TW201701760A - Insecticidal arylpyrrolidines, processes for preparation thereof and use thereof as active ingredients for controlling animal pests - Google Patents

Abstract

The present invention relates to N-[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarboxamides in enantiomerically pure or in an enantiomerically enriched form, to processes for preparation thereof and to the use thereof for controlling animal pests.

Description

殺蟲的芳基吡咯啶、製備其之方法及其作為控制動物有害生物之活性成分之用途 Insecticidal arylpyrrole, method for preparing the same, and use thereof as an active ingredient for controlling animal pests

本發明係關於下文進一步顯示之呈鏡像異構物純或呈鏡像異構物富集形式之式(I)之N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺、製備其之方法及其用於控制動物有害生物之用途。 The present invention relates to N -[[2-fluoro-4-[2-hydroxy-3-(3,4) of formula (I), which is further shown below in the form of a spectroscopically pure or in the form of a specomer. ,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide, a process for preparing the same, and use thereof for controlling animal pests .

人們已知式(I)化合物N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及其殺有害生物性質(參見WO 2012/035011 A1)。其化學合成產生外消旋混合物。 The compound of formula (I) is known as N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrole Pyridyl]phenyl]methyl]cyclopropanecarbamide and its pesticidal properties (see WO 2012/035011 A1). Its chemical synthesis produces a racemic mixture.

迄今尚未闡述呈鏡像異構物純或鏡像異構物富集形式之N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之鏡像異構物、其分離及合成。 N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-), which is in the form of a pure or mirror image-enriched form, has not been described so far. A mirror image isomer of (trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide, separation and synthesis thereof.

然而，具體鏡像異構物純的對掌性芳基吡咯啶及相應衍生物在醫藥(WO 2014/039489 A1)及農用化學品工業(WO 2008/128711 A1、WO 2010/043315 A1、WO 2013/135724 A1)中令人感興趣，乃因其可有利地為醫藥或化學作物保護劑提供生物活性或活性更多之鏡像異構物或非鏡像異構物。此不僅防止製程中之浪費且亦避免可能由不期望之鏡像異構物引起之可能副效應(Nugent等人，Science 1993,259, 479；Noyori等人，CHEMTECH 1992,22,360)。 However, the specific mirror image isomers of pure palmitic aryl pyrrolidines and corresponding derivatives are in medicine (WO 2014/039489 A1) and agrochemical industry (WO 2008/128711 A1, WO 2010/043315 A1, WO 2013/ 135724 A1) is of interest because it can advantageously provide a biologically active or more active mirror image or non-image isomer for a pharmaceutical or chemical crop protection agent. This not only prevents waste in the process but also avoids possible side effects that may be caused by undesirable mirror image isomers (Nugent et al, Science 1993 , 259 , 479; Noyori et al, CHEMTECH 1992 , 22 , 360).

已闡述個別芳基吡咯啶(例如(3S)-4-[3-(3,5-二氯苯基)-3-(三氟甲基)吡咯啶-1-基]-2-甲酸甲酯)之鏡像選擇性合成(WO 2013/050301 A1)。 Have been described individually pyrrolidine aryl group (e.g., (3 S) -4- [3- ( 3,5- dichlorophenyl) -3- (trifluoromethyl) pyrrolidin-l-yl] -2-carboxylic acid Mirror-selective synthesis of esters (WO 2013/050301 A1).

亦已知藉助將β-芳基-β-三氟甲基取代之烯酮不對稱共軛氰化以形成(3R)-3,4-二氫-3,5-二苯基-3-(三氟甲基)-2H-吡咯、(2S,4R)-2,4-二苯基-4-(三氟甲基)吡咯啶及(2R,4R)-2,4-二苯基-4-(三氟甲基)吡咯啶來合成對掌性三氟甲基取代之二芳基吡咯啉及二芳基吡咯啶(參見H.Kawai等人，Angew.Chem.,Intern.Ed.51(20),4959-4962,2012)。 It is also known to asymmetrically conjugate cyanide of β-aryl-β-trifluoromethyl substituted ketene to form (3 R )-3,4-dihydro-3,5-diphenyl-3- (trifluoromethyl)-2 H -pyrrole, (2 S ,4 R )-2,4-diphenyl-4-(trifluoromethyl)pyrrolidine and (2 R ,4 R )-2,4 -Diphenyl-4-(trifluoromethyl)pyrrolidine to synthesize a palmitic trifluoromethyl-substituted diarylpyrroline and a diarylpyrrolidine (see H. Kawai et al., Angew. Chem., Intern.Ed. 51(20), 4959-4962, 2012 ).

迄今為止，藉由文獻方法以外消旋形式獲得之芳基吡咯啶之個別鏡像異構物一直係藉由複雜分離藉助在對掌性相上進行HPLC獲得。然而，在對掌性固定相上層析分離鏡像異構物通常不適於相對大量的活性成分，而僅用於提供相對少量。在對掌性相上使用HPLC之成本極大，因為尤其在製備型規模上所用材料成本較高且花費相當多的時間。 Heretofore, the individual mirror image isomers of arylpyrrolidine obtained by the racemic form of the literature method have been obtained by HPLC on the palm phase by complex separation. However, chromatographic separation of the mirror image isomers on the palmitic stationary phase is generally not suitable for relatively large amounts of active ingredient, but is only used to provide a relatively small amount. The cost of using HPLC on the palm phase is significant because the materials used, especially on the preparative scale, are costly and take considerable time.

就上文所概述之缺點及問題而言，業內急需可在工業及經濟上實施用於提供鏡像異構物富集之式(I)之N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之簡易製程 In view of the shortcomings and problems outlined above, there is an urgent need in the industry to industrially and economically implement N -[[2-fluoro-4-[2-hydroxyl] of formula (I) for providing enrichment of mirror image isomers. Simple process for -3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide

其中立體異構源碳原子係藉由*來標識。 The stereogenic source carbon atom is identified by *.

式(I)化合物可呈式(Ia)之(2S,3S)-非鏡像異構物、式(Ib)之(2R,3S)- 非鏡像異構物、式(Ic)之(2S,3R)-非鏡像異構物及式(Id)之(2R,3R)-非鏡像異構物之形式： The compound of formula (I) may be (2S, 3S)-non -image isomer of formula (Ia), (2R, 3S) of formula (Ib ) - non-image isomer, (2S, 3R of formula (Ic) ) - a non-image isomer and the form of (2R, 3R) - non-image isomer of formula (Id):

該目標係藉由製備鏡像異構物富集之式(I)之N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之製程來達成 The target is N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-) of formula (I) enriched by preparation of the mirror image isomer. Process for the formation of (trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide

其中立體異構源碳原子係藉由*來標識，該製程之特徵在於，在第一步驟中，式(II)之外消旋3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶 Wherein the stereogenic source carbon atom is identified by *, the process is characterized in that, in the first step, racemic 3-(3,4,5-trichlorophenyl)-3 is of formula (II) -(trifluoromethyl)pyrrolidine

其中立體異構源碳原子係藉由*來標識，借助於適宜鏡像異構物純的酸分離成式(IIa)及(IIb)之鏡像異構物 Wherein the stereogenic source carbon atom is identified by *, and is separated into the mirror image isomers of formulae (IIa) and (IIb) by means of a suitable image-isomerically pure acid.

且然後，在第二反應步驟中，使式(IIa)化合物在觸媒存在下與式(IV)之N-[(4-溴-2-氟苯基)甲基]環丙烷甲醯胺反應， And then, in a second reaction step, a compound of formula (IIa) is reacted with N-[(4-bromo-2-fluorophenyl)methyl]cyclopropanecarbamide of formula (IV) in the presence of a catalyst. ,

從而得到化合物式(IIIa)之N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之(S)-鏡像異構物 Thus, N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]benzene of the formula (IIIa) is obtained. (S)-mirroromer of (meth)cyclopropanecarbamide

且然後在第三反應步驟中在適宜氧化劑存在下在2位將該(S)-鏡像異構物羥基化，從而獲得式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺作為主要組份，或者使式(IIb)化合物在觸媒存在下與式(IV)之N-[(4-溴-2-氟苯基)甲基]環丙烷甲醯胺反應， And then the (S)-mirroromer is hydroxylated at the 2-position in the presence of a suitable oxidizing agent in a third reaction step to obtain ( 2S , 3S )- ( + ) - N- of formula (Ia) [[2-Fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]- ring Propanecarbamide as a main component or reacting a compound of the formula (IIb) with N-[(4-bromo-2-fluorophenyl)methyl]cyclopropanecarbamide of the formula (IV) in the presence of a catalyst ,

從而得到化合物式(IIIb)之N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之(R)-鏡像異構物 Thus, N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]benzene of the formula (IIIb) is obtained. (R)-mirroromer of (meth)cyclopropanecarbamide

且然後在第三反應步驟中在適宜氧化劑存在下在2位將該(R)-鏡像異構物羥基化，從而獲得式(Id)之(2R,3R)-(-)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺作為主要組份。 And then the (R)-mirroromer is hydroxylated at the 2-position in the presence of a suitable oxidizing agent in a third reaction step to obtain (2R,3R)-(-)-N-[[ 2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropane A Indoleamine is the main component.

較佳者係呈(2S,3S)-非鏡像異構物(Ia)或(2R,3S)-非鏡像異構物(Ib)之形式之式(I)化合物。 Preferred are compounds of formula (I) in the form of (2S,3S)-non -image isomer (Ia) or (2R,3S ) -non -image isomer (Ib).

尤佳者亦係由(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺(Ia)及(2R,3S)-非鏡像異構物(Ib)組成之(2S,3S)-非鏡像異構物富集之混合物。 Especially preferred is (2S,3S)- ( + ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(three composition diastereomers (Ib) of (2 S, 3 S) - fluoro-methyl) -1-pyrrolidinyl] phenyl] methyl] cyclopropanecarboxamide Amides (Ia) and (2R, 3S) - A mixture of non-image isomers enriched.

極尤佳者係式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺。 (2 S , 3 S )- ( + ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl) of the formula (Ia) --3-(Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide.

由於半胺縮醛結構，式(I)化合物可呈(2S,3S)-非鏡像異構物(Ia)或(2R,3S)-非鏡像異構物(Ib)或(2S,3R)-非鏡像異構物(Ic)或(2R,3R)-非鏡像異構物(Id)之形式(亦參見B.B.Snyder等人，J.Org.Chem.65,793-800,2000)。 Due to the half-amine acetal structure, the compound of formula (I) may be (2S, 3S) - non-image isomer (Ia) or (2R, 3S) - non-image isomer (Ib) or (2S, 3R) - The form of the non-image isomer (Ic) or (2R, 3R) - non-image isomer (Id) (see also BBSnyder et al, J. Org. Chem. 65, 793-800, 2000 ).

式(III)化合物可呈(S)-鏡像異構物(IIIa)及(R)-鏡像異構物(IIIb)之形式。 The compound of formula (III) may be in the form of (S) -mironomer (IIIa) and (R) -mirrromer (IIIb).

較佳者係式(IIIa)之(S)-鏡像異構物。 Preferred is the (S) -mirrromer of the formula (IIIa).

鏡像異構物富集之式(I)之N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺可藉由本發明製程以高鏡像異構物純度以及良好產率來製備。此外，本發明製程使得鏡像異構物比率能夠發生變化。更具體而言，期望之化合物係在不使用對掌性層析或同樣複雜的純化方法下獲得。 N-[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)) of the formula (I) enriched by the mirror image isomer The 1-pyridolidinyl]phenyl]methyl]cyclopropanecarbamide can be prepared by the process of the present invention in high image isomer purity as well as in good yields. In addition, the process of the present invention enables the image isomer ratio to vary. More specifically, the desired compounds are obtained without the use of palm chromatography or the same complicated purification method.

已發現式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之功效好於外消旋N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺(自WO 2012/035011 A1得知)。 (2 S , 3 S )- ( + ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3) of formula (Ia) -(Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide is more effective than racemic N -[[2-fluoro-4-[2-hydroxy-3-( 3,4,5-Trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide (known from WO 2012/035011 A1).

已進一步發現由式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(Ib)之(2R,3S)-非鏡像異構物組成之(2S,3S)-非鏡像異構物富集之混合物針對動物有害生物之功效好於外消旋N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺。 It has been further discovered that (2 S , 3 S )- ( + ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)) of formula (Ia) 3- (trifluoromethyl) -1-pyrrolidinyl] phenyl] methyl] cyclopropanecarboxamide and Amides of formula (Ib) of (2R, 3S) - diastereomers composition of (2 S, The mixture of 3 S )-non-mironomer is enriched for animal pests better than racemic N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichloro) Phenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide.

在此情形下，其中所存在之式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(Ib)之(2R,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之混合比率可為 51：49至61：39、71：29至81：19或91：9至99：1。 In this case, (2 S , 3 S )- ( + ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-) of the formula (Ia) Trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide and (2 R ,3 S )- ( + ) - (Ib) N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl The mixing ratio of cyclopropanecarbamide may be 51:49 to 61:39, 71:29 to 81:19 or 91:9 to 99:1.

另外已發現由主要組份式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(Ib)之(2R,3S)-非鏡像異構物亦及第二組份式(Ic)之(2S,3R)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(Id)之(2R,3R)-非鏡像異構物組成之(2S,3S)-(+)-非鏡像異構物富集之混合物之功效好於外消旋N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺。 Further, it has been found that the (2S,3S)-(+)-N-[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl) group of the main component (Ia) -3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide and (2R,3S)-non -image isomer of formula (Ib) and the second group (2 S ,3 R )- ( + ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3- (trifluoromethyl) -1-pyrrolidinyl] phenyl] methyl] cyclopropanecarboxamide and Amides of formula (Id) of (2R, 3R) - diastereomers composition of (2 S, 3 S) - ( + ) - The mixture of non-image isomers is better than racemic N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)) -3-(Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide.

反應方案I顯示(例如)式(Ia)之(S,S)-非鏡像異構物之製備： Reaction Scheme I shows the preparation of , for example, ( S,S )-non-image isomers of formula (Ia):

使式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶反應與式(IV)之N-[(4-溴-2-氟苯基)甲基]環丙烷甲醯胺，從而得到式(IIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺。 The reaction of (3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (IIa) with N-[(()) 4-bromo-2-fluorophenyl)methyl]cyclopropanecarbamide, thereby obtaining (3S)-(+)-N-[[2-fluoro-4-[3-(3, 4,5-Trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide.

已發現可在乙酸鉀及適宜氧來源(例如水或氧)存在下利用適宜氧 化劑(例如利用碘)將式(IIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺優先轉化為主要組份式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺(參見製備實例1)。 It has been found that suitable oxygen can be utilized in the presence of potassium acetate and a suitable source of oxygen such as water or oxygen. (3S)-(+)-N-[[2-Fluoro-4-[3-(3,4,5-trichlorophenyl)-3-) of the formula (IIIa) (for example, using iodine) (Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide is preferentially converted to (2S,3S)-(+)-N-[[2- in the main component formula (Ia) Fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide (See Preparation Example 1).

3-芳基-3-(三氟甲基)吡咯啶已為人所知且可藉由常用方法獲得。式(II)之外消旋3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶之製備已經闡述(參見WO 2008/128711 A1、WO 2010/043315 A1、WO 2013/135724 A1、WO 2014/039489 A1)。光學活性3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶在WO 2013/050301中有提及(參見第74頁表A中之化合物1)，但未報告任何物理化學數據。 3-Aryl-3-(trifluoromethyl)pyrrolidine is known and can be obtained by a usual method. The preparation of racemic 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (II) has been described (see WO 2008/128711 A1, WO 2010/043315 A1). WO 2013/135724 A1, WO 2014/039489 A1). Optically active 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine is mentioned in WO 2013/050301 (see compound 1 in Table A on page 74), but No physicochemical data was reported.

另外，人們已知藉助L-(+)-酒石酸或層析分離將外消旋3-(3,5-二氯苯基)-3-(三氟甲基)吡咯啶鏡像異構物分離為相應(3R)-及(3S)-鏡像異構物(參見WO 2012/045700 A1、WO 2013/050301 A1)。 In addition, it is known to separate racemic 3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine mirror isomers by means of L - ( + ) -tartaric acid or chromatographic separation. the corresponding (3 R) - and (3 S) - enantiomers (see WO 2012/045700 A1, WO 2013/050301 A1) .

現已發現可借助於適宜鏡像異構物純的酸將式(II)之外消旋3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶分離為式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶及式(IIb)之(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶。 It has now been found that racemic 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (II) can be isolated by means of an acid which is a suitable mirror image of the pure isomer. (3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (IIa) and (3R)-(- of formula (IIb) --3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine.

適於此分離之鏡像異構物純的酸係苦杏仁酸，例如D-及L-苦杏仁酸、(R)-O-乙醯基苦杏仁酸、(S)-O-乙醯基苦杏仁酸、(S)-及(R)-(-)-3-氯苦杏仁酸；(R)-及(S)-甲氧基苯基乙酸；酒石酸衍生物，例如L-及D-酒石酸、二-對-甲苯基-L-酒石酸、二苯甲醯基-L-酒石酸、二苯甲醯基-D-酒石酸、N,N-二甲基-(-)-及(+)-O,O‘-二苯甲醯基-L-酒石醯胺；(2R,3R)-酒石酸；芳基丙酸，例如(R)-及(S)-萘普生(naproxene)、(R)-及(S)-布洛芬(ibuprofen)；鄰苯二甲酸衍生物，例如(R)-及(S)-N-(1-苯基乙基)鄰苯二甲酸；或其他酸，例如(S)-及(R)-2-[(苯基胺基)羰基氧基]丙酸；(-)-薄荷氧基乙酸；L-馬來酸；(R)-2-羥基-2-甲基琥珀 酸；L-焦麩胺酸、(S)-(-)-2-乙醯氧基丙酸、(S)-(+)-苯基琥珀酸；磷酸衍生物，例如Anicyphos P、Anicyphos N、(S)-及(R)-1,1‘-聯萘-2,2‘-二磷酸氫酯；磺酸，例如(+)-及(-)-樟腦-10-磺酸；及自糖製得之酸衍生物，例如(-)-2,2：4,6-二-O-亞異丙基-2-酮-L-古洛糖酸單水合物。 An acid-based mandelic acid suitable for this separation, such as D- and L -mandelic acid, ( R )-O-acetamidomyric acid, ( S )-O-acetamido Mandelic acid, ( S )- and ( R )- ( - ) -3-chloromandelic acid; ( R )- and ( S )-methoxyphenylacetic acid; tartaric acid derivatives such as L- and D -tartaric acid , di- p -tolyl- L -tartaric acid, benzhydryl- L -tartaric acid, benzhydryl- D -tartaric acid, N,N -dimethyl- ( - ) - and ( + ) - O , O '- benzophenone acyl - L - Amides tartar; (2 R, 3 R) - tartaric acid; arylpropionic acids such as (R) - and (S) - naproxen (naproxene), ( R) - and (S) - ibuprofen; phthalic acid derivatives such as (R) - and (S) - N - (1-phenylethyl) phthalic acid; or other acids , for example, (S) - and (R) -2-[(phenylamino)carbonyloxy]propionic acid; ( - ) -menthyloxyacetic acid; L -maleic acid; ( R )-2-hydroxy- 2-methylsuccinic acid; L -pyroglutamic acid, (S) - ( - ) -2-ethoxypropoxypropionic acid, (S) - ( + ) -phenylsuccinic acid; phosphoric acid derivatives such as Anicyphos P, anicyphos N, (S) - and (R) -1,1'- binaphthyl-2,2'-diyl hydrogen phosphate Sulfonic acids, such as (+) - and (-) - camphor-10-sulfonic acid; and a sugar-acid derivatives obtained from the system, such as (-) 2,2: 4,6-di - O - isopropylidene Keto-2-keto- L -gulonic acid monohydrate.

尤佳可使用式(Va)及(Vb)之(S)-(+)-及(R)-(-)-2-[(苯基胺基)羰基氧基]丙酸用於分離式(II)之外消旋3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶(參見反應方案II)。 It is preferred to use (S) - ( + ) - and (R) - ( - ) -2-[(phenylamino)carbonyloxy]propionic acid of formula (Va) and (Vb) for separation ( II) Racemic 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine (see Scheme II).

最佳地，使用式(Vb)之(R)-(-)-2-[(苯基胺基)羰基氧基]丙酸分離式(II)之外消旋3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶。 Most preferably, the (R) - ( - ) -2-[(phenylamino)carbonyloxy]propionic acid of the formula (Vb) is used to separate the formula (II) by racemic 3-(3,4,5 -Trichlorophenyl)-3-(trifluoromethyl)pyrrolidine.

對於分離，在第一反應步驟中，首先將1mol式(II)之外消旋3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶裝填於適宜溶劑中，並添加0.5mol溶解於適宜溶劑中之式(Vb)(R)-(-)-2-[(苯基胺基)羰基氧基]丙酸。所形成之式(IIa)-(Vb)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶鎓鹽沈澱出來且可以簡易方式去除。式(IIb)之(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶留於溶液中。為釋放式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶，在第二反應步驟中，將式(IIa)-(Vb)之鹽與適宜鹼性輔助物(鹼)一起攪拌且然後用適宜溶劑萃取(參見反應方案II及製備實例1，反應步驟1及2)。 For the separation, in the first reaction step, 1 mol of the racemic 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (II) is first charged in a suitable solvent. And adding 0.5 mol of the formula (Vb) (R) - ( - ) -2-[(phenylamino)carbonyloxy]propionic acid dissolved in a suitable solvent. The formed (3S)- ( + )- 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidinium salt of the formula (IIa)-(Vb) is precipitated and Can be removed in a simple way. (3R)-(-)-3-(3,4,5-Trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (IIb) is left in solution. To release (3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (IIa), in the second reaction step, The salt of (IIa)-(Vb) is stirred with a suitable basic auxiliary (base) and then extracted with a suitable solvent (see Reaction Scheme II and Preparation Example 1, Reaction Steps 1 and 2).

此處式(IIa)-(Vb)鹽之結晶所需要之時間有利地相對較短且該鹽具有極好過濾性。 The time required for the crystallization of the salt of the formula (IIa)-(Vb) here is advantageously relatively short and the salt has excellent filterability.

反應方案IIReaction Scheme II

式(Va)及(Vb)之(S)-(+)-及(R)-(-)-2-[(苯基胺基)羰基氧基]丙酸可自市面購得(例如(S)-鏡像異構物：Acros Organics,Alfa Aesar；(R)-鏡像異構物：Aurora Building Blocks)或可藉由普遍已知之方法獲得(對於(S)-鏡像異構物參見DE 19619445 C1)。 (S) - ( + ) - and (R) - ( - ) -2-[(phenylamino)carbonyloxy]propionic acid of the formulae (Va) and (Vb) are commercially available (for example (S ) - enantiomers: Acros Organics, Alfa Aesar; ( R) - enantiomer: Aurora Building Blocks) or may be obtained by the methods generally known (for (S) - enantiomer see DE 19619445 C1) .

反應步驟1(反應方案II)之適宜溶劑係二甲基亞碸、N-甲基吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、環丁碸、四甲基脲、1,3-二甲基-2-咪唑啶酮、芳香族烴(例如甲苯)、脂肪族烴(例如正庚烷)、醚(例如四氫呋喃、2-甲基四氫呋喃、甲基第三丁基醚(MTBE)及二乙二醇二甲基醚(例如五乙二醇、六乙二醇及聚乙二醇)及所提及溶劑之混合物。 Suitable solvents for the reaction step 1 (Reaction Scheme II) are dimethyl hydrazine, N-methylpyrrolidone, N,N -dimethylacetamide, N,N -dimethylformamide, and cyclobutylene. Anthracene, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, aromatic hydrocarbons (such as toluene), aliphatic hydrocarbons (such as n-heptane), ethers (such as tetrahydrofuran, 2-methyltetrahydrofuran, A mixture of methyl tert-butyl ether (MTBE) and diethylene glycol dimethyl ether (eg, pentaethylene glycol, hexaethylene glycol, and polyethylene glycol) and the solvents mentioned.

較佳者係使用醚(例如四氫呋喃、2-甲基四氫呋喃、甲基第三丁基醚(MTBE)及二乙二醇二甲基醚)作為反應步驟1(反應方案II)之溶 劑。 Preferably, an ether such as tetrahydrofuran, 2-methyltetrahydrofuran, methyl tertiary butyl ether (MTBE) and diethylene glycol dimethyl ether is used as the reaction step 1 (reaction scheme II). Agent.

極尤佳者係使用甲基第三丁基醚(MTBE)作為反應步驟1(反應方案II)之溶劑。 It is especially preferred to use methyl tert-butyl ether (MTBE) as the solvent for reaction step 1 (Reaction Scheme II).

適於反應步驟1(反應方案II)之鹼性輔助物(鹼)係無機碳酸鹽(例如碳酸鉀或碳酸鈉)、鹼性四級銨鹽(例如苄基三甲基氫氧化銨)、無機氫化物(例如氫化鋰、氫化鉀或氫化鈉)、鹼金屬二異丙基醯胺、鹼金屬六甲基二矽烷胺化物(例如六甲基二矽烷胺化鋰及六甲基二矽烷胺化鈉)、鹼金屬烷氧化物(例如第三丁醇鋰、第三丁醇鉀或第三丁醇鈉、異丙醇鋰、異丙醇鉀或異丙醇鈉、甲醇鋰、甲醇鉀或甲醇鈉)、胺(例如氨)、1,8-二氮雜二環[5.4.0]十一-7-烯、1,4-二氮雜二環[2.2.2]辛烷及1,8-雙(二甲基胺基)萘及所提及鹼性輔助物之混合物。 A basic auxiliary (base) suitable for reaction step 1 (reaction scheme II) is an inorganic carbonate (for example, potassium carbonate or sodium carbonate), a basic quaternary ammonium salt (for example, benzyltrimethylammonium hydroxide), and inorganic a hydride (such as lithium hydride, potassium hydride or sodium hydride), an alkali metal diisopropyl decylamine, an alkali metal hexamethyldioxane aminide (such as lithium hexamethyldioxane and hexamethyldioxanylation) Sodium), an alkali metal alkoxide (such as lithium tributoxide, potassium or potassium t-butoxide, lithium isopropoxide, potassium isopropoxide or sodium isopropoxide, lithium methoxide, potassium methoxide or methanol Sodium), amines (eg ammonia), 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane and 1,8 a mixture of bis(dimethylamino)naphthalene and the mentioned basic auxiliary.

尤其適於反應步驟1(反應方案II)之鹼性輔助物(鹼)係水性或非水性無機鹼，例如氫氧化鉀、氫氧化鈉、氫氧化鋰、碳酸鉀、碳酸鈉及碳酸鋰。 The basic auxiliary (base) which is particularly suitable for the reaction step 1 (Reaction Scheme II) is an aqueous or non-aqueous inorganic base such as potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate and lithium carbonate.

式(IV)之N-[(4-溴-2-氟苯基)甲基]環丙烷甲醯胺已為人所知且自市面購得(參見CAS登記號：1389737-44-3；Akos Out of Stock Catalog,Germany；Aurora Screening Library,USA)或可藉由標準製備方法獲得，例如根據WO 2008/070447 A1藉助N-醯化自4-溴-2-氟苄基胺(購自：ABCR,ACROS)及環丙烷羰基氯獲得(參見其中所闡述在二氯甲烷中且在N-乙基二異丙基胺存在下自4-溴苄基胺及環丙烷羰基氯製備N-[(4-溴-2-氟苯基)甲基]環丙烷甲醯胺)。 N-[(4-bromo-2-fluorophenyl)methyl]cyclopropanecarbamide of formula (IV) is known and commercially available (see CAS Registry Number: 1389737-44-3; Akos) Out of Stock Catalog, Germany; Aurora Screening Library, USA) may be obtained by standard preparation methods, for example by N -deuterated from 4-bromo-2-fluorobenzylamine according to WO 2008/070447 A1 (purchased from: ABCR) , ACROS) and cyclopropanecarbonyl chloride (see the preparation of N -[(4) from 4-bromobenzylamine and cyclopropanecarbonyl chloride in dichloromethane and in the presence of N -ethyldiisopropylamine. -Bromo-2-fluorophenyl)methyl]cyclopropanecarbamamine).

可藉由自文獻已知之方法、例如根據闡述於WO 2012/035011 A1中針對外消旋化合物之變體在溶劑、鹼性輔助物(鹼)及適宜觸媒系統存在下，利用式(IV)之N-[(4-溴-2-氟苯基)甲基]環丙烷甲醯胺對式(IIa)之(3S)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶實施N-芳基化以形成式(IIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲 基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺。 Formula (IV) can be utilized by methods known in the literature, for example, in the presence of solvents, basic auxiliaries (bases) and suitable catalyst systems in accordance with WO 2012/035011 A1 for variants of racemic compounds. N-[(4-bromo-2-fluorophenyl)methyl]cyclopropanecarbamide to (3 S )- ( - ) -3-(3,4,5-trichlorobenzene of formula (IIa) N -arylation of benzyl-3-(trifluoromethyl)pyrrolidine to form (3S)-(+)-N-[[2-fluoro-4-[3-(3, 4,5-Trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide.

在反應步驟1(反應方案I)中用於N-芳基化之溶劑係甲苯及鹼性輔助物第三丁醇鈉(對於式(IIa)之(3S)-鏡像異構物亦參見製備實例1反應步驟3)。適宜觸媒系統之實例係在4,5-雙(二苯基膦基)-9,9-二甲基呫噸存在下之參(二亞苄基丙酮)二鈀(0)。 Reaction Step 1 (Reaction Scheme I) N for at - sodium tert-butoxide arylation of toluene, and solvent-based alkaline aid ((3 S) for the formula (IIa) - The enantiomeric Also see Preparation Example 1 Reaction Step 3). An example of a suitable catalyst system is ginseng (dibenzylideneacetone) dipalladium (0) in the presence of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene.

另一選擇為，亦可藉由多階段反應自式(II)之外消旋3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶繼續進行製備式(I)化合物(參見WO 2010/043315)。 Alternatively, the preparation can be continued by multi-stage reaction from racemic 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (II). (I) Compound (see WO 2010/043315).

此製備變體可同樣使用式(IIa)之(3S)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶、使用由式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶及式(IIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物及使用式(IIb)之(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶來進行(亦參見製備實例2及3)。 This preparation variant can also be used (3S) -3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (IIa), using formula (IIa) ( 3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine and (3R) - ( - ) -an image isomer of formula (IIb) the composition (3 S) - (+) - enantiomer enriched mixtures and the use of formula (IIb) of (3R) - (-) - 3- (3,4,5- trichlorophenyl) -3 -(Trifluoromethyl)pyrrolidine was carried out (see also Preparation Examples 2 and 3).

反應方案III顯示(例如)自式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶繼續進行製備式(Ia)之(S,S)-非鏡像異構物。 Reaction Scheme III shows, for example, the preparation of (3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine from formula (IIa) ( S,S )-non-image isomers of (Ia).

在此程序中，藉由自文獻已知之方法在反應步驟1中使式(IIa)之 (3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶與式(VI)之2,4-二氟苯甲腈反應，從而得到式(VIIa)之(3S)-(+)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲腈(N-芳基化)，然後在二-(第三丁基羰基)酸酐(Boc₂O)及氯化鎳(II)存在下發生反應，從而得到式(VIIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]-第三丁基氧基羰基甲醯胺。 In this procedure, (3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(III) of formula (IIa) is reacted in the reaction step 1 by a method known from the literature. fluoromethyl) pyrrolidine of formula (VI) of 2,4-difluorobenzonitrile, to yield formula (Vila) of (3 S) - (+) -2- fluoro-4- [3- (3 ,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]benzonitrile ( N -arylate), then in di-(t-butylcarbonyl) anhydride ( The reaction occurs in the presence of Boc ₂ O) and nickel (II) chloride, thereby obtaining (3 S )- ( + ) - N -[[2-fluoro-4-[3-(3,4, 5-Trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]-t-butyloxycarbonylcarbamidine.

後續N-去封端(Boc拆解)及利用環丙基羰基氯之N-醯化產生式(IIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺，藉助氧化(C-2羥基化)將其轉化為式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺(參見製備實例3)。 Subsequent N -deblocking (Boc disassembly) and N -deuteration using cyclopropylcarbonyl chloride to produce (3S)-(+)-N-[[2-fluoro-4-[3- (3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide, by oxidation (C-2 hydroxylation) It is converted into (2S,3S)-(+)-N-[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-) of formula (Ia) (Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide (see Preparation Example 3).

反應步驟1(反應方案III)中所使用之式(VI)之2,4-二氟苯甲腈係自市面購得的。 The 2,4-difluorobenzonitrile of the formula (VI) used in Reaction Step 1 (Reaction Scheme III) is commercially available.

可藉由自文獻已知之方法、例如對於外消旋化合物根據闡述於WO 2010/043315 A1中之變體在溶劑及鹼性輔助物(鹼)存在下，對式(IIa)之(3S)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶實施N-芳基化以形成式(VIIa)之(3S)-(-)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲腈。 (3 S ) of formula (IIa) can be obtained by a method known from the literature, for example, for a racemic compound according to the variants described in WO 2010/043315 A1 in the presence of a solvent and a basic auxiliary (base) - (-) - 3- (3,4,5-trichlorophenyl) -3- (trifluoromethyl) pyrrolidine embodiment N - aryl group to form the formula (Vila) of (3 S) - (- ) -2-fluoro-4- [3- (3,4,5-trichlorophenyl) -3- (trifluoromethyl) -1-pyrrolidinyl] benzonitrile.

在反應步驟1(反應方案III)中在N-芳基化中使用之溶劑可為N,N-二甲基甲醯胺(DMF)及鹼性輔助物三乙胺(對於式(VIIb)之(3R)-鏡像異構物亦參見製備實例2反應步驟3)。 The solvent used in the N -arylation in the reaction step 1 (reaction scheme III) may be N,N -dimethylformamide (DMF) and the basic auxiliary triethylamine (for the formula (VIIb)) ( 3R )-mirrible isomers are also described in Preparation Example 2, Reaction Step 3).

根據反應步驟2對式(VIIa)化合物中腈功能實施還原及後續對原位形成之(3S)-(-)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲胺實施N-醯化以形成式(VIIIb)之(3R)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]-第三丁基氧基羰基甲醯胺，係在溶劑、適宜還原劑及醯化劑存在下進行。 Reduction of the nitrile function in the compound of formula (VIIa) according to reaction step 2 and subsequent formation of ( 3S )- ( - ) -2-fluoro-4-[3-(3,4,5-trichlorobenzene) in situ yl) -3- (trifluoromethyl) -1-pyrrolidinyl] benzylamine embodiment N - acylated to form formula (Vlllb) of (3 R) - (-) - N - [[2- fluoro - 4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]-t-butyloxycarbonylcarbamidine It is carried out in the presence of a solvent, a suitable reducing agent, and a hydrating agent.

在反應步驟2(反應方案III)中式(VIIa)化合物中腈功能之還原及後續原位N-醯化中使用之溶劑係(例如)甲醇及1,4-二噁烷之溶劑混合物。所用還原劑可為氯化鎳(II)且後續N-醯化可(例如)在二碳酸二-第三丁基酯存在下進行。 The solvent used in the reduction of the nitrile function and the subsequent in situ N -deuteration in the compound of the formula (VIIa) in Reaction Scheme 2 (Reaction Scheme III) is, for example, a solvent mixture of methanol and 1,4-dioxane. The reducing agent used may be nickel (II) chloride and the subsequent N-deuteration may be carried out, for example, in the presence of di-tert-butyl dicarbonate.

反應步驟3(反應方案III)中式(VIIIa)之(3S)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]-第三丁基氧基羰基甲醯胺之N-去封端(Boc保護基團之拆解)可在室溫下在酸性輔助物(例如於1,4-二噁烷中之4N鹽酸)存在下實現。 (3 S )- ( - ) - N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-) of the formula (VIIIa) in Reaction Scheme 3 (Reaction Scheme III) N -deblocking (disassembly of Boc protecting group) of (trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]-t-butyloxycarbonylcarbamidine at room temperature This is achieved in the presence of an acidic adjuvant such as 4N hydrochloric acid in 1,4-dioxane.

隨後，在適宜溶劑存在下且在鹼性輔助物存在下利用環丙基羰基氯醯化式(IXa)之(3S)-(-)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲基氯化銨。 Subsequently, (3 S )- ( - ) -2-fluoro-4-[3-(3,4) of formula (IXa) is deuterated with cyclopropylcarbonyl chloride in the presence of a suitable solvent and in the presence of a basic auxiliary. , 5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]benzyl ammonium chloride.

在反應步驟3(反應方案III)中在N-醯化中所使用之溶劑係二氯甲烷及鹼性輔助物吡啶(對於式(IIIb)之(3R)-鏡像異構物亦參見製備實例2反應步驟6)。 Also see Preparation Example enantiomers - in the N (Reaction Scheme III), the reaction step 3 - Solvent-based alkaline dichloromethane and pyridine aid in the use of acylated (for the formula (IIIb) of (3 R) 2 reaction step 6).

可在適宜溶劑存在下且在適宜氧化劑存在下對式(IIIa)之(3S)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺實施最終氧化(C-2羥基化)，從而得到式(Ia)之(2S,3S)-(-)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺。 (3 S )- ( - ) - N -[[2-fluoro-4-[3-(3,4,5-trichlorobenzene) of formula (IIIa) in the presence of a suitable solvent in the presence of a suitable oxidizing agent (3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide is subjected to final oxidation (C-2 hydroxylation) to give (2 S of formula (Ia) ,3 S )- ( - ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1- Pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide.

在反應步驟3(反應方案III)中在氧化(C-2羥基化)式(IIIa)化合物中所使用之溶劑係甲醇，且氧化劑係碘，在乙酸鉀存在下進行(對於式(IIIb)之(2R,3R)-鏡像異構物亦參見製備實例2反應步驟7)。 The solvent used in the oxidation (C-2 hydroxylation) of the compound of the formula (IIIa) in the reaction step 3 (reaction scheme III) is methanol, and the oxidizing agent is iodine, which is carried out in the presence of potassium acetate (for the formula (IIIb)) (2 R , 3 R )-mirromer is also described in Preparation Example 2, Reaction Step 7).

可用於羥基化反應之氧化劑並不受製於任何特殊要求。原則上可使用能夠在2位氧化N-芳基吡咯啶之任何氧化劑。適於製備N-芳基-(2-羥基)吡咯啶之氧化劑係(例如)過氧化氫、二氧化錳、高錳酸鉀、氧化釕(VIII)；過酸，例如間氯過氧苯甲酸(MCPBA)；醌，例如2,3- 二氯-5,6-二氰基-1,4-苯醌(DDQ)、四氯-1,2-苯醌(鄰四氯苯醌)、四氯-1,4-苯醌(四氯苯醌)；鈰(IV)鹽，例如硝酸鈰(IV)銨(CAN)；銀鹽，例如無機或有機銀(II)鹽，例如氟化銀(II)、雙(α,α‘-聯吡啶)硝酸銀(II)、雙(α,α‘-聯吡啶)過氧二硫酸銀(II)、吡啶甲酸銀(II)及四(吡啶)銀(II)；超價碘化合物，例如[雙(三氟乙醯氧基)碘]苯、[雙(乙醯氧基)碘]苯、氧碘苯、五氟氧碘苯、2-二氧碘基苯甲酸，在乙酸鉀及/或水存在下、在水及腈或氧存在下之碘(亦參見WO2012/035011)。 The oxidizing agent which can be used for the hydroxylation reaction is not subject to any special requirements. Any oxidizing agent capable of oxidizing N -arylpyrrolidine at the 2-position can be used in principle. Suitable oxidizing agents for the preparation of N-aryl-(2-hydroxy)pyrrolidine are, for example, hydrogen peroxide, manganese dioxide, potassium permanganate, cerium oxide (VIII); peracids such as m-chloroperoxybenzoic acid (MCPBA); hydrazine, for example, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,2-benzoquinone (o-tetrachlorobenzoquinone), four Chloro-1,4-benzoquinone (tetrachlorophenylhydrazine); cerium (IV) salt, such as cerium (IV) ammonium nitrate (CAN); silver salt, such as inorganic or organic silver (II) salt, such as silver fluoride ( II), bis(α,α'-bipyridyl) silver nitrate (II), bis(α,α'-bipyridine) silver peroxydisulfate (II), silver (II) picolinate and tetra (pyridine) silver ( II); supervalent iodine compounds, such as [bis(trifluoroethyloxy)iodo]benzene, [bis(ethyloxy)iodo]benzene, oxyiodobenzene, pentafluorooxyiodobenzene, 2-dioxyiodo Benzoic acid, iodine in the presence of potassium acetate and/or water in the presence of water and nitrile or oxygen (see also WO2012/035011).

較佳氧化劑係在乙酸鉀及水存在下之碘。氧化劑對N-芳基吡咯啶之莫耳比在3.5：1至5.5：1之範圍內，較佳地介於4.0：1與5.0：1之間。 Preferred oxidizing agents are iodine in the presence of potassium acetate and water. The molar ratio of oxidant to N -arylpyrrolidine is in the range of from 3.5:1 to 5.5:1, preferably between 4.0:1 and 5.0:1.

可在溶劑存在下將式(III)化合物氧化為式(I)化合物。適宜溶劑尤其包括：醚，例如THF、二噁烷、二乙基醚、二甘二甲醚、甲基第三丁基醚(MTBE)、第三戊基甲基醚(TAME)、二甲基醚(DME)、2-甲基-THF、乙腈、丁腈、甲苯、二甲苯、1,3,5-三甲苯、乙酸乙酯、乙酸異丙基酯、醇(例如甲醇、乙醇、丙醇、丁醇、乙二醇)、碳酸伸乙酯、碳酸伸丙酯、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基吡咯啶酮、氫鹵烴及芳香族烴(尤其氫氯烴例如四氯乙烯、四氯乙烷、二氯丙烷、二氯甲烷、二氯丁烷、氯仿、四氯化碳、三氯乙烷、三氯乙烯、五氯乙烷、二氟苯、1,2-二氯乙烷、氯苯、溴苯、二氯苯、氯甲苯、三氯苯)；4-甲氧基苯、氟化脂肪族化合物及芳香族化合物(例如三氯三氟乙烷、三氟甲苯、4-氯三氟甲苯)及水。亦可使用溶劑混合物。 The compound of formula (III) can be oxidized to the compound of formula (I) in the presence of a solvent. Suitable solvents include, in particular, ethers such as THF, dioxane, diethyl ether, dimethyl dimethyl ether, methyl tert-butyl ether (MTBE), third amyl methyl ether (TAME), dimethyl Ether (DME), 2-methyl-THF, acetonitrile, butyronitrile, toluene, xylene, 1,3,5-trimethylbenzene, ethyl acetate, isopropyl acetate, alcohol (eg methanol, ethanol, propanol) , butanol, ethylene glycol), ethyl carbonate, methyl propyl carbonate, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, hydrogen Halon and aromatic hydrocarbons (especially hydrochlorocarbons such as tetrachloroethylene, tetrachloroethane, dichloropropane, dichloromethane, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichloroethylene, Pentachloroethane, difluorobenzene, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene); 4-methoxybenzene, fluorinated aliphatic compounds and aromatics Group compounds (eg trichlorotrifluoroethane, trifluorotoluene, 4-chlorobenzotrifluoride) and water. A solvent mixture can also be used.

氧化(C-2羥基化)通常係在介於20℃與100℃之間、較佳地介於40℃與80℃之間、最佳地介於50℃與60℃之間的溫度下且在標準壓力下進行。 Oxidation (C-2 hydroxylation) is typically between 20 ° C and 100 ° C, preferably between 40 ° C and 80 ° C, optimally between 50 ° C and 60 ° C and Performed under standard pressure.

式(I)化合物之製備可根據(例如)WO 2012/035011 A1進行。 The preparation of the compounds of the formula (I) can be carried out, for example, according to WO 2012/035011 A1.

可例如藉由在處理後去除(參見製備實例1)或藉由層析純化(參見 製備實例2至4)分離期望之式(I)化合物。 Can be removed, for example, by treatment (see Preparation Example 1) or by chromatography (see Preparation Examples 2 to 4) The desired compound of formula (I) was isolated.

藉由本發明製程，所獲得式(III)化合物具有(+)：(-)-鏡像異構物50.5：49.5至99.5：0.5、較佳地60：40至95：5且更佳地75：25至90：10、最佳地(+)：(-)-鏡像異構物80：20至85：15之鏡像異構物比率。因此，在指定範圍內，較佳者係彼等具有過量(+)-鏡像異構物之鏡像異構物比率。 By the process of the present invention, the compound of formula (III) obtained has ( + ):( - ) -image isomer 50.5:49.5 to 99.5:0.5, preferably 60:40 to 95:5 and more preferably 75:25 Up to 90:10, optimally ( + ): ( - ) - mirror image isomer ratio of 80:20 to 85:15. Therefore, within the specified range, it is preferred that they have a ratio of mirror image isomers of excess ( + ) -image isomers.

因此，鏡像異構物過量可在0% ee與99% ee之間。鏡像異構物過量係化合物之鏡像異構物純度的間接量度且指示純鏡像異構物在混合物中之比例，該混合物之其他部分係化合物之外消旋物。 Thus, the image isomer excess can be between 0% ee and 99% ee. An indirect measure of the purity of the enantiomers of the enantiomers of the image isomer and indicates the ratio of pure opal isomers in the mixture. The other part of the mixture is the racemate of the compound.

藉由本發明製程獲得之式(I)化合物具有(+)：(-)-非鏡像異構物65：35至99.5：0.5、較佳地75：25至95：5且更佳地80：20至90：10、最佳地(+)：(-)-非鏡像異構物84：16至88：12之非鏡像異構物比率。因此，在指定範圍內，較佳者係彼等具有過量(+)-非鏡像異構物之鏡像異構物比率。 The compound of formula (I) obtained by the process of the invention has ( + ):( - ) -non-image isomer 65:35 to 99.5:0.5, preferably 75:25 to 95:5 and more preferably 80:20 Up to 90:10, optimally ( + ): ( - ) - non-image isomer 84: 16 to 88: 12 non-image isomer ratio. Thus, within the specified ranges, it is preferred that they have an image (or ) ratio of excess ( + ) -non-image isomers.

方法及用途 Method and use

本發明亦係關於控制動物有害生物之方法，其中式(I)化合物被允許作用於動物有害生物及/或其行為。較佳地在農業及林業中及在材料保護中實施動物有害生物之控制。手術或治療性治療人類或動物身體之方法及在人類或動物身體上實施之診斷方法較佳地排除在此之外。 The invention also relates to a method of controlling an animal pest, wherein the compound of formula (I) is allowed to act on an animal pest and/or its behavior. Control of animal pests is preferably carried out in agriculture and forestry and in the protection of materials. Methods of surgical or therapeutic treatment of the human or animal body and diagnostic methods performed on the human or animal body are preferably excluded.

本發明進一步係關於式(I)化合物之用途，其用作殺有害生物劑，尤其作物保護劑。 The invention further relates to the use of a compound of formula (I) for use as a pesticide, especially a crop protectant.

在本申請案之上下文中，術語「殺有害生物劑」亦總包含術語「作物保護劑」。 In the context of this application, the term "killing agent" also always includes the term "crop protection agent".

式(I)化合物鑒於良好植物抗逆性、有利的恆溫動物毒性及良好的環境相容性適於保護植物及植物器官免受生物及非生物應力因素，適於增加收穫產量，適於改良收穫物質之品質且適於控制動物有害生 物，尤其昆蟲、蛛形類、蠕蟲、線蟲及軟體動物，該等有害生物係在農業中、在園藝中、在畜牧業中、在水生養殖中、在林業中、在花園及娛樂設施中、在儲存產品及材料之保護中及在衛生部門中遇到的。 The compound of the formula (I) is suitable for protecting plants and plant organs from biotic and abiotic stress factors in view of good plant stress resistance, favorable constant temperature animal toxicity and good environmental compatibility, and is suitable for increasing harvest yield and suitable for improving harvest. The quality of the substance and is suitable for controlling the harmfulness of animals Objects, especially insects, arachnids, worms, nematodes and mollusks, in agriculture, in horticulture, in animal husbandry, in aquaculture, in forestry, in gardens and in recreational facilities. , in the protection of stored products and materials and in the health sector.

