
如果实际的杀虫率超出计算值,则混剂的杀死活性是超加合的,即存在增效作用。在这种情况下,实际观测的杀伤率必须大于由上述公式计算的预期杀伤率(E)的数值。
实施例A
猿叶甲(Phaedon)幼虫试验
溶剂:7重量份二甲基甲酰胺
乳化剂:2重量份烷基芳基聚乙二醇醚
为制备适合的活性化合物制剂,将1重量份活性化合物与上述量的溶剂和乳化剂混合,并用含有乳化剂的水稀释浓缩物至所需浓度。
将甘蓝叶片(Brassica oleracea)浸在所需浓度的活性化合物制剂中进行处理,然后在甘蓝叶片上定殖十字花科甲虫(辣根猿叶甲(Phaedon cochleariae))的幼虫同时一直保持叶片湿润。
在预定的一段时间后,测定杀虫活性,以%表示。100%表示已杀死所有辣根猿叶甲幼虫(K_ferlarven);0%表示没有杀死一头辣根猿叶甲幼虫。测定的致死率是采用Colby公式计算的(见页1)。
在该试验中,本申请的下列活性化合物混剂与单独使用的各活性化合物相比表现出增效活性:
表A页1
侵染植物的昆虫
猿叶甲幼虫试验
活性化合物 | 活性化合物浓度ppm | 3天后的致死率% | |
噁二唑虫 | 0.5 | 20 | |
吡虫啉 | 3 | 0 | |
本发明的噁二唑虫+吡虫啉 | 0.5+3 | 观测值* | 计算值** |
100 | 20 |
观测值 *=观测活性
计算值 **=Colby公式的计算活性
表A页2
侵染植物的昆虫
猿叶甲幼虫试验
活性化合物 | 活性化合物浓度ppm | 6天后的致死率% | |
噁二唑虫 | 0.5 | 45 | |
Thiacloprid | 3 | 0 | |
本发明的噁二唑虫+Thiacloprid | 0.5+3 | 观测值* | 计算值** |
85 | 45 |
观测值 *=观测活性
计算值 **=Colby公式的计算活性
实施例B
菜蛾(Plutella)试验(普通敏感种群)
溶剂:7重量份二甲基甲酰胺
乳化剂:2重量份烷基芳基聚乙二醇醚
为制备适合的活性化合物制剂,将1重量份活性化合物与上述量的溶剂和乳化剂混合,并用含有乳化剂的水稀释浓缩物至所需浓度。
将甘蓝叶片(Brassica oleracea)浸在所需浓度的活性化合物制剂中进行处理,然后在甘蓝叶片上定殖普通敏感小菜蛾(Plutellaxylostella)幼虫同时一直保持叶片湿润。
在预定的一段时间后,测定杀虫活性,以%表示。100%表示已杀死所有幼虫;0%表示没有杀死一头幼虫。测定的致死率是采用Colby公式计算的(见页1)。
在该试验中,本申请的下列活性化合物混剂与单独使用的各活性化合物相比表现出增效活性:
表B
侵染植物昆虫
菜蛾试验(普通敏感种群)
活性化合物 | 活性化合物浓度ppm | 6天后的致死率% | |
噁二唑虫 | 0.1 | 65 | |
Thiacloprid | 3 | 0 | |
本发明的噁二唑虫+Thiacloprid | 0.1+3 | 观测值* | 计算值** |
100 | 65 |
观测值 *=观测活性
计算值 **=Colby公式的计算活性
实施例C
菜蛾试验(抗性种群)
溶剂:7重量份二甲基甲酰胺
乳化剂:2重量份烷基芳基聚乙二醇醚
为制备适合的活性化合物制剂,将1重量份活性化合物与上述量的溶剂和乳化剂混合,并用含有乳化剂的水稀释浓缩物至所需浓度。
将甘蓝叶片(Brassica oleracea)浸在所需浓度的活性化合物制剂中进行处理,然后在甘蓝叶片上定殖具有抗性的小菜蛾幼虫同时一直保持叶片湿润。
在预定的一段时间后,测定杀虫活性,以%表示。100%表示已杀死所有幼虫;0%表示没有杀死一头幼虫。测定的致死率是采用Colby公式计算的(见页1)。
在该试验中,本申请的下列活性化合物混剂与单独使用的各活性化合物相比表现出增效活性:
表C
侵染植物昆虫
菜蛾试验(抗性种群)
活性化合物 | 活性化合物浓度ppm | 6天后的致死率% | |
噁二唑虫 | 0.1 | 55 | |
Thiacloprid | 3 | 0 | |
本发明的噁二唑虫+Thiacloprid | 0.1+3 | 观测值* | 计算值** |
85 | 55 |
观测值 *=观测活性
计算值 **=Colby公式的计算活性
实施例D
草地粘虫(Spodoptera frugiperda)试验
溶剂:7重量份二甲基甲酰胺
乳化剂:2重量份烷基芳基聚乙二醇醚
为制备适合的活性化合物制剂,将1重量份活性化合物与上述量的溶剂和乳化剂混合,并用含有乳化剂的水稀释浓缩物至所需浓度。
将甘蓝叶片(Brassica oleracea)浸在所需浓度的活性化合物制剂中进行处理,然后在甘蓝叶片上定殖草地粘虫的幼虫同时一直保持叶片湿润。
在预定的一段时间后,测定杀虫活性,以%表示。100%表示已杀死所有幼虫;0%表示没有杀死一头幼虫。测定的致死率是采用Colby公式计算的(见页1)。
在该试验中,本申请的下列活性化合物混剂与单独使用的各活性化合物相比表现出增效活性:
表D
侵染植物的昆虫
草地粘虫试验
活性化合物 | 活性化合物浓度ppm | 6天后的致死率% | |
噁二唑虫 | 0.02 | 0 | |
吡虫啉 | 0.6 | 0 | |
本发明的噁二唑虫+吡虫啉 | 0.02+0.6 | 观测值* | 计算值** |
100 | 0 |
观测值 *=观测活性
计算值 **=Colby公式的计算活性
实施例E
美洲烟夜蛾(Heliothis virescens)试验
溶剂:7重量份的二甲基甲酰胺
乳化剂:2重量份的烷基芳基聚乙二醇醚
为制备适合的活性化合物制剂,将1重量份活性化合物与上述量的溶剂和乳化剂混合,并用含有乳化剂的水稀释浓缩物至所需浓度。
将大豆苗(Glycine max)浸入所需浓度的活性化合物制剂中进行处理,然后在其上定殖美洲烟夜蛾幼虫,同时一直保持叶片湿润。
在规定的一段时间后,测定杀虫活性,以%表示。100%表示已杀死所有幼虫;0%表示没有杀死一头幼虫。测定的致死率是采用Colby公式计算的(见页1)。
在该试验中,本申请的下列活性化合物混剂与单独使用的各活性化合物相比表现出增效活性:
表E
侵染植物的昆虫
美洲烟夜蛾试验
活性化合物 | 活性化合物浓度ppm | 3天后的致死率% | |
噁二唑虫 | 0.1 | 0 | |
吡虫啉 | 3 | 15 | |
本发明的噁二唑虫+吡虫啉 | 0.1+3 | 观测值* | 计算值** |
100 | 15 |
观测值 *=观测活性
计算值 **=Colby公式的计算活性
用于评估来自两种活性化合物混剂的增效活性的计算公式
两种活性化合物的混剂的预期活性可根据下述方法计算(参见Carpenter,C.S.,“Mammalian Toxicity of 1-Naphthyl-N-methylcarbamate[Sevin Insecticide]”,Agricultural and FoodChemistry,Vol.9,No.1,pages 30-39,1961):
如果
Pa 混合物中活性化合物A的比例
Pb 混合物中活性化合物B的比例
LC50(或95)a 用活性化合物A处理致死动物50%(或95%)的浓度以及
LC50(或95)b 用活性化合物B处理致死动物50%(或95%)的浓度,
如果计算的LC50(或95)值大于实测值并在置信区间(Vertrauensbereichs)外,则该混剂的活性是超加合的,即存在增效作用。
实施例A
猿叶甲幼虫试验
溶剂:7重量份二甲基甲酰胺
乳化剂:2重量份烷基芳基聚乙二醇醚
为制备适合的活性化合物制剂,将1重量份活性化合物与上述量的溶剂和乳化剂混合,并用含有乳化剂的水稀释浓缩物至所需浓度。
将甘蓝叶片(Brassica oleracea)浸在所需浓度的活性化合物制剂中进行处理,然后在甘蓝叶片上定殖十字花科甲虫(辣根猿叶甲)的幼虫同时一直保持叶片湿润。
在预定的一段时间后,测定杀虫活性,以%表示。100%表示已杀死所有辣根猿叶甲幼虫;0%表示没有杀死一头辣根猿叶甲幼虫。测定的致死率是采用Carpenter公式计算的(见页1)。
在该试验中,本申请的下列活性化合物混剂与单独使用的各活性化合物相比表现出增效活性:
表A
侵染植物的昆虫
猿叶甲幼虫试验
活性化合物 | 6天后的LC50 |
噁二唑虫已知 | 0.1ppm |
Clothianidin(X)已知 | 2.372ppm |
本发明的噁二唑虫+Clothianidin(X)(1∶6) | 计算值 ** 0.558ppm观测值 * 0.1ppm |
观测值 *=观测活性
计算值 **=Carpenter公式的计算活性
实施例B
菜蛾试验(敏感种群)
溶剂:7重量份二甲基甲酰胺
乳化剂:2重量份烷基芳基聚乙二醇醚
为制备适合的活性化合物制剂,将1重量份活性化合物与上述量的溶剂和乳化剂混合,并用含有乳化剂的水稀释浓缩物至所需浓度。
将甘蓝叶片(Brassica oleracea)浸在所需浓度的活性化合物制剂中进行处理,然后在甘蓝叶片上定殖小菜蛾幼虫(敏感种群),同时一直保持叶片湿润。