在本專利申請案之上下文中，術語「衛生」應理解為意指目的係預防病症(具體而言傳染性疾病)及用來保持人類、動物及/或環境健康及/或維持清潔之所有措施、過程及程序之整體。根據本發明，此包括具體而言對(例如)紡織品或主要玻璃、木材、混凝土、瓷器、陶瓷、塑膠或金屬之固體表面之清潔、消毒及滅菌，及保持其清潔掉衛生有害生物及/或其糞便之措施。根據本發明就此而言亦排除手術或治療性治療人類或動物身體之過程及在人類或動物身體上進行之診斷過程。 In the context of this patent application, the term "hygienic" is understood to mean the purpose of preventing a condition, in particular an infectious disease, and all measures for maintaining human, animal and/or environmental health and/or maintaining cleanliness. The whole process, process and procedure. According to the invention, this includes, in particular, the cleaning, disinfection and sterilization of, for example, textiles or solid surfaces of mainly glass, wood, concrete, porcelain, ceramics, plastics or metals, and keeping them clean of hygienic pests and/or The measure of its feces. In accordance with the invention, the process of surgical or therapeutic treatment of the human or animal body and the diagnostic process performed on the human or animal body are also excluded.

因此，術語「衛生部門」包括其中該等衛生措施、過程及程序至關重要之所有區域、技術領域及商業利用場所，例如在廚房、麵包房、機場、浴室、游泳池、購物中心、旅館、醫院、畜舍等中之衛生。 Therefore, the term “health sector” includes all areas, technical areas and commercial uses where such health measures, processes and procedures are essential, such as in kitchens, bakeries, airports, bathrooms, swimming pools, shopping centres, hotels, hospitals. Health in the barn, etc.

因此，術語「衛生有害生物」應理解為意指一或多種具體而言出於健康原因其存在在衛生部門中較成問題之動物有害生物。因此，主要目的係在衛生部門中最少化或預防衛生有害生物或與其接觸。具體而言，此可藉由使用殺有害生物劑來實現，其中該藥劑可在預防上及僅在感染之情形下使用以控制有害生物。亦可使用藉由避免或減少與有害生物接觸而起作用之藥劑。衛生有害生物係(例如)下文素提及之有機體。 Thus, the term "hygienic pest" is understood to mean one or more animal pests that are more problematic in the health sector for health reasons. Therefore, the primary objective is to minimize or prevent the exposure of health pests in the health sector. In particular, this can be achieved by the use of a pesticidal agent, wherein the agent can be used prophylactically and only in the case of infection to control pests. Agents that act by avoiding or reducing contact with pests can also be used. Hygienic pests (for example) organisms mentioned below.

因此，術語「衛生保護」包括用於維持及/或改良該等衛生措施、過程及程序之所有行動。 Therefore, the term "hygiene protection" includes all actions for maintaining and/or improving such health measures, processes and procedures.