在预定的一段时间后,测定杀虫活性,以%表示。100%表示已杀死所有幼虫;0%表示没有杀死一头幼虫。测定的致死率是采用Carpenter公式计算的(见页1)。
在该试验中,本申请的下列活性化合物混剂与单独使用的各活性化合物相比表现出增效活性:
表B
侵染植物的昆虫
菜蛾试验,敏感种群
活性化合物 | 6天后的LC95 |
噁二唑虫已知 | 0.531ppm |
Clothianidin(X)已知 | 26.037ppm |
本发明的噁二唑虫+Clothianidin(X)(1∶6) | 计算值 ** 3.311ppm观测值 * 0.322ppm |
观测值 *=观测活性
计算值 **=Carpenter公式的计算活性
实施例C
菜蛾试验,抗性种群
溶剂:7重量份二甲基甲酰胺
乳化剂:2重量份烷基芳基聚乙二醇醚
为制备适合的活性化合物制剂,将1重量份活性化合物与上述量的溶剂和乳化剂混合,并用含有乳化剂的水稀释浓缩物至所需浓度。
将甘蓝叶片(Brassica oleracea)浸在所需浓度的活性化合物制剂中进行处理,然后在甘蓝叶片上定殖小菜蛾幼虫(抗性种群),同时一直保持叶片湿润。
在预定的一段时间后,测定杀虫活性,以%表示。100%表示已杀死所有幼虫;0%表示没有杀死一头幼虫。测定的致死率是采用Carpenter公式计算的(见页1)。
在该试验中,本申请的下列活性化合物混剂与单独使用的各活性化合物相比表现出增效活性:
表C
侵染植物昆虫
菜蛾试验,抗性种群
活性化合物 | 6天后的LC95 |
噁二唑虫已知 | 0.234ppm |
Clothianidin(X)已知 | 50.722ppm |
本发明的噁二唑虫+Clothianidin(X)(1∶6) | 计算值 ** 1.592ppm观测值 * 0.214ppm |
观测值 *=观测活性
计算值 **=Carpenter公式的计算活性
实施例D
草地粘虫试验
溶剂:7重量份二甲基甲酰胺
乳化剂:2重量份烷基芳基聚乙二醇醚
为制备适合的活性化合物制剂,将1重量份活性化合物与上述量的溶剂和乳化剂混合,并用含有乳化剂的水稀释浓缩物至所需浓度。
将甘蓝叶片(Brassica oleracea)浸在所需浓度的活性化合物制剂中进行处理,然后在甘蓝叶片上定殖草地粘虫的幼虫,同时一直保持叶片湿润。
在预定的一段时间后,测定杀虫活性,以%表示。100%表示已杀死所有幼虫;0%表示没有杀死一头幼虫。测定的致死率是采用Colby公式计算的(见页1)。
在该试验中,本申请的下列活性化合物混剂与单独使用的各活性化合物相比表现出增效活性:
表D
侵染植物的昆虫
草地粘虫试验
活性化合物 | 6天后的LC50 |
噁二唑虫已知 | 0.136ppm |
Clothianidin已知 | 0.662ppm |
本发明的噁二唑虫+Clothianidin(X)(1∶30) | 计算值 ** 0.589ppm观测值 * 0.027ppm |
观测值 *=观测活性
计算值 **=Carpenter公式的计算活性
Claims (2)
1.混合物,其包括下式的活性化合物噁二唑虫
和式(X)的Clothianidin
其中,所述噁二唑虫与所述Clothianidin以重量份计的比例为1∶1-1∶50。
2.权利要求1的混合物用于制备用于防治动物害虫的组合物的用途。
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AR032250A1 (es) | 2003-10-29 |
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AU2002228035A1 (en) | 2002-07-30 |
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BR0206550A (pt) | 2004-06-22 |
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EP1359803B1 (de) | 2007-12-19 |
EP1359803A1 (de) | 2003-11-12 |
MXPA03006481A (es) | 2004-10-15 |
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TWI244892B (en) | 2005-12-11 |
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