可較佳地使用式(I)化合物作為殺有害生物劑。該等化合物針對通常敏感且抗逆之物種亦及針對所有或一些發育階段具有活性。上文 所提及之有害生物包括：來自節肢動物門(Arthropoda)、尤其來自蜘蛛綱(Arachnida)之有害生物，例如粉蟎屬(Acarus spp.)(例如粗腳粉蟎(Acarus siro)、枸杞瘤節蜱(Aceria kuko)、柑橘瘤癭蟎(Aceria sheldoni))、剌皮節蜱屬(Aculops spp.)、刺節蜱屬(Aculus spp.)(例如福氏刺節蜱(Aculus fockeui)、蘋果刺節蜱(Aculus schlechtendali))、大壁蝨屬(Amblyomma spp.)、橫紋葉蟎(Amphitetranychus viennensis)、銳緣壁蝨屬(Argas spp.)、牛尾壁蝨屬(Boophilus spp.)、短須蟎屬(Brevipalpus spp.)(例如紫紅短須蟎(Brevipalpus phoenicis))、麥苔蟎(Bryobia graminum)、苜蓿苔蟎(Bryobia praetiosa)、刺尾蠍屬(Centruroides spp.)、足蟎屬(Chorioptes spp.)、雞蟎(Dermanyssus gallinae)、歐洲室塵蟎(Dermatophagoides pteronyssinus)、美洲塵蟎(Dermatophagoides farinae)、矩頭壁蝨屬(Dermacentor spp.)、始葉蟎屬(Eotetranychus spp.)(例如核桃始葉蟎(Eotetranychus hicoriae))、梨上節蜱(Epitrimerus pyri)、真葉蟎屬(Eutetranychus spp.)(例如班氏真葉蟎(Eutetranychus banksi))、節蜱屬(Eriophyes spp.)(例如梨節蜱(Eriophyes pyri))、家食甜蟎(Glycyphagus domesticus)、紅足海鐮螯蟎(Halotydeus destructor)、半跗線蟎屬(Hemitarsonemus spp.)(例如茶半跗線蟎(Hemitarsonemus latus)(=茶黃蟎(Polyphagotarsonemus latus))、長鬚壁蝨屬(Hyalomma spp.)、真壁蝨屬(Ixodes spp.)、寡婦蜘蛛屬(Latrodectus spp.)、棕蜘蛛屬(Loxosceles spp.)、歐洲秋收恙蟎(Neutrombicula autumnalis)、奴合撒屬(Nuphersa spp.)、赤葉蟎屬(Oligonychus spp.)(例如克氏赤葉蟎(Oligonychus coniferarum))、冬青赤葉蟎(Oligonychus ilicis)、印度赤葉蟎(Oligonychus indicus)、芒果赤葉蟎(Oligonychus mangiferus)、草地赤葉蟎(Oligonychus pratensis)、石榴赤葉蟎(Oligonychus punicae)、樟赤葉蟎(Oligonychus yothersi))、鳥壁蝨屬(Ornithodorus spp.)、禽刺蟎屬(Ornithonyssus spp.)、葉蟎屬(Panonychus spp.)(例如柑橘葉蟎(Panonychus citri)(=柑橘全爪蟎(Metatetranychus citri)、蘋果葉蟎(Panonychus ulmi)(=蘋果全爪蟎(Metatetranychus ulmi))、柑桔皺葉刺節蜱(Phyllocoptruta oleivora)、多爪寬葉蟎(Platytetranychus multidigituli)、茶黃蟎、癢蟎屬(Psoroptes spp.)、扇頭壁蝨屬(Rhipicephalus spp.)、根蟎屬(Rhizoglyphus spp.)、疥蟎屬(Sarcoptes spp.)、中東金蠍(Scorpio maurus)、細蟎屬(Steneotarsonemus spp.)、稻細蟎(Steneotarsonemus spinki)、跗線蟎屬(Tarsonemus spp.)(例如亂跗線蟎(Tarsonemus confuses)、白跗線蟎(Tarsonemus pallidus))、葉蟎屬(Tetranychus spp.)(例如加拿大葉蟎(Tetranychus canadensis)、朱砂葉蟎(Tetranychus cinnabarinus)、土耳其斯坦葉蟎(Tetranychus turkestani)、二點葉蟎(Tetranychus urticae))、阿氏秋恙蟎(Trombicula alfreddugesi)、獄神蠍屬(Vaejovis spp.)、番茄斜背瘤節蜱(Vasates lycopersici)；來自唇足綱(Chilopoda)之有害生物，例如地蜈蚣屬(Geophilus spp.)、蚰蜒屬(Scutigera spp.)；來自黏管目(Collembola)或黏管綱之有害生物，例如武裝棘跳蟲(Onychiurus armatus)；綠圓跳蟲(Sminthurus viridis)；來自倍足綱(Diplopoda)之有害生物，例如具斑馬陸(Blaniulus guttulatus)；來自昆蟲綱(Insecta)之有害生物，例如來自蜚蠊目(Blattodea)之有害生物，例如東方蜚蠊(Blatta orientalis)、亞洲蜚蠊(Blattella asahinai)、德國蜚蠊(Blattella germanica)、馬德拉蜚蠊(Leucophaea maderae)、姬蜚蠊科(Loboptera decipiens)、家屋斑蠊(Neostylopyga rhombifolia)、古巴蠊屬(Panchlora spp.)、稀蠊屬(Parcoblatta spp.)、 家蠊屬(Periplaneta spp.)(例如美洲家蠊(Periplaneta americana)、澳洲家蠊(Periplaneta australasiae))、蘇利南潛蠊(Pycnoseelus surinamensis)、棕帶姬蠊(Supella longipalpa)；來自鞘翅目(Coleoptera)之有害生物，例如條紋葉甲(Acalymma vittatum)、菜豆象(Acanthoscelides obtectus)、褐金龜屬(Adoretus spp.)、小蜂甲(Aethina tumida)、藍毛臀螢葉甲(Agelastica alni)、叩甲屬(Agriotes spp.)(例如具條叩甲(Agriotes linneatus)、小麥叩甲(Agriotes mancus)、黑菌蟲(Alphitobius diaperinus)、六月金龜子(Amphimallon solstitialis)、家具竊蠹(Anobium punctatum)、星天牛屬(Anoplophora spp.)、花象屬(Anthonomus spp.)(例如棉鈴花象(Anthonomus grandis))、圓皮囊屬(Anthrenus spp.)、長喙小象屬(Apion spp.)、甘蔗金龜屬(Apogonia spp.)、隱食甲屬(Atomaria spp.)(例如甜菜隱食甲(Atomaria linearis))、毛皮囊屬(Attagenus spp.)、天藍巴利斯(Baris caerulescens)、惡條豆象(Bruchidius obtectus)、豆象屬(Bruchus spp.)(例如豌豆象(Bruchus pisorum)、蠶豆象(Bruchus rufimanus))、龜金花蟲屬(Cassida spp.)、菜豆螢葉甲(Cerotoma trifurcata)、象甲屬(Ceutorrhynchus spp.)(例如甘藍莢象甲(Ceutorrhynchus assimilis)、油菜莖象甲(Ceutorrhynchus quadridens)、蕪菁象甲(Ceutorrhynchus rapae))、凹脛跳甲屬(Chaetocnema spp.)(例如甘薯凹脛跳甲(Chaetocnema confinis)、玉米葉凹脛跳甲(Chaetocnema denticulata)、荒地玉米跳甲(Chaetocnema ectypa))、門第庫斯方喙象(Cleonus mendicus)、寬胸金針蟲屬(Conoderus spp.)、根頸象屬(Cosmopolites spp.)(例如香蕉根頸象(Cosmopolites sordidus))、新西蘭肋翅腿金龜(Costelytra zealandica)、叩甲屬(Ctenicera spp.)、象鼻蟲屬(Curculio spp.)，例如美核桃象鼻蟲(Curculio caryae))、大栗象鼻蟲(Curculio caryatrypes)、栗鈍象鼻蟲(Curculio obtusus)、小栗象鼻蟲(Curculio sayi)、鏽赤扁穀盜(Cryptolestes ferrugineus)、長角扁穀盜(Cryptolestes pusillus)、楊幹隱喙象(Cryptorhynchus lapathi)、芒果隱喙象(Cryptorhynchus mangiferae)、細枝象屬(Cylindrocopturus spp.)、密點細枝象(Cylindrocopturus adspersus)、洋松細枝象(Cylindrocopturus furnissi)、皮囊屬(Dermestes spp.)、葉甲屬(Diabrotica spp.)(例如黃瓜條葉甲(Diabrotica balteata)、玉米根葉甲(Diabrotica barberi)、十一星葉甲食根亞種(Diabrotica undecimpunctata howardi)、十一星瓜葉甲幼蟲(Diabrotica undecimpunctata undecimpunctata)、玉米根螢葉甲(Diabrotica virgifera virgifera)、墨西哥玉米根葉甲(Diabrotica virgifera zeae)、蛀野螟屬(Dichocrocis spp.)、稻鐵甲蟲(Dicladispa armigera)、兜蟲屬(Diloboderus spp.)、象甲屬(Epicaerus spp.)、食植瓢蟲屬(Epilachna spp.)(例如南瓜食植瓢蟲(Epilachna borealis)、墨西哥豆食植瓢蟲(Epilachna varivestis))、毛跳甲屬(Epitrix spp.)(例如黃瓜毛跳甲(Epitrix cucumeris)、茄毛跳甲(Epitrix fuscula)、煙草毛跳甲(Epitrix hirtipennis)、美國馬鈴薯毛跳甲(Epitrix subcrinita)、塊莖毛跳甲(Epitrix tuberis))、鑽孔蟲屬(Faustinus spp.)、裸蛛甲(Gibbium psylloides)、闊角穀盜(Gnathocerus cornutus)、菜心野螟(Hellula undalis)、黑異爪蔗金龜(Heteronychus arator)、寡節鰓金龜屬(Heteronyx spp.)、優雅海拉莫法(Hylamorpha elegans)、家天牛(Hylotrupes bajulus)、苜蓿葉象甲(Hypera postica)、金象甲(Hypomeces squamosus)、咪小蠹屬(Hypothenemus spp.)(例如咖啡果咪小蠹(Hypothenemus hampei)、蘋枝褐咪小蠹(Hypothenemus obscurus)、柔毛咪小蠹(Hypothenemus pubescens))、甘蔗大褐齒爪鰓金龜(Lachnosterna consanguinea)、鋸角毛食骸甲(Lasioderma serricorne)、長首穀盜(Latheticus oryzae)、薪甲屬(Lathridius spp.)、 合爪負泥蟲屬(Lema spp.)、科羅拉多馬鈴薯葉甲(Leptinotarsa decemlineata)、銀潛蛾屬(Leucoptera spp.)(例如咖啡銀潛蛾(Leucoptera coffeella))、水稻水象鼻蟲(Lissorhoptrus oryzophilus)、蔔象屬(Listronotus spp.)(=象甲屬(Hyperodes spp.))、筒喙象屬(Lixus spp.)、螢葉甲屬(Luperodes spp.)、黃胸寡毛跳甲(Luperomorpha xanthodera)、粉囊屬(Lyctus spp.)、美洲葉甲屬(Megascelis spp.)、梳爪叩甲屬(Melanotus spp.)(例如隆魯斯喔瑞萘斯叩甲(Melanotus longulus oregonensis))、油菜露尾甲(Meligethes aeneus)、鰓金龜屬(Melolontha spp.)(例如西方五月鰓金龜(Melolontha melolontha))、米多魯斯屬(Migdolus spp.)、黑天牛屬(Monochamus spp.)、葡萄短須蟎(Naupactus xanthographus)、隱跗郭公蟲屬(Necrobia spp.)、新絨螢金花蟲屬(Neogalerucella spp.)、金黃蛛甲(Niptus hololeucus)、椰蛀犀金龜(Oryctes rhinoceros)、鋸胸粉扁蟲(Oryzaephilus surinamensis)、稻喔紮法古斯(Oryzaphagus oryzae)、耳喙象屬(Otiorhynchus spp.)(例如蘋果耳喙象(Otiorhynchus cribricollis)、苜蓿耳喙象(Otiorhynchus ligustici)、草莓根耳喙象(Otiorhynchus ovatus)、如索魯斯黑耳象(Otiorhynchus rugosostriarus)、葡萄黑耳喙象(Otiorhynchus sulcatus))、負泥蟲屬(Oulema spp.)(例如黑角負泥蟲(Oulema melanopus)、水稻負泥蟲(Oulema oryzae))、小青花金龜(Oxycetonia jucunda)、辣根猿葉甲(Phaedon cochleariae)、六月鰓角金龜屬(Phyllophaga spp.)、海來利六月鰓角金龜(Phyllophaga helleri)、條跳甲屬(Phyllotreta spp.)(例如辣根闊條跳甲(Phyllotreta armoraciae)、西方黑條跳甲(Phyllotreta pusilla)、拉莫撒條跳甲(Phyllotreta ramosa)、黃條跳甲(Phyllotreta striolata))、日本金龜子(Popillia japonica)、小象甲屬(Premnotrypes spp.)、大穀囊(Prostephanus truncatus)、蚤跳甲屬(Psylliodes spp.)(例如近緣蚤跳甲(Psylliodes affinis)、油菜蚤跳甲 (Psylliodes chrysocephala)、互布跳甲(Psylliodes punctulata))、蛛甲屬(Ptinus spp.)、暗色瓢蟲(Rhizobius ventralis)、穀囊(Rhizopertha dominica)、棕櫚象屬(Rhynchophorus spp.)、紅棕象甲(Rhynchophorus ferrugineus)、棕櫚象甲(Rhynchophorus palmarum)、六齒長蠹蟲(Sinoxylon perforans)、象蟲屬(Sitophilus spp.)(例如穀象蟲(Sitophilus granarius)、羅望子象蟲(Sitophilus linearis)、米象蟲(Sitophilus oryzae)、玉米象蟲(Sitophilus zeamais))、尖隱喙象屬(Sphenophorus spp.)、藥材甲(Stegobium paniceum)、莖幹象屬(Sternechus spp.)(例如豆莖幹象(Sternechus paludatus)、絲法雷特屬(Symphyletes spp.)、纖毛象屬(Tanymecus spp.)(例如玉米纖毛象(Tanymecus dilaticollis)、印度纖毛象(Tanymecus indicus)、驢豆纖毛象(Tanymecus palliatus))、黃粉蟲(Tenebrio molitor)、大穀盜(Tenebrioides mauretanicus)、擬穀盜屬(Tribolium spp.)(例如美洲黑擬穀盜(Tribolium audax)、赤擬穀盜(Tribolium castaneum)、雜擬穀盜(Tribolium confusum))、斑皮囊屬(Trogoderma spp.)、籽相屬(Tychius spp.)、脊虎天牛屬(Xylotrechus spp.)、距步甲屬(Zabrus spp.)(例如玉米距步甲(Zabrus tenebrioides))；來自革翅目(Dermaptera)之有害生物，例如海肥螋(Anisolabis maritime)、歐洲秋螋(Forficula auricularia)、溪岸蠼螋(Labidura riparia)；來自雙翅目(Diptera)之有害生物，例如斑蚊屬(Aedes spp.)(例如埃及斑蚊(Aedes aegypti))、白線斑蚊(Aedes albopictus)、叮刺斑蚊(Aedes sticticus)、白肋斑蚊(Aedes vexans)，潛蠅屬(Agromyza spp.)(例如苜蓿斑潛蠅(Agromyza frontella)、玉米斑潛蠅(Agromyza parvicornis))、果實蠅屬(Anastrepha spp.)、瘧蚊屬(Anopheles spp.)(例如四斑瘧蚊(Anopheles quadrimaculatus)、岡比亞瘧蚊(Anopheles gambiae))，瘦蚊屬(Asphondylia spp.)、桿角石屬(Bactrocera spp.)(例 如瓜實蠅(Bactrocera cucurbitae)、東方果實蠅(Bactrocera dorsalis)、橄欖實蠅(Bactrocera oleae))，花園毛蚊(Bibio hortulanus)、琉璃蠅(Calliphora erythrocephala)、紅頭麗蠅(Calliphora vicina)、地中海果實蠅(Ceratitis capitata)、搖蚊屬(Chironomus spp.)、金蠅屬(Chrysomya spp.)、斑虻屬(Chrysops spp.)、高額麻虻(Chrysozona pluvialis)、螺旋蠅屬(Cochliomya spp.)、癭蚊屬(Contarinia spp.)(例如葡萄癭蚊(Contarinia johnsoni)、甘藍癭蚊(Contarinia nasturtii)、梨癭蚊(Contarinia pyrivora)、向日葵癭蚊(Contarinia schulzi)、高粱癭蚊(Contarinia sorghicola)、麥黃吸漿蟲(Contarinia tritici))、人皮蠅(Cordylobia anthropophaga)、稻環搖蚊(Cricotopus sylvestris)、家蚊屬(Culex spp.)(例如地下家蚊(Culex pipiens)、熱帶家蚊(Culex quinquefasciatus))、糠蚊屬(Culicoides spp.)、脈毛蚊屬(Culiseta spp.)、野生齧齒蠅屬(Cuterebra spp.)、橄欖蠅(Dacus oleae)、葉癭蚊屬(Dasineura spp.)(例如油菜莢葉癭蚊(Dasineura brassicae))、地種蠅屬(Delia spp.)(例如蔥地種蠅(Delia antiqua)、麥地種蠅(Delia coarctata)、毛跗地種蠅(Delia florilega)、灰地種蠅(Delia platura)、甘藍地種蠅(Delia radicum))、人膚蠅(Dermatobia hominis)、果蠅屬(Drosophila spp.)(例如黑腹果蠅(Drosophila melanogaster)、斑翅果蠅(Drosophila suzukii))、稻象屬(Echinocnemus spp.)、芹菜尤列實蠅(Euleia heraclei)、廁蠅屬(Fannia spp.)、馬蠅屬(Gasterophilus spp.)、採採蠅屬(Glossina spp.)、斑蛀屬(Haematopota spp.)、毛眼水蠅屬(Hydrellia spp.)、小灰毛眼水蠅(Hydrellia griseola)、種蠅屬(Hylemya spp.)、虱蠅屬、牛蠅屬(Hypoderma spp.)、斑潛蠅屬(Liriomyza spp.)(例如菜斑潛蠅(Liriomyza brassicae)、南美斑潛蠅(Liriomyza huidobrensis)、蔬菜斑潛蠅(Liriomyza sativae))、綠蠅屬(Lucilia spp.)(例如絲光綠蠅(Lucilia cuprina))、沙蠅屬(Lutzomyia spp.)、孟松 文屬(Mansonia spp.)、蒼蠅屬(Musca spp.)(例如家蠅(Musca domestica)、舍蠅(Musca domestica vicina))、狂蠅屬(Oestrus spp.)、黑麥稈蠅(Oscinella frit)、擬長跗搖蚊屬(Paratanytarsus spp.)、蘇氏擬特包尼拉(Paralauterborniella sucincta)、泉蠅屬(Pegomya spp.)(例如甜菜泉蠅(Pegomya betae)、天仙子泉蠅(Pegomya hyoscyami)、懸鉤子泉蠅(Pegomya rubivora))、白蛉屬(Phlebotomus spp.)、草種蠅屬(Phorbia spp.)、玻璃蠅屬(Phormia spp.)、鎧氏酪蠅(Piophila casei)、蘆筍實蠅(Platyparea poeciloptera)、普地羅斯屬(Prodiplosis spp.)、胡蘿蔔莖蠅(Psila rosae)、繞實蠅屬(Rhagoletis spp.)(例如櫻桃繞實蠅(Rhagoletis cingulata)、核桃繞實蠅(Rhagoletis completa)、黑櫻桃繞實蠅(Rhagoletis fausta)、西部櫻桃繞實蠅(Rhagoletis indifferens)、越桔繞實蠅(Rhagoletis mendax)、蘋果繞實蠅(Rhagoletis pomonella))、麻蠅屬(Sarcophaga spp.)、蚋屬(Simulium spp.)(例如南方蚋(Simulium meridionale))、刺蠅屬(Stomoxys spp.)、牛虻屬(Tabanus spp.)、根斑蠅屬(Tetanops spp.)、大蚊屬(Tipula spp.)(例如歐洲大蚊(Tipula paludosa)、牧場大蚊(Tipula simplex)、番木瓜長尾實蠅(Toxotrypana curvicauda)；來自半翅目(Hemiptera)之有害生物，例如阿白萘虱(Acizzia acaciaebaileyanae)、多多萘虱(Acizzia dodonaeae)、木虱(Acizzia uncatoides)、狹背蚱猛(Acrida turrita)、無網長管蟲牙屬(Acyrthosipon spp.)(例如豌豆蟲牙(Acyrthosiphon pisum))、阿羅穀尼屬(Acrogonia spp.)、沫蜂屬(Aeneolamia spp.)、木虱屬(Agonoscena spp.)、刺粉虱屬(Aleurocanthus spp.)、歐洲甘藍粉虱(Aleyrodes proletella)、甘蔗穴粉蝨(Aleurolobus barodensis)、軟毛粉虱(Aleurothrixus floccosus)、植蓮木虱(Allocaridara malayensis)、芒果葉蟬屬(Amrasca spp.)(例如小綠葉蟬(Amrasca bigutulla)、苯甲醒對葉蟬(Amrasca devastans))、飛廉 短尾蚜(Anuraphis cardui)、介殼蟲屬(Aonidiella spp.)(例如橘紅腎圓盾介殼蟲(Aonidiella aurantii)、橘黃腎圓盾介殼蟲(Aonidiella citrina)、木瓜腎圓盾介殼蟲(Aonidiella inornata))、梨腎圓盾介殼蟲(Aphanostigma piri)、蚜蟲屬(Aphis spp.)(例如橘捲菜蚜(Aphis citricola)、豆蚜(Aphis craccivora)、豆衛矛蚜(Aphis fabae)、草莓根蚜(Aphis forbesi)、大豆蚜(Aphis glycines)、棉蚜(Aphis gossypii)、常春藤蚜(Aphis hederae)、麥綠蚜(Aphis illinoisensis)、米德頓蚜(Aphis middletoni)、鼠李馬鈴薯蚜(Aphis nasturtii)、夾竹桃蚜(Aphis nerii)、蘋果蚜(Aphis pomi)、異繡線菊蚜(Aphis spiraecola)、棉蚜(Aphis viburniphila))、葡萄斑葉蟬(Arboridia apicalis)、阿太尼拉屬(Arytainilla spp.)、小圓盾蚧屬(Aspidiella spp.)、薄圓盾介殼蟲屬(Aspidiotus spp.)(例如常春藤薄圓盾介殼蟲(Aspidiotus nerii))、圓盾蚧屬(Atanus spp.)、茄無網長管蚜(Aulacorthum solani)、煙草粉蝨種群(Bemisia tabaci)、澳大利亞木虱(Blastopsylla occidentalis)、美樂家虱(Boreioglycaspis melaleucae)、光管舌尾蚜(Brachycaudus helichrysi)、微管蟲牙屬(Brachycolus spp.)、甘藍蚜(Brevicoryne brassicae)、喀木虱屬(Cacopsylla spp.)(例如梨木虱(Cacopsylla pyricola))、小褐稻虱(Calligypona marginata)、卡普麗尼屬(Capulinia spp.)、麗黃大頭葉蟬(Carneocephala fulgida)、甘蔗綿蚜(Ceratovacuna lanigera)、吹沫蟲科(Cercopidae)、蠟蚧屬(Ceroplastes spp.)、草莓毛管蚜(Chaetosiphon fragaefolii)、蔗黃雪盾蚧(Chionaspis tegalensis)、荼綠葉蜂(Chlorita onukii)、棉蝗(Chondracris rosea)、核桃黑斑蚜(Chromaphis juglandicola)、褐圓蚧(Chrysomphalus aonidum)、褐圓介殼蟲(Chrysomphalus ficus)、玉米葉蟬(Cicadulina mbila)、庫可替魯斯屬(Coccomytilus halli)、軟蚧屬(Coccus spp.)(例如褐軟蚧(Coccus hesperidum)、長橢圓軟蚧(Coccus longulus)、橘軟蚧(Coccus pseudomagnoliarum)、咖啡綠軟蚧(Coccus viridis))、茶藨隱瘤額蚜(Cryptomyzus ribis)、可普萘撒屬(Cryptoneossa spp.)、梳木虱屬(Ctenarytaina spp.)、角頂葉蜂屬(Dalbulus spp.)、杜鵑裸粉虱(Dialeurodes chittendeni)、柑橘裸粉虱(Dialeurodes citri)、柑橘木虱(Diaphorina citri)、盾介殼蟲屬(Diaspis spp.)、雙尾蚜屬(Diuraphis spp.)、草履蚧屬(Drosicha spp.)、西圓尾蚜屬(Dysaphis spp.)(例如鏽條蚜(Dysaphis apiifolia)、車前西圓尾蚜(Dysaphis plantaginea)、百合西圓尾蚜(Dysaphis tulipae))、嫡粉介殼蟲屬(Dysmicoccus spp.)、小綠葉蟬屬(Empoasca spp.)(例如西部馬鈴薯小綠葉蟬(Empoasca abrupta)、馬鈴薯小綠葉蟬(Empoasca fabae)、蘋果小綠葉蟬(Empoasca maligna)、索拉納小綠葉蟬(Empoasca solana)、斯第文思小綠葉蟬(Empoasca stevensi))、綿蚜屬(Eriosoma spp.)(例如美洲綿蚜(Eriosoma americanum)、蘋果綿蚜(Eriosoma lanigerum)、梨綿蚜(Eriosoma pyricola))、葡萄斑葉蟬屬(Erythroneura spp.)、油普拉馬屬(Eucalyptolyma spp.)、褐木虱屬(Euphyllura spp.)、鈍鼻葉蟬(Euscelis bilobatus)、腺刺粉蚧屬(Ferrisia spp.)、圍盾介殼蟲屬(Fiorinia spp.)、大洋盾蚧(Furcaspis oceanica)、咖啡粉蚧(Geococcus coffeae)、格卡匹斯屬(Glycaspis spp.)、銀合歡木蝨(Heteropsylla cubana)、頰木虱(Heteropsylla spinulosa)、琉璃葉蟬(Homalodisca coagulata)、桃大尾蚜(Hyalopterus arundinis)、桃粉蚜(Hyalopterus pruni)、吹綿介殼蟲屬(Icerya spp.)(例如吹綿介殼蟲(Icerya purchasi)、片角葉蟬屬(Idiocerus spp.)、扁喙葉蟬屬(Idioscopus spp.)、斑飛蝨(Laodelphax striatellus)、球蚧屬(Lecanium spp.)(例如水土堅蚧(Lecanium corni)(=扁平球堅蚧(Parthenolecanium corni)))、牡蠣蚧屬(Lepidosaphes spp.)(例如榆牡蠣蚧(Lepidosaphes ulmi))、偽菜蚜(Lipaphis erysimi)、長白盾蚧(Lopholeucaspis japonica)、斑衣蠟蟬(Lycorma delicatula)、長管蚜屬 (Macrosiphum spp.)(例如大戟長管蚜(Macrosiphum euphorbiae)、百合紫斑長管蚜(Macrosiphum lilii)、薔薇長管蚜(Macrosiphum rosae))、二點葉蜂(Macrosteles facifrons)、沫蟬屬(Mahanarva spp.)、甘蔗黃蚜(Melanaphis sacchari)、美卡非拉屬(Metcalfiella spp.)、蛾蠟蟬(Metcalfa pruinosa)、麥無網長管蚜(Metopolophium dirhodum)、黑緣平翅斑蚜(Monellia costalis)、派克斯較抗黃蚜蟲(Monelliopsis pecanis)、瘤蚜屬(Myzus spp.)(例如冬蔥瘤蚜(Myzus ascalonicus)、李瘤蚜(Myzus cerasi)、女貞瘤蚜(Myzus ligustri)、堇菜瘤蚜(Myzus ornatus)、桃瘤蚜(Myzus persicae)、菸瘤蚜(Myzus nicotianae))、萵苣衲長管蚜(Nasonovia ribisnigri)、新馬粉蝨屬(Neomaskellia spp.)、黑尾葉蟬屬(Nephotettix spp.)(例如偽黑尾葉蟬(Nephotettix cincticeps)、二條斑黑尾葉蟬(Nephotettix nigropictus))、光譜萘穀尼拉(Nettigoniclla spectra)、褐飛虱(Nilaparvata lugens)、昂美妥皮屬(Oncometopia spp.)、普來隆旌介殼蟲(Orthezia praelonga)、中華稻蝗(Oxya chinensis)、芽瘦木虱屬(Pachypsylla spp.)、楊梅粉虱(Parabemisia myricae)、薯個木風屬(Paratrioza spp.)(例如馬鈴薯木虱(Paratrioza cockerelli))、片盾介殼蟲屬(Parlatoria spp.)、癭綿蚜屬(Pemphigus spp.)(例如囊柄癭綿蚜(Pemphigus bursarius)、楊脈癭綿蚜(Pemphigus populivenae))、玉米蠟蟬(Peregrinus maidis)、扁角飛虱屬(Perkinsiella spp.)、綿粉蚧屬(Phenacoccus spp.)(例如美地綿粉蚧(Phenacoccus madeirensis))、楊平翅綿蚜(Phloeomyzus passerinii)、指頭蚜(Phorodon humuli)、根瘤蚜屬(Phylloxera spp.)(例如葡萄根瘤蚜(Phylloxera devastatrix)、警根瘤蚜(Phylloxera notabilis))、蜘蛛抱蛋並盾蚧(Pinnaspis aspidistrae)、臀紋粉介殼蟲屬(Planococcus spp.)(例如桔臀紋粉介殼蟲(Planococcus citri))、黃色普羅皮拉(Prosopidopsylla flava)、梨形原綿蚧(Protopulvinaria pyriformis)、桑白盾蚧 (Pseudaulacaspis pentagona)、粉蚧屬(Pseudococcus spp.)(例如柑棲粉蚧(Pseudococcus calceolariae)、康氏粉蚧(Pseudococcus comstocki)、擬長尾粉蚧(Pseudococcus longispinus)、葡萄粉蚧(Pseudococcus maritimus)、暗色粉蚧(Pseudococcus viburni))、皮羅普斯屬(Psyllopsis spp.)、木虱屬(Psylla spp.)(例如布希木虱(Psylla buxi)、蘋果木虱(Psylla mali)、梨木虱(Psylla pyri))、金小蜂屬(Pteromalus spp.)、綿蚧屬(Pulvinaria spp.)、飛虱屬(Pyrilla spp.)、圓盾蚧屬(Quadraspidiotus spp.)(例如胡桃圓盾蚧(Quadraspidiotus juglansregiae)、楊笠圓盾蚧(Quadraspidiotus ostreaeformis)、梨枝圓盾蚧(Quadraspidiotus perniciosus))、牡蠣蚧(Quesada gigas)、平粉蚧屬(Rastrococcus spp.)、縊管蚜屬(Rhopalosiphum spp.)(例如玉米縊管蚜(Rhopalosiphum maidis)、蘋草縊管蚜(Rhopalosiphum oxyacanthae)、禾谷縊管蚜(Rhopalosiphum padi)、紅腹縊管蚜(Rhopalosiphum rufiabdominale))、硬介殼蟲屬(Saissetia spp.)(例如咖啡硬介殼蟲(Saissetia coffeae)、米蘭蓮硬介殼蟲(Saissetia miranda)、圓形硬介殼蟲(Saissetia neglecta)、工背硬介殼蟲(Saissetia oleae))、葡萄帶葉蟬(Scaphoideus titanus)、麥二叉蚜(Schizaphis graminum)、刺盾蚧(Selenaspidus articulatus)、麥長管蚜(Sitobion avenae)、長唇基飛虱屬(Sogata spp.)、白背飛虱(Sogatella furcifera)、稻飛蝨屬(Sogatodes spp.)、非替那角蟬(Stictocephala festina)、梣粉虱(Siphoninus phillyreae)、馬來台拉法拉(Tenalaphara malayensis)、台諾非拉屬(Tetragonocephela spp.)、美洲山核桃長斑蚜(Tinocallis caryaefoliae)、廣胸沫蟬屬(Tomaspis spp.)、桔蚜屬(Toxoptera spp.)(例如橘二叉蚜(Toxoptera aurantii)、大桔蚜(Toxoptera citricidus))、溫室粉虱(Trialeurodes vaporariorum)、個木虱屬(Trioza spp.)(例如尖翅個木虱(Trioza diospyri))、小葉蜂屬(Typhlocyba spp.)、尖盾蚧屬(Unaspis spp.)、葡萄根瘤蚜(Viteus vitifolii)、松葉蜂屬(Zygina spp.)；來自異翅亞目(Heteroptera)之有害生物，例如麥蝽屬(Aelia spp.)、南瓜緣蝽(Anasa tristis)、擬麗蝽屬(Antestiopsis spp.)、波色阿屬(Boisea spp.)、長蝽屬(Blissus spp.)、赤條盲蝽屬(Calocoris spp.)、斑腿微刺盲蝽(Campylomma livida)、異背長蝽屬(Cavelerius spp.)、臭蟲屬(Cimex spp.)(例如阿氏臭蟲(Cimex adjunctus)、熱帶臭蟲(Cimex hemipterus)、溫帶臭蟲(Cimex lectularius)、蝠臭蟲(Cimex pilosellus))、白辧麥寄蠅屬(Collaria spp.)、綠盲蝽(Creontiades dilutus)、胡椒緣蝽(Dasynus piperis)、福氏地車羅斯(Dichelops furcatus)、厚氏長棒網蜂(Diconocoris hewetti)、棉紅蝽屬(Dysdercus spp.)、美洲蝽屬(Euschistus spp.)(例如大豆褐美洲蝽(Euschistus heros)、褐臭美洲蝽(Euschistus servus)、三色美洲蝽(Euschistus tristigmus)、單點美洲蝽(Euschistus variolarius))、菜蝽屬(Eurydema spp.)、扁盾蝽屬(Eurygaster spp.)、茶翅蝽(Halyomorpha halys)、錘盲蝽屬(Heliopeltis spp.)、具凹巨股長蝽(Horcias nobilellus)、稻緣蝽屬(Leptocorisa spp.)、異稻緣蝽(Leptocorisa varicornis)、西部喙緣蝽(Leptoglossus occidentalis)、葉喙緣蝽(Leptoglossus phyllopus)、麗盲蝽屬(Lygocoris spp.)(例如原麗盲蝽(Lygocoris pabulinus))、草盲蝽屬(Lygus spp.)(例如豆莢灰盲蝽(Lygus elisus)、雄性金星草盲椿(Lygus hesperus)、牧草盲蝽(Lygus lineolaris))、蔴漂長蝽(Macropes excavatus)、篩豆龜蝽(Megacopta cribraria)、盲椿象科(Miridae)、金光綠盲蝽(Monalonion atratum)、綠蝽屬(Nezara spp.)(例如稻綠蝽(Nezara viridula))、小長蝽屬(Nysius spp.)、稻蝽屬(Oebalus spp.)、蝽科(Pentomidae)、方背皮蝽(Piesma quadrata)、壁蝽屬(Piezodorus spp.)(例如蓋德擬壁蝽(Piezodorus guildinii))、雜盲蝽屬(Psallus spp.)、鱷梨網蝽(Pseudacysta persea)、紅獵蝽屬(Rhodnius spp.)、可 可斑褐盲蝽(Sahlbergella singularis)、栗花椿象(Scaptocoris castanea)、黑蝽屬(Scotinophora spp.)、梨冠網蝽(Stephanitis nashi)、替拉卡屬(Tibraca spp.)、錐獵蝽屬(Triatoma spp.)；來自膜翅目(Hymenoptera)之有害生物，例如頂切葉蟻屬(Acromyrmex spp.)、殘青葉蜂屬(Athalia spp.)(例如短斑殘青葉蜂(Athalia rosae))、切葉蟻屬(Atta spp.)、巨山蟻屬(Camponotus spp.)、長黃胡蜂屬(Dolichovespula spp.)、松葉蜂屬(Diprion spp.)(例如類歐松葉蜂(Diprion similis))、長角葉蜂屬(Hoplocampa spp.)(例如庫氏長角葉蜂(Hoplocampa cookei)、長角葉蜂蘋果長角葉蜂(Hoplocampa testudinea))、毛山蟻屬(Lasius spp.)、阿根廷螞蟻(Linepithema humile)(阿根廷虹臭蟻(Iridiomyrmex humile))、小黃家蟻(Monomorium pharaonis)、黃山蟻屬(Paratrechina spp.)、黃胡蜂屬(Paravespula spp.)、箭蟻屬(Plagiolepis spp.)、樹蜂屬(Sirex spp.)、入侵紅火蟻(Solenopsis invicta)、酸臭蟻屬(Tapinoma spp.)、白跗節狡臭蟻(Technomyrmex albipes)、大樹蜂屬(Urocerus spp.)、胡蜂屬(Vespa spp.)(例如黃邊胡蜂(Vespa crabro))、小火蟻(Wasmannia auropunctata)、黑樹蜂屬(Xeris spp.)；來自等足目(Isopoda)之有害生物，例如鼠婦(Armadillidium vulgare)、潮蟲(Oniscus asellus)、平甲鼠婦(Porcellio scaber)；來自等翅目(Isoptera)之有害生物，例如家白蟻屬(Coptotermes spp.)(例如臺灣家白蟻(Coptotermes formosanus))、白蟻(Cornitermes cumulans)、堆砂白蟻屬(Cryptotermes spp.)、楹白蟻屬(Incisitermes spp.)、木白蟻屬(Kalotermes spp.)、甘鹿白蟻(Microtermes obesi)、象白蟻屬(Nasutitermes spp.)、土白蟻屬(Odontotermes spp.)、洞白蟻屬(Porotermes spp.)、散白蟻屬(Reticulitermes spp.)(例如北美散白蟻(Reticulitermes flavipes)、西方散白蟻(Reticulitermes Hesperus))； 來自鱗翅目(Lepidoptera)之有害生物，例如小蠟螟(Achroia grisella)、桑劍紋夜蛾(Acronicta major)、捲葉蛾屬(Adoxophyes spp.)(例如茶姬捲葉蛾(Adoxophyes orana))、白斑煩夜蛾(Aedia leucomelas)、地老虎屬(Agrotis spp.)(例如黃地老虎(Agrotis segetum)、小地老虎(Agrotis ipsilon))、波紋夜蛾屬(Alabama spp.)(例如棉葉波紋夜蛾(Alabama argillacea))、臍橙螟(Amyelois transitella)、條麥蛾屬(Anarsia spp.)、幹煞夜蛾屬(Anticarsia spp.)(例如大豆干煞夜蛾(Anticarsia gemmatalis))、條小捲蛾屬(Argyroploce spp.)、丫紋夜蛾屬(Autographa spp.)、甘藍夜蛾(Barathra brassicae)、蘋髓尖蛾(Blastodacna atra)、秈弄蝶(Borbo cinnara)、棉潛蛾(Bucculatrix thurberiella)、松尺蠖(Bupalus piniarius)、蛀褐夜蛾屬(Busseola spp.)、捲葉蛾屬(Cacoecia spp.)、茶細蛾(Caloptilia theivora)、菸捲蛾(Capua reticulana)、蘋果蠹蛾(Carpocapsa pomonella)、桃小食心蟲(Carposina niponensis)、冬尺蛾(Cheimatobia brumata)、禾草螟屬(Chilo spp.)(例如七星稻螟(Chilo plejadellus)、二化螟(Chilo suppressalis))、蘋果舞蛾(Choreutis pariana)、色捲蛾屬(Choristoneura spp.)、錁紋夜蛾(Chrysodeixis chalcites)、葡萄果蠹蛾(Clysia ambiguella)、縱捲葉野螟屬(Cnaphalocerus spp.)、稻縱捲葉野螟(Cnaphalocrocis medinalis)、雲捲蛾屬(Cnephasia spp.)、細蛾屬(Conopomorpha spp.)、球頸象屬(Conotrachelus spp.)、庫塔斯屬(Copitarsia spp.)、小捲蛾屬(Cydia spp.)(例如豌豆小捲蛾(Cydia nigricana))、蘋果蠹蛾(Cydia pomonella))、諾土德達拉卡(Dalaca noctuides)、絹野螟屬(Diaphania spp.)、棉鈴蟲屬(Diparopsis spp.)、小蔗桿草螟(Diatraea saccharalis)、金剛鑽屬(Earias spp.)、柑桔天牛(Ecdytolopha aurantium)、南美玉米苗斑螟(Elasmopalpus lignosellus)、甘薯桿螟(Eldana saccharina)、粉斑螟屬(Ephestia spp.) (例如菸草粉斑螟(Ephestia elutella)、地中海粉斑螟(Ephestia kuehniella))、葉小捲蛾屬(Epinotia spp.)、蘋果褐捲蛾(Epiphyas postvittana)、松尺蛾屬(Erannis spp.)、灰紋捲蛾(Erschoviella musculana)、莢斑螟屬(Etiella spp.)、豔葉夜蛾屬(Eudocima spp.)、掠捲蛾屬(Eulia spp.)、葡萄與蘋果捲葉蛾(Eupoecilia ambiguella)、黃毒蛾屬(Euproctis spp.)(例如黃毒蛾(Euproctis chrysorrhoea))、切根蟲屬(Euxoa spp.)、髒切夜蛾屬(Feltia spp.)、大蠟螟(Galleria mellonella)、細蛾屬(Gracillaria spp.)、小食心蟲屬(Grapholitha spp.)(例如梨小食心蟲(Grapholita molesta)、杏小食心蟲(Grapholita prunivora))、蝕葉野螟屬(Hedylepta spp.)、夜蛾屬(Helicoverpa spp.)(例如番茄夜蛾(Helicoverpa armigera)、玉米夜蛾(Helicoverpa zea))、實夜蛾屬(Heliothis spp.)(例如菸芽實夜蛾(Heliothis virescens))、褐織蛾(Hofmannophila pseudospretella)、斑螟屬(Homoeosoma spp.)、長捲蛾屬(Homona spp.)、櫻桃巢蛾(Hyponomeuta padella)、柿蔕蟲蛾(Kakivoria flavofasciata)、亮灰蝶屬(Lampides spp.)、夜蛾屬(Laphygma spp.)、梨小蠹螟(Laspeyresia molesta)、茄黃斑螟(Leucinodes orbonalis)、銀潛蛾屬(例如咖啡銀潛蛾)、潛葉細蛾屬(Lithocolletis spp.)(例如蘋果斑幕潛葉細蛾(Lithocolletis blancardella))、綠果冬夜蛾(Lithophane antennata)、花翅小蛾屬(Lobesia spp.)(例如葡萄花翅小蛾(Lobesia botrana))、豆白隆切根蟲(Loxagrotis albicosta)、毒蛾屬(Lymantria spp.)(例如舞毒蛾(Lymantria dispar))、潛蛾屬(Lyonetia spp.)(例如桃潛蛾(Lyonetia clerkella))、天幕毛蟲(Malacosoma neustria)、豆莢野螟(Maruca testulalis)、甘藍夜蛾(Mamestra brassicae)、稻暮眼蝶(Melanitis leda)、毛脛夜蛾屬(Mocis spp.)、莫匹沃維拉(Monopis obviella)、黏蟲(Mythimna separata)、橡長角蛾(Nemapogon cloacellus)、水螟屬 (Nymphula spp.)、沃替克斯屬(Oiketicus spp.)、蠹野螟屬(Omphisa spp.)、尺蛾屬(Operophtera spp.)、巫夜蛾屬(Oria spp.)、瘤叢螟屬(Orthaga spp.)、桿野螟屬(Ostrinia spp.)(例如玉米桿野螟(Ostrinia nubilalis))、松夜蛾(Panolis flammea)、稻弄蝶屬(Parnara spp.)、紅鈴蟲屬(Pectinophora spp.)(例如棉紅鈴蟲(Pectinophora gossypiella))、潛跳甲屬(Perileucoptera spp.)、茄麥蛾屬(Phthorimaea spp.)(例如馬鈴薯塊莖蛾(Phthorimaea operculella))、柑橘潛葉蛾(Phyllocnistis citrella)、小潛細蛾屬(Phyllonorycter spp.)(例如幕斑小潛細蛾(Phyllonorycter blancardella)、山楂小潛細蛾(Phyllonorycter crataegella))、白粉蝶屬(Pieris spp.)(例如紋白蝶(Pieris rapae))、荷蘭石竹小捲蛾(Platynota stultana)、印度穀螟(Plodia interpunctella)、金翅夜蛾屬(Plusia spp.)、小菜蛾(Plutella xylostella)(=小菜蛾(Plutella maculipennis))、小白巢蛾屬(Prays spp.)、斜紋夜蛾屬(Prodenia spp.)、菸草天蛾(Protoparce spp.)、黏蟲屬(Pseudaletia spp.)(例如一星黏蟲(Pseudaletia unipuncta)、尺夜蛾(Pseudoplusia includes)、歐洲玉蜀黍螟(Pyrausta nubilalis)、薄荷灰夜蛾(Rachiplusia nu)、禾螟屬(Schoenobius spp.)(例如三化禾螟(Schoenobius bipunctifer))、白禾螟屬(Scirpophaga spp.)(例如稻白禾螟(Scirpophaga innotata))、黃地老虎(Scotia segetum)、蛀莖夜蛾屬(Sesamia spp.)(例如稻蛀莖夜蛾(Sesamia inferens))、長須捲蛾屬(Sparganothis spp.)、灰翅夜蛾屬(Spodoptera spp.)(例如厄地那灰翅夜蛾(Spodoptera eradiana)、甜菜灰翅夜蛾(Spodoptera exigua)、草地灰翅夜蛾(Spodoptera frugiperda))、條狀黏蟲(Spodoptera praefica)、舉肢蛾屬(Stathmopoda spp.)、黃鵪菜屬(Stenoma spp.)、花生須峭麥蛾(Stomopteryx subsecivella)、透翅蛾屬(Synanthedon spp.)、安第斯馬鈴薯塊莖蛾(Tecia solanivora)、異舟蛾屬(Thaumetopoea spp.)、大豆色美斯(Thermesia gemmatalis)、木塞 穀蛾(Tinea cloacella)、袋穀蛾(Tinea pellionella)、幕穀蛾(Tineola bisselliella)、捲葉蟲屬(Tortrix spp.)、毛氈衣蛾(Trichophaga tapetzella)、粉夜蛾屬(Trichoplusia spp.)(例如粉紋夜蛾(Trichoplusia ni))、三化螟(Tryporyza incertulas)、番茄斑潛蠅(Tuta absoluta)、灰蝶屬(Virachola spp.)；來自直翅目(Orthoptera)或跳躍亞目(Saltatoria)之有害生物，例如家蟋蟀(Acheta domesticus)、地綽勒斯屬(Dichroplus spp.)、螻蛄屬(Gryllotalpa spp.)(例如歐洲螻蛄(Gryllotalpa gryllotalpa))、蔗蝗屬(Hieroglyphus spp.)、飛蝗屬(Locusta spp.)(例如東亞飛蝗(Locusta migratoria))、黑蝗屬(Melanoplus spp.)(例如破壞黑蝗(Melanoplus devastator))、烏蘇裡擬寰螽(Paratlanticus ussuriensis)、沙漠蝗(Schistocerca gregaria)；來自毛虱目(Phthiraptera)之有害生物，例如畜虱屬(Damalinia spp.)、血虱屬(Haematopinus spp.)、長齶虱屬(Linognathus spp.)、虱蝨屬(Pediculus spp.)、葡萄根瘤蚜(Phylloxera vastatrix)、恥陰虱(Phthirus pubis)、毛虱屬(Trichodectes spp.)；來自囓蟲目(Psocoptera)之有害生物，例如鱗蟲齒屬(Lepinotus spp.)、書虱屬(Liposcelis spp.)；來自隱翅目(Siphonaptera)之有害生物，例如角葉蚤屬(Ceratophyllus spp.)、櫛頭蚤屬(Ctenocephalides spp.)(例如犬櫛頭蚤(Ctenocephalides canis)、貓櫛頭蚤(Ctenocephalides felis))、人蚤(Pulex irritans)、穿皮潛蚤(Tunga penetrans)、印鼠客蚤(Xenopsylla cheopis)；來自纓翅目(Thysanoptera)之有害生物，例如玉米黃呆薊馬(Anaphothrips obscurus)、稻薊馬(Baliothrips biformis)、中斑圍孔薊馬(Chaetanaphothrips leeuweni)、鮮食葡萄鐮薊馬(Drepanothrips reuteri)、黃化恩薊馬(Enneothrips flavens)、花薊馬屬(Frankliniella spp.)(例如菸褐花薊馬(Frankliniella fusca)、西花薊馬(Frankliniella occidentalis)、梳缺花薊馬(Frankliniella schultzei)、美東花薊馬(Frankliniella tritici)、越橘花薊馬(Frankliniella vaccinii)、威廉期花薊馬(Frankliniella williamsi))、簡管薊馬屬(Haplothrips spp.)、陽薊馬屬(Heliothrips spp.)、溫室條籬薊馬(Hercinothrips femoralis)、卡薊馬屬(Kakothrips spp.)、腹鉤薊馬(Rhipiphorothrips cruentatus)、硬薊馬屬(Scirtothrips spp.)、豆塔薊馬(Taeniothrips cardamomi)、薊馬屬(Thrips spp.)(例如南黃薊馬(Thrips palmi)、蔥薊馬(Thrips tabaci))；來自衣魚亞目(Zygentoma)(=纓尾目(Thysanura))之有害生物，例如柿衣魚屬(Ctenolepisma spp.)、衣魚(Lepisma saccharina)、盜火蟲(Lepismodes inquilinus)、小灶衣魚(Thermobia domestica)；來自結閥綱(Symphyla)之有害生物，例如如麼蚰屬(Scutigerella spp.)，例如無斑點如麼蚰(Scutigerella immaculata)；來自軟體動物門、具體而言來自雙殼綱(Bivalvia)有害生物，例如飾貝屬(Dreissena spp.)；亦及來自腹足綱(Gastropoda)之有害生物，例如阿勇蛞蝓屬(Arion spp.)(例如愛特盧夫斯阿勇蛞蝓(Arion ater rufus))、雙臍螺屬(Biomphalaria spp.)、泡螺屬(Bulinus spp.)、野蛞蝓屬(Deroceras spp.)(例如光滑野蛞蝓(Deroceras laeve))、土蝸屬(Galba spp.)、椎實螺屬(Lymnaea spp.)、釘螺屬(Oncomelania spp.)、福壽螺屬(Pomacea spp.)、琥珀螺屬(Succinea spp.)；來自扁形動物門(Platyhelminthes)及圓形動物門(Nematoda)之動物及人類寄生蟲，例如貓圓線蟲屬(Aelurostrongylus spp.)、裂口線蟲屬(Amidostomum spp.)、鉤口線蟲屬(Ancylostoma spp.)(例如十二指腸鉤口線蟲(Ancylostoma duodenale))、錫蘭鉤口線蟲(Ancylostoma ceylanicum)、巴西鉤口線蟲(Acylostoma braziliensis)、管圓線蟲屬(Angiostrongylus spp.)、異尖線蟲屬(Anisakis spp.)、裸頭絛蟲屬(Anoplocephala spp.)、蛔蟲屬(Ascaris spp.)、蛔蟲屬(Ascaridia spp.)、蛔屬(Baylisascaris spp.)、布魯線蟲屬(Brugia spp.)(例如馬來布魯線蟲(Brugia malayi)、帝紋布魯線蟲(Brugia timori))、仰口線蟲屬(Bunostomum spp.)、毛細線蟲屬(Capillaria spp.)、夏伯特屬(Chabertia spp.)、支睾吸蟲屬(Clonorchis spp.)、古柏線蟲屬(Cooperia spp.)、環體線蟲屬(Crenosoma spp.)、杯口線蟲屬(Cyathostoma spp.)、雙腔吸蟲屬(Dicrocoelium spp.)、網尾線蟲屬(Dictyocaulus spp.)(例如絲狀網尾線蟲(Dictyocaulus filarial))、裂頭絛蟲屬(Diphyllobothrium spp.)(例如闊節裂頭絛蟲(Diphyllobothrium latum))、複孔絛蟲屬(Dipylidium spp.)、惡絲蟲屬(Dirofilaria spp.)、龍線蟲屬(Dracunculus spp.)(例如麥地那龍線蟲(Dracunculus medinensis))、棘球絛蟲屬(Echinococcus spp.)(例如細粒棘球絛蟲(Echinococcus granulosus)、多房棘球絛蟲(Echinococcus multilocularis))、棘口吸蟲屬(Echinostoma spp.)、蟯蟲屬(Enterobius spp.)(例如蠕形住腸蟯蟲(Enterobius vermicularis))、優鞘屬(Eucoleus spp.)、片吸蟲屬(Fasciola spp.)、擬片形吸蟲屬(Fascioloides spp.)、薑片吸蟲屬(Fasciolopsis spp.)、類線蟲屬(Filaroides spp.)、筒線蟲屬(Gongylonema spp.)、三代蟲屬(Gyrodactylus spp.)、麗線蟲屬(Habronema spp.)、血矛線蟲屬(Haemonchus spp.)、螺旋線蟲屬(Heligmosomoides spp.)、異刺線蟲屬(Heterakis spp.)、膜殼絛蟲屬(Hymenolepis spp.)(例如微小膜殼絛蟲(Hymenolepis nana))、豬圓線蟲屬(Hyostrongylus spp.)、類平滑絲蟲屬(Litomosoides spp.)、羅阿絲蟲屬(Loa spp.)(例如羅阿羅阿絲蟲(Loa Loa))、後圓線蟲屬(Metastrongylus spp.)、次睾吸蟲屬(Metorchis spp.)、中殖孔絛蟲屬(Mesocestoides spp.)、莫尼茨絛蟲屬(Moniezia spp.)、繆勒線蟲屬(Muellerius spp.)、板口線蟲屬(Necator spp.)、細頸線蟲屬(Nematodirus spp.)、日圓線蟲屬(Nippostrongylus spp.)、結節線蟲屬(Oesophagostomum spp.)、盤頭線蟲屬(Ollulanus spp.)、盤尾線蟲屬(Onchocerca spp)(例如旋盤尾線蟲(Onchocerca volvulus))、後睾吸蟲屬(Opisthorchis spp.)、奧斯勒絲蟲屬(Oslerus spp.)、奧斯特線蟲屬(Ostertagia spp.)、尖尾線蟲屬(Oxyuris spp.)、毛細線蟲屬、副絲蟲屬(Parafilaria spp.)、併殖吸蟲屬(Paragonimus spp.)、同端盤吸蟲屬(Paramphistomum spp.)、副裸頭屬(Paranoplocephala spp.)、副蛔蟲屬(Parascaris spp.)、栓尾線蟲屬(Passalurus spp.)、原圓線蟲屬(Protostrongylus spp.)、住血吸蟲屬(Schistosoma spp.)、腹腔絲蟲屬(Setaria spp.)、尾旋線蟲屬(Spirocerca spp.)、冠絲蟲屬(Stephanofilaria spp.)、冠尾屬(stephanurus spp.)、類圓線蟲屬(Strongyloides spp.)(例如福氏類圓線蟲(Strongyloides fuelleborni)、糞類圓線蟲(Strongyloides stercoralis))、圓線蟲屬(Strongylus spp.)、比翼線蟲屬(Syngamus spp.)、絛蟲屬(Taenia spp.)(例如牛肉絛蟲(Taenia saginata)、豬肉絛蟲(Taenia solium))、背帶線蟲屬(Teladorsagia spp.)、吸吮線蟲屬(Thelazia spp.)、弓蛔線蟲屬(Toxascaris spp.)、弓首線蟲屬(Toxocara spp.)、旋毛蟲屬(Trichinella spp.)(例如旋毛形線蟲(Trichinella spiralis)、本地旋毛蟲(Trichinella nativa)、布氏旋毛蟲(Trichinella britovi)、納氏旋毛蟲(Trichinella nelsoni)、偽方寵旋毛蟲(Trichinella pseudopsiralis))、毛畢屬(Trichobilharzia spp.)、毛圓線蟲屬(Trichostrongylus spp.)、鞭蟲屬(Trichuris spp.)(例如人鞭蟲(Trichuris trichuria))、彎蟲屬(Uncinaria spp.)、吳策線蟲屬(Wuchereria spp.)(例如班氏吳策線蟲(Wuchereria bancrofti))；來自圓形動物門之植物有害生物，即植物寄生線蟲，尤其野外 墊刃線蟲屬(Aglenchus spp.)(例如居農野外墊刃線蟲(Aglenchus agricola))、粒線蟲屬(Anguina spp.)(例如小麥粒線蟲(Anguina tritici))、滑刃線蟲屬(Aphelenchoides spp.)(例如花生滑刃線蟲(Aphelenchoides arachidis)、草莓滑刃線蟲(Aphelenchoides fragariae))、刺線蟲屬(Belonolaimus spp.)(例如細小刺線蟲(Belonolaimus gracilis)、雜草刺線蟲(Belonolaimus longicaudatus)、諾頓剌線蟲(Belonolaimus nortoni))、傘滑刃線蟲屬(Bursaphelenchus spp.)(例如椰樹傘滑刃線蟲(Bursaphelenchus cocophilus)、荒漠傘滑刃線蟲(Bursaphelenchus eremus)、松材傘滑刃線蟲(Bursaphelenchus xylophilus))、壞死線蟲屬(Cacopaurus spp.)(例如癌疫壞死線蟲(Cacopaurus pestis))、小環線蟲屬(Criconemella spp.)(例如彎曲小環線蟲(Criconemella curvata)、刻線小環線蟲(Criconemella onoensis)、裝飾小環線蟲(Criconemella ornata)、如思木小環線蟲(Criconemella rusium)、薄葉小環線蟲(Criconemella xenoplax)(=異盤中環線蟲(Mesocriconema xenoplax)))、輪線蟲屬(Criconemoides spp.)(例如非尼艾輪線蟲(Criconemoides ferniae)、蝸諾昔輪線蟲(Criconemoides onoense)、蝸那土輪線蟲(Criconemoides ornatum))、莖線蟲屬(Ditylenchus spp.)(例如鱗球莖莖線蟲(Ditylenchus dipsaci))、錐線蟲屬(Dolichodorus spp.)、球胞囊線蟲屬(Globodera spp.)(例如馬鈴薯球胞囊線蟲(Globodera pallida)、馬鈴薯金線蟲(Globodera rostochiensis))、螺旋線蟲屬(Helicotylenchus spp.)(例如雙宮螺旋線蟲(Helicotylenchus dihystera))、半輪線蟲屬(Hemicriconemoides spp.)、鞘線蟲屬(Hemicycliophora spp.)、異皮線蟲屬(Heterodera spp.)(例如燕麥異皮線蟲(Heterodera avenae)、大豆異皮線蟲(Heterodera glycines)、甜菜異皮線蟲(Heterodera schachtii))、紐帶線蟲屬(Hoplolaimus spp.)、長針線蟲屬(Longidorus spp.)(例如非洲長針線蟲 (Longidorus africanus))、根結線蟲屬(Meloidogyne spp.)(例如哥倫比亞根結線蟲(Meloidogyne chitwoodi)、偽根結線蟲(Meloidogyne fallax)、北方根結線蟲(Meloidogyne hapla)、南方根結線蟲(Meloidogyne incognita))、瓢線蟲屬(Meloinema spp.)、珍珠線蟲屬(Nacobbus spp.)、擬莖線蟲屬(Neotylenchus spp.)、擬長針線蟲屬(Paralongidorus spp.)、擬滑刃屬(Paraphelenchus spp.)、擬毛刺線蟲屬(Paratrichodorus spp.)(例如微小擬毛刺線蟲(Paratrichodorus minor))、短體線蟲屬(Pratylenchus spp.)(例如穿刺短體線蟲(Pratylenchus penetrans))、偽哈蘭克斯線蟲屬(Pseudohalenchus spp.)、平滑墊刃線蟲屬(Psilenchus spp.)、斑皮線蟲屬(Punctodera spp.)、五溝線蟲屬(Quinisulcius spp.)、穿孔線蟲屬(Radopholus spp.)(例如柑橘穿孔線蟲(Radopholus citrophilus)、香蕉穿孔線蟲(Radopholus similis))、腎型線蟲屬(Rotylenchulus spp.)、盤旋線蟲屬(Rotylenchus spp.)、盾線蟲屬(Scutellonema spp.)、亞粒線蟲屬(Subanguina spp.)、毛刺線蟲屬(Trichodorus spp.)(例如鈍毛刺線蟲(Trichodorus obtusus)、原始毛刺線蟲(Trichodorus primitives))、矮化線蟲屬(Tylenchorhynchus spp.)(例如飾環矮化線蟲(Tylenchorhynchus annulatus))、穿刺線蟲屬(Tylenchulus spp.)(例如半穿刺線蟲(Tylenchulus semipenetrans))、劍線蟲屬(Xiphinema spp.)(例如標記劍線蟲(Xiphinema index))。 The compound of the formula (I) can be preferably used as a pesticidal agent. Such compounds are active against commonly sensitive and stress resistant species as well as against all or some stages of development. Above The pests mentioned include: from Arthropoda, especially from Arachnida, such as Acarus spp. ) (eg Acarus siro, Aceria kuko, Aceria sheldoni), Aculops spp. ), Aculus spp. ) (eg Aculus fockeui, Aculus schlechtendali), Amblyomma spp. ), Aphitum sinensis (Amphitetrany sinensis), Argas spp. ), Bovineus spp. ), Berberis spp. (eg, Brevipalpus phoenicis), Bryobia graminum, Bryobia praetiosa, Centruroides spp. ), Foot genus (Chorioptes spp. ), Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp. ), Eotetranychus spp. (eg Eotetranychus hicoriae), Epitrimerus pyri, Eutetranychus spp. ) (eg Eutetranychus banksi), Eriophyes spp. (eg Eriophyes pyri), Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp. (for example, Hemitarsonemus latus) (= Polyphagotarsonemus latus), Hymenoma spp. ), the true genus Ixodes spp. ), widow spider genus (Latrodectus spp. ), brown spider genus (Loxosceles spp. ), European autumn harvest (Neutrombicula autumnalis), slave genus (Nuphersa spp. ), A. genus (Oligonychus spp. (eg Oligonychus coniferarum), Oligonychus ilicis, Oligonychus indicus, Oligonychus mangiferus, Oligonychus pratensis, Oligonychus punicae, Oligonychus Yothersi)), bird genus (Ornithodorus spp. ), Avian Robinia (Ornithonyssus spp. ), leaf genus (Panonychus spp. (for example, Panonychus citri (=Metatetranychus citri), Panonychus ulmi (=Metatetranychus ulmi), Phyllocoptruta oleivora ), Platytetranychus multidigituli, sassafras, genus Psoroptes spp. ), the genus Rhipicephalus spp. ), Rhizoglyphus spp. ), genus (Sarcoptes spp. ), Scorpio maurus, Steneotarsonemus spp. ), Steneotarsonemus spinki, Tarsonemus spp. ) (for example, Tarsonemus confuses, Tarsonemus pallidus), Tetranychus spp. (eg, Tetranychus canadensis, Tetranychus cinnabarinus, Tetranychus turkestani, Tetranychus urticae), Trembula alfreddugesi, prison god Genus (Vaejovis spp. ), tomato ascorbic acid (Vasates lycopersici); a pest from the genus Chilopoda, such as the genus Geophilus spp. ), genus (Scutigera spp. ) a pest from the genus Collembola or the genus Skeleton, such as the armored spiny worm (Onychiurus armatus); the Sminthurus viridis; the pest from the genus Diplopoda, such as a zebra Blaniulus guttulatus; a pest from the Insecta, such as a pest from the genus Blattodea, such as Blatta orientalis, Blattella asahinai, and Blattella Germanica), Leucophaea maderae, Loboptera decipiens, Neostyylopyga rhombifolia, Panchlora spp. ), Rare genus (Parcoblatta spp. ), Family genus (Periplaneta spp. (eg, Periplaneta americana, Periplaneta australasiae), Pycnoseelus surinamensis, Supella longipalpa; pests from Coleoptera, such as striped leaves Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp. ), Aethina tumida, Agelastica alni, Agriotes spp. ) (eg Agriotes linneatus, Agriotes mancus, Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora Spp. ), genus (Anthonomus spp. ) (eg, Anthonomus grandis), Anthrenus spp. ), the genus Papaver (Apion spp. ), Sugarcane genus (Apogonia spp. ), Atomaria spp. ) (eg Atomaria linearis), Furgenus spp. ), Baris caerulescens, Bruchidius obtectus, Bruchus spp. ) (eg pea elephant (Bruchus pisorum), broad bean elephant (Bruchus rufimanus)), Cassida spp. ), Cerotoma trifurcata, Ceutorrhynchus spp. (eg, Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae), Chaetocnema spp. (eg Chaetocnema confinis, Chaetocnema denticulata, Chaetocnema ectypa), Cleonus mendicus, Golden worm Genus (Conoderus spp. ), the root genus (Cosmopolites spp. ) (eg, Cosmopolites sordidus), New Zealand ribbed-legged tortoise (Costelytra zealandica), genus Ctenicera spp. ), weevil (Curculio spp. ), such as the curculio caryae, the big chest weevil (Curculio) Caryatrypes), Curculio obtusus, Curculio sayi, Cryptolestes ferrugineus, Cryptolestes pusillus, Cryptorhynchus lapathi, Mango concealer (Cryptorhynchus mangiferae), Twig genus (Cylindrocopturus spp. ), Cylindrocopturus adspersus, Cylindrocopturus furnissi, Dermestes spp. ), A. genus (Diabrotica spp. (eg, Diabrotica balteata, Diabrotica barberi, Diabrotica undecimpunctata howardi, Diabrotica undecimpunctata undecimpunctata, maize) Diabrotica virgifera virgifera, Diabrotica virgifera zeae, Dichocrocis spp. ), rice iron beetle (Dicladispa armigera), genus Paphiopedilum (Diloboderus spp. ), the genus Apicae (Epicaerus spp. ), Escherichia sinensis (Epilachna spp. ) (eg, Epilachna borealis, Epilachna varivestis), Epitrix spp. (eg, Epitrix cucumeris, Epitrix fuscula, Epitrix hirtipennis, Epitrix subcrinita, Epitrix tuberis), Botrytis (Faustinus spp. ), Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Heteronyx spp. ), Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus spp. (eg, Hypothenemus hampei, Hypothenemus obscurus, Hypothenemus pubescens), Lacnosterna consanguinea, sawhorn hair Lasioderma serricorne, Latheticus oryzae, Lathridius spp. ), Lemur spp. ), Colorado potato leaf beetle (Leptinotarsa decemlineata), silver genus Leucoptera spp. ) (eg Leucoptera coffeella), Lisorhoptrus oryzophilus, Listronotus spp. ) (=Hyperodes spp. )), genus Lithus spp. ), Luperodes spp. ), Luperomorpha xanthodera, Lyctus spp. ), American genus (Megascelis spp. ), Melanotus spp. ) (eg Melanotus longulus oregonensis), Meligerethes aeneus, Melonontha spp. ) (eg Western Melothatha melolontha), Midodus spp. ), Black genus (Monochamus spp. ), Naupactus xanthographus, Necrobia spp. ), Neogolder nectar (Neogalerucella spp. ), Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorhynchus spp. ) (eg, Otiorhynchus cribricollis, Otiorhynchus ligustici, Otiorhynchus ovatus, Otiorhynchus rugosostriarus, Otiorhynchus) Sulcatus)), negative worm (Oulema spp. ) (eg Oulema melanopus, Oulema oryzae), Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp . ), Haili Li, Phyllophaga helleri, Phyllotreta spp. ) (eg Phyllotreta armoraciae, Phyllotreta pusilla, Phyllotreta ramosa, Phyllotreta striolata), Japanese chafer (Popillia japonica) ), the small genus (Premnotrypes spp. ), Prostephanus truncatus, Psylliodes spp. ) (eg Psylliodes affinis, rapeseed jumper) (Psylliodes chrysocephala), Psylliodes punctulata, and Ptinus spp. ), Rhizobius ventralis, Rhizopertha dominica, Rhynchophorus spp. ), Rhynchophorus ferrugineus, Rhynchophorus palmarum, Sinoxylon perforans, Sitophilus spp. (eg Sitophilus granarius, Sitophilus linearis, Sitophilus oryzae, Sitophilus zeamais), Sphenophorus spp. ), Stegobium paniceum, stem genus (Sternechus spp. ) (eg Sternechus paludatus, Symphyletes spp. ), cilia (Tanymecus spp. (eg, Tanymecus dilaticollis, Tanymecus indicus, Tanymecus palliatus), Tenebrio molitor, Tenebrioides mauretanicus, and genus Tribolium spp. (eg, Tribolium audax, Tribolium castaneum, Tribolium confusum), Trogderma spp. ), seed genus (Tychius spp. ), Xylotrechus spp. ), from the genus of the genus (Zabrus spp. (eg Mabrus tenebrioides); pests from the order of Dermaptera, such as Anisolabis maritime, Forficula auricularia, Labidura riparia; A pest from the order Diptera, such as Aedes spp. (eg Aedes aegypti), Aedes albopictus, Aedes sticticus, Aedes vexans, Agromyza spp. ) (eg Agromyza frontella, Agromyza parvicornis), Anastrepha spp. ), Anopheles spp. (eg Anopheles quadrimaculatus, Anopheles gambiae), Asphondylia spp. ), Bactrocera spp. )(example Such as Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera oleae, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Mediterranean Ceratitis capitata, Chironomus spp. ), Chrysomya spp. ), genus Chrysops spp. ), Chrysozona pluvialis, Cochliomya spp. ), Aphis genus (Contarinia spp. (eg, Contarinia johnsoni, Contarinia nasturtii, Contarinia pyrivora, Contarinia schulzi, Contarinia sorghicola, Contarinia tritici) ), Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp. (eg Culex pipiens, Culex quinquefasciatus), Culicoides spp. ), Culexeta spp. ), the wild rodent genus (Cuterebra spp. ), Olive fly (Dacus oleae), Leaf genus (Dasineura spp. (eg Dasineura brassicae), Delia spp. (eg Delia antiqua, Delia coarctata, Delia florilega, Delia platura, Delia radicum), Dermatobia hominis, Drosophila spp. (eg Drosophila melanogaster, Drosophila suzukii), Echinocnemus spp. ), Euleia heraclei, Fannia spp. ), the genus of the genus Gasterophilus spp. ), T. genus (Glossina spp. ), Haematopota spp. ), Hydralis genus (Hydrellia spp. ), Hydrellia griseola, Hylexya spp. ), genus, genus Hypoderma spp. ), Liriomyza spp. (eg Liriomyza brassicae, Liriomyza huidobrensis, Liriomyza sativae), Lucilia spp. ) (eg Lucilia cuprina), Lutzomyia spp. Meng Song Genus (Mansonia spp. ), the genus Musca spp. ) (eg Musca domestica, Musca domestica vicina), Oestro spp. ), Oscinella frit, Paratanytarsus spp. ), Paralauterborniella sucincta, Pegomya spp. (eg Pegamya betae, Pegomya hyoscyami, Pegomya rubivora), Phlebotomus spp. ), the genus of the genus Phorbia spp. ), the genus Phormia spp. ), Piophila casei, Platyparea poeciloptera, Prodiplosis spp. ), Psila rosae, Rhagoletis spp. (eg, Rhagoletis cingulata, Rhagoletis completa, Rhagoletis fausta, Rhagoletis indifferens, Rhagoletis mendax) , Rhagoletis pomonella, Sarcophaga spp. ), genus (Simulium spp. ) (eg Simulium meridionale), Stomoxys spp. ), Burdock (Tabanus spp. ), the genus Tetanops spp. ), the genus of the genus (Tipula spp. (eg, Tipula paludosa, Tipula simplex, Toxotry pana curvicauda; pests from Hemiptera, such as Acizzia acaciaebaileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp. ) (eg Acyrthosiphon pisum), Acrogonia spp. ), A. mellifera (Aeneolamia spp. ), hibiscus (Agonoscena spp. ), Aleurocanthus spp. ), Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp. ) (eg Amrasca bigutulla, Amrasca devastans), Feilian Anuraphis cardui, Aonidiella spp. ) (eg Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata), Aphanostigma piri, Aphid (Aphis spp. (eg Aphis citricola, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis hederae, Aphis illinoisensis, Aphis middletoni, Aphis nasturtii, Aphis nerii, Aphis pomi, and different embroidery Aphis spiraecola, Aphis viburniphila, Arboridia apicalis, Arytainilla spp. ), Aspidiella spp. ), thin round shield genus (Aspidiotus spp. ) (eg, Ivy snail (Aspidiotus nerii), Atanus spp. ), Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, Boreioglycaspis melaleucae, Brachycaudus helichrysi, Microtuber Genus (Brachycolus spp. ), Bravicoryne brassicae, Cacopsylla spp. (eg Cacopsylla pyricola), Calligypona marginata, Capulinia spp. ), Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp. ), Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chondracris rosea, Chromaphis juglandicola, Chrysomphalus aonidum, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp. ) (eg Coccus hesperidum, Coccus longulus, Coccus) Pseudomagnoliarum), Coccus viridis, Cryptomyzus ribis, Cryptoneossa spp. ), Ctenary genus (Ctenarytaina spp. ), Dalbulus spp. ), Dialeurodes chittendeni, Dialeurodes citri, Diaphorina citri, Diaspis spp. ), two-tailed genus (Diuraphis spp. ), Drosicha spp. ), Dysaphis spp. (eg Dysaphis apiifolia, Dysaphis plantaginea, Dysaphis tulipae), Dysmicoccus spp. ), small green leaf genus (Empoasca spp. (eg, Empoasca abrupta, Empoasca fabae, Emppoasca maligna, Empoasca solana, and Smectas green leafhopper (Empoasca) Stevenis)), Eriosoma spp. ) (eg Eriosoma americanum, Eriosoma lanigerum, Eriosoma pyricola), Erythroneura spp. ), oil prasuma (Eucalyptolyma spp. ), eucalyptus (Euphyllura spp. ), Euscelis bilobatus, Ferrisia spp. ), Shield genus Fiorinia spp. ), Turcaspis oceanica, Geococcus coffeae, Glycaspis spp. ), Heteropsylla cubana, Heteropsylla spinulosa, Homalodisca coagulata, Hyalopterus arundinis, Hyalopterus pruni, Pseudomonas Icerya spp. ) (eg, Icerya purchasi, Idiocerus spp. ), Aphis genus (Idioscopus spp. ), the genus Laodelphax striatellus, the genus Lecanium spp. ) (eg Lecanium corni (= Parthenolecanium corni)), oyster (Lepidosaphes spp. ) (eg Lepidosaphes ulmi), Lipaphis erysimi, Lopholeucaspis japonica, Lycorma delicatula, Cymbidium (Macrosiphum spp. ) (eg Macrosiphum euphorbiae, Macrosiphum lilii, Macrosiphum rosae), Macrosteles facifrons, Mahanarva spp. ), cane yellow radix (Melanaphis sacchari), mecafilella spp. ), Metcalfa pruinosa, Metopolophium dirhodum, Monellia costalis, Monexopsis pecanis, Myzus spp. (eg Myzus ascalonicus, Myzus cerasi, Myzus ligustri, Myzus ornatus, Myzus persicae, Tobacco) Myzus nicotianae)), Nasonovia ribisnigri, Neomoskellia spp. ), Nephotettix spp. (eg, Nephotettix cincticeps, Nephotettix nigropictus), Nettigoniclla spectra, Nilaparvata lugens, Oncometopia Spp. ), Orthezia praelonga, Oxya chinensis, Pachypsylla spp. ), Parabemisia myricae, Paratrioza spp. ) (eg Paratrio cockerelli), Parlatoria spp. ), 瘿 蚜 (Pemphigus spp. ) (eg Pemphigus bursarius, Pemphigus populivenae), Peregrinus maidis, Perkinsiella spp. ), Phenacoccus spp. ) (eg Phenacoccus madeirensis), Phloeomyzus passerinii, Phorodon humuli, Phyloxera spp. (eg Phylloxera devastatrix, Phylloxera notabilis), Pinnaspis aspidistrae, Planococcus spp. ) (eg, Planococcus citri), Prosopidopsylla flava, Protopulvinaria pyriformis, Mulberry shield (Pseudaulacaspis pentagona), Pseudococcus spp. (eg, Pseudococcus calceolariae, Pseudococcus comstocki, Pseudococcus longispinus, Pseudococcus maritimus, Pseudococcus viburni), Pirop Genus (Psyllopsis spp. ), hibiscus (Psylla spp. ) (eg Psylla buxi, Psylla mali, Psylla pyri), Pteromalus spp. ), Pulvinaria spp. ), spider genus (Pyrilla spp. ), Circular Shield (Quadraspidiotus spp. (for example, Quadraspidiotus juglansregiae, Quadraspidiotus ostreaeformis, Quadraspidiotus perniciosus), oysters (Quesada gigas), and Rastrococcus spp. ), 缢管蚜 (Rhopalosiphum spp. (eg Rhopalosiphum maidis, Rhopalosiphum oxyacanthae, Rhopalosiphum padi, Rhopalosiphum rufiabdominale), Saitetia spp . (eg, Saissetia coffeae, Saissetia miranda, Saissetia neglecta, Saissetia oleae), Scaphoideus titanus ), Schizaphis graminum, Selenaspidus articulatus, Sitobion avenae, Sogata spp. ), Sogatella furcifera, Sogatodes spp. ), Stictocephala festina, Siphoninus phillyreae, Tenalaphara malayensis, Tetragonocephela spp. ), pecan (Tinocallis caryaefoliae), genus of the genus Tomaspis spp. ), citrus (Toxoptera spp. ) (eg Toxoptera aurantii, Toxoptera citricidus), Trialeurodes vaporariorum, Trioza spp. ) (eg Trioza diospyri), Typhlocyba spp. ), Shield genus (Unaspis spp. ), grape root nodules (Viteus) Vitifolii), Zygina spp. ); a pest from the Heteroptera, such as Aelia spp. ), Anasa tristis, Antestiopsis spp. ), Bosna spp. ), long genus (Blissus spp. ), Calcutris spp. ), Campylomma livida, Cavelleus spp. ), bedbug (Cimex spp. (eg Cimex adjunctus, Cimex hemipterus, Cimex lectularius, Cimex pilosellus), Collies sp. ), the genus Creontiades dilutus, the Dasynus piperis, the Diechels furcatus, the Diconocoris hewetti, and the Dysdercus spp. ), American genus Euschistus spp. (eg, Euschistus heros, Euschistus servus, Euschistus tristigmus, Euschistus variolarius), Eurydema spp. ), Eustochaster spp. ), Halomorpha halys, Heliopeltis spp. ), with a large giant scorpion (Horcias nobilellus), genus Leptocorisa spp. ), Leptocorisa varicornis, Leptoglossus occidentalis, Leptoglossus phyllopus, Lygocoris spp. ) (eg Lygocoris pabulinus), Lygus spp. ) (eg Lygus elisus, male genus Lygus hesperus, Lygus lineolaris), Macropes excavatus, Megacopta cribraria, blind Miridae, Monalonion atratum, Nezara spp. ) (eg Nezara viridula), Nysius spp. ), Oysterus (Oebalus spp. ), Penentidae, Piesema quadrata, and genus Piezodorus spp. ) (eg Piezodorus guildinii), Psallus spp. ), avocado nets (Pseudacysta persea), red scorpion genus (Rhodnius spp. ),can Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp. ), Stephanitis nashi, Tibraca spp. ), Trietoma spp. ); a pest from Hymenoptera, such as the genus Acromyrmex spp. ), Athalia spp. ) (eg Athalia rosae), Atta spp. ), Giant Mountain Ant (Camponotus spp. ), the genus Polychaete (Dolichovespula spp. ), Dipterus spp. ) (eg Diprion similis), Hoplocampa spp. (eg, Hoplocampa cookei, Hoplocampa testudinea), Lasius spp. ), Linepithema humile (Iridiomyrmex humile), Monomorium pharaonis, Paratrechina spp. ), Vespa (Paravespula spp. ), Arrow genus (Plagiolepis spp. ), Tree Bee (Sirex spp. ), invading red ant (Solenopsis invicta), acid odorant (Tapinoma spp. ), the genus Technomyrmex albipes, the genus Urocerus spp. ), Vespa (Vespa spp. ) (eg Vespa crabro), Wasmannia auropunctata, Xeris spp. ) from the Isopoda pests, such as the Armadillidium vulgare, the Oniscus asellus, the Porcellio scaber; the pests from the Isoptera, such as the home Termite genus (Coptotermes spp. ) (for example, Coptotermes formosanus, Termirmes cumulans, Cryptotermes spp. ), Termite genus (Incisitermes spp. ), wood termite genus (Kalotermes spp. ), termite termite (Microtermes obesi), genus termite (Nasutitermes spp. ), the termite genus (Odontotermes spp. ), Termite genus (Porotermes spp. ), Termites (Reticulitermes spp. (eg, Reticulitermes flavipes, Reticulitermes Hesperus); Pests from Lepidoptera, such as Achroia grisella, Acronicta major, Adoxophyes spp. ) (eg Adoxophyes orana), Aedia leucomelas, Agrotis spp. ) (eg Agrotis segetum, Agrotis ipsilon), Alabama spp. ) (eg Alabama argillacea), Amyelois transitella, Anarsia spp. ), Anticarsia spp. ) (eg, Anticarsia gemmatalis), Argyroploce spp. ), Autographa spp. ), Barathra brassicae, Blastodacna atra, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp . ), Cacoecia spp. ), Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp. (eg Chilo plejadellus, Chilo suppressalis), Choreutis pariana, Choristoneura spp. ), Chrysodeixis chalcites, Clysia ambiguella, Cnaphalocerus spp. ), Cnaphalocrocis medinalis, Cnephasia spp. ), Conopomorpha spp. ), Conotrachelus spp. ), Kutas (Copitarsia spp. ), Cydia spp. ) (eg Cydia nigricana), Cydia pomonella, Dalaca noctuides, Diaphania spp. ), Helicoverpa armigera (Diparopsis spp. ), Diatraea saccharalis, Eadas spp. ), Ecdytolopha aurantium, South American corn (Elasmopalpus lignosellus), Eldana saccharina, Ephestia spp. ) (eg Ephestia elutella, Ephestia kuehniella), Epinotia spp. ), Epiphyas postvittana, Erannis spp. ), Erschoviella musculana, Etiella spp. ), Euphoria spp. ), Elia spp. ), grape and apple leaf moth (Eupoecilia ambiguella), genus Euproctis spp. ) (eg Euproctis chrysorrhoea), cut genus (Euxoa spp. ), the genus Spodoptera (Feltia spp. ), Galleria mellonella, Grecilla spp. ), the small heartworm (Grapholitha spp. ) (eg, Grapholita molesta, Grapholita prunivora), Hedylepta spp. ), Noctuidae (Helicoverpa spp. ) (eg, Helicoverpa armigera, Helicoverpa zea), Heliothis spp. ) (eg Heliothis virescens), Hofmannophila pseudospretella, Homoeosoma spp. ), Homona spp. ), Hyponomeuta padella, Kakivoria flavofasciata, Lampides spp. ), Noctuidae (Laphygma spp. ), Laspeyresia molesta, Leucinodes orbonalis, silver genus (such as coffee silver moth), Lithocolletis spp. (eg Lithocolletis blancardella), Lithophane antennata, Lobesia spp. ) (for example, Lobesia botrana), Loxaltis albicosta, Lymantria spp. ) (eg Lymantria dispar), Lynonetia spp. (eg, Lyonetia clerkella), Malacosoma neustria, Maruca testulalis, Mamestra brassicae, Melanitis leda, Mocis Spp. ), Monopis obviella, Mythimna separata, Nemapogon cloacellus, leeches (Nymphula spp. ), Oticaticus spp. ), Oyster genus (Omphisa spp. ), the genus Moper (Operophtera spp. ), Woratus spp. ), Orthaga spp. ), Ostrinia spp. ) (eg Ostrillia nubilalis), Panolis flammea, Parnara spp. ), red bollworm (Pectinophora spp. ) (eg Pectinophora gossypiella), Perileucoptera spp. ), Solanum genus (Phthorimaea spp. (eg, Phthorimaea operculella), Phyllocnistis citrella, Phyllonycter spp. ) (eg Phyllonycter blancardella, Phyllonycter crataegella), Pieris spp. ) (eg, Pieris rapae), Platynota stultana, Plodia interpunctella, Plusia spp. ), Plutella xylostella (=Plutella maculipennis), Prays spp. ), Spodoptera spp. ), tobacco hawk moth (Protoparce spp. ), genus Pseudaletia spp. (eg, Pseudaletia unipuncta, Pseudoplusia includes, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp. ) (eg Schoenobius bipunctifer), Scirpophaga spp. ) (eg, Scirpophaga innotata), Scotia segetum, Sesamia spp. ) (eg, Sesamia inferens), Sparganothis spp. ), Spodoptera spp. (eg, Spodoptera eradiana, Spodoptera exigua, Spodoptera frugiperda), Spodoptera praefica, genus Moth ( Stathmopoda spp. ), Scutellaria (Stenoma spp. ), Stomopteryx subsecivella, Synanthedon spp. ), Andean potato tuber moth (Tecia solanivora), Thaumetopoea spp. ), Thermesia gemmatalis, cork Tinea cloacella, Tinea pellionella, Tineola bisselliella, and Tortrix spp. ), Trichophaga tapetzella, Trichoplusia spp. ) (eg Trichoplusia ni), Tryporyza incertulas, Tuta absoluta, Virachola spp. ); pests from Orthoptera or Saltatoria, such as Acheta domesticus, Dichroplus spp. ), genus (Gryllotalpa spp. ) (eg, Gryllotalpa gryllotalpa), Cane genus (Hieroglyphus spp. ), genus Locusta spp. ) (eg Locusta migratoria), Melanoplus spp. (eg, Melanoplus devastator), Paratlanticus ussuriensis, Schistocerca gregaria; pests from Phthiraptera, such as the genus Damalinia spp. ), blood genus (Haematopinus spp. ), long genus (Linognathus spp. ), genus Pediculus spp. ), Phylloxera vastatrix, Phthirus pubis, Trichodectes spp. ); a pest from the genus Psocoptera, such as the genus Lepinotus spp. ), the book genus (Liposcelis spp. ); a pest from the genus Siphonaptera, such as Ceratophyllus spp. ), Ctenocephalides spp. (eg Ctenocephalides canis, Ctenocephalides felis), Pulex irritans, Tunga penetrans, Xenopsylla cheopis; Thysanoptera pests such as Anaphothrips obscurus, Baliothrips biformis, Chaetanaphothrips leeuweni, and fresh grape thrips (Drepanothrips) Reuteri), Enneothrips flavens, and Frankliniella spp. (eg Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, Frankliniella vaccinii) , Frankliniella williamsi, Haplothrips spp. ), Yangshuo horses (Heliothrips spp. ), Greenhouse fence horse (Hercinothrips femoralis), Karthomas spp. ), Rhipiphorothrips cruentatus, and hard humus (Scirtothrips spp. ), Taeniothrips cardamomi, Thrips spp. (eg, Thrips palmi, Thrips tabaci); pests from Zygentoma (=Thysanura), such as the genus Ctenolepisma spp. ), Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica; pests from the genus Symphyla, such as Scutigerella spp. ), for example, Scutigerella immaculata; from mollusk gates, in particular from Bivalvia pests, such as Dreissena spp. ); also from the pests of Gastropoda, such as Arion spp. ) (eg Arion ater rufus), Biomphalaria spp. ), genus Bulinus spp. ), the wild genus (Deroceras spp. ) (eg, Deroceras laeve), genus (Galba spp. ), Lymnaea spp. ), Oncomelania spp. ), Pomacea spp. ), Amber snail (Succinea spp. ); animal and human parasites from the genus Platyhelminthes and Nematoda, such as Aelurostrongylus spp. ), Amitos nematode (Amidostomum spp. ), Crohn's nematode (Ancylostoma spp. ) (eg Ancylostoma duodenale), C. elegans (Ancylostoma) Ceylanicum), Acylostoma braziliensis, Angiostrongylus spp. ), Anisakis spp. ), Anopheles genus (Anoplocephala spp. ), Ascaris spp. ), Aphidida spp. ), genus (Baylisascaris spp. ), Brugia spp. ) (eg Brugia malayi, Brugia timori), Bunostomum spp. ), Capillaria spp. ), Chabertia spp. ), Clostridium sp. ), Cooperaria spp. ), C. elegans (Crenosoma spp. ), C. elegans (Cyathostoma spp. ), Dicrocoelium spp. ), Dictyocaulus spp. ) (eg, Dictyocaulus filarial), Diphyllobothrium spp. ) (eg Diphyllobothrium latum), Dipylidium spp. ), Dirofilaria spp. ), Dracunculus spp. ) (eg Dracunculus medinensis), Echinococcus spp. (eg Echinococcus granulosus, Echinococcus multilocularis), Echinostoma spp. ), Aphid (Enterobius spp. ) (eg, Enterobius vermicularis), Eucalose spp. ), flukes (Fasciola spp. ), Fascioloides spp. ), Fasciolopsis spp. ), the genus Nematode (Filaroides spp. ), genus Nematode (Gongylonema spp. ), the third generation of genus (Gyrodactylus spp. ), Nematode (Habronema spp. ), Haemonchus spp. ), Heliconia genus (Heligmosomoides spp. ), Heterarias spp. ), membrane shell aphid (Hymenolepis spp. ) (eg Hymenolepis nana), Hyostrongylus spp. ), a genus of the genus Litomosoides spp. ), Loa spp. ) (eg Loa Loa), Metastrongylus spp. ), the genus Paragonimus (Metorchis spp. ), Mesocestoides spp. ), Moniz Locust (Moniezia) Spp. ), Muellerius spp. ), Necator spp. ), Nematodirus spp. ), N. elegans (Nippostrongylus spp. ), the nodular nematode (Oesophagostomum spp. ), Panthera genus (Ollulanus spp. ), Onchocerca spp (such as Onchocerca volvulus), Epizoa spp. ), Oslerus spp. ), Ostertaglia spp. ), Oxyuris spp. ), Capreolus, Parafilaria spp. ), Paragonimus spp. ), Paragonimum spp. ), the parasitic genus Paranoplocephala spp. ), Parascaris spp. ), genus Nematode (Passalurus spp. ), Protostrongylus spp. ), living in the genus Schistosoma spp. ), the genus Filaria (Setaria spp. ), Trichomonas (Spirocerca spp. ), Crown genus (Stephanofilaria spp. ), crown genus (stephanurus spp. ), genus Nematode (Strongyloides spp. (eg, Strongyloides fuelleborni, Strongyloides stercoralis), Strongylus spp. ), genus Heteropharus (Syngamus spp. ), genus Taenia spp. ) (eg Taenia saginata, Taenia solium), Teladorsagia spp. ), sucking nematode (Thelazia spp. ), Toxascaris spp. ), Toxoca serrata (Toxocara spp. ), Trichinella spp. (eg Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis), Mao Bi Genus (Trichobilharzia spp. ), Trichostrongylus spp. ), Trichuris spp. ) (eg Trichuris trichuria), Uncinaria spp. ), Wucer nematode (Wuchereria spp. ) (eg Wuchereria bancrofti); plant pests from round animal gates, ie plant parasitic nematodes, especially in the wild Nematode spp. ) (eg Aglenchus agricola), Anguina spp. ) (eg Anguina tritici), Aphelenchoides spp. (eg Aphelenchoides arachidis, Aphelenchoides fragariae), Nematodes (Belonolaimus spp. (eg, Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni), Bursaphelenchus spp. (eg, Bursaphelenchus cocophilus, Bursaphelenchus eremus, Bursaphelenchus xylophilus), nematode nematode (Cacopaurus spp. ) (eg, Cacopaurus pestis), Crionemella spp. ) (eg Criconemella curvata, Criconemella onoensis, Criconemella ornata, Criconemella rusium, Criconemella xenoplax) (=Mesocriconema xenoplax), Criconemoides spp. (eg, Criconemoides ferniae, Criconemoides onoense, Criconemoides ornatum), Ditylenchus spp. ) (eg Ditylenchus dipsaci), Coniche genus (Dolichodorus spp. ), Globodera spp. ) (eg, Globodera pallida, Globodera rostochiensis), Helicopterus spp. (eg Helicotylenchus dihystera), Hemicriconemoides spp. ), Nematode (Hemicycliophora spp. ), Heterodera spp. (eg Heterodera avenae, Heterodera glycines, Heterodera schachtii), Hoplolaimus spp. ), the long-necked nematode (Longidorus spp. (for example, A. elegans) (Longidorus africanus)), Meloidogyne spp. (eg, Meloidogyne chitwoodi, Meloidogyne fallax, Meloidogyne hapla, Meloidogyne incognita), Melolinema spp. ), pearl nematode (Nacobbus spp. ), Nematolinus spp. ), the genus Aphididae (Paralongidorus spp. ), Parapterlenus spp. ), Trichoderma genus (Paratrichodorus spp. ) (eg Paratrichodorus minor), Platylenchus spp. ) (eg, Pratylenchus penetrans), Pseudohalenchus spp. ), smoothing edge nematode (Psilenchus spp. ), Candida nematode (Punctodera spp. ), Quercus elegans (Quinisulcius spp. ), perforated nematode (Radopholus spp. (eg Radopholus citrophilus, Radopholus similis), Rotylenchulus spp. ), the genus Nematode (Rotylenchus spp. ), Shield genus (Scutellonema spp. ), Subanguina spp. ), Trichoderma genus (Trichodorus spp. ) (eg Trichodorus obtusus, Trichodorus primitives), Tylenchorhynchus spp. ) (eg, Tylenchorhynchus annulatus), Tylenchulus spp. ) (eg Tylenchulus semipenetrans), Xiphinema spp. ) (for example, marking the Xiphinema index).

另外，其可控制來自原生動物亞界、球蟲目(Coccidia)之有害生物，例如艾美耳球蟲屬(Eimeria spp)。 In addition, it can control pests from the protozoan subfamily, Coccidia, such as Eimeria spp.

式(I)化合物可視情況在某些濃度或施加率下，亦用作除草劑、安全劑、生長調節劑或藥劑以改良植物性質，作為殺微生物劑或殺配子劑，例如作為殺真菌劑、抗黴劑、殺細菌劑、殺病毒劑(包括針對類病毒之藥劑)或作為針對MLO(類黴漿菌有機體(mycoplasma-like organism))及RLO(類立克次體有機體(rickettsia-like organism))之藥 劑。若適當，其亦可用作合成其他活性成分之中間體或前體。 The compounds of formula (I) may also be used as herbicides, safeners, growth regulators or agents at certain concentrations or rates of application to improve plant properties, as microbicides or gametocides, for example as fungicides, Antifungal agents, bactericides, virucides (including agents for viroids) or as MLO (mycoplasma-like organisms) and RLO (rickettsia-like organisms) )) Agent. If appropriate, it can also be used as an intermediate or precursor for the synthesis of other active ingredients.

調配物 Formulation

本發明進一步係關於調配物及自其製備作為殺有害生物劑之使用形式(例如浸泡、滴落及噴霧液劑)，其包含至少一種式(I)化合物。視情況，該等使用形式包含其他殺有害生物劑及/或改良作用之佐劑，例如滲透劑，例如植物油(例如菜籽油、向日葵油)、礦物油(例如石蠟油)、植物脂肪酸之烷基酯(例如菜籽油甲基酯或大豆油甲基酯)或烷醇烷氧基化物及/或展布劑(例如烷基矽氧烷)及/或鹽，例如有機或無機銨或鏻鹽(例如硫酸銨或磷酸氫二銨)及/或保留促進劑(例如磺基丁二酸二辛基酯或羥丙基瓜爾膠聚合物)及/或濕潤劑(例如甘油)及/或肥料(例如含銨、鉀或磷肥料)。 The invention further relates to formulations and preparations for use as pesticides (e.g., soaking, dripping and spray liquors) comprising at least one compound of formula (I). Optionally, such use forms comprise other pesticidal and/or modifying adjuvants, such as penetrants such as vegetable oils (eg, rapeseed oil, sunflower oil), mineral oils (eg, paraffin oil), and plant fatty acid alkanes. a base ester (such as rapeseed oil methyl ester or soybean oil methyl ester) or an alkanol alkoxylate and/or a spreading agent (such as an alkyl siloxane) and/or a salt, such as an organic or inorganic ammonium or hydrazine a salt (such as ammonium sulfate or diammonium hydrogen phosphate) and/or a retention promoter (such as dioctyl sulfosuccinate or hydroxypropyl guar polymer) and/or a humectant (such as glycerin) and/or Fertilizer (eg ammonium, potassium or phosphorus fertilizer).

常用調配物係(例如)水溶性液體(SL)、乳液濃縮物(EC)、於水中之乳液(EW)、懸浮液濃縮物(SC、SE、FS、OD)、水可分散顆粒(WG)、顆粒(GR)及膠囊濃縮物(CS)；該等及其他可能調配物類型係例如由Crop Life International且在Pesticide Specifications,Manual on development and use of FAO and WHO specifications for pesticides,FAO Plant Production and Protection Papers-173中闡述，其係藉由FAO/WHO Joint Meeting on Pesticide Specifications,2004,ISBN：9251048576來製備。除一或多種式(I)化合物以外，調配物視情況包含其他活性農用化學品成分。 Commonly formulated formulations such as water soluble liquid (SL), emulsion concentrate (EC), emulsion in water (EW), suspension concentrate (SC, SE, FS, OD), water dispersible granules (WG) , granules (GR) and capsule concentrates (CS); these and other possible formulation types are for example from Crop Life International and in Pesticide Specifications, Manual on development and use of FAO and WHO specifications for pesticides, FAO Plant Production and Protection As described in Papers-173, it is prepared by the FAO/WHO Joint Meeting on Pesticide Specifications, 2004, ISBN: 9251048576. In addition to one or more compounds of formula (I), the formulation optionally contains other active agrochemical ingredients.

較佳者係包含輔助物、例如增量劑、溶劑、自發性促進劑、載劑、乳化劑、分散劑、防凍保護劑、殺生物劑、增稠劑及/或其他輔助物(例如佐劑)之調配物或使用形式。佐劑在此背景下係增強調配物之生物效應之組份，而該組份本身無任何生物效應。佐劑之實例係促進保留、展布、與葉表面附接或滲透之藥劑。 Preferred are auxiliary substances such as extenders, solvents, spontaneous accelerators, carriers, emulsifiers, dispersants, antifreeze protectants, biocides, thickeners and/or other adjuvants (eg adjuvants) The formulation or form of use. Adjuvants in this context are components that enhance the biological effects of the formulation without any biological effects. Examples of adjuvants are agents that promote retention, spreading, attachment to or penetration of the leaf surface.

該等調配物係以已知方式來製備，例如藉由混合式(I)化合物與 諸如增量劑、溶劑及/或固體載劑等輔助物及/或諸如表面活性劑等其他輔助物來製備。調配物係在適宜設備中或者在施用之前或在施用期間製造。 The formulations are prepared in a known manner, for example by mixing a compound of formula (I) with It is prepared by an auxiliary such as an extender, a solvent and/or a solid carrier, and/or other auxiliary such as a surfactant. Formulations are made in a suitable device or prior to administration or during administration.

所用輔助物可為適於將特殊性質(諸如某些物理、技術及/或生物性質)賦予式(I)化合物之調配物或賦予自該等調配物製備之使用形式(例如即用型殺有害生物劑，諸如噴霧液劑或拌種產品)之物質。 The auxiliary used may be a formulation suitable for imparting a particular property (such as certain physical, technical and/or biological properties) to a compound of formula (I) or a form of use imparted from the preparation of such a formulation (eg, ready-to-use killing) A substance of a biological agent, such as a spray liquid or a seed dressing product.

適宜增量劑係例如水、極性及非極性有機化學液體，例如來自以下類別：芳香族及非芳香族烴(諸如石蠟、烷基苯、烷基萘、氯苯)、醇及多元醇(若適當，其亦可經取代、醚化及/或酯化)、酮(諸如丙酮、環己酮)、酯(包括脂肪及油)及(聚)醚，簡單及經取代之胺、醯胺、內醯胺(諸如N-烷基吡咯啶酮)及內酯，碸及亞碸(諸如二甲基亞碸)。 Suitable extenders are, for example, water, polar and non-polar organic chemical liquids, for example from the following classes: aromatic and non-aromatic hydrocarbons (such as paraffin, alkylbenzene, alkylnaphthalene, chlorobenzene), alcohols and polyols (if Suitably, it may also be substituted, etherified and/or esterified), ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, simple and substituted amines, guanamines, Endouramides (such as N-alkylpyrrolidone) and lactones, hydrazine and hydrazine (such as dimethyl hydrazine).

若所用增量劑係水，則亦可使用例如有機溶劑作為輔助溶劑。有用液體溶劑基本上係：芳香族化合物，諸如二甲苯、甲苯或烷基萘；氯化芳香族或氯化脂肪族烴，諸如氯苯、氯乙烯或二氯甲烷；脂肪族烴，諸如環己烷或石蠟，例如礦物油餾分、礦物油及植物油；醇(諸如丁醇或二醇)及其醚及酯；酮，諸如丙酮、甲基乙基酮、甲基異丁基酮或環己酮；強極性溶劑，諸如二甲基甲醯胺及二甲基亞碸；及水。 If the extender used is water, it is also possible to use, for example, an organic solvent as an auxiliary solvent. Useful liquid solvents are essentially: aromatic compounds such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons such as cyclohexane Alkanes or paraffins, such as mineral oil fractions, mineral oils and vegetable oils; alcohols (such as butanol or glycols) and ethers and esters thereof; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone Strong polar solvents such as dimethylformamide and dimethylhydrazine; and water.

原則上，可使用所有適宜溶劑。適宜溶劑之實例係芳香族烴，諸如二甲苯、甲苯或烷基萘；氯化芳香族或脂肪族烴，諸如氯苯、氯乙烯或二氯甲烷；脂肪族烴，諸如環己烷、石蠟、礦物油餾分、礦物油及植物油；醇(諸如甲醇、乙醇、異丙醇、丁醇或二醇)及其醚及酯；酮，諸如丙酮、甲基乙基酮、甲基異丁基酮或環己酮；強極性溶劑，諸如二甲基亞碸；亦及水。 In principle, all suitable solvents can be used. Examples of suitable solvents are aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene; chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or dichloromethane; aliphatic hydrocarbons such as cyclohexane, paraffin, Mineral oil fractions, mineral oils and vegetable oils; alcohols (such as methanol, ethanol, isopropanol, butanol or glycols) and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone; a strong polar solvent such as dimethyl hydrazine; also water.

原則上，可使用所有適宜載劑。有用載劑尤其包括：例如銨鹽 及粉狀天然礦物(諸如高嶺土、黏土、滑石粉、白堊、石英、鎂鋁海泡石(attapulgite)、蒙脫石或矽藻土)及粉狀合成礦物質(諸如細粒二氧化矽、氧化鋁)，及天然或合成矽酸鹽、樹脂、蠟及/或固體肥料。同樣可使用該等載劑之混合物。有用之顆粒載劑包括：例如粉碎及分化(fractionated)之天然岩石，諸如方解石、大理石、浮石、海泡石、白雲石，及無機及有機粉之合成顆粒，亦及有機材料(諸如鋸屑、紙、椰子殼、玉米及煙草莖稈)之顆粒。 In principle, all suitable carriers can be used. Useful carriers include, inter alia, ammonium salts And powdered natural minerals (such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth) and powdered synthetic minerals (such as fine-grained cerium oxide, oxidation Aluminum), and natural or synthetic silicates, resins, waxes and/or solid fertilizers. Mixtures of such carriers can likewise be used. Useful particulate carriers include, for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, and synthetic particles of inorganic and organic powders, as well as organic materials such as sawdust and paper. Granules of coconut shell, corn and tobacco stalks.

亦可使用液化氣態增量劑或溶劑。尤其適宜者係彼等在標準溫度下及在大氣壓力下為氣態之增量劑或載劑，例如氣溶膠推進劑，例如鹵化烴，亦及丁烷、丙烷、氮及二氧化碳。 Liquefied gaseous extenders or solvents can also be used. Particularly suitable are extenders or carriers which are gaseous at standard temperature and at atmospheric pressure, such as aerosol propellants, such as halogenated hydrocarbons, but also butane, propane, nitrogen and carbon dioxide.

具有離子或非離子性質之乳化劑及/或泡沫形成劑、分散劑或潤濕劑或該等表面活性物質之混合物之實例係聚丙烯酸之鹽、木質素磺酸之鹽、酚磺酸或萘磺酸之鹽、環氧乙烷與脂肪醇或與脂肪酸或與脂肪胺、與經取代酚(較佳地烷基酚或芳基酚)之聚縮物、磺基琥珀酸酯之鹽、牛磺酸衍生物(較佳地牛磺酸烷基酯)、聚乙氧化醇或酚之磷酯、多元醇之脂肪酸酯，及含有硫酸酯、磺酸酯及磷酸酯之化合物之衍生物，例如烷基芳基聚二醇醚、磺酸烷基酯、硫酸烷基酯、磺酸芳基酯、蛋白水解產物、木質素亞硫酸鹽廢液及甲基纖維素。若式(I)化合物中之一者及/或惰性載劑中之一者不溶於水且當在水中應用時，表面活性劑之存在係有利的。 Examples of emulsifiers and/or foam formers, dispersants or wetting agents or mixtures of such surface-active substances having ionic or nonionic properties are polyacrylic acid salts, ligninsulfonic acid salts, phenolsulfonic acid or naphthalene a salt of a sulfonic acid, an ethylene oxide and a fatty alcohol or a fatty acid or a fatty amine, a polycondensate of a substituted phenol (preferably an alkylphenol or an arylphenol), a salt of a sulfosuccinate, a cow a sulfonic acid derivative (preferably an alkyl taurate), a polyethoxylated alcohol or a phenolic phospholipid, a fatty acid ester of a polyhydric alcohol, and a derivative of a compound containing a sulfate, a sulfonate, and a phosphate, For example, alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, protein hydrolysates, lignin sulfite waste liquids, and methyl cellulose. If one of the compounds of formula (I) and/or one of the inert carriers is insoluble in water and when used in water, the presence of a surfactant is advantageous.

可存於調配物及自其衍生之使用形式中之其他輔助物係染料，例如無機顏料，例如氧化鐵、氧化鈦及普魯士藍(Prussian Blue)，及有機染料，例如茜素染料、偶氮染料及金屬酞青染料；及營養素及微量營養素，例如鐵、錳、硼、銅、鈷、鉬及鋅之鹽。 Other auxiliary dyes which may be present in the formulation and the forms derived therefrom, such as inorganic pigments such as iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes And metal indigo dyes; and nutrients and micronutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts.

可存在之其他組份係穩定劑，例如冷穩定劑、防腐劑、抗氧化劑、光穩定劑或改良化學及/或物理穩定性之其他藥劑。亦可存在泡 沫生成劑或防沫劑。 Other components which may be present are stabilizers such as cold stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve chemical and/or physical stability. Bubbles can also exist A foaming agent or antifoaming agent.

另外，調配物及自其衍生之使用形式亦可包含黏著劑(例如羧甲基纖維素及呈粉末、顆粒或膠乳形式之天然及合成型聚合物，例如***樹膠(gum arabic)、聚乙烯醇及聚乙酸乙烯酯或天然磷脂質(例如腦磷脂及卵磷脂)及合成型磷脂質)作為其他輔助物。其他輔助物可為礦物油及植物油。 In addition, the formulations and the forms derived therefrom may also contain an adhesive such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol. And polyvinyl acetate or natural phospholipids (such as cephalin and lecithin) and synthetic phospholipids as other auxiliary substances. Other auxiliary materials may be mineral oil and vegetable oil.

若適當再其他輔助物可存於調配物及自其衍生之使用形式中。該等添加劑之實例係香料、保護性膠體、結合劑、黏著劑、增稠劑、觸變劑、滲透劑、保留促進劑、穩定劑、螯合劑、錯合劑、濕潤劑、展布劑。一般而言，式(I)化合物可與出於調配目的通常使用之任一固體或液體添加劑組合。 If appropriate, other ancillary materials may be present in the formulation and the forms of use derived therefrom. Examples of such additives are perfumes, protective colloids, binders, adhesives, thickeners, thixotropic agents, penetrants, retention promoters, stabilizers, chelating agents, complexing agents, wetting agents, spreading agents. In general, the compound of formula (I) can be combined with any solid or liquid additive commonly used for formulation purposes.

有用保留促進劑包括所有彼等降低動態表面張力(例如磺基丁二酸二辛基酯)或增加黏彈性(例如羥丙基瓜爾聚合物(hydroxypropylguar polymer))之物質。 Useful retention promoters include all materials which reduce dynamic surface tension (e.g., dioctyl sulfosuccinate) or increase viscoelasticity (e.g., hydroxypropylguar polymer).

在本發明背景中適宜之滲透劑係所有彼等通常用於改良農用化學品活性成分向植物中滲透之物質。滲透劑在此背景下係由其自(通常水性)施加液劑及/或自噴霧塗層滲透至植物表皮中且因此增加活性成分在表皮中之移動性之能力來定義。可使用闡述於文獻(Baur等人，1997,Pesticide Science 51,131-152)中之方法確定此性質。實例包括醇烷氧基化物(例如椰子脂肪乙氧基化物(10)或異十三烷基乙氧基化物(12))、脂肪酸酯(例如菜籽油甲基酯或大豆油甲基酯)、脂肪胺烷氧基化物(例如牛脂基伯胺乙氧基化物(15))或銨及/或鏻鹽(例如硫酸銨或磷酸氫二銨)。 Suitable penetrants in the context of the present invention are all those which are commonly used to improve the penetration of agrochemical active ingredients into plants. In this context, penetrants are defined by their ability to permeate from the (usually aqueous) application liquid and/or self-spray coating into the plant epidermis and thus increase the mobility of the active ingredient in the epidermis. This property can be determined using methods described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152). Examples include alcohol alkoxylates (such as coconut fat ethoxylate (10) or isotridecyl ethoxylate (12)), fatty acid esters (such as rapeseed oil methyl ester or soybean oil methyl ester) ), a fatty amine alkoxylate (such as a bovine-based primary amine ethoxylate (15)) or an ammonium and/or phosphonium salt (such as ammonium sulfate or diammonium hydrogen phosphate).

基於調配物之重量，調配物較佳地包含介於0.00000001重量%與98重量%之間之式(I)化合物、更佳地介於0.01重量%與95重量%之間之式(I)化合物、最佳地介於0.5重量%與90重量%之間之式(I)化合物。 The formulation preferably comprises between 0.00000001% and 98% by weight of a compound of formula (I), more preferably between 0.01% and 95% by weight, based on the weight of the formulation, of a compound of formula (I). Preferably, the compound of formula (I) is between 0.5% and 90% by weight.

自調配物製備之使用形式(具體而言殺有害生物劑)中式(I)化合物之含量可在寬範圍內變化。基於使用形式之重量，使用形式中式(I)化合物之濃度可通常介於0.00000001重量%與95重量%之間之式(I)化合物、較佳地介於0.00001重量%與1重量%之間。施加係以適於使用形式之常用方式來實現。 The amount of the compound of formula (I) in the form of use of the formulation (particularly the pesticidal agent) can vary over a wide range. The concentration of the compound of formula (I) in the form used may generally be between 0.00000001% and 95% by weight, based on the weight of the use form, of the compound of formula (I), preferably between 0.00001% and 1% by weight. The application is carried out in a conventional manner suitable for the form of use.

混合物 mixture

式(I)化合物亦可與一或多種適宜殺真菌劑、殺細菌劑、殺蟎劑、殺軟體動物劑、殺線蟲劑、殺昆蟲劑、微生物製劑、有益有機體、除草劑、肥料、避鳥劑、植物強化劑、滅菌劑、安全劑、訊息化合物及/或植物生長調節劑一起在混合物中使用，由此以便(例如)加寬作用譜、延長作用時段、增強作用率、預防排斥性或預防抗性進化。另外，此類活性成分組合可改良植物生長及/或對非生物因素(例如高溫或低溫)、對乾旱或對升高之水含量或土壤鹽度之耐受性。亦可改良開花及結果性能，最佳化發芽力及根系發育，有利於收穫及改良產量，影響成熟，改良收穫產物之品質及/或營養價值，延長儲存壽命及/或改良收穫產物之加工性。 The compound of formula (I) may also be combined with one or more suitable fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbial preparations, beneficial organisms, herbicides, fertilizers, birds Agents, plant enhancers, sterilizing agents, safeners, message compounds and/or plant growth regulators are used together in a mixture to, for example, broaden the spectrum of action, prolong the duration of action, enhance the rate of action, prevent repellency or Prevent the evolution of resistance. In addition, such active ingredient combinations may improve plant growth and/or tolerance to abiotic factors such as high or low temperatures, to drought or to elevated water content or soil salinity. It can also improve flowering and performance, optimize germination and root development, facilitate harvesting and improve yield, affect maturity, improve the quality and/or nutritional value of harvested products, extend shelf life and/or improve processability of harvested products. .

另外，式(I)化合物可與其他活性成分或訊息化合物(例如誘引劑及/或避鳥劑)及/或植物活化劑及/或生長調節劑及/或肥料一起存於混合物中。同樣，式(I)化合物可與改良植物性質(例如收穫物質之生長、產量及品質)之藥劑一起在混合物中使用。 Alternatively, the compound of formula (I) may be present in admixture with other active ingredients or message compounds (for example, attractants and/or avians) and/or plant activators and/or growth regulators and/or fertilizers. Likewise, the compounds of formula (I) can be used in mixtures with agents which improve plant properties, such as the growth, yield and quality of the harvested material.

在本發明之具體實施例中，式(I)化合物與其他化合物、較佳地彼等如下文所闡述者一起在混合物中存於調配物中或於自該等調配物製備之使用形式中。 In a particular embodiment of the invention, the compound of formula (I) is present in the mixture in a mixture with other compounds, preferably as described below, or in a form for use in the preparation of such formulations.

若下文所提及化合物中之一者可以不同互變異構形式出現，則該等形式即便在每一情形下均未明確提及亦包括在內。 If one of the compounds mentioned below can occur in different tautomeric forms, such forms are not explicitly mentioned in every case.

殺昆蟲劑/殺蟎劑/殺線蟲劑 Insecticide / acaricide / nematicide

本文以其通用名稱活性成分已為人所知且闡述於(例如)「The Pesticide Manual」，第16版，British Crop Protection Council 2012中，或可在網際網路(例如http：//www.alanwood.net/pesticides)上搜索。 This document is known by its generic name and is described, for example, in "The Pesticide Manual", 16th Edition, British Crop Protection Council 2012, or on the Internet (eg http://www.alanwood) Search on .net/pesticides ).

(1)乙醯膽鹼酶(AChE)抑制劑，例如，胺基甲酸酯，例如棉鈴威(alanycarb)、涕滅威(aldicarb)、惡蟲威(bendiocarb)、丙硫克百威(benfuracarb)、丁酮威(butocarboxim)、丁酮碸威(butoxycarboxim)、甲萘威(carbaryl)、克百威(carbofuran)、丁硫克百威(carbosulfan)、乙硫苯威(ethiofencarb)、仲丁威(fenobucarb)、覆滅蟎(formetanate)、呋線威(furathiocarb)、異丙威(isoprocarb)、甲硫威(methiocarb)、滅多威(methomyl)、速滅威(metolcarb)、殺線威(oxamyl)、抗蚜威(pirimicarb)、殘殺威(propoxur)、硫雙威(thiodicarb)、久效威(thiofanox)、唑蚜威(triazamate)、混殺威(trimethacarb)、XMC及滅殺威(xylylcarb)；或有機磷酸酯，例如乙醯甲胺磷(acephate)、甲基吡啶磷(azamethiphos)、乙基穀硫磷(azinphos-ethyl)、甲基穀硫磷(azinphos-methyl)、硫線磷(cadusafos)、氯氧磷(chlorethoxyfos)、氯芬松(chlorfenvinphos)、氯甲磷(chlormephos)、毒死蜱(chlorpyrifos)、甲基毒死蜱、蠅毒磷(coumaphos)、殺螟腈(cyanophos)、甲基內吸磷(demeton-S-methyl)、二嗪農(diazinon)、二氯松/DDVP(dichlorvos/DDVP)、百治磷(dicrotophos)、大滅松(dimethoate)、甲基毒蟲畏(dimethylvinphos)、乙拌磷(disulfoton)、EPN、乙硫磷(ethion)、滅線磷(ethoprophos)、胺磺磷(famphur)、苯線磷(fenamiphos)、殺螟松(fenitrothion)、芬殺松(fenthion)、噻唑磷(fosthiazate)、庚烯磷(heptenophos)、新煙磷(imicyafos)、異柳磷(isofenphos)、O-(甲氧基胺基硫磷醯基)水楊酸異丙基酯、加福松(isoxathion)、馬拉松(malathion)、滅加松(mecarbam)、達馬松 (methamidophos)、滅大松(methidathion)、美文松(mevinphos)、久效磷(monocrotophos)、二溴磷(naled)、氧化樂果(omethoate)、亞碸磷(oxydemeton-methyl)、巴拉松(parathion)、甲基巴拉松、稻豐散(phenthoate)、甲拌磷(phorate)、伏殺硫磷(phosalone)、亞胺硫磷(phosmet)、大滅蟲(phosphamidon)、辛硫磷(phoxim)、甲基嘧啶磷(pirimiphos-methyl)、丙溴磷(profenofos)、胺丙畏(propetamphos)、丙硫磷(prothiofos)、吡唑硫磷(pyraclofos)、噠嗪硫磷(pyridaphenthion)、喹硫磷(quinalphos)、硫特普(sulfotep)、丁基嘧啶磷(tebupirimfos)、雙硫磷(temephos)、特丁硫磷(terbufos)、殺蟲畏(tetrachlorvinphos)、甲基乙拌磷(thiometon)、***磷(triazophos)、敵百蟲(triclorfon)及蚜滅多(vamidothion)。 (1) Acetylcholinease (AChE) inhibitors, for example, urethanes such as alanycarb, aldicarb, bendiocarb, benfuracarb ), butocarbboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, zhongding Fenobucarb, formetanate, furathiocarb, isoprocarb, metiocarb, methomyl, metolcarb, oxamyl ), pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, and xylylcarb Or; an organic phosphate such as acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, sulphur phosphorus (cadusafos), chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, methyl chlorpyrifos, fly Coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos , dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, benzene phosphate (fenamiphos), fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, O-(methoxy Isopropyl thiophosphonyl) isopropyl salicylate, isoxathion, malathion, mecarbam, damasson (methamidophos), methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, balason ( Parathion), methyl balazon, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim Phoxim), pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphthion, Quinphophos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, methyl ethion Thiometon), triazophos, triclofon, and vamidothion.

(2)GABA門控氯離子通道拮抗劑，例如環戊二烯-有機氯，例如氯丹(chlordane)及安殺番(endosulfan)或苯基吡唑(費普(fiproles))，例如乙蟲腈(ethiprole)及芬普尼(fipronil)。 (2) GABA-gated chloride channel antagonists, such as cyclopentadiene-organochlorines, such as chlordane and endosulfan or phenylpyrazole (fiproles), such as acetaminophen Nitrile (ethiprole) and fipronil (fipronil).

(3)鈉通道調節劑/電壓門控鈉通道阻斷劑，例如擬除蟲菊酯(pyrethroid)，例如氟丙菊酯(acrinathrin)、丙烯除蟲菊(allethrin)、右旋-順-反丙烯除蟲菊、右旋-反丙烯除蟲菊、聯苯菊酯(bifenthrin)、反丙烯除蟲菊(bioallethrin)、反丙烯除蟲菊S-環戊烯基異構物、除蟲菊酯(bioresmethrin)、乙氰菊酯(cycloprothrin)、氟氯氰菊酯(cyfluthrin)、β-氟氯氰菊酯、功夫菊酯(cyhalothrin)、λ-功夫菊酯、γ-功夫菊酯、氯氰菊酯(cypermethrin)、α-氯氰菊酯、β-氯氰菊酯、θ-氯氰菊酯、ζ-氯氰菊酯、苯醚氰菊酯(cyphenothrin)[(1R)-反式異構物]、溴氰菊酯(deltamethrin)、右旋烯炔菊酯(empenthrin)[(EZ)-(1R)異構物]、殺滅阿菊酯(esfenvalerate)、依芬普司(etofenprox)、甲氰菊酯(fenpropathrin)、氰戊菊酯(fenvalerate)、氟氰菊酯(flucythrinate)、氟氯苯菊酯(flumethrin)、τ-氟胺氰菊酯(tau-fluvalinate)、苄蟎醚 (halfenprox)、依普寧(imiprothrin)、噻恩菊酯(kadethrin)、茂氟瑞(momfluorothrin)、撲滅司林(permethrin)、苯氧司林(phenothrin)[(1R)-反式異構物]、炔烯菊酯(prallethrin)、除蟲菊素(pyrethrin)(除蟲菊(pyrethrum))、苄呋菊酯(resmethrin)、西拉福芬(silafluofen)、七氟菊酯(tefluthrin)、四甲司林(tetramethrin)、四甲司林[(1R)異構物)]、四溴菊酯(tralomethrin)及四氟苯菊酯(transfluthrin)或DDT或甲氧滴滴涕(methoxychlor)。 (3) Sodium channel modulators/voltage-gated sodium channel blockers, such as pyrethroids, such as flurinathrin, allethrin, dextro-cis-reverse Pyrethroid, dextrorotatory, pyrethroid, bifenthrin, bioallethrin, anti-propylene pyrethrum S-cyclopentenyl isomer, pyrethrin (bioresmethrin), cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-fungalrin, gamma-fungery, cypermethrin, alpha-cypermethrin , β-cypermethrin, θ-cypermethrin, cypermethrin, cyphenothrin [(1R)-trans isomer], deltamethrin, dextromethrin [(EZ)-(1R) isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, cypromethrin (flucythrinate), flumethrin, tau-fluvalinate, benzalkonium ether (halfenprox), imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(1R)-trans isomer] , prallethrin, pyrethrin (pyrethrum), pyrethrin (resmethrin), silafluofen, tefluthrin, tetra Tetramethrin, tetramethyl sulin [(1R) isomer), tetralomethrin and transfluthrin or DDT or methoxychlor.

(4)菸鹼能乙醯膽鹼受體(nAChR)拮抗劑，例如新菸鹼(neonicotinoid)，例如啶蟲脒(acetamiprid)、噻蟲胺(clothianidin)、呋蟲胺(dinotefuran)、吡蟲啉(imidacloprid)、尼藤吡藍(nitenpyram)、噻蟲啉(thiacloprid)及噻蟲嗪(thiamethoxam)或菸鹼(nicotine)或碸蟲啶(sulfoxaflor)或氟吡呋喃酮(flupyradifurone)。 (4) Nicotine acetylcholine receptor (nAChR) antagonists, such as neonicotinoids, such as acetamiprid, clothianidin, dinotefuran, imidacloprid ( Imidacloprid), nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.

(5)菸鹼能乙醯膽鹼受體(nAChR)之別構活化劑，例如多殺菌素(spinosyn)，例如乙基多殺菌素(spinetoram)及多殺黴素(spinosad)。 (5) Allosteric activators of nicotine acetylcholine receptor (nAChR), such as spinosyn, such as spinetoram and spinosad.

(6)氯離子通道活化劑，例如阿維菌素(avermectins)/殺蟎菌素(milbemycins)，例如阿巴美丁(abamectin)、埃瑪菌素苯甲酸鹽(emamectin benzoate)、雷皮菌素(lepimectin)及彌拜菌素(milbemectin)。 (6) Chloride channel activators, such as avermectins/milbemycins, such as abamectin, emamectin benzoate, Leipi Lepimectin and milbemectin.

(7)保幼激素模擬物，例如，保幼激素類似物，例如烯蟲乙酯(hydroprene)、烯蟲炔酯(kinoprene)及烯蟲酯(methoprene)或苯氧威(fenoxycarb)或吡丙醚(pyriproxyfen)。 (7) Juvenile hormone mimics, for example, juvenile hormone analogs, such as hydroprene, kinoprene and metoprene or fenoxycarb or pyridin Ether (pyriproxyfen).

(8)具有未知或非特定作用機制之活性化合物，例如烷基鹵化物，例如甲基溴及其他烷基鹵化物；或三氯硝基甲烷(chloropicrine)或硫醯氟或硼砂或吐酒石。 (8) Active compounds having an unknown or non-specific mechanism of action, such as alkyl halides such as methyl bromide and other alkyl halides; or chloropicrine or thiopurine or borax or tartar .

(9)選擇性抗食物質，例如吡蚜酮(pymetrozine)或氟啶蟲醯胺(flonicamid)。 (9) Selective anti-food quality, such as pymetrozine or flonicamid.

(10)蟎生長抑制劑，例如四蟎嗪(clofentezine)、噻蟎酮(hexythiazox)及氟蟎嗪(diflovidazin)或乙蟎唑(etoxazole)。 (10) An inhibitor of sputum growth, such as clofentezine, hexythiazox, and diflovidazin or etoxazole.

(11)昆蟲腸絨膜之微生物破壞劑，例如蘇雲金芽孢桿菌亞種以色列(Bacillus thuringiensis subspecies israelensis)、球形芽孢桿菌(Bacillus sphaericus)、蘇雲金芽孢桿菌鯰澤亞種(Bacillus thuringiensis subspecies aizawai)、蘇雲金芽孢桿菌庫斯塔克亞種(Bacillus thuringiensis subspecies kurstaki)、蘇雲金芽孢桿菌擬步行甲亞種(Bacillus thuringiensis subspecies tenebrionis)及BT植物蛋白：Cry1Ab、Cry1Ac、Cry1Fa、Cry2Ab、mCry3A、Cry3Ab、Cry3Bb、Cry34/35Ab1。 (11) Microbial disrupting agents of insect intestinal velum, such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis and BT plant proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1 .

(12)氧化磷酸化抑制劑、ATP破壞劑，例如丁醚脲(diafenthiuron)或有機錫化合物，例如***錫(azocyclotin)、環己錫(cyhexatin)及六苯丁錫氧(fenbutatin oxide)或炔蟎特(propargite)或三氯殺蟎碸(tetradifon)。 (12) oxidative phosphorylation inhibitors, ATP breakers such as diafenthiuron or organotin compounds such as azocyclotin, cyhexatin and fenbutatin oxide or Propargite or tetradifon.

(13)中斷H質子梯度之氧化磷酸化去偶聯劑，例如溴蟲腈(chlorfenapyr)、DNOC及氟蟲胺(sulfluramid)。 (13) An oxidative phosphorylation decoupling agent that interrupts the H proton gradient, such as chlorfenapyr, DNOC, and sulfluramid.

(14)菸鹼能乙醯膽鹼受體拮抗劑，例如殺蟲磺(bensultap)、巴丹鹽酸鹽(cartap hydrochloride)、殺蟲環(thiocyclam)及殺蟲雙(thiosultap-sodium)。 (14) Nicotine acetylcholine receptor antagonists, such as bensultap, cartap hydrochloride, thiocyclam, and thiosultap-sodium.

(15)幾丁質生物合成抑制劑，類型0，例如雙三氟蟲脲(bistrifluron)、氟啶脲(chlorfluazuron)、除蟲脲(diflubenzuron)、氟環脲(flucycloxuron)、氟蟲脲(flufenoxuron)、氟鈴脲(hexaflumuron)、虱蟎脲(lufenuron)、雙苯氟脲(novaluron)、多氟脲(noviflurnuron)、氟苯脲(teflubenzuron)及殺鈴脲(triflumuron)。 (15) Chitin biosynthesis inhibitors, type 0, such as bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron ), hexaflumuron, lufenuron, novaluron, noviflurnuron, teflubenzuron, and triflumuron.

(16)幾丁質生物合成抑制劑，類型1，例如噻嗪酮(buprofezin)。 (16) Chitin biosynthesis inhibitor, type 1, such as buprofezin.

(17)蛻皮抑制劑(尤其針對雙翅目，即雙持類昆蟲)，例如滅蠅胺 (cyrcmazine)。 (17) ecdysone inhibitors (especially for dipterans, ie, double-holding insects), such as chlortetracycline (cyrcmazine).

(18)蛻皮激素受體拮抗劑，例如環蟲醯肼(chromafenozide)、氯蟲醯肼(halofenozide)、甲氧蟲醯肼(methoxyfenozide)及蟲醯肼(tebufenozide)。 (18) ecdysone receptor antagonists, such as chromafenozide, halofenozide, methoxyfenozide, and tebufenozide.

(19)章魚胺能拮抗劑，例如雙甲脒(amitraz)。 (19) Octopaminergic antagonists, such as amitraz.

(20)複合物-III電子傳輸抑制劑，例如伏蟻腙(hydramethylnon)或滅蟎醌(acequinocyl)或嘧蟎酯(fluacrypyrim)。 (20) Complex-III electron transport inhibitors, such as hydramethylnon or acequinocyl or fluacrypyrim.

(21)複合物-I電子傳輸抑制劑，例如METI殺蟎劑，例如喹蟎醚(fenazaquin)、唑蟎酯(fenpyroximate)、嘧蟎醚(pyrimidifen)、噠蟎靈(pyridaben)、吡蟎胺(tebufenpyrad)及唑蟲醯胺(tolfenpyrad)或魚藤酮(rotenone)(魚藤屬(Derris))。 (21) Complex-I electron transport inhibitors, such as METI acaricides, such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, pyridoxamine (tebufenpyrad) and tolfenpyrad or rotenone (Derris).

(22)電壓門控鈉通道阻斷劑，例如茚蟲威(indoxacarb)或氰氟蟲腙(metaflumizone)。 (22) Voltage-gated sodium channel blockers, such as indoxacarb or metaflumizone.

(23)乙醯基-CoA羧酶之抑制劑，例如特窗酸(tetronic acid)及特胺酸(tetramic acid)酸衍生物，例如螺蟎酯(spirodiclofen)、螺甲蟎酯(spiromesifen)及螺蟲乙酯(spirotetramat)。 (23) Inhibitors of acetyl-CoA carboxylase, such as tetronic acid and tetramic acid acid derivatives, such as spirodiclofen, spiromesifen, and Spirotetramat.

(24)複合物-IV電子傳輸抑制劑，例如膦，例如磷化鋁、磷化鈣、膦及磷化鋅或氰化物。 (24) Complex-IV electron transport inhibitors such as phosphines such as aluminum phosphide, calcium phosphide, phosphine and zinc phosphide or cyanide.

(25)複合物-II電子傳輸抑制劑，例如腈吡蟎酯(cyenopyrafen)及丁氟蟎酯(cyflumetofen)。 (25) Complex-II electron transport inhibitors, such as cyenopyrafen and cyflumetofen.

(28)蘭尼鹼(Ryanodine)受體效應器，例如二醯胺，例如氯蟲苯甲醯胺(chlorantraniliprole)、氰蟲醯胺(cyantraniliprole)及氟蟲醯胺(flubendiamide)。 (28) Ryanodine receptor effectors, such as diamines, such as chlorantraniliprole, cyantraniliprole, and flubendiamide.

具有未知或不明確作用機制之其他活性成分，例如阿多吡噴(afidopyropen)、阿佛拉那(afoxolaner)、印楝素(azadirachtin)、苯氯噻唑(benclothiaz)、苯蟎特(benzoximate)、聯苯肼酯(bifenazate)、布蘭 利得(broflanilide)、溴蟎酯(bromopropylate)、滅蟎猛(chinomethionat)、冰晶石(cryolite)、環溴蟲醯胺(cyclaniliprole)、環氧蟲啶(cycloxaprid)、氯氟氰蟲醯胺(cyhalodiamide)、二氯美唑替茲(dicloromezotiaz)、三氯殺蟎醇(dicofol)、氟蟎嗪(diflovidazin)、氟美妥昆(flometoquin)、氟甾多利新(fluazaindolizine)、聯氟碸(fluensulfone)、蜜蟲胺(flufenerim)、氟菌蟎酯(flufenoxystrobin)、丁烯氟蟲腈(flufiprole)、氟己豐(fluhexafon)、氟吡菌醯胺(fluopyram)、氟拉蘭(fluralaner)、氟美醯胺(fluxametamide)、呋喃蟲醯肼(fufenozide)、戊吡蟲胍(guadipyr)、七氟斯瑞(heptafluthrin)、氯噻啉(imidaclothiz)、異菌脲(iprodione)、羅替蘭(lotilaner)、氯氟醚菊酯(meperfluthrin)、派蟲啶(paichongding)、吡氟布米得(pyflubumide)、啶蟲丙醚(pyridalyl)、新喹唑啉(間二氮雜苯)(pyrifluquinazon)、嘧蟎胺(pyriminostrobin)、撒洛蘭(sarolaner)、四氟醚菊酯(tetramethylfluthrin)、四尼利洛(tetraniliprole)、四氯蟲苯甲醯胺、替氧雜芬(tioxazafen)、三氟美唑嘧(triflumezopyrim)及碘甲烷；另外及基於堅強芽孢桿菌(Bacillus firmus)之製劑(I-1582,BioNeem,Votivo)，及以下已知活性化合物：1-{2-氟-4-甲基-5-[(2,2,2-三氟乙基)亞磺醯基]苯基}-3-(三氟甲基)-1H-1,2,4-***-5-胺(自WO2006/043635得知)、{1'-[(2E)-3-(4-氯苯基)丙-2-烯-1-基]-5-氟螺[吲哚-3,4'-六氫吡啶]-1(2H)-基}(2-氯吡啶-4-基)甲酮(自WO2003/106457得知)、2-氯-N-[2-{1-[(2E)-3-(4-氯苯基)丙-2-烯-1-基]六氫吡啶-4-基}-4-(三氟甲基)苯基]異菸醯胺(自WO2006/003494得知)、3-(2,5-二甲基苯基)-4-羥基-8-甲氧基-1,8-二氮雜螺[4.5]癸-3-烯-2-酮(自WO2009/049851得知)、碳酸3-(2,5-二甲基苯基)-8-甲氧基-2-側氧基-1,8-二氮雜螺[4.5]癸-3-烯-4-基乙基酯(自WO2009/049851得知)、4-(丁-2-炔-1-基氧基)-6-(3,5-二甲基六氫吡啶-1-基)-5-氟嘧啶(自 WO2004/099160得知)、4-(丁-2-炔-1-基氧基)-6-(3-氯苯基)嘧啶(自WO2003/076415得知)、PF1364(CAS登記號1204776-60-2)、2-[2-({[3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基]羰基}胺基)-5-氯-3-甲基苯甲醯基]-2-甲基肼甲酸甲酯(自WO2005/085216得知)、2-[2-({[3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基]羰基}胺基)-5-氰基-3-甲基苯甲醯基]-2-乙基肼甲酸甲酯(自WO2005/085216得知)、2-[2-({[3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基]羰基}胺基)-5-氰基-3-甲基苯甲醯基]-2-甲基肼甲酸甲酯(自WO2005/085216得知)、2-[3,5-二溴-2-({[3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基]羰基}胺基)苯甲醯基]-2-乙基肼甲酸甲酯(自WO2005/085216得知)、N-[2-(5-胺基-1,3,4-噻二唑-2-基)-4-氯-6-甲基苯基]-3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-甲醯胺(自CN102057925得知)、4-[5-(3,5-二氯苯基)-5-(三氟甲基)-4,5-二氫-1,2-噁唑-3-基]-2-甲基-N-(1-氧橋硫雜環丁烷-3-基)苯醯胺(自WO2009/080250得知)、N-[(2E)-1-[(6-氯吡啶-3-基)甲基]吡啶-2(1H)-亞基]-2,2,2-三氟乙醯胺(自WO2012/029672得知)、1-[(2-氯-1,3-噻唑-5-基)甲基]-4-側氧基-3-苯基-4H-吡啶并[1,2-a]嘧啶-1-鎓-2-醇酯(自WO2009/099929得知)、1-[(6-氯吡啶-3-基)甲基]-4-側氧基-3-苯基-4H-吡啶并[1,2-a]嘧啶-1-鎓-2-醇酯(自WO2009/099929得知)、4-(3-{2,6-二氯-4-[(3,3-二氯丙-2-烯-1-基)氧基]苯氧基}丙氧基)-2-甲氧基-6-(三氟甲基)嘧啶(自CN101337940得知)、N-[2-(第三丁基胺甲醯基)-4-氯-6-甲基苯基]-1-(3-氯吡啶-2-基)-3-(氟甲氧基)-1H-吡唑-5-甲醯胺(自WO2008/134969得知)、[2-(2,4-二氯苯基)-3-側氧基-4-氧雜螺[4.5]癸-1-烯-1-基]碳酸丁基酯(自CN 102060818得知)、(3E)-3-[1-[(6-氯-3-吡啶基)甲基]-2-亞吡啶基]-1,1,1-三氟丙-2-酮(自WO2013/144213得知)、N-(甲基磺醯基)-6-[2-(吡啶-3-基)-1,3-噻唑-5-基]吡啶-2-甲醯胺(自WO2012/000896得知)、N-[3-(苄基胺甲醯基)-4-氯苯基]-1-甲基-3-(五氟乙基)-4-(三氟甲基)-1H-吡唑-5- 甲醯胺(自WO2010/051926得知)、5-溴-4-氯-N-[4-氯-2-甲基-6-(甲基胺甲醯基)苯基]-2-(3-氯-2-吡啶基)吡唑-3-甲醯胺(自CN103232431得知)。 Other active ingredients with unknown or ambiguous mechanisms of action, such as afidopyropen, afoxolaner, azadirachtin, benclothiaz, benzoximate, Bifenazate, Bran Broflanilide, bromopropylate, chinomethionat, cryolite, cyclaniliprole, cycloxaprid, cyhalodiamide ), diclolozozoaz, dicofol, diflovidazin, flometoquin, fludazaindolizine, fluensulfone, honeydew (flufenerim), flufenoxystrobin, flufiprole, fluhexafon, fluopyram, flulalaner, flumametamide ), fufenozide, guadipyr, heptafluthrin, imidaclothiz, iprodione, lotilaner, chlorofluoroether Meperfluthrin, paichongding, pyrfluumumide, pyridalyl, neoquinazoline (pyrifluquinazon), pyridamine (pyriminostrobin) ), sarolan, tetramethylfluthrin, tetranilot ( Tetraniliprole), tetrachloropyr benzepidine, tioxazafen, triflumezopyrim and methyl iodide; and a formulation based on Bacillus firmus (I-1582, BioNeem, Votivo), and the following known active compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(three Fluoromethyl)-1H-1,2,4-triazole-5-amine (known from WO2006/043635), {1'-[(2E)-3-(4-chlorophenyl)propan-2- Alken-1-yl]-5-fluorospiro[吲哚-3,4'-hexahydropyridine]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (from WO2003/106457 Known), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]hexahydropyridin-4-yl}-4- (Trifluoromethyl)phenyl]isonicosamine (known from WO2006/003494), 3-(2,5-dimethylphenyl)-4-hydroxy-8-methoxy-1,8- Diazaspiro[4.5]non-3-en-2-one (known from WO2009/049851), 3-(2,5-dimethylphenyl)-8-methoxy-2-sideoxycarbonate Base-1,8-diazaspiro[4.5]dec-3-en-4-ylethyl ester (known from WO2009/049851), 4-(but-2-yn-1-yloxy)- 6-(3,5-Dimethylhexahydropyridin-1-yl)-5-fluoropyrimidine (from WO2004/099160,) 4-(but-2-yn-1-yloxy)-6-(3-chlorophenyl)pyrimidine (known from WO2003/076415), PF1364 (CAS registration number 1204776-60 -2), 2-[2-({[3-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-chloro-3- Methyl benzhydryl]-2-methylindolecarboxylate (known from WO2005/085216), 2-[2-({[3-bromo-1-(3-chloropyridin-2-yl)-) Methyl 1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzylidene]-2-ethylindolecarboxylate (known from WO2005/085216), 2-[ 2-({[3-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzhydryl Methyl 2-methyl phthalate (known from WO2005/085216), 2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)) -1H-pyrazol-5-yl]carbonyl}amino)benzimidyl]-2-ethylindolecarboxylic acid methyl ester (known from WO2005/085216), N-[2-(5-amino-1) ,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5- Formamide (from CN102057925), 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-1,2-oxazole-3 -yl]-2-methyl-N-(1-oxo-bridgedetidin-3-yl)phenylguanamine (known from WO2009/080250), N-[( 2E)-1-[(6-chloropyridin-3-yl)methyl]pyridine-2(1H)-ylidene-2,2,2-trifluoroacetamide (known from WO2012/029672), 1-[(2-chloro-1,3-thiazol-5-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[1,2-a]pyrimidin-1-yl- 2-alcohol ester (known from WO2009/099929), 1-[(6-chloropyridin-3-yl)methyl]-4-o-oxo-3-phenyl-4H-pyrido[1,2- a] pyrimidine-1-indol-2-ol ester (known from WO2009/099929), 4-(3-{2,6-dichloro-4-[(3,3-dichloroprop-2-ene-) 1-yl)oxy]phenoxy}propoxy)-2-methoxy-6-(trifluoromethyl)pyrimidine (known from CN101337940), N-[2-(t-butylamine A) Mercapto)-4-chloro-6-methylphenyl]-1-(3-chloropyridin-2-yl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (from WO2008/134969, [2-(2,4-dichlorophenyl)-3-oxo-4-oxaspiro[4.5]dec-1-en-1-yl]butyl carbonate ( (3E)-3-[1-[(6-Chloro-3-pyridyl)methyl]-2-pyridinyl]-1,1,1-trifluoroprop-2- Ketones (known from WO 2013/144213), N-(methylsulfonyl)-6-[2-(pyridin-3-yl)-1,3-thiazol-5-yl]pyridine-2-carboxamide (known from WO2012/000896), N-[3-(benzylaminemethanyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(three Fluoromethyl)-1H-pyrazole-5- Formamide (known from WO2010/051926), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylamine-methyl)phenyl]-2-(3) -Chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431).

殺真菌劑 Fungicide

本文以其通用名稱指定之活性成分已為人所知且闡述於(例如)「Pesticide Manual」中或於網際網路(例如：http：//www.alanwood.net/pesticides)上。 The active ingredients specified herein under their generic names are well known and described, for example, in the "Pesticide Manual" or on the Internet (eg http://www.alanwood.net/pesticides ).

在類別(1)至(15)中列示之所有殺真菌混合組份若存在適宜官能基則皆可視情況與相應鹼或酸形成鹽。另外，若互變異構現象係可能的，則類別(1)至(15)中列示之殺真菌混合組份亦包括互變異構形式。 All of the fungicidal mixed components listed in the categories (1) to (15) may form a salt with the corresponding base or acid, if appropriate, in the presence of a suitable functional group. Further, if tautomerism is possible, the fungicidal mixed components listed in the categories (1) to (15) also include tautomeric forms.

(1)麥角固醇生物合成抑制劑，例如(1.01)阿敵嗎啉(aldimorph)、(1.02)阿紮康唑(azaconazole)、(1.03)聯苯***醇(bitertanol)、(1.04)糠菌唑(bromuconazole)、(1.05)環丙唑醇(cyproconazole)、(1.06)苄氯***醇(diclobutrazole)、(1.07)苯醚甲環唑(difenoconazole)、(1.08)烯唑醇(diniconazole)、(1.09)烯唑醇-M、(1.10)嗎菌靈(dodemorph)、(1.11)嗎菌靈乙酸鹽、(1.12)氟環唑(epoxiconazole)、(1.13)乙環唑(etaconazole)、(1.14)氯苯嘧啶醇(fenarimol)、(1.15)腈苯唑(fenbuconazole)、(1.16)環醯菌胺(fenhexamid)、(1.17)苯鏽啶(fenpropidin)、(1.18)丁苯嗎啉(fenpropimorph)、(1.19)氟喹唑(fluquinconazole)、(1.20)呋嘧醇(flurprimidol)、(1.21)氟矽唑(flusilazole)、(1.22)粉唑醇(flutriafole)、(1.23)呋菌唑(furconazole)、(1.24)呋嘧醇(furconazole-cis)、(1.25)己唑醇(hexaconazole)、(1.26)抑黴唑(imazalil)、(1.27)抑黴唑硫酸鹽、(1.28)亞胺唑(imibenconazole)、(1.29)種菌唑(ipconazole)、(1.30)葉菌唑(metconazole)、(1.31)腈菌唑(myclobutanil)、(1.32)萘替芬(naftifin)、(1.33)氟苯嘧啶醇(nuarimol)、(1.34)噁咪唑 (oxpoconazole)、(1.35)多效唑(paclobutrazole)、(1.36)稻瘟酯(pefurazoate)、(1.37)配那唑(penconazole)、(1.38)粉病靈(piperalin)、(1.39)丙氯靈(prochloraz)、(1.40)丙環唑(propiconazole)、(1.41)丙硫菌唑(prothioconazole)、(1.42)稗草丹(pyributicarb)、(1.43)消斑肟(pyrifenox)、(1.44)唑喹菌酮(quinconazole)、(1.45)矽氟唑(simeconazole)、(1.46)螺噁茂胺(spiroxamine)、(1.47)戊唑醇(tebuconazole)、(1.48)特比萘芬(terbinafin)、(1.49)氟醚唑(tetraconazole)、(1.50)***酮(triadimefon)、(1.51)***醇(triadimenol)、(1.52)克啉菌(tridemorph)、(1.53)粉鏽胺(triflumizole)、(1.54)嗪胺靈(triforine)、(1.55)滅菌唑(triticonazole)、(1.56)烯效唑(uniconazole)、(1.57)烯效唑-P、(1.58)烯霜苄唑(viniconazole)、(1.59)伏立康唑(voriconazole)、(1.60)1-(4-氯苯基)-2-(1H-1,2,4-***-1-基)環庚醇、(1.61)1-(2,2-二甲基-2,3-二氫-1H-茚-1-基)-1H-咪唑-5-甲酸甲酯、(1.62)N'-{5-(二氟甲基)-2-甲基-4-[3-(三甲基矽基)丙氧基]苯基}-N-乙基-N-甲基亞胺基甲醯胺、(1.63)N-乙基-N-甲基-N'-{2-甲基-5-(三氟甲基)-4-[3-(三甲基矽基)丙氧基]苯基}亞胺基甲醯胺、(1.64)O-[1-(4-甲氧基苯氧基)-3,3-二甲基丁-2-基]-1H-咪唑1-硫代羧酸酯、(1.65)啶菌噁唑(pyrisoxazole)、(1.66)2-{[3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.67)1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-***-5-基硫氰酸酯、(1.68)5-(烯丙基磺醯基)-1-{[3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-***、(1.69)2-[1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.70)2-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.71)2-{[rel(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-2,4-二氫-3H-1,2,4- ***-3-硫酮、(1.72)1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-***-5-基硫氰酸酯、(1.73)1-{[re1(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-***-5-基硫氰酸酯、(1.74)5-(烯丙基磺醯基)-1-{[rel(2R,3S)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-***、(1.75)5-(烯丙基磺醯基)-1-{[re1(2R,3R)-3-(2-氯苯基)-2-(2,4-二氟苯基)環氧乙烷-2-基]甲基}-1H-1,2,4-***、(1.76)2-[(2S,4S,5S)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.77)2-[(2R,4S,5S)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.78)2-[(2R,4R,5R)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.79)2-[(2S,4R,5R)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.80)2-[(2S,4S,5R)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.81)2-[(2R,4S,5R)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.82)2-[(2R,4R,5S)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.83)2-[(2S,4R,5S)-1-(2,4-二氯苯基)-5-羥基-2,6,6-三甲基庚-4-基]-2,4-二氫-3H-1,2,4-***-3-硫酮、(1.84)2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-***-1-基)丙-2-醇、(1.85)2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-***-1-基)丁-2-醇、(1.86)2-[4-(4-氯苯氧基)-2-(三氟甲基)苯基]-1-(1H-1,2,4-***-1-基)戊-2-醇、(1.87)2-[2-氯-4-(4-氯苯氧基)苯基]-1-(1H-1,2,4-***-1-基)丁-2-醇、(1.88)2-[2-氯-4-(2,4-二氯苯氧基)苯基]-1-(1H-1,2,4-***-1-基)丙-2-醇、(1.89)(2R)-2-(1-氯環丙基)-4-[(1R)-2,2-二氯環丙基]-1-(1H-1,2,4-***-1-基)丁-2-醇、(1.90)(2R)-2-(1-氯環丙基)-4-[(1S)-2,2-二氯環丙基]-1-(1H- 1,2,4-***-1-基)丁-2-醇、(1.91)(2S)-2-(1-氯環丙基)-4-[(1S)-2,2-二氯環丙基]-1-(1H-1,2,4-***-1-基)丁-2-醇、(1.92)(2S)-2-(1-氯環丙基)-4-[(1R)-2,2-二氯環丙基]-1-(1H-1,2,4-***-1-基)丁-2-醇、(1.93)(1S,2R,5R)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-***-1-基甲基)環戊醇、(1.94)(1R,2S,5S)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-***-1-基甲基)環戊醇、(1.95)5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-***-1-基甲基)環戊醇。 (1) ergosterol biosynthesis inhibitors, for example, (1.01) adimorph, (1.02) azaconazole, (1.03) biter triol (bitertanol), (1.04) Bromuconazole, (1.05) cyproconazole, (1.06) diclobutrazole, (1.07) difenoconazole, (1.08) diniconazole ), (1.09) diniconazole-M, (1.10) morpholine, (1.11) carbendazim acetate, (1.12) epoxiconazole, (1.13) etaconazole, (1.14) fenarimol, (1.15) fenbuconazole, (1.16) fenhexamid, (1.17) fenpropidin, (1.18) butyl morpholine ( Fenpropimorph), (1.19) fluquinconazole, (1.20) furrprimidol, (1.21) flusilazole, (1.22) flutriafole, (1.23) furazolid ( Furconazole), (1.24) furconazole-cis, (1.25) hexaconazole, (1.26) imazalil, (1.27) imazalil sulfate, (1.28) imidazole (imibenconazole), (1.29) inoconazole (ipconazole), (1.30) meconazole (me) Tconazole), (1.31) myclobutanil, (1.32) naftifin, (1.33) fluoroanilide, (1.34) moxalimidazole (oxpoconazole), (1.35) paclobutrazole, (1.36) pefurazoate, (1.37) penconazole, (1.38) piperalin, (1.39) prochloraz (prochloraz) ), (1.40) propiconazole, (1.41) prothioconazole, (1.42) pyributicarb, (1.43) pyrifenox, (1.44) zolapril (quinconazole), (1.45) simeconazole, (1.46) spiroxamine, (1.47) tebuconazole, (1.48) terbinafin, (1.49) fluoride Tetraconazole, (1.50) triadimefon, (1.51) triadimenol, (1.52) tridemorph, (1.53) triflumizole, (1.54) azine Triforine, (1.55) triticonazole, (1.56) uniconazole, (1.57) uniconazole-P, (1.58) viniconazole, (1.59) voriconazole ( Voriconazole), (1.60) 1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol, (1.61) 1-(2,2-dimethyl Methyl-2,3-dihydro-1H-indol-1-yl)-1H-imidazole-5-carboxylic acid methyl ester, (1.62) N'-{5-(difluoromethyl)-2-methyl-4 -[3-(trimethylhydrazine) ) propoxy]phenyl}-N-ethyl-N-methyliminocarbamidine, (1.63) N-ethyl-N-methyl-N'-{2-methyl-5-( Trifluoromethyl)-4-[3-(trimethylsulfonyl)propoxy]phenyl}imidocarboxamide, (1.64) O-[1-(4-methoxyphenoxy) -3,3-dimethylbutan-2-yl]-1H-imidazole 1-thiocarboxylate, (1.65) pyridoxazole, (1.66) 2-{[3-(2-chloro Phenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-sulfur Ketone, (1.67) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2, 4-triazol-5-ylthiocyanate, (1.68) 5-(allylsulfonyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluoro Phenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.69) 2-[1-(2,4-dichlorophenyl)-5-hydroxy- 2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.70)2-{[rel(2R, 3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2 , 4-triazole-3-thione, (1.71) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)epoxy Alkan-2-yl]methyl}-2,4-dihydro-3H-1,2,4- Triazole-3-thione, (1.72) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2 -yl]methyl}-1H-1,2,4-triazol-5-ylthiocyanate, (1.73) 1-{[re1(2R,3R)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-ylthiocyanate, (1.74) 5-(() Allylsulfonyl)-1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl] Methyl}-1H-1,2,4-triazole, (1.75) 5-(allylsulfonyl)-1-{[re1(2R,3R)-3-(2-chlorophenyl)- 2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.76)2-[(2S,4S,5S)- 1-(2,4-Dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole -3-thione, (1.77) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4- 2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.78)2-[(2R,4R,5R)-1-(2,4-dichlorobenzene 5-)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.79)2 -[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro- 3H-1,2,4-triazole-3-thione, (1.80)2-[(2S,4S,5R)-1-(2,4-dichlorobenzene 5-)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.81)2 -[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro- 3H-1,2,4-triazole-3-thione, (1.82)2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6 ,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.83)2-[(2S,4R,5S)- 1-(2,4-Dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole -3-thione, (1.84) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazole-1 -yl)propan-2-ol, (1.85) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-tri Zin-1-yl)butan-2-ol, (1.86) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2, 4-triazol-1-yl)pentan-2-ol, (1.87) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4- Triazol-1-yl)butan-2-ol, (1.88) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4 -Triazol-1-yl)propan-2-ol, (1.89)(2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]- 1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.90)(2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2 2-dichlorocyclopropane ] -1- (1H- 1,2,4-triazol-1-yl)butan-2-ol, (1.91)(2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichloro Cyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.92)(2S)-2-(1-chlorocyclopropyl)-4-[ (1R)-2,2-Dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.93)(1S,2R,5R)- 5-(4-Chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.94) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl Cyclopentanol, (1.95) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl) ) cyclopentanol.

2)在複合物I或II下呼吸鏈之抑制劑，例如(2.01)聯苯吡菌胺(bixafen)、(2.02)啶醯菌胺(boscalid)、(2.03)萎鏽靈(carboxin)、(2.04)二氟林(diflumetorim)、(2.05)甲呋醯胺(fenfuram)、(2.06)氟吡菌醯胺(fluopyram)、(2.07)氟醯胺(flutolanil)、(2.08)氟唑菌醯胺(fluxapyroxad)、(2.09)福拉比(furametpyr)、(2.10)茂谷樂(furmecyclox)、(2.11)吡唑萘菌胺(isopyrazam)(順差向異構外消旋物1RS,4SR,9RS及反差向異構外消旋物1RS,4SR,9SR之混合物)、(2.12)吡唑萘菌胺(反差向異構外消旋物1RS,4SR,9SR)、(2.13)吡唑萘菌胺(反差向異構鏡像異構物1R,4S,9S)、(2.14)吡唑萘菌胺(反差向異構鏡像異構物1S,4R,9R)、(2.15)吡唑萘菌胺(順差向異構外消旋物1RS,4SR,9RS)、(2.16)吡唑萘菌胺(順差向異構鏡像異構物1R,4S,9R)、(2.17)吡唑萘菌胺(順差向異構鏡像異構物1S,4R,9S)、(2.18)滅鏽胺(mepronil)、(2.19)氧化萎鏽靈(oxycarboxin)、(2.20)戊苯吡菌胺(penflufen)、(2.21)吡噻菌胺(penthiopyrad)、(2.22)環丙吡菌胺(sedaxan)、(2.23)噻呋醯胺(thifluzamid)、(2.24)1-甲基-N-[2-(1,1,2,2-四氟乙氧基)苯基]-3-(三氟甲基)-1H-吡唑-4-甲醯胺、(2.25)3-(二氟甲基)-1-甲基-N-[2-(1,1,2,2-四氟乙氧基)苯基]-1H-吡唑-4-甲醯胺、(2.26)3-(二氟甲基)-N-[4-氟-2-(1,1,2,3,3,3-六氟丙氧基)苯基]-1-甲基-1H-吡唑-4-甲醯胺、(2.27)N-[1-(2,4-二氯苯基)-1-甲氧基丙-2-基]-3-(二氟甲 基)-1-甲基-1H-吡唑-4-甲醯胺、(2.28)5,8-二氟-N-[2-(2-氟-4-{[4-(三氟甲基)吡啶-2-基]氧基}苯基)乙基]喹唑啉-4-胺、(2.29)苯并烯氟菌唑(benzovindiflupyr)、(2.30)N-[(1S,4R)-9-(二氯亞甲基)-1,2,3,4-四氫-1,4-甲酮萘-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲醯胺、(2.31)N-[(1R,4S)-9-(二氯亞甲基)-1,2,3,4-四氫-1,4-甲酮萘-5-基]-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲醯胺、(2.32)3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氫-1H-茚-4-基)-1H-吡唑-4-甲醯胺、(2.33)1,3,5-三甲基-N-(1,1,3-三甲基-2,3-二氫-1H-茚-4-基)-1H-吡唑-4-甲醯胺、(2.34)1-甲基-3-(三氟甲基)-N-(1,1,3-三甲基-2,3-二氫-1H-茚-4-基)-1H-吡唑-4-甲醯胺、(2.35)1-甲基-3-(三氟甲基)-N-[(3R)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.36)1-甲基-3-(三氟甲基)-N-[(3S)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.37)3-(二氟甲基)-1-甲基-N-[(3S)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.38)3-(二氟甲基)-1-甲基-N-[(3R)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.39)1,3,5-三甲基-N-[(3R)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.40)1,3,5-三甲基-N-[(3S)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.41)麥鏽靈(benodanil)、(2.42)2-氯-N-(1,1,3-三甲基-2,3-二氫-1H-茚-4-基)吡啶-3-甲醯胺、(2.43)異丙噻菌胺(isofetamid)、(2.44)1-甲基-3-(三氟甲基)-N-[2'-(三氟甲基)聯苯-2-基]-1H-吡唑-4-甲醯胺、(2.45)N-(4'-氯聯苯-2-基)-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲醯胺、(2.46)N-(2',4'-二氯聯苯-2-基)-3-(二氟甲基)-1-甲基-1H-吡唑-4-甲醯胺、(2.47)3-(二氟甲基)-1-甲基-N-[4'-(三氟甲基)聯苯-2-基]-1H-吡唑-4-甲醯胺、(2.48)N-(2',5'-二氟聯苯-2-基)-1-甲基-3-(三氟甲基)-1H-吡唑-4-甲醯胺、(2.49)3-(二氟甲基)-1-甲基-N-[4'-(丙-1-炔-1-基)聯苯-2-基]-1H-吡唑-4-甲醯胺、(2.50)5-氟-1,3-二甲基-N-[4'-(丙-1-炔-1-基)聯苯-2-基]-1H-吡唑- 4-甲醯胺、(2.51)2-氯-N-[4'-(丙-1-炔-1-基)聯苯-2-基]菸鹼醯胺、(2.52)3-(二氟甲基)-N-[4'-(3,3-二甲基丁-1-炔-1-基)聯苯-2-基]-1-甲基-1H-吡唑-4-甲醯胺、(2.53)N-[4'-(3,3-二甲基丁-1-炔-1-基)聯苯-2-基]-5-氟-1,3-二甲基-1H-吡唑-4-甲醯胺、(2.54)3-(二氟甲基)-N-(4'-乙炔基聯苯-2-基)-1-甲基-1H-吡唑-4-甲醯胺、(2.55)N-(4'-乙炔基聯苯-2-基)-5-氟-1,3-二甲基-1H-吡唑-4-甲醯胺、(2.56)2-氯-N-(4'-乙炔基聯苯-2-基)菸鹼醯胺、(2.57)2-氯-N-[4'-(3,3-二甲基丁-1-炔-1-基)聯苯-2-基]菸鹼醯胺、(2.58)4-(二氟甲基)-2-甲基-N-[4'-(三氟甲基)聯苯-2-基]-1,3-噻唑-5-甲醯胺、(2.59)5-氟-N-[4'-(3-羥基-3-甲基丁-1-炔-1-基)聯苯-2-基]-1,3-二甲基-1H-吡唑-4-甲醯胺、(2.60)2-氯-N-[4'-(3-羥基-3-甲基丁-1-炔-1-基)聯苯-2-基]菸鹼醯胺、(2.61)3-(二氟甲基)-N-[4'-(3-甲氧基-3-甲基丁-1-炔-1-基)聯苯-2-基]-1-甲基-1H-吡唑-4-甲醯胺、(2.62)5-氟-N-[4'-(3-甲氧基-3-甲基丁-1-炔-1-基)聯苯-2-基]-1,3-二甲基-1H-吡唑-4-甲醯胺、(2.63)2-氯-N-[4'-(3-甲氧基-3-甲基丁-1-炔-1-基)聯苯-2-基]菸鹼醯胺、(2.64)1,3-二甲基-N-(1,1,3-三甲基-2,3-二氫-1H-茚-4-基)-1H-吡唑-4-甲醯胺、(2.65)1,3-二甲基-N-[(3R)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2,66)1,3-二甲基-N-[(3S)-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1H-吡唑-4-甲醯胺、(2.67)3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-(2,4,6-三氯苯基)丙-2-基]-1H-吡唑-4-甲醯胺、(2.68)3-(二氟甲基)-N-(7-氟-1,1,3-三甲基-2,3-二氫-1H-茚-4-基)-1-甲基-1H-吡唑-4-甲醯胺、(2.69)3-(二氟甲基)-N-[(3R)-7-氟-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲醯胺、(2.70)3-(二氟甲基)-N-[(3S)-7-氟-1,1,3-三甲基-2,3-二氫-1H-茚-4-基]-1-甲基-1H-吡唑-4-甲醯胺。 2) inhibitors of the respiratory chain under complex I or II, for example (2.01) bixafen, (2.02) boscalid, (2.03) carboxin, ( 2.04) diflumetorim, (2.05) fenfuram, (2.06) fluopyram, (2.07) flutolanil, (2.08) flurazepam (fluxapyroxad), (2.09) Furabi (furametpyr), (2.10) furocyclox (furmecyclox), (2.11) pyrazolamide (isopyrazam) (sequential racemate 1RS, 4SR, 9RS and contrast To a heteromeric racemate 1RS, a mixture of 4SR, 9SR), (2.12) pyrazolamide (anti-isomeric racemate 1RS, 4SR, 9SR), (2.13) pyrazolamide (contrast To the heterogeneous mirror isomers 1R, 4S, 9S), (2.14) pyrazolamide (converse isomer imager 1S, 4R, 9R), (2.15) pyrazolamide (situation Racemic racemates 1RS, 4SR, 9RS), (2.16) pyrazolamide (semi-isomeromeromers 1R, 4S, 9R), (2.17) pyrazolamide (situ isomerism mirror) Isomers 1S, 4R, 9S), (2.18) mepronil, (2.19) oxycarboxin, (2.20) penflufen, (2.21) Amine (penthiopyrad), (2.22) cyprodin (sedaxan), (2.23) thifluzamid, (2.24) 1-methyl-N-[2-(1,1,2,2- Tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, (2.25) 3-(difluoromethyl)-1-methyl-N-[ 2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide, (2.26) 3-(difluoromethyl)-N-[4-fluoro -2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide, (2.27) N-[1- (2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl) 1-methyl-1H-pyrazole-4-carboxamide, (2.28) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl) Pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.29) benzovindiflupyr, (2.30) N-[(1S,4R)-9 -(Dichloromethylene)-1,2,3,4-tetrahydro-1,4-carbonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyridyl Oxazole-4-carboxamide, (2.31) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-carbonaphthalene-5 -yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.32) 3-(difluoromethyl)-1-methyl-N-(1 , 1,3-trimethyl-2,3-dihydro-1H-indol-4-yl)-1H-pyrazole-4-carboxamide, (2.33) 1,3,5-trimethyl-N -(1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl)-1H-pyrazole-4-carboxamide, (2.34) 1-methyl-3-( Trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl)-1H-pyrazole-4-carboxamide, (2.35)1 -methyl-3-(trifluoromethyl)-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1H-pyrazole 4-carbamamine, (2.36) 1-methyl-3-(trifluoromethyl)-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-茚-4-yl]-1H-pyrazole-4-carboxamide, (2.37) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl yl-2,3-dihydro-1H-茚-4-yl]-1H-pyrazole-4-carboxamide, (2.38) 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethyl Benzyl-2,3-dihydro-1H-indol-4-yl]-1H-pyrazole-4-carboxamide, (2.39) 1,3,5-trimethyl-N-[(3R)-1 , 1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1H-pyrazole-4-carboxamide, (2.40) 1,3,5-trimethyl-N -[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1H-pyrazole-4-carboxamide, (2.41) wheat rust Benodani), (2.42) 2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl)pyridine-3-carboxamide, (2.43) Isothiazide, (2.44) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole- 4-carbamide, (2.45) N-(4'-chlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 2.46) N-(2',4'-Dichlorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.47)3 -(Difluoromethyl)-1-methyl-N-[4'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.48) N-( 2',5'-Difluorobiphenyl-2-yl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, (2.49) 3-(difluoromethyl) -1-methyl-N-[4'-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.50)5 -fluoro-1,3-dimethyl-N-[4'-(prop-1-yn-1-yl)biphenyl-2-yl]-1H-pyrazole- 4-carbamamine, (2.51) 2-chloro-N-[4'-(prop-1-yn-1-yl)biphenyl-2-yl]nicotinium amide, (2.52)3-(difluoro Methyl)-N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamidine Amine, (2.53) N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-5-fluoro-1,3-dimethyl-1H -pyrazole-4-carbamide, (2.54) 3-(difluoromethyl)-N-(4'-ethynylbiphenyl-2-yl)-1-methyl-1H-pyrazole-4- Formamide, (2.55) N-(4'-ethynylbiphenyl-2-yl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, (2.56)2 -Chloro-N-(4'-ethynylbiphenyl-2-yl)nicotinium amide, (2.57) 2-chloro-N-[4'-(3,3-dimethylbut-1-yne- 1-yl)biphenyl-2-yl]nicotinium amide, (2.58) 4-(difluoromethyl)-2-methyl-N-[4'-(trifluoromethyl)biphenyl-2- ]]-1,3-thiazole-5-formamide, (2.59) 5-fluoro-N-[4'-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl- 2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide, (2.60) 2-chloro-N-[4'-(3-hydroxy-3-methylbut-1- Alkyn-1-yl)biphenyl-2-yl]nicotinium amide, (2.61) 3-(difluoromethyl)-N-[4'-(3-methoxy-3-methylbut-1 -alkyn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.62) 5-fluoro-N-[4'-(3-methoxy -3- Butyl-1-yn-1-yl-biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamide, (2.63) 2-chloro-N-[4' -(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]nicotinium amide, (2.64)1,3-dimethyl-N-(1, 1,3-Trimethyl-2,3-dihydro-1H-indol-4-yl)-1H-pyrazole-4-carboxamide, (2.65)1,3-dimethyl-N-[( 3R)-1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1H-pyrazole-4-carboxamide, (2,66)1,3-di Methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1H-pyrazole-4-carboxamide, (2.67) 3-(Difluoromethyl)-N-methoxy-1-methyl-N-[1-(2,4,6-trichlorophenyl)propan-2-yl]-1H-pyrazole-4 -carbamamine, (2.68) 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl)- 1-methyl-1H-pyrazole-4-carboxamide, (2.69) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2 ,3-dihydro-1H-indol-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.70) 3-(difluoromethyl)-N-[(3S)- 7-Fluoro-1,1,3-trimethyl-2,3-dihydro-1H-indol-4-yl]-1-methyl-1H-pyrazole-4-carboxamide.

3)在複合物III下呼吸鏈之抑制劑，例如(3.01)唑嘧菌胺(ametoctradin)、(3.02)安美速(amisulbrom)、(3.03)腈嘧菌酯 (azoxystrobin)、(3.04)腈霜唑(cyazofamid)、(3.05)甲香菌酯(coumethoxystrobin)、(3.06)丁香菌酯(coumoxystrobin)、(3.07)醚菌胺(dimoxystrobin)、(3.08)烯肟菌酯(enoxastrobin)、(3.09)噁唑菌酮(famoxadone)、(3.10)咪唑菌酮(fenamidone)、(3.11)氟菌蟎酯、(3.12)氟咪菌酯(fluoxastrobin)、(3.13)甲氧胺菌靈(kresoxim-methyl)、(3.14)苯氧菌胺(metominostrobin)、(3.15)肟醚菌胺(orysastrobin)、(3.16)啶氧菌酯(picoxystrobin)、(3.17)唑菌胺酯(pyraclostrobin)、(3.18)唑胺菌酯(pyrametostrobin)、(3.19)正唑菌酯(pyraoxystrobin)、(3.20)吡菌苯威(pyribencarb)、(3.21)氯啶菌酯(triclopyricarb)、(3.22)肟菌酯(trifloxystrobin)、(3.23)(2E)-2-(2-{[6-(3-氯-2-甲基苯氧基)-5-氟嘧啶-4-基]氧基}苯基)-2-(甲氧基亞胺基)-N-甲基乙醯胺、(3.24)(2E)-2-(甲氧基亞胺基)-N-甲基-2-(2-{[({(1E)-1-[3-(三氟甲基)苯基]乙亞基}胺基)氧基]甲基}苯基)乙醯胺、(3.25)(2E)-2-(甲氧基亞胺基)-N-甲基-2-{2-[(E)-({1-[3-(三氟甲基)苯基]乙氧基}亞胺基)甲基]苯基}乙醯胺、(3.26)(2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-氟-2-苯基乙烯基]氧基}苯基)乙亞基]胺基}氧基)甲基]苯基}-2-(甲氧基亞胺基)-N-甲基乙醯胺、(3.27)烯肟菌胺(fenaminostrobin)、(3.28)5-甲氧基-2-甲基-4-(2-{[({(1E)-1-[3-(三氟甲基)苯基]乙亞基}胺基)氧基]甲基}苯基)-2,4-二氫-3H-1,2,4-***-3-酮、(3.29)(2E)-2-{2-[({環丙基[(4-甲氧基苯基)亞胺基]甲基}磺醯基)甲基]苯基}-3-甲氧基丙烯酸甲酯、(3.30)N-(3-乙基-3,5,5-三甲基環己基)-3-甲醯胺基-2-羥基苯醯胺、(3.31)2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙醯胺、(3.32)2-{2-[(2,5-二甲基苯氧基)甲基]苯基}-2-甲氧基-N-甲基乙醯胺、(3.33)(2E,3Z)-5-{[1-(4-氯苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亞胺基)-N,3-二甲基戊-3-烯醯胺。 3) Inhibitors of the respiratory chain under complex III, for example (3.01) amytoctradin, (3.02) amisulbrom, (3.03) azoxystrobin (azoxystrobin), (3.04) cyazofamid, (3.05) coumethoxystrobin, (3.06) coumoxystrobin, (3.07) dimoxystrobin, (3.08) olefin Enoxastrobin, (3.09) famoxadone, (3.10) fenamidone, (3.11) flufenicol, (3.12) fluoxastrobin, (3.13) Kresoxim-methyl, (3.14) methotrexate, (3.15) oressastrobin, (3.16) picoxystrobin, (3.17) pyraclostrobin (pyraclostrobin), (3.18) pyramatetostrobin, (3.19) pyraoxystrobin, (3.20) pyridencarb, (3.21) triclopyricarb, (3.22) ) trifloxystrobin, (3.23) (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy} Phenyl)-2-(methoxyimino)-N-methylacetamide, (3.24) (2E)-2-(methoxyimino)-N-methyl-2-(2 -{[({(1E)-1-[3-(Trifluoromethyl)phenyl]ethinyl}amino)oxy]methyl}phenyl)acetamide, (3.25)(2E)- 2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3-( Fluoromethyl)phenyl]ethoxy}imido)methyl]phenyl}acetamide, (3.26)(2E)-2-{2-[({[(1E)-1-(3-) {[(E)-1-Fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino) -N-methylacetamide, (3.27) fenaminostrobin, (3.28) 5-methoxy-2-methyl-4-(2-{[({(1E)-1-[[ 3-(Trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one, (3.29) (2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}sulfonyl)methyl]phenyl}-3-methoxy Methyl acrylate, (3.30) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-carboxamido-2-hydroxybenzamine, (3.31)2-{2 -[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.32)2-{2-[(2,5-di) Methylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.33)(2E,3Z)-5-{[1-(4-chlorophenyl)- 1H-Pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enylamine.

(4)有絲***及細胞***抑制劑，例如(4.01)苯菌靈(benomyl)、(4.02)多菌靈(carbendazim)、(4.03)苯咪唑菌(chlorfenazole)、(4.04)乙 黴威(diethofencarb)、(4.05)噻唑菌胺(ethaboxam)、(4.06)氟吡菌胺(fluopicolid)、(4.07)麥穗寧(fuberidazole)、(4.08)戊菌隆(pencycuron)、(4.09)噻菌靈(thiabendazole)、(4.10)甲基硫菌靈(thiophanate-methyl)、(4.11)硫菌靈、(4.12)苯醯菌胺(zoxamide)、(4.13)5-氯-7-(4-甲基六氫吡啶-1-基)-6-(2,4,6-三氟苯基)[1,2,4]***并[1,5-a]嘧啶及(4.14)3-氯-5-(6-氯吡啶-3-基)-6-甲基-4-(2,4,6-三氟苯基)噠嗪。 (4) Mitosis and cell division inhibitors, such as (4.01) benomyl (benomyl), (4.02) carbendazim, (4.03) chlorfenazole, (4.04) Diethofencarb, (4.05) ethaboxam, (4.06) fluopicolid, (4.07) fuberidazole, (4.08) pencycuron, (4.09) Thiabendazole, (4.10) thiophanate-methyl, (4.11) thiophanate, (4.12) zoxamide, (4.13) 5-chloro-7-(4 -methylhexahydropyridin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine and (4.14)3- Chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine.

5)能夠具有多位點作用之化合物，例如(5.01)波爾多混合物(Bordeaux mixture)、(5.02)敵菌丹(captafol)、(5.03)克菌丹(captan)、(5.04)百菌清(chlorothalonil)、(5.05)氫氧化銅、(5.06)環烷酸銅(copper naphthenate)、(5.07)氧化銅、(5.08)氯氧化銅、(5.09)硫酸銅(2+)、(5.10)抑菌靈(dichlofluanid)、(5.11)二噻農(dithianon)、(5.12)多果定(dodine)、(5.13)多果定游離鹼、(5.14)福美鐵(ferbam)、(5.15)氟滅菌丹(fluorofolpet)、(5.16)滅菌丹、(5.17)雙胍辛鹽(guazatine)、(5.18)雙胍辛乙酸鹽、(5.19)雙胍辛胺(iminoctadine)、(5.20)雙胍辛胺烷基苯磺酸鹽(iminoctadine albesilate)、(5.21)雙胍辛胺三乙酸鹽(iminoctadine triacetate)、(5.22)代森錳銅(mancopper)、(5.23)代森錳鋅(mancozeb)、(5.24)代森錳(maneb)、(5.25)代森聯(metiram)、(5.26)代森聯鋅(metiram zinc)、(5.27)喹啉酮(oxine-copper)、(5.28)普羅帕脒(propamidine)、(5.29)丙森鋅(propineb)、(5.30)硫磺及硫磺製劑(包括多硫化鈣)、(5.31)塞蘭姆(thiram)、(5.32)對甲抑菌靈(tolylfluanid)、(5.33)代森鋅(zineb)、(5.34)福美鋅(ziram)、(5.35)敵菌靈(anilazine)。 5) Compounds capable of multi-site action, such as (5.01) Bordeaux mixture, (5.02) captafol, (5.03) captan, (5.04) chlorothalonil ), (5.05) copper hydroxide, (5.06) copper naphthenate, (5.07) copper oxide, (5.08) copper oxychloride, (5.09) copper sulfate (2+), (5.10) bacteriostatic (dichlofluanid), (5.11) dithianon, (5.12) dodine, (5.13) polyglycine free base, (5.14) ferram (ferbam), (5.15) fluorofolpet (fluorofolpet) ), (5.16) sterilized Dan, (5.17) bismuth octyl salt (guazatine), (5.18) bisindole octanoic acid acetate, (5.19) bisinooctylamine (iminoctadine), (5.20) bis octyl octylamine benzene sulfonate (iminoctadine) Albesilate), (5.21) iminoctadine triacetate, (5.22) mancopper, (5.23) mancozeb, (5.24) mangan, (maneb), 5.25) metiram, (5.26) metiram zinc, (5.27) oxine-copper, (5.28) propamidine, (5.29) propidium zinc ( Propineb), (5.30) sulfur and sulfur preparations (including polysulfide Calcium), (5.31) thiram, (5.32) tolylfluanid, (5.33) zineb, (5.34) ziram, (5.35) Anilazine.

6)能夠誘導宿主防禦之化合物，例如(6.01)阿拉酸式苯-S-甲基(acibenzolar-S-methyl)、(6.02)異噻菌胺(isotianil)、(6.03)烯丙苯噻唑(probenazole)、(6.04)噻醯菌胺(tiadinil)、(6.05)昆布多醣(laminarin)。 6) Compounds capable of inducing host defense, such as (6.01) acibenzolar-S-methyl, (6.02) isotianil, (6.03) allylbenzazole (probenazole) ), (6.04) tiadinil, (6.05) laminarin.

7)胺基酸及/或蛋白生物合成之抑制劑，例如(7.01)胺撲滅 (andoprim)、(7.02)滅瘟素(blasticidin-S)、(7.03)嘧菌環胺(cyprodinil)、(7.04)春日黴素(kasugamycin)、(7.05)春日黴素鹽酸鹽水合物、(7.06)嘧菌胺(mepanipyrim)、(7.07)嘧黴胺(pyrimethanil)、(7.08)3-(5-氟-3,3,4,4-四甲基-3,4-二氫異喹啉-1-基)喹啉、(7.09)氧四環素(oxytetracycline)、(7.10)鏈黴素(streptomycin)。 7) inhibitors of amino acid and/or protein biosynthesis, such as (7.01) amine extinguishing (andoprim), (7.02) blasticidin-S, (7.03) cyprodinil, (7.04) kasugamycin, (7.05) kasugamycin hydrochloride hydrate, (7.06) ) mepanipyrim, (7.07) pyrimethanil, (7.08) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinoline- 1-yl)quinoline, (7.09) oxytetracycline, (7.10) streptomycin.

8)ATP產生之抑制劑，例如(8.01)三苯基乙酸錫(fentin acetate)、(8.02)三苯基氯化錫(fentin chloride)、(8.03)三苯基氫氧化錫(fentin hydroxide)、(8.04)矽噻菌胺(silthiofam)。 8) inhibitors of ATP production, such as (8.01) fentin acetate, (8.02) fentin chloride, (8.03) fentin hydroxide, (8.04) Silthiofam.

9)細胞壁合成之抑制劑，例如(9.01)苯噻菌胺(benthiavalicarb)、(9.02)烯醯嗎啉(dimethomorph)、(9.03)氟嗎啉(flumorph)、(9.04)異丙菌胺(iprovalicarb)、(9.05)雙炔醯菌胺(mandipropamid)、(9.06)多氧菌素(polyoxins)、(9.07)保粒黴素(polyoxorim)、(9.08)有效黴素A(validamycin A)、(9.09)霜黴滅(valifenalate)、(9.10)多氧菌素B、(9.11)(2E)-3-(4-第三丁基苯基)-3-(2-氯吡啶-4-基)-1-(嗎啉-4-基)丙-2-烯-1-酮、(9.12)(2Z)-3-(4-第三丁基苯基)-3-(2-氯吡啶-4-基)-1-(嗎啉-4-基)丙-2-烯-1-酮。 9) Inhibitors of cell wall synthesis, such as (9.01) benthiavalicarb, (9.02) dimethomorph, (9.03) flumorph, (9.04) isopropylidene (iprovalicarb) ), (9.05) mandipropamid, (9.06) polyoxins, (9.07) polyoxorim, (9.08) validamycin A, (9.09) ) valifenalate, (9.10) polyoxin B, (9.11) (2E)-3-(4-t-butylphenyl)-3-(2-chloropyridin-4-yl)- 1-(morpholin-4-yl)prop-2-en-1-one, (9.12)(2Z)-3-(4-t-butylphenyl)-3-(2-chloropyridine-4- Base)-1-(morpholin-4-yl)prop-2-en-1-one.

10)脂質及膜合成之抑制劑，例如(10.01)聯苯、(10.02)氯苯甲醚(chloroneb)、(10.03)氯硝胺(dicloran)、(10.04)敵瘟磷(edifenphos)、(10.05)土菌靈(etridiazole)、(10.06)引多克(iodocarb)、(10.07)異稻瘟淨(iprobenfos)、(10.08)稻瘟靈(isoprothiolane)、(10.09)霜黴威(propamocarb)、(10.10)鹽酸霜黴威、(10.11)硫菌威(prothiocarb)、(10.12)吡菌磷(pyrazophos)、(10.13)五氯硝苯(quintozene)、(10.14)四氯硝基苯(tecnazene)、(10.15)甲基立枯磷(tolclofos-methyl)。 10) Inhibitors of lipid and membrane synthesis, such as (10.01) biphenyl, (10.02) chloroneb (chloroneb), (10.03) chloramine (dicloran), (10.04) enemenphos (edifenphos), (10.05 ) etridiazole, (10.06) iodocarb, (10.07) iprobenfos, (10.08) isoprothiolane, (10.09) propamocarb, ( 10.10) propamocarb hydrochloride, (10.11) prothiocarb, (10.12) pyrazophos, (10.13) quintozene, (10.14) tetrachloronitrobenzene (tecnazene), (10.15) Tolclofos-methyl.

11)黑色素生物合成之抑制劑，例如(11.01)環丙醯菌胺(carpropamid)、(11.02)雙氯氰菌胺(diclocymet)、(11.03)禾草靈(fenoxanil)、(11.04)酞內酯(phthalide)、(11.05)咯喹酮(pyroquilon)、 (11.06)三環唑(tricyclazole)、(11.07)2,2,2-三氟乙基{3-甲基-1-[(4-甲基苯甲醯基)胺基]丁-2-基}胺基甲酸酯。 11) Inhibitors of melanin biosynthesis, such as (11.01) carpropamid, (11.02) diclocymet, (11.03) fenoxanil, (11.04) azlactone (phthalide), (11.05) pyrroquinone, (11.06) Tricyclazole, (11.07) 2,2,2-trifluoroethyl {3-methyl-1-[(4-methylbenzylidene)amino]butan-2-yl } Aminoformates.

12)核酸合成之抑制劑，例如(12.01)苯霜靈(benalaxyl)、(12.02)(苯霜靈-M(精苯霜靈(kiralaxyl))、(12.03)磺嘧菌靈(bupirimate)、(12.04)克勞拉康(clozylacon)、(12.05)二甲嘧酚(dimethirimol)、(12.06)乙菌定(ethirimol)、(12.07)呋霜靈(furalaxyl)、(12.08)惡黴靈(hymexazole)、(12.09)甲霜靈(metalaxyl)、(12.10)甲霜靈-M(精甲霜靈(mefenoxam))、(12.11)甲呋醯胺(ofurace)、(12.12)惡霜靈(oxadixyl)、(12.13)惡喹酸(oxolinic acid)、(12.14)辛噻酮(octhilinone)。 12) Inhibitors of nucleic acid synthesis, such as (12.01) benylaxyl, (12.02) (bensulma-M (kiralaxyl), (12.03) bupirimate, ( 12.04) clozylacon, (12.05) dimethirimol, (12.06) ethirimol, (12.07) furalaxyl, (12.08) hymexazole (12.09) metalaxyl, (12.10) metalaxyl-M (mefenoxam), (12.11) forurace, (12.12) oxadixyl, (12.13) Oxolinic acid, (12.14) octubilinone.

13)信號轉導之抑制劑，例如(13.01)乙菌利(chlozolinate)、(13.02)拌種咯(fenpielonil)、(13.03)咯菌腈(fludioxonil)、(13.04)異菌脲、(13.05)腐黴利(procymidone)、(13.06)喹氧靈(quinoxyfen)、(13.07)伐菌唑靈(vinclozolin)、(13.08)丙氧喹啉(proquinazid)。 13) Inhibitors of signal transduction, such as (13.01) chlozolinate, (13.02) fenpielonil, (13.03) fludioxonil, (13.04) iprodione, (13.05) Procymidone, (13.06) quinoxyfen, (13.07) vinclozolin, (13.08) proquinazid.

14)能夠充當解聯劑之化合物，例如(14.01)樂殺蟎(binapacryl)、(14.02)消蟎普(dinocap)、(14.03)嘧菌腙(ferimzone)、(14.04)氟啶胺(fluazinam)、(14.05)消蟎多(meptyldinocap)。 14) A compound capable of acting as a de-linking agent, for example, (14.01) binapacryl, (14.02) dinocap, (14.03) ferimzone, (14.04) fluazinam (14.05) Meptyldinocap.

15)其他化合物，例如(15.001)苯噻硫氰(benthiazole)、(15.002)魅菌酮(bethoxazin)、(15.003)卡巴西黴素(capsimycin)、(15.004)香芹酮(carvone)、(15.005)滅蟎猛(chinomethionat)、(15.006)甲氧苯唳菌(pyriofenone)(氯芬酮(chlazafenone))、(15.007)硫雜靈(cufraneb)、(15.008)環氟菌胺(cyflufenamid)、(15.009)霜脲氰(cymoxanil)、(15.010)環丙磺醯胺(cyprosulfamide)、(15.011)福美甲酯(dazomet)、(15.012)咪菌威(debacarb)、(15.013)二氯芬(dichlorophen)、(15.014)敵菌米嗪(diclomezine)、(15.015)燕麥枯(difenzoquat)、(15.016)燕麥枯硫酸二甲酯、(15.017)二苯基胺、(15.018)艾考同伴(ecomate)、(15.019)胺苯吡菌酮(fenpyrazamine)、(15.020)氟聯苯菌(flumetover)、 (15.021)氟裡醚(fluoroimide)、(15.022)磺菌胺(flusulfamide)、(15.023)氟噻菌淨(flutianil)、(15.024)三乙膦酸鋁(fosetyl-aluminium)、(15.025)三乙膦酸鈣、(15.026)三乙膦酸鈉、(15.027)六氯苯、(15.028)人間黴素(irumamycin)、(15.029)磺菌威(methasulfocarb)、(15.030)甲基異硫氰酸酯、(15.031)苯菌酮(metrafenone)、(15.032)滅粉黴素(mildiomycin)、(15.033)納他黴素(natamycin)、(15.034)二甲基二硫基胺基甲酸鎳、(15.035)酞菌酯(nitrothal-isopropyl)、(15.036)惡莫克(oxamocarb)、(15.037)氧芬新(oxyfenthiin)、(15.038)五氯酚及鹽、(15.039)苯氧司林(phenothrin)、(15.040)亞磷酸及其鹽、(15.041)霜黴威乙膦酸鹽(propamocarb-fosetylate)、(15.042)丙諾新鈉鹽(propanosin-sodium)、(15.043)吡嗎啉(pyrimorph)、(15.044)吡咯尼林(pyrrolnitrin)、(15.045)特布氟奎琳(tebufloquin)、(15.046)酞枯酸(tecloftalam)、(15.047)甲磺菌胺(tolnifanide)、(15.048)咪唑嗪(triazoxide)、(15.049)水楊菌胺(trichlamide)、(15.050)氰菌胺(zarilamid)、(15.051)(3S,6S,7R,8R)-8-苄基-3-[({3-[(異丁醯基氧基)甲氧基]-4-甲氧基吡啶-2-基}羰基)胺基]-6-甲基-4,9-二側氧基-1,5-二氧雜環壬-7-基2-甲基丙酸酯、(15.052)1-(4-{4-[(5R)-5-(2,6-二氟苯基)-4,5-二氫-1,2-噁唑-3-基]-1,3-噻唑-2-基}六氫吡啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(15.053)1-(4-{4-[(5S)-5-(2,6-二氟苯基)-4,5-二氫-1,2-噁唑-3-基]-1,3-噻唑-2-基}六氫吡啶-1-基)-2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酮、(15.054)氧噻匹普林(oxathiapiproline)、(15.055)1H-咪唑-1-甲酸1-(4-甲氧基苯氧基)-3,3-二甲基丁-2-基酯、(15.056)2,3,5,6-四氯-4-(甲基磺醯基)吡啶、(15.057)2,3-二丁基-6-氯噻吩并[2,3-d]嘧啶-4(3H)-酮、(15.058)2,6-二甲基-1H,5H-[1,4]二噻英并[2,3-c：5,6-c']二吡咯-1,3,5,7(2H,6H)-四酮、(15.059)2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]-1-(4-{4-[(5R)-5-苯基- 4,5-二氫-1,2-噁唑-3-基]-1,3-噻唑-2-基}六氫吡啶-1-基)乙酮、(15.060)2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]-1-(4-{4-[(5S)-5-苯基-4,5-二氫-1,2-噁唑-3-基]-1,3-噻唑-2-基}六氫吡啶-1-基)乙酮、(15.061)2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]-1-{4-[4-(5-苯基-4,5-二氫-1,2-噁唑-3-基)-1,3-噻唑-2-基]六氫吡啶-1-基}乙酮、(15.062)2-丁氧基-6-碘-3-丙基-4H-色滿-4-酮、(15.063)2-氯-5-[2-氯-1-(2,6-二氟-4-甲氧基苯基)-4-甲基-1H-咪唑-5-基]吡啶、(15.064)2-苯基苯酚及鹽、(15.065)3-(4,4,5-三氟-3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉、(15.066)3,4,5-三氯吡啶-2,6-二甲腈、(15.067)3-氯-5-(4-氯苯基)-4-(2,6-二氟苯基)-6-甲基噠嗪、(15.068)4-(4-氯苯基)-5-(2,6-二氟苯基)-3,6-二甲基噠嗪、(15.069)5-胺基-1,3,4-噻二唑-2-硫醇、(15.070)5-氯-N'-苯基-N'-(丙-2-炔-1-基)噻吩-2-磺醯肼、(15.071)5-氟-2-[(4-氟苄基)氧基]嘧啶-4-胺、(15.072)5-氟-2-[(4-甲基苄基)氧基]嘧啶-4-胺、(15.073)5-甲基-6-辛基[1,2,4]***并[1,5-a]嘧啶-7-胺、(15.074)(2Z)-3-胺基-2-氰基-3-苯基丙烯酸乙基酯、(15.075)N'-(4-{[3-(4-氯苄基)-1,2,4-噻二唑-5-基]氧基}-2,5-二甲基苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.076)N-(4-氯苄基)-3-[3-甲氧基-4-(丙-2-炔-1-基氧基)苯基]丙醯胺、(15.077)N-[(4-氯苯基)(氰基)甲基]-3-[3-甲氧基-4-(丙-2-炔-1-基氧基)苯基]丙醯胺、(15.078)N-[(5-溴-3-氯吡啶-2-基)甲基]-2,4-二氯菸鹼醯胺、(15.079)N-[1-(5-溴-3-氯吡啶-2-基)乙基]-2,4-二氯菸鹼醯胺、(15.080)N-[1-(5-溴-3-氯吡啶-2-基)乙基]-2-氟-4-碘菸鹼醯胺、(15.081)N-{(E)-[(環丙基甲氧基)亞胺基][6-(二氟甲氧基)-2,3-二氟苯基]甲基}-2-苯基乙醯胺、(15.082)N-{(Z)-[(環丙基甲氧基)亞胺基][6-(二氟甲氧基)-2,3-二氟苯基]甲基}-2-苯基乙醯胺、(15.083)N'-{4-[(3-第三丁基-4-氰基-1,2-噻唑-5-基)氧基]-2-氯-5-甲基苯基}-N-乙基-N-甲基亞胺基甲醯胺、(15.084)N-甲基-2-(1-{[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙醯 基}六氫吡啶-4-基)-N-(1,2,3,4-四氫萘-1-基)-1,3-噻唑-4-甲醯胺、(15.085)N-甲基-2-(1-{[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-N-[(1R)-1,2,3,4-四氫萘-1-基]-1,3-噻唑-4-甲醯胺、(15.086)N-甲基-2-(1-{[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-N-[(1S)-1,2,3,4-四氫萘-1-基]1,3-噻唑-4-甲醯胺、(15.087){6-[({[(1-甲基-1H-四唑-5-基)(苯基)亞甲基]胺基}氧基)甲基]吡啶-2-基}胺基甲酸戊酯、(15.088)啡嗪-1-甲酸、(15.089)喹啉-8-醇、(15.090)喹啉-8-醇硫酸酯(2：1)、(15.091){6-[({[(1-甲基-1H-四唑-5-基)(苯基)亞甲基]胺基}氧基)甲基]吡啶-2-基}胺基甲酸第三丁基酯、(15.092)(5-溴-2-甲氧基-4-甲基吡啶-3-基)(2,3,4-三甲氧基-6-甲基苯基)甲酮、(15.093)N-[2-(4-{[3-(4-氯苯基)丙-2-炔-1-基]氧基}-3-甲氧基苯基)乙基]-N2-(甲基磺醯基)纈胺醯胺、(15.094)4-側氧基-4-[(2-苯基乙基)胺基]丁酸、(15.095){6-[({[(Z)-(1-甲基-1H-四唑-5-基)(苯基)亞甲基]胺基}氧基)甲基]吡啶-2-基}胺基甲酸丁-3-炔-1-基酯、(15.096)4-胺基-5-氟嘧啶-2-醇(互變異構形式：4-胺基-5-氟嘧啶-2(1H)-酮)、(15.097)3,4,5-三羥基苯甲酸丙酯、(15.098)[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(15.099)(S)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(15.100)(R)-[3-(4-氯-2-氟苯基)-5-(2,4-二氟苯基)-1,2-噁唑-4-基](吡啶-3-基)甲醇、(15.101)2-氟-6-(三氟甲基)-N-(1,1,3-三甲基-2,3-二氫-1H-茚-4-基)苯醯胺、(15.102)2-(6-苄基吡啶-2-基)喹唑啉、(15.103)2-[6-(3-氟-4-甲氧基苯基)-5-甲基吡啶-2-基]喹唑啉、(15.104)3-(4,4-二氟-3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉、(15.105)脫落酸、(15.106)N'-[5-溴-6-(2,3-二氫-1H-茚-2-基氧基)-2-甲基吡啶-3-基]-N-乙基-N-甲基亞胺基甲醯胺、(15.107)N'-{5-溴-6-[1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(15.108)N'-{5- 溴-6-[(1R)-1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(15.109)N'-{5-溴-6-[(1S)-1-(3,5-二氟苯基)乙氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(15.110)N'-{5-溴-6-[(順式-4-異丙基環己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(15.111)N'-{5-溴-6-[(反式-4-異丙基環己基)氧基]-2-甲基吡啶-3-基}-N-乙基-N-甲基亞胺基甲醯胺、(15.112)N-環丙基-3-(二氟甲基)-5-氟-N-(2-異丙基苄基)-1-甲基-1H-吡唑-4-甲醯胺、(15.113)N-環丙基-N-(2-環丙基苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.114)N-(2-第三丁基苄基)-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.115)N-(5-氯-2-乙基苄基)-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.116)N-(5-氯-2-異丙基苄基)-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.117)N-環丙基-3-(二氟甲基)-N-(2-乙基-5-氟苄基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.118)N-環丙基-3-(二氟甲基)-5-氟-N-(5-氟-2-異丙基苄基)-1-甲基-1H-吡唑-4-甲醯胺、(15.119)N-環丙基-N-(2-環丙基-5-氟苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.120)N-(2-環戊基-5-氟苄基)-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.121)N-環丙基-3-(二氟甲基)-5-氟-N-(2-氟-6-異丙基苄基)-1-甲基-1H-吡唑-4-甲醯胺、(15.122)N-環丙基-3-(二氟甲基)-N-(2-乙基-5-甲基苄基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.123)N-環丙基-3-(二氟甲基)-5-氟-N-(2-異丙基-5-甲基苄基)-1-甲基-1H-吡唑-4-甲醯胺、(15.124)N-環丙基-N-(2-環丙基-5-甲基苄基)-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.125)N-(2-第三丁基-5-甲基苄基)-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.126)N-[5-氯-2-(三氟甲基)苄基]-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.127)N-環丙基-3-(二氟甲基)-5-氟-1-甲基-N-[5-甲基-2-(三氟 甲基)苄基]-1H-吡唑-4-甲醯胺、(15.128)N-[2-氯-6-(三氟甲基)苄基]-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.129)N-[3-氯-2-氟-6-(三氟甲基)苄基]-N-環丙基-3-(二氟甲基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.130)N-環丙基-3-(二氟甲基)-N-(2-乙基-4,5-二甲基苄基)-5-氟-1-甲基-1H-吡唑-4-甲醯胺、(15.131)N-環丙基-3-(二氟甲基)-5-氟-N-(2-異丙基苄基)-1-甲基-1H-吡唑-4-硫代甲醯胺、(15.132)N'-(2,5-二甲基-4-苯氧基苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.133)N'-{4-[(4,5-二氯-1,3-噻唑-2-基)氧基]-2,5-二甲基苯基}-N-乙基-N-甲基亞胺基甲醯胺、(15.134)N-(4-氯-2,6-二氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.135)9-氟-2,2-二甲基-5-(喹啉-3-基)-2,3-二氫-1,4-苯并氧氮呯、(15.136)2-{2-氟-6-[(8-氟-2-甲基喹啉-3-基)氧基]苯基}丙-2-醇、(15.137)2-{2-[(7,8-二氟-2-甲基喹啉-3-基)氧基]-6-氟苯基}丙-2-醇、(15.138)4-(2-氯-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.139)4-(2-氯-4-氟苯基)-N-(2,6-二氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.140)4-(2-氯-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.141)4-(2-溴-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.142)N-(2-溴-6-氟苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.143)4-(2-溴-4-氟苯基)-N-(2-溴苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.144)4-(2-溴-4-氟苯基)-N-(2-溴-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.145)4-(2-溴-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.146)N-(2-溴苯基)-4-(2-氯-4-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.147)4-(2-氯-4-氟苯基)-N-(2-氯苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.148)4-(2-溴-4-氟苯基)-N-(2,6-二氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.149)4-(2-溴-4-氟苯基)-N-(2-氟苯基)-1,3-二甲基-1H-吡唑-5-胺、(15.150)N'-(4-{3-[(二氟甲基)磺醯基]苯氧基}-2,5-二甲基苯基)-N-乙基-N-甲基 亞胺基甲醯胺、(15.151)N'-(2,5-二甲基-4-{3-[(1,1,2,2-四氟乙基)磺醯基]苯氧基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.152)N'-(2,5-二甲基-4-{3-[(2,2,2-三氟乙基)磺醯基]苯氧基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.153)N'-(2,5-二甲基-4-{3-[(2,2,3,3-四氟丙基)磺醯基]苯氧基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.154)N'-(2,5-二甲基-4-{3-[(五氟乙基)磺醯基]苯氧基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.155)N'-(4-{[3-(二氟甲氧基)苯基]磺醯基}-2,5-二甲基苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.156)N'-(2,5-二甲基-4-{[3-(1,1,2,2-四氟乙氧基)苯基]磺醯基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.157)N'-(2,5-二甲基-4-{[3-(2,2,2-三氟乙氧基)苯基]磺醯基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.158)N'-(2,5-二甲基-4-{[3-(2,2,3,3-四氟丙氧基)苯基]磺醯基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.159)N'-(2,5-二甲基-4-{[3-(五氟乙氧基)苯基]磺醯基}苯基)-N-乙基-N-甲基亞胺基甲醯胺、(15.160)2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)六氫吡啶-1-基]乙酮、(15.161)2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氟-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)六氫吡啶-1-基]乙酮、(15.162)2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{5-[2-氯-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)六氫吡啶-1-基]乙酮、(15.163)甲烷磺酸2-{3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}苯基酯、(15.164)甲烷磺酸2-{3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}-3-氯苯基酯、(15.165)2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{(5S)-5-[2-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)六氫吡啶-1-基]乙酮、(15.166)2- [3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{(5R)-5-[2-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)六氫吡啶-1-基]乙酮、(15.167)2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{(5S)-5-[2-氟-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)六氫吡啶-1-基]乙酮、(15.168)2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{(5R)-5-[2-氟-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)六氫吡啶-1-基]乙酮、(15.169)2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{(5S)-5-[2-氯-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)六氫吡啶-1-基]乙酮、(15.170)2-[3,5-雙(二氟甲基)-1H-吡唑-1-基]-1-[4-(4-{(5R)-5-[2-氯-6-(丙-2-炔-1-基氧基)苯基]-4,5-二氫-1,2-噁唑-3-基}-1,3-噻唑-2-基)六氫吡啶-1-基]乙酮、(15.171)甲烷磺酸2-{(5S)-3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}苯基酯、(15.172)甲烷磺酸2-{(5R)-3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}苯基酯、(15.173)甲烷磺酸2-{(5S)-3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}-3-氯苯基酯、(15.174)甲烷磺酸2-{(5R)-3-[2-(1-{[3,5-雙(二氟甲基)-1H-吡唑-1-基]乙醯基}六氫吡啶-4-基)-1,3-噻唑-4-基]-4,5-二氫-1,2-噁唑-5-基}-3-氯苯基酯。 15) Other compounds, such as (15.001) benthiazole, (15.002) bethoxazin, (15.003) capsimycin, (15.004) carvone, (15.005) ) chinomethionat, (15.006) pyrofenone (chlazafenone), (15.007) thiafraneb, (15.008) cyflufenamid, ( 15.009) Cymoxanil, (15.010) cyprosulfamide, (15.011) dazomet, (15.012) debacarb, (15.013) dichlorophen (15.014) diclomezine, (15.015) difenzoquat, (15.016) oat dimethyl sulfate, (15.017) diphenylamine, (15.018) ecocom (ecomate), ( 15.019) fenpyrazamine, (15.020) flumetover, (15.021) fluoroimide, (15.022) flusulfamide, (15.023) flutianil, (15.024) triethylphosphonate (fosetyl-aluminium), (15.025) triethyl Calcium phosphonate, (15.026) sodium triethionate, (15.027) hexachlorobenzene, (15.028) irumamycin, (15.029) methasulfocarb, (15.030) methyl isothiocyanate , (15.031) metrafenone, (15.032) mildiomycin, (15.033) natamycin, (15.034) nickel dimethyldithiocarbamate, (15.035) Nitrothal-isopropyl, (15.036) oxamocarb, (15.037) oxyfenthiin, (15.038) pentachlorophenol and salt, (15.039) phenothrin, ( 15.040) phosphorous acid and its salt, (15.041) propamocarb-fosetylate, (15.042) propanosin-sodium, (15.043) pyromorph, (15.044) Pyrrolnitrin, (15.045) tebufloquin, (15.046) tecloftalam, (15.047) tolnifanide, (15.048) triazoxide, (15.049) Salicillin (trichla Mide), (15.050) cylinide, (15.051) (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutylideneoxy)methoxy]-) 4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-di-oxy-1,5-dioxan-7-yl 2-methylpropionic acid Ester, (15.052) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]- 1,3-thiazol-2-yl}hexahydropyridin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.053 ) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3- Thiazol-2-yl}hexahydropyridin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.054) oxythiophene Oxathiapiproline, (15.055) 1H-imidazole-1-carboxylic acid 1-(4-methoxyphenoxy)-3,3-dimethylbut-2-yl ester, (15.056) 2,3, 5,6-tetrachloro-4-(methylsulfonyl)pyridine, (15.057) 2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one, (15.058) 2,6-Dimethyl-1H,5H-[1,4]dithiaindole[2,3-c:5,6-c']dipyrrole-1,3,5,7 (2H ,6H)-tetraketone, (15.059) 2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5R)- 5-phenyl- 4,5-Dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}hexahydropyridin-1-yl)ethanone, (15.060) 2-[5-methyl -3-(trifluoromethyl)-1H-pyrazol-1-yl]-1-(4-{4-[(5S)-5-phenyl-4,5-dihydro-1,2-oxo Zyrid-3-yl]-1,3-thiazol-2-yl}hexahydropyridin-1-yl)ethanone, (15.061) 2-[5-methyl-3-(trifluoromethyl)-1H- Pyrazol-1-yl]-1-{4-[4-(5-phenyl-4,5-dihydro-1,2-oxazol-3-yl)-1,3-thiazol-2-yl Hexahydropyridin-1-yl}ethanone, (15.062) 2-butoxy-6-iodo-3-propyl-4H-chroman-4-one, (15.063) 2-chloro-5-[2 -Chloro-1-(2,6-difluoro-4-methoxyphenyl)-4-methyl-1H-imidazol-5-yl]pyridine, (15.064) 2-phenylphenol and salt, (15.065 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.066) 3,4,5-trichloropyridine -2,6-Dicarbonitrile, (15.067) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (15.068) 4 -(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (15.069) 5-amino-1,3,4-thiadiazole- 2-thiol, (15.070) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene-2-sulfonate, (15.071) 5-fluoro-2-[ (4-fluorobenzyl)oxy]pyrimidine-4-amine, (15.072) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidine Pyridin-4-amine, (15.073) 5-methyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidin-7-amine, (15.074)(2Z)-3- Ethyl-2-cyano-3-phenylethyl acrylate, (15.075) N'-(4-{[3-(4-chlorobenzyl)-1,2,4-thiadiazole-5- (yloxy)-2,5-dimethylphenyl)-N-ethyl-N-methyliminocarbamidine, (15.076) N-(4-chlorobenzyl)-3-[3 -Methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamine, (15.077) N-[(4-chlorophenyl)(cyano)methyl]-3- [3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamine, (15.078) N-[(5-bromo-3-chloropyridin-2-yl)- -2,4-dichloronicotinium amide, (15.079) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloronicotinium amide , (15.080) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodonicotinium amide, (15.081) N-{(E)-[ (cyclopropylmethoxy)imido][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide, (15.082) N-{ (Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide, 15.083) N'-{4-[(3-Tertibutyl-4-cyano-1,2-thiazol-5-yl)oxy]-2-chloro-5-methylphenyl}-N- Ethyl-N-methylimidocarbamidine, 15.084) N-Methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetamidine 六}hexahydropyridin-4-yl)-N-(1,2,3,4-tetrahydronaphthalen-1-yl)-1,3-thiazole-4-carboxamide, (15.085) N-methyl -2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethenyl}hexahydropyridin-4-yl)-N-[(1R) -1,2,3,4-tetrahydronaphthalen-1-yl]-1,3-thiazole-4-carboxamide, (15.086) N-methyl-2-(1-{[5-methyl- 3-(Trifluoromethyl)-1H-pyrazol-1-yl]ethenyl}hexahydropyridin-4-yl)-N-[(1S)-1,2,3,4-tetrahydronaphthalene- 1-yl]1,3-thiazole-4-carboxamide, (15.087){6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amine) Ethyl)methyl]pyridin-2-yl}amyl formate, (15.088) phenazine-1-carboxylic acid, (15.089) quinoline-8-ol, (15.090) quinoline-8-ol sulphate Ester (2:1), (15.091) {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino)oxy)methyl]pyridine -2-yl}butyl carbamic acid tert-butyl ester, (15.092) (5-bromo-2-methoxy-4-methylpyridin-3-yl) (2,3,4-trimethoxy-6 -methylphenyl)methanone, (15.093) N-[2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxy Phenyl)ethyl]-N2-(methylsulfonyl) amidoxime, (15.094) 4-oxo-4-[(2-phenylethyl)amino]butyric acid, (15.095) {6-[({[(Z)-(1-A) -1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}aminocarbamic acid but-3-yn-1-yl ester, (15.096) 4-Amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidine-2(1H)-one), (15.097) 3,4,5-trihydroxybenzoic acid Propyl ester, (15.098) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridine-3- Methanol, (15.099) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl] (pyridin-3-yl)methanol, (15.100)(R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazole 4-yl](pyridin-3-yl)methanol, (15.101)2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro- 1H-indol-4-yl)benzamine, (15.102) 2-(6-benzylpyridin-2-yl)quinazoline, (15.103) 2-[6-(3-fluoro-4-methoxy Phenyl)-5-methylpyridin-2-yl]quinazoline, (15.104) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline-1 -yl)quinoline, (15.105) abscisic acid, (15.106) N'-[5-bromo-6-(2,3-dihydro-1H-indol-2-yloxy)-2-methylpyridine- 3-yl]-N-ethyl-N-methyliminocarbamidine, (15.107) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy ]-2-methylpyridin-3-yl}-N- Ethyl-N-methylimidocarbamamine, (15.108) N'-{5- Bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidocarba Indoleamine, (15.109) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N -ethyl-N-methyliminocarbamidine, (15.110) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridine -3-yl}-N-ethyl-N-methyliminocarbamidine, (15.111) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy ]-2-methylpyridin-3-yl}-N-ethyl-N-methyliminocarbamidine, (15.112) N-cyclopropyl-3-(difluoromethyl)-5-fluoro -N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (15.113) N-cyclopropyl-N-(2-cyclopropylbenzyl)- 3-(Difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.114) N-(2-tert-butylbenzyl)-N-cyclopropyl -3-(Difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.115) N-(5-chloro-2-ethylbenzyl)-N- Cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.116) N-(5-chloro-2-isopropylbenzyl -N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.117) N-cyclopropyl-3-(di) Fluoromethyl)-N-(2- Ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.118) N-cyclopropyl-3-(difluoromethyl)-5- Fluorine-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (15.119) N-cyclopropyl-N-(2-cyclopropane 5--5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.120) N-(2-cyclopentyl- 5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.121) N-cyclopropyl -3-(Difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (15.122)N -cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.123) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4 -Proline, (15.124) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H -pyrazole-4-carbamide, (15.125) N-(2-t-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro- 1-methyl-1H-pyrazole-4-carboxamide, (15.126) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl) 5-)fluoro-1-methyl-1H-pyrazole-4- Methionamine, (15.127) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoro Methyl)benzyl]-1H-pyrazole-4-carboxamide, (15.128) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(di) Fluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.129) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl] -N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.130) N-cyclopropyl-3-(difluoro Methyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (15.131) N-cyclopropane 3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-thiocarbamamine, (15.132)N' -(2,5-Dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyliminocarbamidine, (15.133) N'-{4-[(4,5- Dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methyliminocarbamidine, (15.134) N-( 4-Chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (15.135) 9- Fluorin-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazide, (15.136)2-{2-fluoro-6- [(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.137) 2-{2-[(7,8-difluoro-2-methyl) Quinoline-3-yl)oxy]-6-fluorophenyl}propan-2-ol, (15.138)4- (2-Chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (15.139) 4-(2-chloro-4 -fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (15.140) 4-(2-chloro-4-fluorobenzene -N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (15.141) 4-(2-bromo-4-fluorophenyl) -N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (15.142) N-(2-bromo-6-fluorophenyl)-4 -(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (15.143) 4-(2-bromo-4-fluorophenyl)-N-( 2-bromophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (15.144) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6- Fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (15.145) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1 ,3-dimethyl-1H-pyrazole-5-amine, (15.146) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl -1H-pyrazole-5-amine, (15.147) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole- 5-amine, (15.148) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine , (15.149) 4-(2-Bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (15.150) N' -(4-{3-[(difluoromethyl)sulfonate ] Phenoxy} -2,5-dimethylphenyl) -N- methyl-ethyl -N- Iminocarbamide, (15.151) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfonyl]phenoxy} Phenyl)-N-ethyl-N-methyliminocarbamidine, (15.152) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoro) Ethyl)sulfonyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarbamidine, (15.153) N'-(2,5-dimethyl-4-{3 -[(2,2,3,3-tetrafluoropropyl)sulfonyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarbamidine, (15.154) N'- (2,5-Dimethyl-4-{3-[(pentafluoroethyl)sulfonyl]phenoxy}phenyl)-N-ethyl-N-methyliminocarbamidine, ( 15.155) N'-(4-{[3-(Difluoromethoxy)phenyl]sulfonyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimino Methionamine, (15.156) N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfonyl}phenyl) -N-ethyl-N-methyliminocarbamamine, (15.157) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy) Phenyl]sulfonyl}phenyl)-N-ethyl-N-methyliminocarbamidine, (15.158) N'-(2,5-dimethyl-4-{[3-( 2,2,3,3-tetrafluoropropoxy)phenyl]sulfonyl}phenyl)-N-ethyl-N-methyliminocarbamidine, (15.159) N'-(2, 5-dimethyl-4-{[3-(pentafluoro) Ethoxy)phenyl]sulfonyl}phenyl)-N-ethyl-N-methyliminocarbamidine, (15.160) 2-[3,5-bis(difluoromethyl)-1H -pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2 -oxazol-3-yl}-1,3-thiazol-2-yl)hexahydropyridin-1-yl]ethanone, (15.161) 2-[3,5-bis(difluoromethyl)-1H- Pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro- 1,2-oxazol-3-yl}-1,3-thiazol-2-yl)hexahydropyridin-1-yl]ethanone, (15.162) 2-[3,5-bis(difluoromethyl) -1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5- Dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)hexahydropyridin-1-yl]ethanone, (15.163) methanesulfonic acid 2-{3-[2- (1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]ethenyl}hexahydropyridin-4-yl)-1,3-thiazol-4-yl]- 4,5-dihydro-1,2-oxazol-5-yl}phenyl ester, (15.164) methanesulfonic acid 2-{3-[2-(1-{[3,5-bis(difluoromethyl) -1H-pyrazol-1-yl]ethenyl}hexahydropyridin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazole- 5-yl}-3-chlorophenyl ester, (15.165) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{( 5S)-5-[2-(prop-2-yn-1- Oxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)hexahydropyridin-1-yl]ethanone, (15.166) 2- [3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{(5R)-5-[2-(prop-2-yn-1-) Benzyl)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)hexahydropyridin-1-yl]ethanone, (15.167 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{(5S)-5-[2-fluoro-6-(propyl) 2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)hexahydropyridine-1- Ethyl ketone, (15.168) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{(5R)-5-[2 -fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl Hexahydropyridin-1-yl]ethanone, (15.169) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{( 5S)-5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazole-3-yl}-1, 3-thiazol-2-yl)hexahydropyridin-1-yl]ethanone, (15.170) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[ 4-(4-{(5R)-5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazole- 3-yl}-1,3-thiazol-2-yl)hexahydropyridin-1-yl]ethanone, (15.171) methanesulfonic acid 2-{(5S)-3-[2-(1-{[3 ,5-bis(difluoromethyl)-1H-pyrazol-1-yl]ethenyl}hexahydropyridin-4-yl)-1,3-thiazole 4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl ester, (15.172) methanesulfonic acid 2-{(5R)-3-[2-(1-{ [3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]ethenyl}hexahydropyridin-4-yl)-1,3-thiazol-4-yl]-4,5- Dihydro-1,2-oxazol-5-yl}phenyl ester, (15.173) methanesulfonic acid 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl) -1H-pyrazol-1-yl]ethenyl}hexahydropyridin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazole- 5-yl}-3-chlorophenyl ester, (15.174) methanesulfonic acid 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyridyl) Zin-1-yl]ethenyl}hexahydropyridin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3 -Chlorophenyl ester.

生物殺有害生物劑作為混合組份 Biological killing biocide as a mixed component

式(I)化合物可與生物殺有害生物劑組合。 The compound of formula (I) can be combined with a biocidal pest.

生物殺有害生物劑尤其包括細菌、真菌、酵母、植物提取物及由微生物形成之產物，包括蛋白質及次級代謝物。 Biological killing agents include, inter alia, bacteria, fungi, yeast, plant extracts, and products formed by microorganisms, including proteins and secondary metabolites.

生物殺有害生物劑包括細菌例如形成芽孢之細菌、根部定殖細菌及充當生物殺昆蟲劑、殺真菌劑或殺線蟲劑之細菌。 Biological killing agents include bacteria such as spore forming bacteria, root colonizing bacteria, and bacteria that act as biological insecticides, fungicides or nematicides.

用作或可用作生物殺有害生物劑之該等細菌之實例係：芽孢枯草桿菌(Bacillus amyloliquefaciens)菌株FZB42(DSM 231179)，或仙人掌桿菌(Bacillus cereus)(尤其仙人掌桿菌(B.cereus)菌株CNCM I-1562)，或堅強芽孢桿菌菌株I-1582(登錄號CNCM I-1582)或短小芽孢桿菌(Bacillus pumilus)(尤其菌株GB34(登錄號ATCC 700814)及菌株QST2808(登錄號NRRL B-30087))，或枯草芽孢桿菌(Bacillus subtilis)(尤其菌株GB03(登錄號ATCC SD-1397)，或枯草芽孢桿菌菌株QST713(登錄號NRRL B-21661)或枯草芽孢桿菌菌株OST 30002(登錄號NRRL B-50421)，蘇雲金芽孢桿菌(尤其蘇雲金芽孢桿菌以色列亞種(B.thuringiensis subspecies israelensis)(血清型H-14)菌株AM65-52(登錄號ATCC 1276)，或蘇雲金芽孢桿菌鯰澤亞種，具體而言菌株ABTS-1857(SD-1372)，或蘇雲金芽孢桿菌庫斯塔克亞種菌株HD-1，或蘇雲金芽孢桿菌擬步行甲亞種菌株NB 176(SD-5428))，穿刺巴斯德桿菌(Pasteuria penetrans)，巴斯德桿菌屬(Pasteuria spp.)腎形線蟲(Rotylenchulus reniformis nematode)-PR3(登錄號ATCC SD-5834)，細黃鏈黴菌(Streptomyces microflavus)菌株AQ6121(=QRD 31.013,NRRL B-50550)，鮮黃鏈黴菌(Streptomyces galbus)菌株AQ 6047(登錄號NRRL 30232)。 Examples of such bacteria used or useful as biocide pesticides are: Bacillus amyloliquefaciens strain FZB42 (DSM 231179), or Bacillus cereus (especially B. cereus strain) CNCM I-1562), or Bacillus lentus strain I-1582 (accession number CNCM I-1582) or Bacillus pumilus (especially strain GB34 (accession number ATCC 700814) and strain QST2808 (accession number NRRL B-30087) )), or Bacillus subtilis (especially strain GB03 (accession number ATCC SD-1397), or Bacillus subtilis strain QST713 (accession number NRRL B-21661) or Bacillus subtilis strain OST 30002 (accession number NRRL B) -50421), Bacillus thuringiensis (especially B. thuringiensis subspecies israelensis (serotype H-14) strain AM65-52 (accession number ATCC 1276), or Bacillus thuringiensis subsp. In terms of strain ABTS-1857 (SD-1372), or Bacillus thuringiensis Kustal subspecies strain HD-1, or Bacillus thuringiensis subsp. subsp. subsp. strain NB 176 (SD-5428)), puncture Pasteur Bacillus (Pasteuria pene Trans), Pasteuria spp. Rotylenchulus reniformis nematode-PR3 (accession number ATCC SD-5834), Streptomyces microflavus strain AQ6121 (=QRD 31.013, NRRL B- 50550), Streptomyces galbus strain AQ 6047 (accession number NRRL 30232).

用作或可用作生物殺有害生物劑之真菌及酵母之實例係：巴氏蠶白僵菌(Beauveria bassiana)(具體而言菌株ATCC 74040)、盾殼黴(Coniothyrium minitans)(具體而言菌株CON/M/91-8(登錄號DSM-9660))、輪枝菌屬(Lecanicillium spp.)(具體而言菌株HRO LEC 12)、蠟蚧輪枝菌(Lecanicillium lecanii)(先前稱為蠟蚧輪刺孢菌(Verticillium lecanii))，具體而言菌株KV01)、黑疆菌(Metarhizium anisopliae)(具體而言菌株F52(DSM3884/ATCC 90448))、核果梅奇酵母(Metschnikowia fructicola)(具體而言菌株NRRL Y-30752)、玫煙色 擬青黴(Paecilomyces fumosoroseus)(新：玫煙色棒束孢(Isaria fumosorosea))(具體而言菌株IFPC 200613或菌株Apopka 97(登錄號ATCC 20874))、淡紫色擬青黴(Paecilomyces lilacinus)(具體而言淡紫色擬青黴(P.lilacinus)菌株251(AGAL 89/030550))、黃色蠕形黴(Talaromyces flavus)(具體而言菌株V117b)、深綠木黴(Trichoderma atroviride)(具體而言菌株SC1(登錄號CBS 122089))、哈氏木黴(Trichoderma harzianum)(具體而言哈茨木黴T39(T.harzianum rifaiT39)(登錄號CNCM I-952))。 Examples of fungi and yeast used or useful as biocide biocides: Beauveria bassiana (specifically strain ATCC 74040), Coniothyrium minitans (specifically strains) CON/M/91-8 (accession number DSM-9660)), Lecanicillium spp. (specifically strain HRO LEC 12), Lecanicillium lecanii (formerly known as wax mites) Verticillium lecanii, in particular strain KV01), Metarhizium anisopliae (specifically strain F52 (DSM3884/ATCC 90448)), Metschnikowia fructicola (specifically Strain NRRL Y-30752) Paecilomyces fumosoroseus (new: Isaria fumosorosea) (specifically strain IFPC 200613 or strain Apopka 97 (accession number ATCC 20874)), Paecilomyces lilacinus (specifically P. lilacinus strain 251 (AGAL 89/030550)), Talaromyces flavus (specifically strain V117b), Trichoderma atroviride (specifically strain SC1) (Accession number CBS 122089)), Trichoderma harzianum (specifically, T. harzianum rifai T39 (accession number CNCM I-952)).

用作或可用作生物殺有害生物劑之病毒之實例係：茶姬捲葉蛾(蘋果捲葉蟲)顆粒增殖病毒(granulosis virus，GV)、蘋果蠹蛾(蘋果捲葉蛾(codling moth))顆粒增殖病毒(GV)、番茄夜蛾(棉鈴蟲)核多角體病毒(NPV)、甜菜灰翅夜蛾(甜菜夜盜蛾)mNPV、草地灰翅夜蛾(秋季夜盜蛾)mNPV、海灰翅夜蛾(Spodoptera littoralis)(非洲棉葉蟲(African cotton leafworm))NPV。 Examples of viruses used as or useful as biocide pesticides: granulosis virus (GV), codling moth, and granulocyte-proliferating virus (GV), tomato night moth (H. armigera) nuclear polyhedrosis virus (NPV), beet genus Spodoptera moth (Beet larvae) mNPV, genus Spodoptera litura (autumn night larvae) mNPV, sea worm (Spodoptera littoralis) (African cotton leafworm) NPV.

亦包括作為「接種劑」添加至植物或植物部分或植物器官之細菌及真菌，且該等憑藉其具體性質促進植物生長及植物健康。可提及之實例係：農桿菌屬(Agrobacterium spp.)、莖瘤固氮根瘤菌(Azorhizobium caulinodans)、固氮螺菌屬(Azospirillum spp.)、固氮菌屬(Azotobacter spp.)、慢生根瘤菌屬(Bradyrhizobium spp.)、伯克氏菌屬(Burkholderia spp.)、(尤其洋蔥伯克氏菌(Burkholderia cepacia)(先前稱為洋蔥假單胞菌(Pseudomonas cepacia))、巨孢囊黴屬(Gigaspora spp.)或單孢巨孢囊黴、球囊黴屬(Glomus spp.)、蠟蘑屬(Laccaria spp.)、布氏乳酸桿菌(Lactobacillus buchneri)、類球囊黴屬(Paraglomus spp.)、豆包菌(Pisolithus tinctorus)、假單胞菌屬(Pseudomonas spp.)、根瘤菌屬(Rhizobium spp.)(尤其三葉草根瘤菌(Rhizobium trifolii)、須腹菌屬 (Rhizopogon spp.)、硬皮馬勃屬(Scleroderma spp.)、乳牛桿菌屬(Suillus spp.)、鏈黴菌屬(Streptomyces spp.)。 Also included are bacteria and fungi that are added as "inoculation agents" to plants or plant parts or plant organs, and which promote plant growth and plant health by virtue of their specific properties. Examples which may be mentioned are: Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Rhizobium sp. (Bradyrhizobium spp.), Burkholderia spp., (especially Burkholderia cepacia (formerly known as Pseudomonas cepacia), genus genus Gigaspora Spp.) or S. monocytogenes, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp. Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp. (especially Rhizobium trifolii, S. bisporus) (Rhizopogon spp.), Scleroderma spp., Suillus spp., Streptomyces spp.

用作或可用作生物殺有害生物劑之植物提取物及由微生物形成之產物(包括蛋白質及次級代謝物)之實例係：大蒜(Allium sativum)、苦艾(Artemisia absinthium)、印楝素、生物保護劑WP(Biokeeper WP)、肉桂(Cassia nigricans)、苦皮藤(Celastrus angulatus)、驅蟲藜(Chenopodium anthelminticum)、幾丁質、Armour-Zen、歐洲鱗毛蕨(Dryopteris filix-mas)、問荊(Equisetum arvense)、Fortune Aza、真菌停(Fungastop)、Heads Up(美國野藜皂素提取物(Chenopodium quinoa saponin extract))、除蟲菊/除蟲菊素、苦木類(Quassia amara)、櫟屬(Quercus)、皂皮樹(Quillaja)、Regalia、「Requiem ^TM殺昆蟲劑」、魚藤酮、尼亞那/蘭尼鹼(ryania/ryanodine)、聚合草(Symphytum officinale)、菊蒿(Tanacetum vulgare)、瑞香草酚、Triact 70、TriCon、旱金蓮(Tropaeulum majus)、異株蕁麻(Urtica dioica)、藜蘆鹼(Veratrin)、槲寄生(Viscum album)、十字花科提取物(Brassicaceae extract)，尤其油菜籽粉末或芥菜粉末。 Examples of plant extracts and products formed by microorganisms (including proteins and secondary metabolites) used as or as biocides: garlic (Allium sativum), Artemisia absinthium, azadirachtin , Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, Chitin, Armour-Zen, Dryopteris filix-mas Equisetum arvense, Fortune Aza, Fungastop, Heads Up (Chenopodium quinoa saponin extract), pyrethrum/pyrethroid, bitter wood (Quassia amara) ), Quercus, Quillaja, Regalia, Requiem ^TM insecticide, rotenone, ryania/ryanodine, Symphytum officinale, Artemisia Tanacetum vulgare), thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae extract ), especially rapeseed Powder or mustard powder.

安全劑作為混合組份 Safener as a mixed component

式(I)化合物可與安全劑組合，例如解草酮(benoxacor)、解草酯(cloquintocet)(-mexyl)、解草胺腈(cyometrinil)、環丙磺醯胺(cyprosulfamide)、二氯丙烯胺(dichlormid)、解草唑(fenchlorazole)(-乙基))、解草啶(fenclorim)、解草胺(flurazole)、氟草肟(fluxofenim)、解草噁唑(furilazole)、雙苯噁唑酸(isoxadifen)(-乙基)、吡唑解草酸(mefenpyr)(-二乙基)、萘二甲酸酐、解草腈(oxabetrinil)、(2-甲氧基-N-({4-[(甲基胺甲醯基)胺基]苯基}磺醯基)苯醯胺(CAS 129531-12-0)、4-(二氯乙醯基)-1-氧雜-4-氮雜螺[4.5]癸烷(CAS 71526-07-3)、2,2,5-三 甲基-3-(二氯乙醯基)-1,3-噁唑啶(CAS 52836-31-4)。 The compound of formula (I) may be combined with a safener such as benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichloropropene Dichlormid, fenchlorazole (-ethyl), fenclorim, flurazole, fluxofenim, furilazole, bisbenzoquinone Isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, (2-methoxy-N-({4- [(Methylamine-mercapto)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroethenyl)-1-oxa-4-aza Snail [4.5] decane (CAS 71526-07-3), 2, 2, 5-three Methyl-3-(dichloroacetamido)-1,3-oxazolidine (CAS 52836-31-4).

植物及植物部分 Plant and plant parts

所有植物及植物部分皆可根據本發明來處理。植物在本文中應理解為意指所有植物及植物群體，例如合意及不合意之野生植物或農作物(包括天然農作物)，例如穀類(小麥、稻米、黑小麥、大麥、黑麥、燕麥)、玉米、大豆、馬鈴薯、糖用甜菜、甘蔗、番茄、豌豆及其他植物物種，棉花、菸草、油菜籽亦及水果植物(具有水果蘋果、梨、柑橘類水果及葡萄)。農作物可為可藉由習用育種及最佳化方法或藉由生物技術及遺傳改造方法或該等方法之組合獲得之植物，包括轉基因植物且包括受植物育種者權利(plant breeders' rights)保護或不受其保護之植物栽培品種。植物部分應理解為意指植物之所有地上及地下部分及器官，例如枝、葉、花及根，可給出之實例係葉、針葉、莖稈、莖、花、子實體、果實及種子，亦及根、塊莖及根莖。植物部分亦包括所收穫材料及營養性及生殖性繁殖材料，例如插枝、塊莖、根莖、插條及種子。 All plants and plant parts can be treated in accordance with the present invention. A plant is understood herein to mean all plants and plant populations, such as desirable and undesired wild plants or crops (including natural crops) such as cereals (wheat, rice, triticale, barley, rye, oats), corn. , soybeans, potatoes, sugar beets, sugar cane, tomatoes, peas and other plant species, cotton, tobacco, rapeseed and fruit plants (with fruit apples, pears, citrus fruits and grapes). The crop may be a plant obtainable by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or a combination of such methods, including transgenic plants and including protection by plant breeders' rights or Plant cultivars that are not protected by them. Plant parts are understood to mean all above-ground and underground parts and organs of plants, such as branches, leaves, flowers and roots, examples of which can be given, leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds. , as well as roots, tubers and rhizomes. The plant part also includes harvested materials and nutritive and reproductive reproductive material such as cuttings, tubers, rhizomes, cuttings and seeds.

利用式(I)化合物對植物及植物部分之本發明處理係直接實現或藉由常用處理方法使該等化合物作用於該等植物及植物部分之環境、生境或儲存空間來實現，例如藉由浸漬、噴霧、蒸發、彌霧、分散、塗抹、注射及在繁殖材料之情形下、尤其在種子之情形下亦藉由施加一或多個包衣來實現。 The treatment of the plants of the plants and plant parts by the use of the compounds of the formula (I) is effected directly or by means of conventional treatments which act on the environment, habitat or storage space of the plants and plant parts, for example by impregnation Spraying, evaporating, misting, dispersing, smearing, injecting, and in the case of propagation materials, especially in the case of seeds, is also achieved by the application of one or more coatings.

如上文已提及，可根據本發明處理所有植物及其部分。在較佳實施例中，處理野生植物物種及植物栽培品種或彼等藉由習用生物育種方法(例如雜交育種或原生質體融合)獲得者及其部分。在另一較佳實施例中，處理藉由遺傳改造方法若適當與習用方法組合獲得之轉基因植物及植物栽培品種(遺傳修飾之有機體)及其部分。術語「部分」或「植物之部分」或「植物部分」已在上文解釋。根據本發明尤佳者 係處理各別商業上常用植物栽培品種的植物或彼等在使用者。植物栽培品種應理解為意指具有新的性質(「特質」)且已藉由習用育種、藉由突變誘發或藉由重組DNA技術生長之植物。其可為栽培品種、變種、生物型或基因型。 As already mentioned above, all plants and parts thereof can be treated in accordance with the invention. In a preferred embodiment, wild plant species and plant cultivars or their recipients and their parts are obtained by conventional biological breeding methods (e.g., cross breeding or protoplast fusion). In another preferred embodiment, the transgenic plants and plant cultivars (genetically modified organisms) and parts thereof obtained by genetic engineering methods, if appropriate in combination with conventional methods, are treated. The term "part" or "part of plant" or "plant part" has been explained above. Particularly preferred according to the invention It is a plant that treats plant cultivars that are commonly used commercially or on the user. Plant cultivars are understood to mean plants which have new properties ("traits") and which have been propagated by conventional breeding, by mutation induction or by recombinant DNA techniques. It can be a cultivar, a variety, a biotype or a genotype.

轉基因植物、種子處理及整合事件 Transgenic plants, seed treatment and integration events

欲根據本發明處理之較佳轉基因植物或植物栽培品種(彼等藉由遺傳改造獲得者)包括藉助遺傳修飾接受賦予該等植物尤其有利的有用性質(「特質」)之遺傳物質之所有植物。該等性質之實例係植物生長更好、對高溫或低溫之耐性有所提高、對乾旱或對水或土壤鹽度之耐性有所提高、開花性能有所增強、收穫較容易、成熟加速、收穫產量較高、品質較高及/或收穫產物之營養價值較高、儲存壽命及/或收穫產物之加工性較好。該等性質之其他及特別強調之實例係植物對動物及微生物有害生物(例如昆蟲、蛛形類、線蟲、蟎、蛞蝓及蝸牛)之抗性有所提高(歸因於(例如)在植物中形成之毒素、具體而言彼等在植物中藉由來自蘇雲金芽孢桿菌之遺傳物質(例如藉由基因CryIA(a)、CryIA(b)、CryIA(c)、CryIIA、CryIIIA、CryIIIB2、Cry9c、Cry2Ab、Cry3Bb及CryIF亦及其組合)形成者)，亦及植物對植物病原真菌、細菌及/或病毒之抗性有所提高(由(例如)系統獲得抗性(SAR)、系統素、植物防禦素、激發子及抗性基因及相應所表現蛋白質及毒素引起)，亦及植物對某些活性除草成分(例如咪唑啉酮、磺脲類藥、甘草膦(glyphosate)或草丁膦(phosphinothricin))之耐性有所提高(例如「PAT」基因)。賦予所述期望性質(「特質」)之基因亦可彼此組合存於轉基因植物中。轉基因植物之實例包括重要農作物，例如穀類(小麥、稻米、黑小麥、大麥、黑麥、燕麥)、玉米、大豆、馬鈴薯、糖用甜菜、甘蔗、番茄、豌豆及其他類型之蔬菜、棉花、菸草、油菜籽亦及水果植物(具有水果蘋果、梨、柑橘類水果及葡萄)，尤其強調玉 米、大豆、小麥、稻米、馬鈴薯、棉花、甘蔗、菸草及油菜籽。尤其強調之性質(「特質」)係植物對昆蟲、蛛形類、線蟲及蛞蝓及蝸牛之耐性有所提高。 Preferred transgenic plants or plant cultivars (which are obtained by genetic engineering) to be treated according to the invention include all plants which, by means of genetic modification, receive genetic material which confers a particularly advantageous useful property ("trait") to such plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or water or soil salinity, enhanced flowering performance, easier harvesting, accelerated acclimation, harvesting The higher yield, higher quality and/or higher nutritional value of the harvested product, better shelf life and/or harvested product are more processable. Other and particularly emphasized examples of these properties are plant resistance to animal and microbial pests such as insects, arachnids, nematodes, mites, mites and snails (due to, for example, in plants) The toxins formed, in particular, in plants, by genetic material from Bacillus thuringiensis (eg by genes CryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab , Cry3Bb and CryIF (and its combination)), as well as plant resistance to phytopathogenic fungi, bacteria and / or viruses (by (for example) systemic resistance (SAR), systemic, plant defense , elicitors and resistance genes and corresponding proteins and toxins), as well as certain active herbicidal components of plants (eg imidazolinones, sulfonylureas, glycphosate or phosphinothricin) ) The tolerance has improved (such as the "PAT" gene). The genes that confer the desired properties ("traits") can also be combined with each other in transgenic plants. Examples of transgenic plants include important crops such as cereals (wheat, rice, triticale, barley, rye, oats), corn, soybeans, potatoes, sugar beets, sugar cane, tomatoes, peas and other types of vegetables, cotton, tobacco , rapeseed and fruit plants (with fruit apples, pears, citrus fruits and grapes), with special emphasis on jade Rice, soybeans, wheat, rice, potatoes, cotton, sugar cane, tobacco and rapeseed. Particular emphasis on the nature ("traits") is the increased tolerance of plants to insects, arachnids, nematodes, and snails and snails.

農作物保護-處理類型 Crop protection - treatment type

利用式(I)化合物直接處理或藉由使用常用處理方法作用於其環境、生境或儲存空間處理植物及植物部分，例如藉由浸漬、噴霧、霧化、灌溉、蒸發、噴灑、彌霧、撒播、發泡、塗抹、撒布、注射、澆水(浸泡)、滴灌及在繁殖材料之情形下、具體而言在種子之情形下另外藉由乾燥種子處理、液體種子處理、漿液處理、藉由覆以皮、藉由利用一或多個包衣塗覆等進行處理。此外可藉由超低體積法或將施用形式或式(I)化合物本身注射至土壤中來施加式(I)化合物。 Treatment of plants and plant parts by direct treatment with compounds of formula (I) or by the use of common treatment methods in their environment, habitat or storage space, for example by dipping, spraying, atomizing, irrigating, evaporating, spraying, misting, spreading , foaming, smearing, spreading, injecting, watering (soaking), drip irrigation and in the case of propagation materials, in particular in the case of seeds, by dry seed treatment, liquid seed treatment, slurry treatment, by coating Treatment is carried out by skin, by coating with one or more coats, and the like. Further, the compound of the formula (I) can be applied by an ultra-low volume method or by injection of the compound or the compound of the formula (I) into the soil.

植物之較佳直接處理係葉面噴施，即將式(I)化合物施加至葉子，其中應根據感染程度以及所述有害生物調節處理頻率及施加率。 The preferred direct treatment of plants is foliar application, i.e., application of a compound of formula (I) to the leaves, wherein the frequency and rate of application should be adjusted depending on the degree of infection and the pest.

在全身活性化合物之情形下，式(I)化合物亦經由根系進入植物。然後藉由式(I)化合物對植物生境之作用處理植物。此可藉由(例如)浸泡或藉由混合至土壤或營養素溶液中來實現，意味著用式(I)化合物之液體形式浸滲植物所在地(例如土壤或水耕系統)，或藉由土壤施用來實現，意味著將式(I)化合物以固體形式(例如呈顆粒形式)引入植物所在地中。在稻穀農作物之情形下，此亦可藉由將式(I)化合物以固體施用形式(例如以顆粒形式)計量供給至冬水稻田中來實現。 In the case of a systemically active compound, the compound of formula (I) also enters the plant via the root system. The plants are then treated by the action of the compound of formula (I) on plant habitat. This can be achieved, for example, by soaking or by mixing into a soil or nutrient solution, meaning that the liquid form of the compound of formula (I) is impregnated with the plant site (eg soil or hydroponic system) or by soil application. By way of realization, it is meant that the compound of formula (I) is introduced into the plant locus in solid form, for example in the form of granules. In the case of rice crops, this can also be achieved by metering the compound of formula (I) in a solid form (for example in the form of granules) into a winter paddy field.

種子處理 Seed treatment

藉由處理植物之種子控制動物有害生物在很久以前即已為人所知且係不斷改良之主題。然而，種子之處理引起一系列問題，該等問題無法總是以令人滿意之方式得到解決。因此，期望研發在儲存期間、在播種之後或在植物萌芽之後免除或至少顯著地減少殺有害生物劑之另外施加用於保護種子及發芽植物之方法。另外期望最佳化所用 活性成分之量以便為種子及發芽植物提供免受動物有害生物侵襲之最佳保護，而所用活性成分不損害植物本身。具體而言，處理種子之方法亦應考慮抗有害生物或耐有害生物之轉基因植物之固有殺蟲或殺線蟲性質，以便在最少支出殺有害生物劑下達成對種子及發芽植物之最佳保護。 Controlling animal pests by treating plant seeds has been known for a long time and is the subject of continuous improvement. However, the handling of seeds causes a series of problems that cannot always be resolved in a satisfactory manner. Therefore, it is desirable to develop a method for protecting seed and germinating plants during storage, after sowing, or after germination of the plant, by additionally applying at least a significant reduction in the killing agent. Also expected to be optimized for use The amount of active ingredient is such that the seed and the germinating plant are provided with the best protection from attack by the animal pest, and the active ingredient used does not damage the plant itself. In particular, the method of treating seeds should also take into account the inherent insecticidal or nematicidal properties of transgenic plants that are resistant to pests or pests to achieve optimal protection of seeds and germinating plants with minimal expenditure on pesticides.

因此，本發明具體而言亦係關於藉由利用式(I)化合物中之一者處理種子來保護種子及發芽植物免受有害生物侵襲之方法。保護種子及發芽植物抵抗有害生物侵襲之本發明方法進一步包含利用式(I)化合物及混合組份在一個操作中同時或依序處理種子之方法。其進一步亦包含利用式(I)化合物及混合組份在不同時間處理種子之方法。 Accordingly, the present invention is also specifically directed to a method of protecting seed and germinating plants from pests by treating the seed with one of the compounds of formula (I). The method of the invention for protecting seed and germinating plants against pest infestation further comprises the method of simultaneously or sequentially treating the seed in one operation using the compound of formula (I) and the mixed component. It further comprises a method of treating the seed at different times using the compound of formula (I) and the mixed component.

本發明同樣係關於式(I)化合物之用途，其用於處理種子以保護種子及所得植物免受動物有害生物。 The invention likewise relates to the use of a compound of formula (I) for treating seed to protect the seed and the resulting plant from animal pests.

本發明進一步係關於已利用式(I)化合物進行處理以保護免受動物有害生物之種子。本發明亦係關於已利用式(I)化合物及混合組份同時處理之種子。本發明進一步係關於已利用式(I)化合物及混合組份在不同時間處理之種子。在已利用式(I)化合物及混合組份在不同時間處理之種子之情形下，個別物質可在不同層中存於種子上。在此情形下，包含式(I)化合物及混合組份之層可視情況由中間體層分離。本發明亦係關於其中已將式(I)化合物及混合組份作為包衣之一部分或作為除包衣以外之另一層或其他層施加之種子。 The invention further relates to seeds which have been treated with a compound of formula (I) to protect against animal pests. The invention also relates to seeds which have been treated simultaneously with the compound of formula (I) and the mixed components. The invention further relates to seeds which have been treated with the compound of formula (I) and the mixed components at different times. In the case where the compound of formula (I) and the mixed component are treated at different times, individual substances may be present on the seed in different layers. In this case, the layer comprising the compound of the formula (I) and the mixed component may optionally be separated from the intermediate layer. The invention is also directed to seeds in which the compound of formula (I) and the mixed component have been applied as part of the coating or as another layer or layer other than the coating.

本發明進一步係關於在利用式(I)化合物處理後經受膜包覆製程以防止種子上粉塵磨損之種子。 The invention further relates to seeds which are subjected to a film coating process after treatment with a compound of formula (I) to prevent dust abrasion on the seed.

全身作用型式(I)化合物所遇到之一個優點在於以下事實：藉由處理種子，不僅可保護種子本身亦及萌芽之後自該種子產生之植物抵抗動物有害生物。以此方式，可免除在播種時或在此後不久立即處理農作物。 One of the advantages encountered by the systemic action of the compound of formula (I) lies in the fact that by treating the seed, not only the seed itself but also the plant produced from the seed after germination is resistant to animal pests. In this way, it is possible to dispense with the treatment of crops at the time of sowing or shortly thereafter.

另一優點係利用式(I)化合物處理種子可增強經處理種子之發芽及萌芽。 Another advantage is that treatment of the seed with a compound of formula (I) enhances germination and germination of the treated seed.

同樣被認為有利的是式(I)化合物尤其亦可用於轉基因種子。 It is also considered to be advantageous that the compounds of the formula (I) are especially useful for transgenic seeds.

此外，式(I)化合物可與信號傳導技術之組合物組合使用，從而引起共生生物(例如，根瘤菌、菌根及/或內寄生細菌或真菌)之較好定殖，及/或最佳化固氮作用。 Furthermore, the compounds of formula (I) can be used in combination with a combination of signaling techniques to cause better colonization of symbiotic organisms (eg, rhizobium, mycorrhiza and/or endoparasite bacteria or fungi), and/or optimal Nitrogen fixation.

式(I)化合物適於保護用於農業、溫室、林業或園藝中之任一植物變種之種子。更具體而言，此包括以下各項之種子：穀類(例如小麥、大麥、黑麥、小米及燕麥)、玉米、棉花、大豆、稻米、馬鈴薯、向日葵、咖啡、菸草、油菜、油菜籽、甜菜(例如糖用甜菜及飼用甜菜)、花生、蔬菜(例如番茄、黃瓜、菜豆、十字花科蔬菜、洋蔥及萵苣)、水果植物、草坪植物及觀賞植物。處理穀類(例如小麥、大麥、黑麥及燕麥)、玉米、大豆、棉花、油菜、油菜籽及稻米之種子尤其有意義。 The compounds of formula (I) are suitable for the protection of seeds for use in any of the plant varieties of agriculture, greenhouse, forestry or horticulture. More specifically, this includes seeds of: cereals (eg, wheat, barley, rye, millet, and oats), corn, cotton, soybeans, rice, potatoes, sunflowers, coffee, tobacco, canola, rapeseed, beets (such as sugar beet and beet), peanuts, vegetables (such as tomatoes, cucumbers, kidney beans, cruciferous vegetables, onions and lettuce), fruit plants, lawn plants and ornamental plants. It is especially useful to treat cereals such as wheat, barley, rye and oats, corn, soybeans, cotton, canola, rapeseed and rice seeds.

如上文已提及，利用式(I)化合物處理轉基因種子亦尤其重要。此涉及通常含有至少一個異源基因之植物之種子，該基因控制具體而言具有殺蟲及/或殺線蟲性質之多肽之表現。轉基因種子中之異源基因在此情形下可源於諸如芽孢桿菌屬、根瘤菌屬、假單胞菌屬、沙雷氏菌屬(Serratia)、木黴屬、棍狀桿菌屬(Clavibacter)、球囊黴屬或黏帚黴屬(Gliocladium)等微生物。本發明尤其適於處理包含至少一個源自芽孢桿菌屬之異源基因之轉基因種子。異源基因更佳地源於蘇雲金芽孢桿菌。 As already mentioned above, the treatment of transgenic seeds with a compound of formula (I) is also of particular importance. This relates to the seed of a plant which usually contains at least one heterologous gene which controls the expression of a polypeptide which in particular has insecticidal and/or nematicidal properties. The heterologous gene in the transgenic seed may in this case be derived from, for example, Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Microorganisms such as the genus Glomus or Gliocladium. The invention is particularly suitable for treating transgenic seeds comprising at least one heterologous gene derived from Bacillus. The heterologous gene is better derived from Bacillus thuringiensis.

在本發明背景下，將式(I)化合物施加至種子。較佳地將種子處理成足夠穩定的在處理過程中不出現損害之狀態。一般而言，可在收穫與播種之間之任一時間處理種子。照慣例使用已自植物分離且不含穗軸、殼、莖稈、包衣、茸毛或水果果肉之種子。例如，可使用已經 收穫、清潔及乾燥至容許儲存之水分含量之種子。另一選擇為，亦可使用在乾燥之後經(例如)水處理且然後再次乾燥(例如萌調處理(priming))之種子。在稻米種子之情形下，亦可使用例如已在水中預膨脹至某一狀態(雞胸狀態)之種子，此可引起改良之發芽及較均勻萌芽。 In the context of the present invention, a compound of formula (I) is applied to the seed. The seed is preferably treated to a state that is sufficiently stable that no damage occurs during processing. In general, the seed can be treated at any time between harvesting and sowing. Seeds that have been isolated from plants and that do not contain cobs, shells, stalks, coatings, velvet or fruit flesh are conventionally used. For example, you can use already Seeds that are harvested, cleaned and dried to a moisture content that allows for storage. Alternatively, seeds that are treated, for example, with water after drying and then dried again (e.g., priming) may also be used. In the case of rice seeds, for example, seeds which have been pre-expanded in water to a certain state (chicken chest state) may be used, which may result in improved germination and more uniform germination.

當處理種子時，必須通常注意選擇施加至種子之式(I)化合物之量及/或其他添加劑之量以使得不會不利地影響種子之發芽或不會損害所得植物。具體而言在某些施加率下可展現植物性毒素效應之活性成分之情形下，此必須得到保證。 When treating seeds, it is generally necessary to pay attention to the amount of the compound of formula (I) applied to the seed and/or the amount of other additives so as not to adversely affect the germination of the seed or damage the resulting plant. In particular, in the case of active ingredients which exhibit a phytotoxic effect at certain application rates, this must be ensured.

一般而言，將式(I)化合物以適宜調配物之形式施加至種子。熟習此項技術者熟知用於種子處理之適宜調配物及過程。 In general, the compound of formula (I) is applied to the seed in the form of a suitable formulation. Suitable formulations and processes for seed treatment are well known to those skilled in the art.

可將式(I)化合物轉化為常用拌種調配物，例如溶液、乳液、懸浮液、粉末、泡沫狀物、漿液或用於種子之其他塗覆組合物，亦及ULV調配物。 The compound of formula (I) can be converted to conventional seed dressing formulations such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seeding, as well as ULV formulations.

該等調配物係以已知方式藉由混合式(I)化合物與常用添加劑(例如常用增量劑)亦及溶劑或稀釋劑、染料、潤濕劑、分散劑、乳化劑、防沫劑、防腐劑、輔助增稠劑(secondary thickener)、黏著劑、赤黴素(gibberellin)亦及水來製備。 These formulations are prepared by mixing the compound of formula (I) with conventional additives (such as conventional extenders) and solvents or diluents, dyes, wetting agents, dispersing agents, emulsifiers, antifoaming agents, Preservatives, secondary thickeners, adhesives, gibberellin, and water are also prepared.

可存於可根據本發明使用之拌種調配物中之染料係常用於該等目的之所有染料。可使用微溶於水中之顏料或溶於水中之染料。實例包括以名稱玫瑰紅B(Rhodamine B)、C.I.顏料紅112及C.I.溶劑紅1已知之染料。 Dyes which may be present in the seed dressing formulations which may be used in accordance with the invention are all dyes which are commonly used for such purposes. A pigment slightly soluble in water or a dye dissolved in water can be used. Examples include dyes known under the names Rhodamine B, C.I. Pigment Red 112, and C.I. Solvent Red 1.

可存於可根據本發明使用之拌種調配物中之有用潤濕劑係促進潤濕且通常用於活性農用化學品成分之調配物之所有物質。較佳可使用烷基萘磺酸酯，例如萘磺酸二異丙基酯或萘磺酸二異丁基酯。 Useful wetting agents which may be present in the seed dressing formulations which may be used in accordance with the invention are all materials which promote wetting and are generally used in the formulation of active agrochemical ingredients. Preferably, an alkylnaphthalenesulfonate such as diisopropyl naphthalenesulfonate or diisobutylene naphthalate is used.

可存於可根據本發明使用之拌種調配物中之適宜分散劑及/或乳 化劑係常用於活性農用化學品成分之調配物之所有非離子、陰離子及陽離子分散劑。較佳可使用非離子或陰離子分散劑或非離子或陰離子分散劑之混合物。適宜非離子分散劑具體而言包括環氧乙烷/環氧丙烷嵌段聚合物、烷基酚聚二醇醚及三苯乙烯基苯酚聚二醇醚及其磷酸酯化或硫酸酯化衍生物。適宜陰離子分散劑尤其係木質素磺酸鹽、聚丙烯酸鹽及芳基磺酸鹽-甲醛縮合物。 Suitable dispersing agents and/or milk which can be present in the seed dressing formulations which can be used according to the invention The agent is commonly used in all nonionic, anionic and cationic dispersants of formulations of active agrochemical ingredients. It is preferred to use a nonionic or anionic dispersant or a mixture of nonionic or anionic dispersants. Suitable nonionic dispersants include, in particular, ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers and their phosphated or sulfated derivatives . Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylates and arylsulfonate-formaldehyde condensates.

可存於可根據本發明使用之拌種調配物中之防沫劑係常用於活性農用化學品成分之調配物之所有泡沫抑制物質。較佳可使用聚矽氧防沫劑及硬脂酸鎂。 Antifoams which may be present in the seed dressing formulations which can be used in accordance with the invention are all suds suppressing substances which are commonly used in the formulation of active agrochemical ingredients. Preferably, a polyoxyn antifoaming agent and magnesium stearate can be used.

可存於可根據本發明使用之拌種調配物中之防腐劑係可出於該等目的在農用化學品組合物中使用之所有物質。實例包括雙氯酚(dichlorophene)及苄基醇半縮甲醛。 Preservatives which may be present in the seed dressing formulations which can be used in accordance with the invention are all materials which can be used in agrochemical compositions for such purposes. Examples include dichlorophene and benzyl alcohol hemiformal.

可存於可根據本發明使用之拌種調配物中之輔助增稠劑係可出於該等目的在農用化學品組合物中使用之所有物質。較佳實例包括纖維素衍生物、丙烯酸衍生物、黃原膠、經改質黏土及細粒二氧化矽。 Auxiliary thickeners which may be present in the seed dressing formulations which can be used in accordance with the invention are all materials which can be used in agrochemical compositions for such purposes. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan gum, modified clay, and fine-grained cerium oxide.

可存於可根據本發明使用之拌種調配物中之有用黏著劑係可在拌種產品中使用之所有常用結合劑。較佳實例包括聚乙烯吡咯啶酮、聚乙酸乙烯酯、聚乙烯醇及填充體。 Useful adhesives which can be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, and fillers.

可存於可根據本發明使用之拌種調配物中之赤黴素較佳地係赤黴素A1、A3(=赤黴酸)、A4及A7；尤佳者係使用赤黴酸。赤黴素已為人所知(參見R.Wegler「Chemie der Pflanzenschutz-und Schädlingsbekämpfungsmittel」[Chemistry of Crop Protection and Pest Control Compositions]，第2卷，Springer Verlag,1970，第401頁至第412頁)。 The gibberellins which may be present in the seed dressing formulations which can be used according to the invention are preferably gibberellins A1, A3 (=gibberellic acid), A4 and A7; particularly preferred are gibberellic acid. Gibberellin is known (see R. Wegler "Chemie der Pflanzenschutz-und Schädlings bekämpfungsmittel" [Chemistry of Crop Protection and Pest Control Compositions], Vol. 2, Springer Verlag, 1970, pages 401 to 412).

可使用可根據本發明使用之拌種調配物直接處理或在提前用水稀釋之後處理眾多種不同種類之種子。例如，可使用濃縮物或可藉由 用水稀釋自其獲得之製劑拌製穀類(例如小麥、大麥、黑麥、燕麥及黑小麥)之種子亦及玉米、稻米、油菜籽、豌豆、菜豆、棉花、向日葵、大豆及甜菜之種子或眾多種不同的植物種子。亦可使用可根據本發明使用之拌種調配物或其稀釋使用形式拌製轉基因植物之種子。 A wide variety of different types of seeds can be treated directly with the seed dressing formulations which can be used in accordance with the invention or after dilution with water in advance. For example, a concentrate can be used or can be used Seeds of cereals (such as wheat, barley, rye, oats and triticale) mixed with water, and seeds of corn, rice, rapeseed, peas, kidney beans, cotton, sunflower, soybeans and beets or many Different plant seeds. Seeds of the transgenic plants may also be mixed using the seed dressing formulations which may be used in accordance with the invention or their diluted use forms.

對於利用可根據本發明使用之拌種調配物或自其製備之使用形式對種子之處理，照慣例可用於拌種之所有混合單元皆可使用。特定而言，拌種之程序為將種子以分批或連續操作置於混合器中，以按原樣或在提前用水稀釋之後添加特別期望量之拌種調配物，並加以混合直至調配物均勻分佈於種子上為止。若適當，此後進行乾燥操作。 For the treatment of seeds with a seed dressing formulation which can be used according to the invention or from the form in which it is prepared, it is customary to use all mixing units which can be used for seed dressing. In particular, the seed dressing procedure is to place the seed in a mixer in batch or continuous operation to add a particular desired amount of the seed dressing formulation as it is or after dilution with water in advance, and mix until the formulation is evenly distributed. On the seed. If appropriate, then dry the operation.

可根據本發明使用之拌種調配物之施加率可在相對寬的範圍內變化。其係由調配物中式(I)化合物之特定含量及由種子指導。式(I)化合物之施加率通常在0.001g/公斤種子與50g/公斤種子之間，較佳地在0.01g/公斤種子與15g/公斤種子之間。 The rate of application of the seed dressing formulations which can be used in accordance with the invention can vary over a relatively wide range. It is based on the specific content of the compound of formula (I) in the formulation and is directed by the seed. The rate of application of the compound of formula (I) is generally between 0.001 g/kg of seed and 50 g/kg of seed, preferably between 0.01 g/kg of seed and 15 g/kg of seed.

動物健康 Animal health

在動物健康領域(即獸醫學之領域)中，式(I)化合物對動物寄生蟲、特別是外寄生蟲或內寄生蟲具有活性。術語「內寄生蟲」尤其包括蠕蟲及原生動物，諸如球蟲目。外寄生蟲通常且較佳地為節肢動物，尤其昆蟲及蟎。 In the field of animal health (i.e. the field of veterinary medicine), the compounds of formula (I) are active against animal parasites, in particular ectoparasites or endoparasites. The term "endoparasite" includes, inter alia, helminths and protozoa, such as coccidia. The ectoparasites are usually and preferably arthropods, especially insects and mites.

在獸醫學之領域中，具有有利恆溫動物毒性之式(I)化合物適於控制發生在牲畜動物育種及畜牧業、育種動物、動物園動物、實驗室動物、實驗動物及家畜中之寄生蟲。該等化合物對寄生蟲發育之所有或特定階段具有活性。 In the field of veterinary medicine, the compounds of formula (I) having an advantageous thermostat animal toxicity are suitable for controlling parasites occurring in livestock breeding and animal husbandry, breeding animals, zoo animals, laboratory animals, laboratory animals and domestic animals. These compounds are active at all or specific stages of parasite development.

農業牲畜包括例如哺乳動物，諸如綿羊、山羊、馬、驢、駱駝、水牛、兔、馴鹿(reindeer)、黇鹿(fallow deer)，及特別是牛及豬；家禽，諸如火雞、鴨、鵝，及特別是雞；魚及甲殼動物，例如在水產養殖中；亦及昆蟲(諸如蜜蜂)。 Agricultural livestock include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffaloes, rabbits, reindeers, fallows, and especially cattle and pigs; poultry such as turkeys, ducks, geese And especially chickens; fish and crustaceans, for example in aquaculture; and insects (such as bees).

家畜包括例如哺乳動物，諸如倉鼠、天竺鼠、大鼠、小鼠、絨鼠(chinchillas)、雪貂(ferrets)，及特別是狗、貓，籠中鳥、爬蟲類、兩棲動物及觀賞魚。 Livestock include, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets, and especially dogs, cats, caged birds, reptiles, amphibians, and ornamental fish.

在一個較佳實施例中，將式(I)化合物投與哺乳動物。 In a preferred embodiment, the compound of formula (I) is administered to a mammal.

在另一較佳實施例中，將式(I)化合物投與鳥(即籠中鳥)，及特別是家禽。 In another preferred embodiment, the compound of formula (I) is administered to birds (i.e., cage birds), and particularly poultry.

使用式(I)化合物控制動物寄生蟲意欲減少或預防疾病、死亡病例及性能降低(在肉、乳、羊毛、皮、蛋、蜂蜜及諸如此類之情形)，以使得畜牧業能夠更經濟且更簡單及可達成更好的動物福祉。 The use of a compound of formula (I) to control animal parasites is intended to reduce or prevent disease, death, and performance degradation (in the case of meat, milk, wool, hide, egg, honey, and the like) to make the livestock industry more economical and simpler. And can achieve better animal welfare.

關於動物健康之領域，術語「控制(control或controlling)」意指式(I)化合物可使感染特定寄生蟲之動物中該等寄生蟲之發生率有效降低至無害程度。更特定而言，「控制(controlling)」在本發明中意指式(I)化合物可殺死各別寄生蟲，抑制其生長或抑制其增殖。 With respect to the field of animal health, the term "control or control" means that the compound of formula (I) can effectively reduce the incidence of such parasites in an animal infected with a particular parasite to an innocuous extent. More specifically, "controlling" in the present invention means that the compound of formula (I) kills individual parasites, inhibits their growth or inhibits their proliferation.

節肢動物包括：來自虱目(Anoplurida)之節肢動物，例如血虱屬、長齶虱屬、虱蝨屬、陰虱屬(Phtirus spp.)、管虱屬(Solenopotes spp.)；來自食毛目(Mallophagida)及亞目鈍角亞目(Amblycerina)及細角亞目(Ischnocerina)之節肢動物，例如毛羽虱屬(Trimenopon spp.)、禽羽虱屬(Menopon spp.)、巨毛屬(Trinoton spp.)、牛虱屬(Bovicola spp.)、韋耐虱屬(Werneckiella spp.)、萊皮虱屬(Lepikentron spp.)、畜虱屬(Damalina spp.)、毛虱屬、貓虱屬(Felicola spp.)；來自雙翅目及亞目長角亞目(Nematocerina)及短角亞目(Brachycerina)之節肢動物，例如斑蚊屬、瘧蚊屬、家蚊屬、蚋屬、真蚋亞屬(Eusimulium spp.)、白蛉屬、羅嶺屬(Lutzomyia spp.)、糠蚊屬、斑虻屬、短蚋亞屬(Odagmia spp.)、維蚋屬(Wilhelmia spp.)、瘤虻屬(Hybomitra spp.)、黃虻屬(Atylotus spp.)、牛虻屬、斑蛀屬、非嶺屬(Philipomyia spp.)、蜂虱蠅 屬(Braula spp.)、家蠅屬(Musca spp.)、齒股蠅屬(Hydrotaea spp.)、刺蠅屬、黑角蠅屬(Haematobia spp.)、莫蠅屬(Morellia spp.)、廁蠅屬、採採蠅屬、麗蠅屬(Calliphora spp.)、綠蠅屬(Lucilia spp.)、金蠅屬(Chrysomyia spp.)、污蠅屬(Wohlfahrtia spp.)、麻蠅屬(Sarcophaga spp.)、狂蠅屬(Oestrus spp.)、牛蠅屬、馬蠅屬、虱蠅屬(Hippobosca spp.)、羊虱蠅屬(Lipoptena spp.)、蜱蠅屬(Melophagus spp.)、鼻狂蠅屬(Rhinoestrus spp.)、大蚊屬；來自蚤目(Siphonapterida)之節肢動物，例如蚤屬(Pulex spp.)、櫛頭蚤屬、潛蚤屬(Tunga spp.)、客蚤屬(Xenopsylla spp.)、鼠蚤屬(Ceratophyllus spp.)；來自異翅目(Heteropterida)之節肢動物，例如臭蟲屬、錐獵蝽屬、紅獵蝽屬、錐蝽屬(Panstrongylus spp.)；亦及來自蜚蠊目(Blattarida)之騷擾性有害生物及衛生有害生物。 Arthropods include: arthropods from the order Anoplurida, such as the genus Heliconia, the genus Eucalyptus, the genus, the genus Phtirus spp., and the genus Solenopotes spp. (Mallophagida) and arthropods of the Ambrycerina and Ischnocerina, such as Trimenopon spp., Menopon spp., Trinoton spp .), Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Ranunculus, Fruccola spp .); arthropods from the order of the Diptera and the suborders Nematocerina and Brachycerina, such as the genus Aedes, the genus Anopheles, the genus Mosquito, the genus genus, and the genus Eusimulium spp.), Amaranthus, Lutzomyia spp., Aphis, Aphis, Odagmia spp., Wilhelmia spp., Hybomitra Spp.), Atylotus spp., Burdock, Veratonia, Philipomyia spp., Beefly Braula spp., Musca spp., Hydrotaea spp., Trichidae, Haematobia spp., Morellia spp., toilet Musca, T. genus, Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp. ), Oestrus spp., Bovidus, Drosophila, Hippotosca spp., Lipoptena spp., Melophagus spp., nose flies Rhinoestrus spp., Aphis genus; Arthropods from Siphonapterida, such as Pulex spp., T. genus, Tunga spp., Xenopsylla spp .), Ceratophyllus spp.; arthropods from Heteropterida, such as the genus Bug, the genus Panthera, the genus Panstrongylus spp.; Harassing pests and health pests of Blattarida.

節肢動物進一步包括：來自蟎蜱目(Acari、Acarina)亞綱及後氣門目(Metastigmata)之節肢動物，例如來自隱喙蜱科(Argasidae)之節肢動物，如銳緣壁蝨屬、鳥壁蝨屬、耳蜱屬(Otobius spp.)，來自硬蜱科(Ixodidae)之節肢動物，如真壁蝨屬、大壁蝨屬、扇頭壁蝨屬(牛尾壁蝨屬)、矩頭壁蝨屬、血蝶屬(Haemophysalis spp.)、長鬚壁蝨屬、扇頭壁蝨屬(多宿主蜱之原屬)；來自中氣門亞目(Mesostigmata)之節肢動物，如皮刺蟎屬(Dermanyssus spp.)、禽刺蟎屬、肺刺蟎屬(Pneumonyssus spp.)、刺利蟎屬(Raillietia spp.)、肺刺蟎屬、胸孔蟎屬(Sternostoma spp.)、瓦蟎屬(Varroa spp.)、蜂盾蟎屬(Acarapis spp.)；來自輻蟎目(Actinedida)(前氣門目(Prostigmata))之節肢動物，例如蜂盾蟎屬、姬螯蟎屬(Cheyletiella spp.)、禽螯蟎屬(Ornithocheyletia spp.)、肉蟎屬(Myobia spp.)、瘡蟎屬(Psorergates spp.)、蠕形蟎屬(Demodex spp.)、秋恙蟎屬(Trombicula spp.)、奈齪蟎屬(Neotrombiculla spp.)、囊凸犛蟎屬 (Listrophorus spp.)；及來自粉蟎亞目(Acaridida)(無氣門目(Astigmata))之節肢動物，例如粉蟎屬、食酪蟎屬(Tyrophagus spp.)、嗜木蟎屬(Caloglyphus spp.)、頸下蟎屬(Hypodectes spp.)、翅蟎屬(Pterolichus spp.)、癢蟎屬、足蟎屬、耳蟎屬(Otodectes spp.)、疥蟎屬、背肛蟎屬(Notoedres spp.)、膝蟎屬(Knemidocoptes spp.)、胞蟎屬(Cytodites spp.)、雞雛蟎屬(Laminosioptes spp)。 Arthropods further include: arthropods from the suborders of Acari, Acarina, and Metastigmata, such as arthropods from the family Argaidae, such as the genus Amaranthus, the genus Aphis, Otobius spp., an arthropod from the genus Ixodidae, such as the genus Aphididae, the genus Aphididae, the genus Aphididae, the genus Aphis genus, the genus Aphis, the genus Haemophysalis spp .), A. genus, Aphis genus (original genus of multi-hosted genus); Arthropods from Mesostigmata, such as Dermanyssus spp., Astragalus, lung Pneumonyssus spp., Raillietia spp., P. striata, Sternostoma spp., Varroa spp., Acarapis spp .); Arthropods from Actinedida (Prostigmata), such as the genus Beetle, the genus Cheyletiella spp., Ornithocheyletia spp., meat mites Genobia spp., Psorergates spp., Demodex spp., Trimculcula spp. ), Neotrombiculla spp., genus (Listrophorus spp.); and arthropods from Acaridida (Astigmata), such as the genus Tyrolium, Tyrophagus spp., Caloglyphus spp. ), Hypodectes spp., Pterolichus spp., Itchy, Angustifolia, Otodectes spp., Aphis genus, Notoedres spp. ), Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

寄生性原生動物包括：鞭毛蟲綱(Mastigophora、Flagellata)，例如錐蟲科(Trypanosomatidae)，例如布氏錐蟲(Trypanosoma b.brucei)、布氏岡比亞錐蟲(T.b.gambiense)、布氏羅得西亞錐蟲(T.b.rhodesiense)、剛果錐蟲(T.congolense)、克氏錐蟲(T.cruzi)、伊氏錐蟲(T.evansi)、馬媾疫錐蟲(T.equinum)、路易氏錐蟲(T.lewisi)、坡氏錐蟲(T.percae)、猿猴錐蟲(T.simiae)、活動錐蟲(T.vivax)、巴西利什曼原蟲(Leishmania brasiliensis)、黑熱病利什曼原蟲(L.donovani)、熱帶利什曼原蟲(L.tropica)，例如毛滴蟲科(Trichomonadidae)，例如蘭伯氏賈第蟲(Giardia lamblia)、犬賈第蟲(G.canis)；肉鞭動物亞門(Sarcomastigophora)(根足蟲綱(Rhizopoda))，例如阿米巴目(Entamoebidae)，例如溶組織內阿米巴(Entamoeba histolytica)、哈氏蟲考牛(Hartmanellidae)，例如棘阿米巴屬(Acanthamoeba sp.)、哈氏蟲屬(Harmanella sp.)；頂複合器蟲(Apicomplexa)(孢子蟲綱(Sporozoa))，例如艾美耳球蟲科(Eimeridae)，例如堆型艾美耳球蟲(Eimeria acervulina)、腺型艾美耳球蟲(E.adenoides)、阿拉巴艾美耳球蟲(E.alabamensis)、鴨艾美耳球蟲(E.anatis)、鵝艾美耳球蟲(E.anserina)、阿爾氏艾美耳球蟲(E.arloingi)、阿沙塔艾美耳球蟲(E.ashata)、奧博艾美耳球蟲(E.auburnensis)、牛艾美耳球蟲(E.bovis)、布氏艾美耳球蟲(E. brunetti)、犬艾美耳球蟲(E.canis)、奇氏艾美耳球蟲(E.chinchillae)、魚艾美耳球蟲(E.clupearum)、鴿艾美耳球蟲(E.columbae)、可氏艾美耳球蟲(E.contorta)、克拉氏艾美耳球蟲(E.crandalis)、蒂氏艾美耳球蟲(E.debliecki)、分散艾美耳球蟲(E.dispersa)、橢圓艾美耳球蟲(E.ellipsoidales)、鐮形艾美耳球蟲(E.falciformis)、福氏艾美耳球蟲(E.faurei)、黃艾美耳球蟲(E.flavescens)、加洛帕沃尼艾美耳球蟲(E.gallopavonis)、哈氏艾美耳球蟲(E.hagani)、腸艾美耳球蟲(E.intestinalis)、伊洛魁艾美耳球蟲(E.iroquoina)、無殘艾美耳球蟲(E.irresidua)、拉氏艾美耳球蟲(E.labbeana)、留氏艾美耳球蟲(E.leucarti)、大型艾美耳球蟲(E.magna)、巨型艾美耳球蟲(E.maxima)、中型艾美耳球蟲(E.media)、火雞艾美耳球蟲(E.meleagridis)、火雞和緩艾美耳球蟲(E.meleagrimitis)、和緩艾美耳球蟲(E.mitis)、毒害艾美耳球蟲(E.necatrix)、雅氏艾美耳球蟲(E.ninakohlyakimovae)、羊艾美耳球蟲(E.ovis)、小型艾美耳球蟲(E.parva)、孔雀艾美耳球蟲(E.pavonis)、穿孔艾美耳球蟲(E.perforans)、雉艾美耳球蟲(E.phasani)、梨形艾美耳球蟲(E.piriformis)、早熟艾美耳球蟲(E.praecox)、殘餘艾美耳球蟲(E.residua)、粗糙艾美耳球蟲(E.scabra)、艾美耳球蟲物種(E.spec.)、斯氏艾美耳球蟲(E.stiedai)、豬艾美耳球蟲(E.suis)、柔嫩艾美耳球蟲(E.tenella)、截形艾美耳球蟲(E.truncata)、特魯特艾美耳球蟲(E.truttae)、邱氏艾美耳球蟲(E.zuernii)、球蟲物種(Globidium spec.)、貝氏同形球蟲(Isospora belli)、犬同形球蟲(I.canis)、貓同形球蟲(I.felis)、俄亥俄同形球蟲(I.ohioensis)、芮氏同形球蟲(I.rivolta)、同形球蟲物種(I.spec.)、豬同形球蟲(I.suis)、囊等孢球蟲物種(Cystisospora spec.)、隱胞子蟲物種(Cryptosporidium spec.)(具體而言小型隱胞子蟲(C.parvum))；例如弓形蟲科(Toxoplasmadidae)，例如弓蟲(Toxoplasma gondii)、海氏哈芒 球蟲(Hammondia heydornii)、犬新孢子蟲(Neospora caninum)、貝氏貝諾孢子蟲(Besnoitia besnoitii)；例如肉孢子蟲科(Sarcocystidae)，例如牛犬肉孢子蟲(Sarcocystis bovicanis)、牛人肉孢子蟲(S.bovihominis)、羊犬肉孢子蟲(S.ovicanis)、歐氏肉孢子蟲(S.ovifelis)、神經肉孢子蟲(S.neurona)、肉孢子蟲物種(S.spec.)、豬人肉孢子蟲(S.suihominis)，例如住白蟲科(Leucozoidae)，例如西氏住白蟲(Leucozytozoon simondi)，例如瘧原蟲科(Plasmodiidae)，例如伯氏瘧原蟲(Plasmodium berghei)、鐮狀瘧原蟲(P.falciparum)、三日瘧原蟲(P.malariae)、卵形瘧原蟲(P.ovale)、間日瘧原蟲(P.vivax)、瘧原蟲物種(P.spec.)，例如梨質綱(Piroplasmea)，例如阿根廷巴貝西蟲(Babesia argentina)、牛巴貝西蟲(B.bovis)、犬巴貝西蟲(B.canis)、巴貝西蟲物種(B.spec.)、小泰勒蟲(Theileria parva)、泰勒蟲物種(Theileria spec.)，例如匿蟲亞目(Adeleina)，例如犬肝簇蟲(Hepatozoon canis)、肝簇蟲物種(H.spec.)。 Parasitic protozoa include: Mastigophora, Flagellata, such as Trypanosomatidae, such as Trypanosoma b. brucei, Tbgambiense, Bude's Rhodesia Tbrhodesiense, T. congolense, T. cruzi, T. evansi, T. equinum, Louise cone T. lewisi, T. percae, T. simiae, T. vivax, Leishmania brasiliensis, black fever Leishman L. domovani, L. tropica, such as Trichomonadidae, such as Giardia lamblia, G. canis Sarcomastigophora (Rhizopoda), such as Entamoebidae, such as Entamoeba histolytica, Hartmanellidae, for example Acanthamoeba sp., Harmanella sp.; Apicomplexa (Sporozoa), such as Le Méridien Eimeridae, such as Eimeria acervulina, E. adenoides, E. alabamensis, and duck Amer E. anatis, E. anserina, E. arloingi, E. ashata, Aobo Ami E. auberensis, E. bovis, Eimeria angustifolia (E. Brunetti), E. canis, E. chinchillae, E. clupearum, E. columbae ), E. contorta, E. crandalis, E. debliecki, E. deficientis (E. Dispersa), E. ellipsoidales, E. falciformis, E. faurei, E. flavescens E.gallopavonis, E. hagani, E. intestinalis, Eimeria elegans (E.iroquoina), E. irresidua, E. labbeana, E. leucarti, large Emerald E.magna, E. maxima, E.media, E. meleagridis, turkey and chilled Amer Coccidia (E. meleagrimitis), E. mitis, E. necatrix, E. nigra Hlyakimovae), E. ovis, E. parva, E. pavonis, E. perforans , E. phasani, E. piriformis, E. praecox, E. residua, E. scabra, E. spec., E. stiedai, E. suis, E. tenella, E. truncata, E. truttae, E. zuernii ), Globidium spec., Isospora belli, I. canis, I. felis, I. ohioensis I. rivolta, Isospecies (I.spec.), I. suis, Cystisospora spec., Cryptosporidium species (Cystisospora spec.) Cryptosporidium spec.) (specifically, C. parvum); for example, Toxoplasmadidae, such as Toxopla Sma gondii) Commonia (Hammondia heydornii), Neospora caninum, Besnoitia besnoitii; for example, Sarcocystidae, such as Sarcocystis bovicanis, bovine human spores S. bovihominis, S. ovicanis, S. ovifelis, S.neurona, Sarcocyst species (S.spec.), S. suihominis, for example, Leucozoidae, such as Leucozytozoon simondi, such as Plasmodiidae, such as Plasmodium berghei, Plasmodium falciparum, P. malariae, P. ovale, P. vivax, Plasmodium species (P .spec.), such as Piroplasmea, such as Babesia argentina, B. bovis, B. canis, Babesia Species (B.spec.), Theileria parva, Theileria spec., such as Adeleina, such as Hepatozoon canis , liver cluster species (H.spec.).

為蠕蟲之病原性內寄生蟲包括扁形動物門(Platyhelmintha)(例如單殖目(Monogenea)、絛蟲及吸蟲)、線蟲、棘頭動物門(Acanthocephala)及舌形動物門(Pentastoma)。該等包括：單殖目：例如：三代蟲屬、指環蟲屬(Dactylogyrus spp.)、多盤吸蟲屬(Polystoma spp.)；絛蟲：來自擬葉目(Pseudophyllidea)之絛蟲，例如：裂頭絛蟲屬、迭宮絛蟲屬(Spirometra spp.)、裂首絛蟲屬(Schistocephalus spp.)、舌狀絛蟲屬(Ligula spp.)、溝槽絛蟲屬(Bothridium spp.)、複殖孔絛蟲屬(Diphlogonoporus spp.)；來自圓葉目(Cyclophyllida)之絛蟲，例如：中殖孔絛蟲屬、裸頭絛蟲屬、副裸頭絛蟲屬、莫尼茨絛蟲屬、遂體絛蟲屬(Thysanosoma spp.)、曲子宮絛蟲屬(Thysaniezia spp.)、無卵黃腺屬(Avitellina spp.)、斯泰勒絛蟲屬(Stilesia spp.)、鳴絛蟲屬(Cittotaenia spp.)、安德裡絛蟲屬(Andyra spp.)、伯特絛蟲屬(Bertiella spp.)、絛蟲屬、棘球絛蟲屬、泡尾帶絛蟲屬(Hydatigera spp.)、戴文絛蟲屬(Davainea spp.)、瑞立絛蟲屬(Raillietina spp.)、膜殼絛蟲屬、棘鱗絛蟲屬(Echinolepis spp.)、棘杯絛蟲(Echinocotyle spp.)、兩睾絛蟲屬(Diorchis spp.)、複孔絛蟲屬、約優克斯絛蟲屬(Joyeuxiella spp.)、倍殖孔絛蟲屬(Diplopylidium spp.)；吸蟲：來自複殖目(Digenea)之吸蟲，例如：雙穴吸蟲屬(Diplostomum spp.)、莖雙穴吸蟲屬(Posthodiplostomum spp.)、住血吸蟲屬、毛畢吸蟲屬(Trichobilharzia spp.)、鳥血吸蟲屬(Ornithobilharzia spp.)、澳血吸蟲屬(Austrobilharzia spp.)、巨畢吸蟲屬(Gigantobilharzia spp.)、彩蚴吸蟲屬(Leucochloridium spp.)、短咽吸蟲屬(Brachylaima spp.)、棘口吸蟲屬、棘緣吸蟲屬(Echinoparyphium spp.)、棘隙吸蟲屬(Echinochasmus spp.)、海泊吸蟲屬(Hyporaeum spp.)、片形吸蟲屬、擬片形吸蟲屬(Fasciolides spp.)、薑片吸蟲屬、環腔吸蟲屬(Cyclocoelum spp.)、盲腔吸蟲屬(Typhlocoelum spp.)、同端盤吸蟲屬、杯殖吸蟲屬(Calicophoron spp.)、殖盤吸蟲屬(Cotylophoron spp.)、巨盤吸蟲屬(Gigantocotyle spp.)、菲策吸蟲屬(Fischoederius spp.)、腹袋吸蟲屬(Gastrothylacus spp.)、背孔吸蟲屬(Notocotylus spp.)、下殖吸蟲屬(Catatropis spp.)、斜睾吸蟲屬(Plagiorchis spp.)、前殖吸蟲屬(Prosthogonimus spp.)、雙腔吸蟲屬、闊盤吸蟲屬(Eurytrema spp.)、鮭吸蟲屬(Troglotrema spp.)、併殖吸蟲屬、肛瘤吸蟲屬(Collyriclum spp.)、侏體吸蟲屬(Nanophyetus spp.)、後睾吸蟲屬、支睾吸蟲屬、次睾吸蟲屬、異形吸蟲屬(Heterophyes spp.)、後殖吸蟲屬(Metagonimus spp.)；線蟲：毛形線蟲科(Trichinellida)，例如：鞭蟲屬、毛細線蟲屬 (Capillaria spp.)、毛細線蟲屬(Paracapillaria spp.))、真鞘線蟲屬(Eucoleus spp.)、三可莫線蟲屬(Trichomosoides spp.)、旋毛線蟲屬(Trichinella spp.)，來自墊刃線蟲目(Tylenchida)之線蟲，例如：細絲鯰屬(Micronema spp.)、類圓線蟲屬；來自小桿圓蟲目(Rhabditida)之線蟲，例如：圓線蟲屬、三齒線蟲屬(Triodontophorus spp.)、食道齒屬(Oesophagodontus spp.)、毛樣線蟲屬(Trichonema spp.)、輻首屬(Gyalocephalus spp.)、柱咽屬(Cylindropharynx spp.)、盂口屬(Poteriostomum spp.)、圓線蟲屬(Cyclococercus spp.)、杯冠線蟲屬(Cylicostephanus spp.)、結節線蟲屬、夏伯特屬、冠尾屬、鉤口線蟲屬、彎蟲屬、板口線蟲屬、仰口線蟲屬、球首線蟲屬(Globocephalus spp.)、比翼線蟲屬、杯口線蟲屬、後圓線蟲屬、網尾線蟲屬、繆勒線蟲屬、原圓線蟲屬、新圓線蟲屬(Neostrongylus spp.)、囊尾線蟲屬(Cystocaulus spp.)、肺圓線蟲屬(Pneumostrongylus spp.)、尖尾線蟲屬(Spicocaulus spp.)、麂圓線蟲屬(Elaphostrongylus spp.)、副鹿圓線蟲屬(Parelaphostrongylus spp.)、環體線蟲屬、擬環體線蟲屬(Paracrenosoma spp.)、奧斯勒線蟲屬(Oslerus spp.)、管圓線蟲屬、貓圓線蟲屬、類線蟲屬、擬類線蟲屬(Parafilaroides spp.)、毛圓線蟲屬、血矛線蟲屬、奧斯特線蟲屬、背帶線蟲屬、馬歇爾線蟲屬(Marshallagia spp.)、古柏線蟲屬、日圓線蟲屬、螺旋線蟲屬、細頸線蟲屬、豬圓線蟲屬、尖柱線蟲屬(Obeliscoides spp.)、裂口線蟲屬、盤頭線蟲屬；來自旋尾目(Spirurida)之線蟲，例如：尖尾線蟲屬、蟯蟲屬、栓尾線蟲屬、管狀線蟲屬(Syphacia spp.)、無刺線蟲屬(Aspiculuris spp.)、異刺線蟲屬；蛔蟲屬、弓蛔線蟲屬、弓首線蟲屬、蛔屬、副蛔蟲屬、異尖線蟲屬、蛔蟲屬；棘顎口線蟲屬(Gnathostoma spp.)、泡翼 線蟲屬(Physaloptera spp.)、吸吮線蟲屬、筒線蟲屬、麗線蟲屬、副柔線蟲屬(Parabronema spp.)、德斯線蟲屬(Draschia spp.)、龍線蟲屬；冠絲蟲屬、副絲蟲屬、腹腔絲蟲屬、羅阿絲蟲屬、惡絲蟲屬、類平滑絲蟲屬、布魯線蟲屬、吳策線蟲屬、盤尾線蟲屬、尾旋線蟲屬；棘頭動物門：來自少棘目(Oligacanthorhynchida)之動物，例如：巨吻棘頭蟲屬(Macracanthorhynchus spp.)、前睪棘頭蟲屬(Prosthenorchis spp.)；來自多形目(Polymorphida)之動物，例如：細頸棘頭蟲屬(Filicollis spp.)；來自鏈珠目(Moniliformida)之動物，例如：念珠棘頭蟲屬(Moniliformis spp.)；來自棘吻目(Echinorhynchida)之動物，例如棘頭花屬(Acanthocephalus spp.)、魚棘頭蟲屬(Echinorhynchus spp.)、似細吻棘頭蟲屬(Leptorhynchoides spp.)；舌形動物門：來自蛇舌形蟲目(Porocephalida)之動物，例如舌形蟲屬(Linguatula spp)。 Pathogenic endoparasites that are helminths include Platyhelmintha (eg, Monogeneea, Aphid and Schistosomiasis), Nematodes, Acanthocephala, and Pentastoma. These include: monoclonal order: for example: three-generation genus, Dactylogyrus spp., Polystoma spp.; aphids: aphids from Pseudophyllidea, such as: S. genus (Spirometra spp.), Schistocephalus spp., Ligula spp., Bothridium spp., Diphlogonoporus Spp.); aphids from the Cyclophyllida, for example: the genus Aphis, the genus Aphis, the genus Aphis, the genus Moniz, the genus Thysanosoma spp. Thysaniezia spp., no yolk gland (Avitellina) Spp.), Stilesia spp., Cittotaenia spp., Andyra spp., Bertiella spp., Aphis, Aphis , Hydatigera spp., Davainea spp., Raillietina spp., Aphis genus, Echinolepis spp., Aphis gossypii (Echinocotyle spp.), two genus Diorchis spp., Aphis genus, Joyeuxiella spp., Diplopylidium spp.; trematode: from colonization Digesta genus, for example: Diplostomum spp., Posthodiplostomum spp., Schistosoma, Trichobilharzia spp., Schistosoma japonicum Genus (Ornithobilharzia spp.), Austrobilharzia spp., Gigantobilharzia spp., Leucochloridium spp., Brachylaima spp., spines Echinoparyphium spp., Echinochasmus spp., seawater sucking Hyporaeum spp., F. genus, Fasciolides spp., Phytophthora, Cyclocoelum spp., Typhlocoelum Spp.), the genus C. genus, Calicophoron spp., Cotylophoron spp., Gigantocotyle spp., F. genus Fischoederius spp.), Gastrothylacus spp., Notocotylus spp., Catatropis spp., Plagiorchis spp., former Prosthogonimus spp., Trichomonas, Eurytrema spp., Troglotrema spp., Paragonimus, Colleutic genus (Collyriclum) Spp.), Nanophyetus spp., S. genus, Clostridium, S. genus, Heterophyes spp., Metagonimus Spp.); nematode: Trichinellida, for example: Whipworm, Capreolus (Capillaria spp.), Paracapillaria spp., Eucoleus spp., Trichomosoides spp., Trichinella spp., from C. elegans A nematode of the genus Tylenchida, for example: Micronema spp., a genus of the genus Nematodes; a nematode from the genus Rhabditida, for example: a genus of the genus, a genus Triodontophorus spp. ), Oesophagodontus spp., Trichonema spp., Gyalocephalus spp., Cylindropharynx spp., Poteriostomum spp., roundworm Cyclococercus spp., Cylicostephanus spp., Nodular nematode, Chaperc, genus, Crohn's nematode, genus, genus, genus, genus, genus Globocephalus spp., Helicobacter, genus, genus, genus, genus, genus, nematode, neostrongylus spp., cystic Cystocaulus spp., Pneumostrongylus spp., Spicocaulus spp., Elaphostrongylus spp., Parelaphostrongylus spp., genus Nematode, Paracrenosoma spp., Osler Nematodes (Oslerus spp.), Angiostrongylus, Trichomonas, Nematodes, Parafilaroides spp., Trichophyton, Haemonchus, Oster nematodes, Nematodes Genus, Marshallagia spp., Cooper nematode, Nematode, Helicover, Nematode, Nematode, Obeliscoides spp., Nematodes, Pan head Nematodes; nematodes from the genus Spirurida, such as: Nematode, Aphis, T. elegans, Syphacia spp., Aspiculuris spp., A. serrata Genus; Aphid, Toxoplasma, A. elegans, Aphis, Aphis, Aphis, Aphid; Gnathostoma spp., Blisters Physaloptera spp., Nematode, Nematode, Nematode, Parabronema spp., Draschia spp., Longsaurid; C. elegans, deputy Filaria, genus Filaria, filaria, filaria, genus, genus, genus Bruce, genus, genus, genus, genus :An animal from the genus Oligacanthorhynchida, for example: Macracanthorhynchus spp., Prosthenorchis spp.; from Polymorphida, for example: fine Filicollis spp.; an animal from Moniliformida, for example: Moniliformis spp.; an animal from Echinorhynchida, such as the genus Hydatid ( Acanthocephalus spp.), Echinorhynchus spp., Leptorhynchoides spp.; lingual animal: an animal from the genus Porocephalida, such as the genus Tongue Genus (Linguatula spp).

在獸醫領域中及在畜牧業中，藉由業內通常已知之方法投與式(I)化合物，例如以適宜製劑形式經由經腸、非經腸、經真皮或經鼻途徑投與。投與可為防禦性或治療性的。 In the veterinary art and in the livestock industry, the compounds of formula (I) are administered by methods generally known in the art, for example by enteral, parenteral, dermal or nasal routes in a suitable formulation. The administration can be defensive or therapeutic.

因此，本發明之一個實施例係關於式(I)化合物作為醫藥之用途。 Accordingly, one embodiment of the invention relates to the use of a compound of formula (I) as a medicament.

另一態樣係關於式(I)化合物之用途，其用作抗內寄生蟲劑、具體而言殺蠕蟲劑或抗原蟲劑。式(I)化合物適於用作抗內寄生蟲劑，尤其作為殺蠕蟲劑或抗原蟲劑，例如在動物育種中，在畜牧業中，在動物房中及在衛生部門中。 Another aspect relates to the use of a compound of formula (I) for use as an anti-endoparasite, in particular an anthelmintic or anti-protozoal agent. The compounds of formula (I) are suitable for use as anti-endoparasite agents, especially as an anthelmintic or antiprotozoal agent, for example in animal breeding, in animal husbandry, in animal houses and in the health sector.

另一態樣又係關於式(I)化合物之用途，其用作抗外寄生蟲劑、具體而言殺節肢動物劑，例如殺昆蟲劑或殺蟎劑。另一態樣係關於式(I)化合物之用途，其用作抗外寄生蟲劑、具體而言殺節肢動物劑(例 如殺昆蟲劑或殺蟎劑)，例如在畜牧業中，在動物育種中，在動物房中或在衛生部門中。 A further aspect relates to the use of a compound of the formula (I) for use as an anti-parasitic agent, in particular an arthropodicide, such as an insecticide or an acaricide. Another aspect relates to the use of a compound of formula (I) for use as an anti-parasitic agent, in particular an arthropodicide (example) Such as insecticides or acaricides, for example in animal husbandry, in animal breeding, in animal rooms or in the health sector.

驅蟲混合組份 Deworming mixed component

可提及以下驅蟲混合組份，例如：活性驅蟲成分，包括殺吸蟲及殺絛蟲活性成分：來自大環內酯類別之成分，例如：阿巴美丁、多拉克汀(doramectin)、埃瑪菌素、依立諾克丁(eprinomectin)、艾弗麥克素(ivermectin)、殺蟎菌素、莫昔克丁(moxidectin)、奈馬克丁(nemadectin)、奈馬克丁(selamectin)；來自苯并咪唑及臨苯并咪唑(probenzimidazole)類別之成分，例如：阿苯達唑(albendazole)、阿苯達唑-亞碸、坎苯達唑(cambendazole)、環苯達唑(cyclobendazole)、非班太爾(febantel)、非班太爾(fenbendazole)、非班太爾(flubendazole)、甲苯達唑(mebendazole)、甲苯達唑(netobimin)、甲苯達唑(oxfendazole)、甲苯達唑(oxibendazole)、甲苯達唑(parbendazole)、噻苯噠唑(thiabendazole)、硫菌靈、三氯苯達唑(triclabendazole)；來自環八縮酚酸肽類(cyclooctadepsipeptide)類別之成分，例如：縮酚羧酸(emodepside)、PF1022；來自胺基乙腈衍生物類別之成分，例如：莫奈盤太爾(monepantel)；來自四氫嘧啶類別之成分，例如：莫侖太爾(morantel)、比蘭太爾(pyrantel)、奧克太爾(oxantel)；來自咪唑并噻唑類別之成分，例如：布他米唑(butamisole)、左旋咪唑(levamisole)、四咪唑(tetramisole)；來自水楊醯苯胺之成分，例如：溴沙尼特(bromoxanide)、溴替尼特(brotianide)、氯碘沙尼(clioxanide)、氯生太爾(closantel)、氯硝 柳胺(niclosamide)、羥氯紮胺(oxyclozanide)、雷複尼特(rafoxanide)、三溴沙侖(tribromsalan)；來自副梅花狀青黴醯胺(paraherquamide)之成分，例如：得曲恩特(derquantel)、副梅花狀青黴醯胺；來自胺基苯基脒之成分，例如：阿米太爾(amidantel)、去醯化阿米太爾(dAMD)、三苯雙脒(tribendimidine)；來自有機磷酸酯之成分，例如：蠅毒磷、克蘆磷酯(crufomate)、二氯松、哈洛酮(haloxone)、那酞磷(naphthalofos)、敵百蟲；來自經取代酚之成分，例如：硫氯酚(bithionol)、二碘硝酚(disophenol)、六氯酚(hexachlorophene)、聯硝氯酚(niclofolan)、美氯弗蘭(meniclopholan)、硝碘酚腈(nitroxynil)；來自六氫吡嗪酮(piperazinone)之成分，例如：吡喹酮(praziquantel)、依西太爾(epsiprantel)；來自各種其他類別之成分，例如：硝硫氰胺(amoscanate)、苄芬寧(bephenium)、丁奈脒(bunamidine)、氯硝西泮(clonazepam)、氯舒隆(clorsulon)、地芬尼泰(diamfenetid)、二氯芬、乙胺嗪(diethylcarbamazine)、依米丁(emetine)、三氯苯六氫吡嗪(hetolin)、海恩酮(hycanthone)、硫恩酮(lucanthone)、竹桃黴素(Miracil)、米拉散(mirasan)、氯硝柳胺(niclosamide)、尼立達唑(niridazole)、硝碘酚腈(nitroxynil)、硝硫氰酯(nitroscanate)、奧替普拉(oltipraz)、奧酞昔(omphalotin)、奧沙尼喹(oxamniquin)、巴龍黴素(paromomycin)、六氫吡嗪、雷瑣太爾(resorantel)。 The following deworming mixed components may be mentioned, for example: active insect repellent ingredients, including mites and acaricidal active ingredients: ingredients from the macrolide class, such as: abamectine, doramectin, Eiminin, eprinomectin, ivermectin, acaricidin, moxidectin, nemadectin, selamectin; Components of the benzimidazole and probenzimidazole classes, for example: albendazole, albendazole-arylene, cambendazole, cyclobendazole, non Febantel, fenbendazole, flubendazole, mebendazole, netobimin, oxfendazole, oxibendazole , parbendazole, thiabendazole, thiabendazole, triclabendazole; components from the cyclooctadepsipeptide class, eg, phenolic carboxylic acid (emodepside), PF 1022; from amino acetonitrile derivatives Other ingredients, such as: monepantel; components from the tetrahydropyrimidine category, such as: morantel, pyrantel, oxantel; Ingredients of the imidazothiazole class, for example: butamisole, levamisole, tetramisole; components derived from salicylanilide, for example: bromoxanide, bromotinib Brotianide, clooxanide, closantel, chlorinated nitrate Nicholsamide, oxyclozanide, rafoxanide, tribromsalan; components from paraherquamide, for example: Destinite ( Derquantel), Penicillium citrinum; a component derived from aminophenyl hydrazine, such as: amidantel, deuterated amidail (dAMD), tribendimidine; from organic Phosphate component, for example: fly phos, crufomate, diclofen, haloxone, naphthalofos, trichlorfon; components derived from substituted phenols, for example: Bithionol, disophenol, hexachlorophene, niclofolan, meniclopholan, nitroxynil; from hexahydropyridyl Components of piperazinone, such as praziquantel, epsiprantel; ingredients from various other categories, such as: amoxicene, bephenium, butyl Bunamidine, clonazepam, clorsulon, difenfen (diamfenetid), diclofen, diethylcarbamazine, emetine, hetolin, hycanthone, lucanthone, oleander Miracil, mirasan, niclosamide, niridazole, nitroxynil, nitroscanate, oltipraz ), omphalotin, oxamniquin, paromomycin, hexahydropyrazine, resorantel.

病媒動物控制 Vector control

式(I)化合物亦可用於病媒動物控制中。在本發明之背景下，病媒動物係能夠將病原體(例如病毒、蠕蟲、單細胞有機體及細菌)自儲主(植物、動物、人類等)傳播給宿主之節肢動物，尤其昆蟲或蛛形 類。病原體可以機械方式(例如沙眼藉由非叮刺蒼蠅)傳播給宿主或在注射後(例如瘧疾寄生蟲藉由蚊子)傳播給宿主。 The compounds of formula (I) are also useful in the control of vector animals. In the context of the present invention, a vector animal is capable of transmitting pathogens (eg, viruses, helminths, unicellular organisms, and bacteria) from a host (plant, animal, human, etc.) to an arthropod of a host, particularly an insect or arachnid. class. The pathogen can be transmitted to the host mechanically (eg, trachoma by non-stinging flies) or to the host after injection (eg, malaria parasites by mosquitoes).

病媒動物及其傳播之疾病或病原體之實例係：1)蚊子-瘧蚊：瘧疾、絲蟲病；-家蚊：日本腦炎(Japanese encephalitis)、絲蟲病、其他病毒疾病、傳播蠕蟲；-斑蚊：黃熱病、登革熱(dengue fever)、絲蟲病、其他病毒疾病；-蚋科(Simuliidae)：傳播蠕蟲，具體而言旋盤尾線蟲；2)蝨子：皮膚感染、流行性斑疹傷寒；3)跳蚤：瘟疫、地方性斑疹傷寒；4)蒼蠅：睡眠病(錐蟲病)；霍亂、其他細菌疾病；5)蟎：蟎病、流行性斑疹傷寒、痘立克次體(rickettsialpox)、土勒病(tularaemia)、聖路易斯型腦炎(Saint Louis encephalitis)、蜱傳腦炎(TBE)、克裡米亞剛果出血熱(Crimean-Congo haemorrhagic fever)、回歸熱；6)蜱：回歸熱，例如中非洲回歸熱螺旋體(Borrelia duttoni)、蜱傳腦炎、Q熱(伯納特氏立克次氏體(Coxiella burnetii))、巴貝斯蟲病(babesioses)(犬焦蟲症(Babesia canis canis))。 Examples of disease vectors and their transmitted diseases or pathogens are: 1) mosquitoes - malaria mosquitoes: malaria, filariasis; - house mosquitoes: Japanese encephalitis, filariasis, other viral diseases, spread worms ;-Aesthes: yellow fever, dengue fever, filariasis, other viral diseases; - Simuliidae: spread worms, specifically snails; 2) scorpions: skin infections, epidemic spots Rash typhoid; 3) Flea: plague, endemic typhus; 4) flies: sleep disease (trypanosis); cholera, other bacterial diseases; 5) sputum: rickets, epidemic typhus, acne ricketts (rickettsialpox), tularaemia, Saint Louis encephalitis, tread-borne encephalitis (TBE), Crimean-Congo haemorrhagic fever, regression fever; 6)蜱: Regression heat, such as the rebrelia duttoni in Central Africa, tick-borne encephalitis, Q-heat (Coxiella burnetii), babeeseses (dogsioses) Babesia canis canis).

在本發明之背景下，病媒動物之實例係可將植物病毒傳播給植物之昆蟲，例如蚜蟲、蒼蠅、葉蟬或薊馬。能夠傳播植物病毒之其他病媒動物係紅葉蟎(spider mite)、蝨子、甲蟲及線蟲。 In the context of the present invention, examples of vector animals are insects which transmit plant viruses to plants, such as aphids, flies, spider mites or thrips. Other vector animals capable of transmitting plant viruses are spider mite, scorpions, beetles and nematodes.

在本發明之背景下，病媒動物之其他實例係可將病原體傳播給動物及/或人類之昆蟲及蛛形類，例如蚊子，尤其斑紋屬、瘧蚊屬之蚊子，例如岡比亞瘧蚊(A.gambiae)、***瘧蚊(A.arabiensis)、催 命瘧蚊(A.funestus)、大劣瘧蚊(A.dirus)(瘧疾)及家蚊、蝨子、跳蚤、蒼蠅、蟎及蜱。 In the context of the present invention, other examples of vector animals are those which transmit pathogens to insects and arachnids of animals and/or humans, such as mosquitoes, especially mosquitoes of the genus Zebra, Anopheles, such as Anopheles gambiae (A) .gambiae), A. arabiensis, reminder A. funestus, A. dirus (malaria) and house mosquitoes, scorpions, fleas, flies, cockroaches and cockroaches.

若式(I)化合物具有抗性突破性，則病媒動物控制亦係可能的。 If the compound of formula (I) is resistant to breakthrough, vector animal control is also possible.

式(I)化合物適用於預防由病媒動物傳播之疾病及/或病原體。因此，本發明之另一態樣係式(I)化合物用於病媒動物控制之用途，例如在農業中，在園藝中，在林業中，在花園中及在娛樂設施中，亦及在材料及儲存產品之保護中。 The compounds of formula (I) are useful for the prevention of diseases and/or pathogens transmitted by vector animals. Thus, another aspect of the invention is the use of a compound of formula (I) for the control of vector animals, such as in agriculture, in horticulture, in forestry, in gardens and in recreational facilities, and in materials. And the protection of stored products.

工業材料之保護 Protection of industrial materials

式(I)化合物適於保護工業材料抵抗(例如)來自鞘翅目、膜翅目、等翅目、鱗翅目、齧蟲目(Psocoptera)及衣魚亞目之昆蟲之侵襲或破壞。 The compounds of formula (I) are suitable for protecting industrial materials against, for example, attack or destruction by insects from the order Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psocoptera and the genus.

工業材料在本發明上下文中應理解為意指無生命的材料，例如較佳地塑膠、黏著劑、漿糊、紙及卡板、皮革、木材、經加工木質產品及塗層組合物。尤佳者係使用本發明保護木材。 Industrial materials are understood in the context of the present invention to mean inanimate materials such as, preferably, plastics, adhesives, pastes, paper and cardboard, leather, wood, processed wood products and coating compositions. Particularly preferred are the use of the present invention to protect wood.

在另一實施例中，式(I)化合物係與至少一種其他殺昆蟲劑及/或至少一種殺真菌劑一起使用。 In another embodiment, the compound of formula (I) is used with at least one other insecticide and/or at least one fungicide.

在另一實施例中，式(I)化合物係作為即用型殺有害生物劑存在，即，可將其在不進行進一步改變下施加至所述材料。適宜之其他殺昆蟲劑或殺真菌劑具體而言係彼等在上文提及者。 In another embodiment, the compound of formula (I) is present as a ready-to-use pesticide, i.e., it can be applied to the material without further modification. Suitable other insecticides or fungicides are specifically those mentioned above.

驚奇地，亦已發現可使用式(I)化合物保護與鹽水或微咸水接觸之物體(具體而言船體、螢幕、捕網、建築物、繫船具及信號傳導系統)免受積垢。同樣可單獨使用或與其他活性成分組合使用式(I)化合物作為防污劑。 Surprisingly, it has also been found that compounds of formula (I) can be used to protect objects (especially hulls, screens, nets, buildings, moorings and signalling systems) in contact with salt water or brackish water from fouling. The compounds of formula (I) can likewise be used alone or in combination with other active ingredients as antifouling agents.

在衛生部門中控制動物有害生物 Control animal pests in the health sector

式(I)化合物適於在衛生部門中控制動物有害生物。更具體而言，本發明可用於養馴保護部門、衛生保護部門及儲存產品保護中， 具體而言用於控制在圍蔽空間(例如寓所、工廠大廳、辦公室、載具座艙)中遇到之昆蟲、蛛形類及蟎。為控制動物有害生物，可單獨使用或與其他活性成分及/或輔助物組合使用式(I)化合物。該等化合物較佳地用於家用殺昆蟲產品中。式(I)化合物可有效抵抗敏感物種及抗逆物種，且可抵抗所有發育階段。 The compounds of formula (I) are suitable for controlling animal pests in the health sector. More specifically, the present invention can be used in the protection of the tamer protection department, the health protection department, and the protection of stored products. Specifically used to control insects, arachnids, and mites encountered in enclosed spaces (such as dwelling houses, factory halls, offices, vehicle cockpits). For the control of animal pests, the compounds of formula (I) can be used alone or in combination with other active ingredients and/or adjuvants. These compounds are preferably used in household insecticidal products. The compound of formula (I) is effective against sensitive species and stress-resistant species and is resistant to all stages of development.

該等有害生物包括(例如)來自蜘蛛綱、來自蠍形目(Scorpiones)、真蜘蛛目(Araneae)及盲蛛目(Opiliones)、來自唇足綱及倍足綱、來自昆蟲綱蜚蠊目、來自鞘翅目、革翅目、雙翅目、異翅亞目、膜翅目、等翅目、鱗翅目、毛蝨目(Phthiraptera)、嚙蟲目(Psocoptera)、跳躍亞目或直翅目、隱翅目及衣魚亞目及來自軟甲亞綱(Malacostraca)等足目之有害生物。 Such pests include, for example, from the arachnid, from the Scorpiones, Araneae and Opiliones, from the Labiatae and the Footbone, from the Insecta, From Coleoptera, Lepidoptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Phthiraptera, Psocoptera, Lepidoptera or Orthoptera, The genus Hymenoptera and the genus Diptera and the harmful organisms from the order of the genus Malacostraca.

施加可以下列各項來實現：例如氣溶膠、非承壓噴霧產品(例如幫浦及霧化噴霧劑)、自動彌霧系統、彌霧器、泡沫、凝膠、具有用錠劑由纖維素或塑膠製得之蒸發器之蒸發器產品、液體蒸發器、凝膠及膜蒸發器、推進器驅動型蒸發器、無動力或無源蒸發系統、捕蛾紙、捕蛾袋及捕蛾凝膠，作為顆粒或粉劑用於撒布用誘餌或誘餌站中。 Application can be achieved by, for example, aerosols, non-pressure spray products (such as pumps and atomized sprays), automatic mist systems, misters, foams, gels, tablets with cellulose or Evaporator products from plastic evaporators, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, unpowered or passive evaporation systems, moth-proof paper, moth-bags and moth-trapping gels, Used as a granule or powder for spreading the bait or bait station.

藉由以下實例詳細闡釋本發明，但該等實例不應以其限制本發明之任一方式來解釋。 The invention is illustrated in detail by the following examples, which should not be construed in any way limiting the invention.

製程及中間體之闡述Description of processes and intermediates

藉由¹H NMR光譜及/或LC-MS(液相層析質譜)表徵產物。 The product was characterized by ¹ H NMR spectroscopy and/or LC-MS (liquid chromatography mass spectrometry).

根據OECD導則117(EC指令92/69/EEC)藉由HPLC(高效液相層析)使用反相(RP)管柱(C18)藉由以下方法來測定logP值： The logP values were determined by HPLC (High Performance Liquid Chromatography) using reversed phase (RP) columns (C18) according to OECD Guideline 117 (EC Directive 92/69/EEC) by:

[a]在pH2.7下利用0.1%甲酸水溶液及乙腈(含有0.1%甲酸)作為溶析劑實現酸性範圍內之LC-MS測定；線性梯度自10%乙腈至95%乙腈。 [a] LC-MS determination in the acidic range was carried out at pH 2.7 using 0.1% aqueous formic acid and acetonitrile (containing 0.1% formic acid) as the eluent; linear gradient from 10% acetonitrile to 95% acetonitrile.

[b]在pH7.8下利用0.001莫耳碳酸氫銨水溶液及乙腈作為溶析劑實現中性範圍內之LC-MS測定；線性梯度自10%乙腈至95%乙腈。 [b] LC-MS determination in the neutral range using a 0.001 molar aqueous solution of ammonium bicarbonate and acetonitrile as the eluent at pH 7.8; linear gradient from 10% acetonitrile to 95% acetonitrile.

使用具有已知logP值之無支鏈烷-2-酮(具有3至16個碳原子)(logP值係基於保留時間藉由兩種連續烷酮之間之線性插值來測定)實施校準。 Calibration was performed using unbranched alkan-2-ones having a known logP value (having from 3 to 16 carbon atoms) (logP values are determined based on retention time by linear interpolation between two consecutive alkanones).

使用安裝有流動探針頭(60μl體積)之Bruker Avance 400測定NMR光譜。在個別情形下，利用Bruker Avance II 600量測NMR光譜。 NMR spectra were determined using a Bruker Avance 400 equipped with a flow probe head (60 μl volume). In individual cases, NMR spectra were measured using a Bruker Avance II 600.

[c]藉助x射線結構分析確定絕對構形係藉助適於x射線分析之單晶來實現，該等單晶係藉由在室溫下自丙酮及水之混合物重結晶獲得。利用具有CCD區域檢測器(Ruby型號)、具有CuK_α輻射之管、單色器及Cryojet低溫裝置(-163.15℃=110K)之繞射計(Oxford Diffraction,XCalibur系列)確定晶體結構。使用以下程式：數據收集及CrysAlis Version(Oxford Diffraction 2010)。借助於直接方法(SHELXTL包，版本6.14,Bruker AXS,2003)進行結構解析且利用XP程式顯現。利用SHELXTL版本6.14程式，Bruker AXS,2003針對F2精修結構。 [c] Determination of the absolute configuration by means of x-ray structural analysis by means of a single crystal suitable for x-ray analysis obtained by recrystallization from a mixture of acetone and water at room temperature. The crystal structure was determined using a diffraction meter (Oxford Diffraction, XCalibur series) having a CCD area detector (Ruby model), a tube with CuK _alpha radiation, a monochromator, and a Cryojet cryogenic device (-163.15 ° C = 110 k). Use the following program: Data Collection and CrysAlis Version (Oxford Diffraction 2010). Structural analysis was performed by means of a direct method (SHELXTL package, version 6.14, Bruker AXS, 2003) and visualized using an XP program. Using the SHELXTL version 6.14 program, Bruker AXS, 2003 refines the structure for F2.

製備實例：Preparation example: 實例1：式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺Example 1: (2S,3S)-(+)-N-[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-) of formula (Ia) (trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide

反應步驟1：Reaction step 1: 式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶之合成3- (trifluoromethyl) Synthesis of (+) - 3- (3,4,5-trichlorophenyl) pyrrolidine - A of formula (IIa) of (3 S)

為分離鏡像異構物，首先在1160ml甲基第三丁基醚(MTBE)中裝填450g(1.39mol)rac-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶(II)(純度：98.5%)，形成澄清淺黃色溶液。然後，在35分鐘內逐滴添加152.2g(0.69mol；0.5當量)式(Vb)之(2R)-(-)-2-[(苯基胺基)羰基氧基)丙酸(91.2% ee)於2850ml MTBE中之溶液。在室溫下攪拌4小時後(固體在約1小時後沈澱出來)，利用抽吸過濾出經沈澱固體，每次利用1000ml MTBE洗滌三次並乾燥。獲得327.8g(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶鎓鹽[(IIa)-(Vb)]，其用於第二反應步驟。 For the separation of the mirror image isomers, first 450 g (1.39 mol) of rac -3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl) was charged in 1160 ml of methyl tert-butyl ether (MTBE). Pyrrolidine (II) (purity: 98.5%) to form a clear pale yellow solution. Then, 152.2 g (0.69 mol; 0.5 equivalent) of ( 2R )- ( - ) -2-[(phenylamino)carbonyloxy)propionic acid of formula (Vb) (91.2%) was added dropwise over 35 minutes. Ee) a solution in 2850 ml MTBE. After stirring at room temperature for 4 hours (solid precipitated after about 1 hour), the precipitated solid was filtered off with suction, washed three times with 1000 ml of MTBE and dried. Obtained 327.8 g of (3 S )- ( + ) -3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidinium salt [(IIa)-(Vb)], which Used in the second reaction step.

反應步驟2：Reaction step 2:

在1750ml水及500ml 45%氫氧化鈉溶液之混合物中攪拌327.8g(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶鎓鹽[(IIa)-(Vb)](來自反應步驟1)，且每次用1500ml MTBE將混合物萃取兩次。在已去除有機相後，將其合併，乾燥並在減壓下濃縮。184.3g(產率：理論之79.2%；純度：99.6%,92% ee)(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶(IIa)。組份式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶：式(IIb)之(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶之鏡像異構物比率為96：4。 327.8 g of (3 S )- ( + ) -3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrole were stirred in a mixture of 1750 ml of water and 500 ml of 45% sodium hydroxide solution. Pyridinium salt [(IIa)-(Vb)] (from reaction step 1), and the mixture was extracted twice with 1500 ml of MTBE each time. After the organic phase has been removed, they are combined, dried and concentrated under reduced pressure. 184.3 g of (yield: 79.2% of theory; purity: 99.6%, 92% ee) (3 S) - (+) -3- (3,4,5- trichlorophenyl) -3- (trifluoromethyl Pyrrolidine (IIa). (3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of the formula (IIa): (3R)- of the formula (IIb) The ratio of the image-isomer of (-)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine was 96:4.

反應步驟3：Reaction step 3: 式(IIIa)之(3S,3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之合成(3 S ,3 S )-(+)- N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl) of formula (IIIa) Synthesis of 1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide

首先在4000ml p.a.甲苯中裝填217.5g(0.67mol)式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶(來自反應步驟2)及185.5g(0.67mol,1.0當量)式(IV)之N-[(4-溴-2-氟苯基)甲基]環丙烷甲醯胺，且在室溫下在保護氣體氣氛(氬)下依序添加以下各項：78.3g(0.81mol,1.2當量)第三丁醇鈉、32.1g(0.03mol,0.05當量)參(二亞苄基丙酮)二鈀(0)及39.7g(0.06mol,0.10當量)4,5-雙(二苯基膦基)-9,9-二甲基呫噸。 First, 217.5 g (0.67 mol) of (3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrole of the formula (IIa) was charged in 4000 ml of PA toluene. Pyridine (from reaction step 2) and 185.5 g (0.67 mol, 1.0 eq.) of N-[(4-bromo-2-fluorophenyl)methyl]cyclopropanecarbamide of formula (IV), and at room temperature The following were added sequentially under a protective gas atmosphere (argon): 78.3 g (0.81 mol, 1.2 equivalents) of sodium tributoxide, 32.1 g (0.03 mol, 0.05 equivalents) of bis(dibenzylideneacetone)dipalladium ( 0) and 39.7 g (0.06 mol, 0.10 equivalent) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene.

隨後，將反應混合物加熱至95℃並在此溫度下繼續攪拌1小時。冷卻後，將175g矽膠及90g矽藻土添加至反應混合物中，利用抽吸過濾出固體並在減壓下濃縮有機相(顯著發泡)。所獲得殘餘物為含有59%(藉由HPLC)期望產品(IIIa)之367.7g黃色固體。 Subsequently, the reaction mixture was heated to 95 ° C and stirring was continued at this temperature for 1 hour. After cooling, 175 g of cerium and 90 g of diatomaceous earth were added to the reaction mixture, and the solid was filtered off with suction and the organic phase was concentrated under reduced pressure (significant foaming). The residue obtained was 367.7 g of a yellow solid containing 59% (by HPLC) of the desired product (IIIa).

隨後使用矽膠(5.0kg)利用二氯甲烷溶析劑層析粗製產物。以兩個流份獲得淺黃色固體狀式(IIIa)之(3S,3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺： The crude product was then chromatographed using oxime (5.0 kg) using dichloromethane. Obtaining (3 S , 3 S )-(+)- N -[[2-fluoro-4-[3-(3,4,5-trichlorobenzene) of formula (IIIa) in two fractions 3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide:

流份1：162.5g(產率：理論之44.8%；純度：95.5%，HPLC) Fraction 1: 162.5 g (yield: theoretical 44.8%; purity: 95.5%, HPLC)

流份2：51.5g(產率：理論之12.7%；純度：85.1%，HPLC) Fraction 2: 51.5 g (yield: theoretical 12.7%; purity: 85.1%, HPLC)

針對(IIIa)在Chiracel AS-RH上之保留時間(R_t)=11.11min。 The retention time (R _t ) of (IIIa) on Chiracel AS-RH = 11.11 min.

旋光度：[α]²⁰=+100.6°(c=1.1；氯仿) Optical rotation: [α] ²⁰ = +100.6 ° (c = 1.1; chloroform)

反應步驟4：Reaction step 4: 式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基1甲基]環丙烷甲醯胺(2S,3S)-(+)-N-[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoro) of formula (Ia) Methyl)-1-pyrrolidinyl]phenylmethyl]cyclopropanecarboxamide

首先在3400ml甲醇中裝填72.0g(0.13mol)式(IIIa)之(3S,3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺(來自反應步驟3)，其中溶解明顯不完全。此後，添加40.9g(0.16mol,1.2當量)碘，並將反應混合物在60℃下攪拌1小時(藉由HPLC：4%(Ia)及94%反應物(IIIa))。隨後，添加22.4g(0.22mol； 1.7當量)乙酸鉀及2.9ml水並將混合物在60℃下再攪拌30分鐘(藉由HPLC：43%(Ia)及反應物52%(IIIa))。此後，以相同方式，在60℃下添加另外40.9g(0.16mol,1.2當量)碘，再過30分鐘後(藉由HPLC：65%(Ia)及反應物29%(IIIa))，最後添加40.9g(0.16mol,1.2當量)碘。再過30分鐘後(藉由HPLC：73%(Ia)及反應物20%(IIIa))，添加另外22.4g(0.22mol；1.7當量)乙酸鉀及2.9ml水。15分鐘(藉由HPLC：88%(Ia)及反應物4%(IIIa))及60分鐘(藉由HPLC：88%(Ia)及反應物1%(IIIa))後對反應之監測顯示反應已結束。隨後，使反應混合物冷卻並添加至8000ml水中(褐色乳液)。在添加1400ml 40%亞硫酸氫鈉水溶液後，發生褪色且粗製產品沈澱出來。利用抽吸過濾出沈澱物並首先用水且然後用500ml二氯甲烷洗滌。此後，用250ml 2-丙醇攪拌殘餘物並添加至3000ml 10%鹽酸中。在攪拌30分鐘之後，利用抽吸過濾出沈澱固體，用水洗滌並在空氣循環烘箱中在45℃下乾燥。此得到64.8g(產率：理論之87.3%,95.1%,94% ee)灰棕色固體狀式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺。 First, 72.0 g (0.13 mol) of (3 S , 3 S )-(+)- N -[[2-fluoro-4-[3-(3,4,5-three) of formula (IIIa) was charged in 3400 ml of methanol. Chlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide (from reaction step 3) wherein the dissolution is significantly incomplete. Thereafter, 40.9 g (0.16 mol, 1.2 equivalents) of iodine was added, and the reaction mixture was stirred at 60 ° C for 1 hour (by HPLC: 4% (Ia) and 94% of the reaction (IIIa)). Subsequently, 22.4 g (0.22 mol; 1.7 equivalent) of potassium acetate and 2.9 ml of water were added and the mixture was further stirred at 60 ° C for 30 minutes (by HPLC: 43% (Ia) and the reaction 52% (IIIa)). Thereafter, in the same manner, an additional 40.9 g (0.16 mol, 1.2 equivalents) of iodine was added at 60 ° C, and after another 30 minutes (by HPLC: 65% (Ia) and the reactant 29% (IIIa)), the last addition was carried out. 40.9 g (0.16 mol, 1.2 equivalents) of iodine. After a further 30 minutes (by HPLC: 73% (Ia) and the reaction 20% (IIIa)), an additional 22.4 g (0.22 mol; 1.7 eq.) of potassium acetate and 2.9 ml of water were added. Monitoring of the reaction after 15 minutes (by HPLC: 88% (Ia) and 4% (IIIa) of the reaction) and 60 minutes (by HPLC: 88% (Ia) and 1% (IIIa) of the reaction) over. Subsequently, the reaction mixture was cooled and added to 8000 ml of water (brown emulsion). After the addition of 1400 ml of a 40% aqueous solution of sodium hydrogen sulfite, fading occurred and the crude product precipitated. The precipitate was filtered off with suction and washed first with water and then with 500 ml of dichloromethane. Thereafter, the residue was stirred with 250 ml of 2-propanol and added to 3000 ml of 10% hydrochloric acid. After stirring for 30 minutes, the precipitated solid was filtered off with suction, washed with water and dried at 45 ° C in an air circulating oven. This gave 64.8 g (yield: 87.3% of theory, 95.1%, 94% ee) of (2S,3S)-(+)-N-[[2-fluoro-4-[ 2-Hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide.

實驗式：C₂₂H₁₉Cl₃F₄N₂O₂ 分子量：525.76g/mol Experimental formula: C ₂₂ H ₁₉ Cl ₃ F ₄ N ₂ O ₂ Molecular weight: 525.76 g/mol

LC-MS(ESI正性)：508.9(M-OH)；R_t=1.52 logP=4.06 LC-MS (ESI positive): 508.9 (M-OH); R _t = 1.52.

旋光度：[α]²⁰=+94.0°(c=1.1；氯仿) Optical rotation: [α] ²⁰ = +94.0 ° (c = 1.1; chloroform)

¹³C NMR(600MHz,DMSO-d₆,ppm)δ=6.6(2×CH₂，環丙基)；14.2(CH，環丙基)；28.2(CH₂，吡咯啶基)；36.9(CH₂-NH)；46.4(CH₂-N，吡咯啶基)；61.3(C-CF₃,)；82.9(C-OH，順式)；100.2；109.2；131.6(C-H，芳基)；162.2(C-F，芳基)；115.2(C-CH₂，芳基)；127.7(CF₃)；132.1(2×C-H，芳基)；130.7(C-Cl，芳基)；133.5(2×C-Cl，芳基)ppm。 ¹³ C NMR (600 MHz, DMSO-d ₆ , ppm) δ = 6.6 (2 × C H ₂ , cyclopropyl); 14.2 ( C H, cyclopropyl); 28.2 ( C H ₂ , pyrrolidinyl); ( C H ₂ -NH); 46.4 ( C H ₂ -N, pyrrolidinyl); 61.3 ( C- CF ₃ ,); 82.9 ( C- OH, cis ); 100.2; 109.2; 131.6 ( C- H, aryl group); 162.2 (C -F, aryl); 115.2 (C -CH _{2, aryl); 127.7 (C F 3)} ; 132.1 (2 × C -H, aryl); 130.7 (C -Cl, Aryl); 133.5 (2 x C- Cl, aryl) ppm.

藉助x射線結構確定確定絕對構形：Determining the absolute configuration with x-ray structure determination:

對掌性：S(C2)、S(C3)，根據式(Ia) Palmarity: S (C2), S (C3), according to formula (Ia)

晶體數據：C₂₂H₁₉C₁₃F₄N₂O₂(525.74g/mol) Crystal data: C ₂₂ H ₁₉ C ₁₃ F ₄ N ₂ O ₂ (525.74 g/mol)

單斜 CuK_α輻射 Monoclinic CuK _α radiation

P2₁ 溫度=110K P2 ₁ temperature = 1010K

a=9.6829(3)Å α=90° 波長=1.54178Å a=9.6829(3)Å α=90° Wavelength=1.54178Å

b=11.3634(4)Å β=95.568(3)°. b=11.3634(4)Å β=95.568(3)°.

c=10.2440(4)Å γ=90°. c=10.2440(4)Å γ=90°.

體積=1121.84(7)ų Volume=1121.84(7)Å ³

Z=2 Z=2

D_x(經計算)=1.556mg/m³ D _x (calculated) = 1.556 mg/m ³

吸收係數=4.217mm^-1 Absorption coefficient = 4.217mm ^-1

F(000) 536 F(000) 536

晶體大小=0.20 x 0.06×0.04mm³ Crystal size = 0.20 x 0.06 × 0.04 mm ³

無色針狀物 Colorless needle

實例2：式(Id)之(2R,3R)-(-)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之合成Example 2: (2 R , 3 R )- ( - ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-) of formula (Id) Synthesis of 3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide

反應步驟1：Reaction step 1:

為進行鏡像異構物分離，首先在100ml甲基第三丁基醚(MTBE)中裝填34.85g(109.4mmol)式(II)之rac-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶，且在室溫下在5分鐘內逐滴添加溶解於180ml MTBE中之9.15g(43.76mmol)(2S)-(+)-2-[(苯基胺基)羰基氧基)丙酸(Va)(88.4% ee)。隨後，將反應混合物在室溫下攪拌30分鐘，用50mg(3R)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶鎓鹽[(IIb)-(Va)]加晶種並在0℃下攪拌另1.5小時。利用抽吸過濾出經沈澱晶體，用MTBE洗滌並在黏 土上乾燥。獲得26.8g(產率：理論之48.1%)(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶鎓鹽[(IIb)-(Va)]，其用於第二反應步驟。 For the separation of the image isomers, first fill 34.85 g (109.4 mmol) of rac -3-(3,4,5-trichlorophenyl) of formula (II) in 100 ml of methyl tert-butyl ether (MTBE). -3-(trifluoromethyl)pyrrolidine, and 9.15 g (43.76 mmol) (2 S )-(+)-2-[(benzene) dissolved in 180 ml of MTBE was added dropwise at room temperature over 5 minutes. Amino)carbonyloxy)propionic acid (Va) (88.4% ee). Subsequently, the reaction mixture was stirred at room temperature for 30 minutes with 50 mg of ( 3R )- ( + )- 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidinium. The salt [(IIb)-(Va)] was seeded and stirred at 0 ° C for another 1.5 hours. The precipitated crystals were filtered off with suction, washed with MTBE and dried on clay. 26.8 g of obtained (Yield: 48.1% of theory) (3 R) - (- ) -3- (3,4,5- trichlorophenyl) -3- (trifluoromethyl) pyrrolidine salt [( IIb)-(Va)], which is used in the second reaction step.

反應步驟2：Reaction step 2:

在298ml乙酸乙酯中攪拌26.8g(52.6mmol)(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶鎓鹽[(IIb)-(Va)](來自反應步驟1)並與167.7ml 2N氫氧化鈉溶液一起攪拌。隨後，去除有機相並用乙酸乙酯將水相萃取兩次。在去除有機相後，將其合併，乾燥並在減壓下濃縮。獲得14.5g(產率：理論之86.5%)式(IIb)之(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶。 298ml ethyl acetate was stirred 26.8g (52.6mmol) (3 R) - (-) -3- (3,4,5- trichlorophenyl) -3- (trifluoromethyl) pyrrolidine salt [ (IIb)-(Va)] (from reaction step 1) and stirred with 167.7 ml of 2N sodium hydroxide solution. Subsequently, the organic phase was removed and the aqueous phase was extracted twice with ethyl acetate. After removal of the organic phase, they were combined, dried and concentrated under reduced pressure. 14.5 g (yield: 86.5% of theory) of (3R)-(-)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (IIb) .

組份式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶：(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶(IIb)之鏡像異構物比率為2.9：97.1。在Chiracel OD-RH上之保留時間(R_t)為對於(IIa)9.79min及對於(IIb)10.38min。 (3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of the formula (IIa): (3 R )-(-)- The ratio of the image isomer of 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine (IIb) was 2.9:97.1. The retention time (R _t ) on Chiracel OD-RH was 9.79 min for (IIa) and 10.38 min for (IIb).

反應步驟3：Reaction step 3: 式(VIIb)之(3R)-(-)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲腈之合成Formula (Vllb) of (3 R) - (-) -2- fluoro-4- [3- (3,4,5-trichlorophenyl) -3- (trifluoromethyl) -1-pyrrolidinyl Synthesis of benzonitrile

在保護氣體氣氛(氬)下將14.5g(45.5mmol)式(IIb)之(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶(來自反應步驟2)溶解於100ml N,N-二甲基甲醯胺(DMF)中，並添加9.2g(91.1mmol,2當量)三乙胺及8.2g(59.2mmol)式(VI)之2,4-二氟苯甲腈。此後，將反應混合物在100℃下攪拌約18小時。為進行處理，在70℃下在減壓下濃縮全部反應混合物。將剩餘粗製產物施加至矽膠並藉助在矽膠上利用環己烷/丙酮(梯度)溶析劑混合物進行管柱層析來純化。獲得14.7g(理論之 73.1%；純度：98.7%)式(VIIb)之(3R)-(-)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲腈。 14.5 g (45.5 mmol) of (3R)-(-)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl) of the formula (IIb) under a protective gas atmosphere (argon) Pyrrolidine (from reaction step 2) was dissolved in 100 ml of N,N -dimethylformamide (DMF), and 9.2 g (91.1 mmol, 2 equivalents) of triethylamine and 8.2 g (59.2 mmol) were added ( VI) 2,4-difluorobenzonitrile. Thereafter, the reaction mixture was stirred at 100 ° C for about 18 hours. For the treatment, the entire reaction mixture was concentrated under reduced pressure at 70 °C. The remaining crude product was applied to the silicone and purified by column chromatography on a silica gel using a cyclohexane/acetone (gradient) solvent mixture. To obtain 14.7g (73.1% of theory; purity: 98.7%) of formula (Vllb) of (3 R) - (-) -2- fluoro-4- [3- (3,4,5-trichlorophenyl) - 3-(Trifluoromethyl)-1-pyrrolidinyl]benzonitrile.

實驗式：C₁₈H₁₁Cl₃F₄N₂分子量：437.64g/mol Experimental formula: C ₁₈ H ₁₁ Cl ₃ F ₄ N ₂ Molecular weight: 437.64 g/mol

LC-MS(ESI正性)：438.9(M+1)；R_t=4.12min logP=5.19 LC-MS (ESI positive): 438.9 (M + 1); R _t = 4.12 min.

反應步驟4：Reaction step 4: 式(VIIIb)之(3R)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]-第三丁基氧基羰基甲醯胺之合成(3 R )- ( - ) - N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1 Synthesis of pyrrolidinyl]phenyl]methyl]-t-butyloxycarbonylcarbamidine

在350ml甲醇及700ml二噁烷之溶劑混合物中攪拌14.7g(33.7mmol)式(VIIb)之(3R)-(-)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲腈(來自反應步驟3)，且添加29.4g(134.9mmol；4.0當量)二碳酸二-第三丁基酯及13.1g(101.2mmol；3當量)氯化鎳(II)。然後，將反應混合物在0℃下攪拌45分鐘。為進行處理，將全部反應混合物與乙酸乙酯混合且然後用水、飽和碳酸氫鈉溶液及飽和氯化鈉溶液振盪。在已去除有機相後，將其乾燥並在減壓下濃縮。藉助在矽膠上利用環己烷/丙酮(梯度)溶析劑混合物進行管柱層析來純化剩餘粗製產物。獲得9.6g(理論之52.3%)式(VIIIb)之(3R)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]-第三丁基氧基羰基甲醯胺，其用於反應步驟5中。 Stirring 14.7g (33.7mmol) of formula (Vllb) of (3 R) in a solvent mixture of 350ml of methanol and 700ml of dioxane - (-) -2-fluoro-4- [3- (3,4,5- Chlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]benzonitrile (from reaction step 3), and 29.4 g (134.9 mmol; 4.0 equivalents) of di-t-butyl dicarbonate were added. And 13.1 g (101.2 mmol; 3 equivalents) of nickel (II) chloride. Then, the reaction mixture was stirred at 0 ° C for 45 minutes. For the treatment, the entire reaction mixture was mixed with ethyl acetate and then shaken with water, a saturated sodium hydrogen carbonate solution and a saturated sodium chloride solution. After the organic phase has been removed, it is dried and concentrated under reduced pressure. The remaining crude product was purified by column chromatography on a silica gel using a cyclohexane/acetone (gradient) solvent mixture. To obtain 9.6g (52.3% of theory) of formula (Vlllb) of (3 R) - (-) - N - [[2- fluoro-4- [3- (3,4,5-trichlorophenyl) -3 -(Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]-tert-butyloxycarbonylcarbamidine, which is used in Reaction Step 5.

反應步驟5：Reaction step 5: 式(IXb)之(3R)-(-)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲基氯化銨之合成(3 R )- ( - ) -2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl of formula (IXb) Synthesis of benzyl ammonium chloride

將9.6g(17.6mmol)式(VIIIb)之(3R)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]-第三丁基氧基羰基甲醯胺(來自反應步驟4)在室溫下在於二噁烷中之50ml(584.5mmol)4N鹽酸中攪拌約18小時。隨後，在減壓下濃縮反應混合物。獲得8.4g(理論之99.2%)式(IXb)之(3R)-(-)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲基氯化銨，其未經進一步純化即用於反應步驟6。 The 9.6g (17.6mmol) of formula (Vlllb) of (3 R) - (-) - N - [[2- fluoro-4- [3- (3,4,5-trichlorophenyl) -3- ( Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]-t-butyloxycarbonylcarbamide (from reaction step 4) 50 ml (584.5 mmol) in dioxane at room temperature Stir in 4N hydrochloric acid for about 18 hours. Subsequently, the reaction mixture was concentrated under reduced pressure. To obtain 8.4g (99.2% of theory) of formula (IXb is) of (3 R) - (-) -2- fluoro-4- [3- (3,4,5-trichlorophenyl) -3- (trifluoromethyl Methyl)-1-pyrrolidinyl]benzyl ammonium chloride, which was used in reaction step 6 without further purification.

反應步驟6：Reaction step 6: 式(IIIb)之(3R)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之合成(3 R )- ( - ) - N -[[2-Fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1 of formula (IIIb) Synthesis of pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide

首先在400ml二氯甲烷中裝填8.4g(17.6mmol)式(IXb)之(3R)-(-)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲基氯化銨(來自反應步驟5)，並在0℃下添加6.1g(77.2mmol；4當量)吡啶。在0℃下攪拌10分鐘後，添加4.4g(42.1mmol)環丙烷羰基氯且然後將全部反應混合物在室溫下攪拌約18小時。為進行處理，利用1M鹽酸振盪反應混合物。隨後，去除有機相，乾燥並在減壓下濃縮。藉助在矽膠上利用環己烷/丙酮(梯度)溶析劑混合物進行管柱層析來純化剩餘粗製產物。藉助在對掌性Pak AS-AH對掌性相上進行等梯度RP管柱層析將2.0g(純度：97.0%)預純化之式(IIIb)之(3R)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺再純化一次。在40℃下在減壓下放掉溶劑(乙腈)並在10毫巴(mbar)下 將殘餘物乾燥約15分鐘。獲得1.5g(理論之16.9%，純度：100%，ee=>99%)式(IIIb)之(3R)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺。對於(IIIb)在對掌性Pak AS-AH上之保留時間(R_t)=11.09min。 First charged 8.4g (17.6mmol) of formula (IXb is) of (3 R) in 400ml dichloromethane - (-) -2-fluoro-4- [3- (3,4,5-trichlorophenyl) - 3-(Trifluoromethyl)-1-pyrrolidinyl]benzyl ammonium chloride (from reaction step 5) and 6.1 g (77.2 mmol; 4 equivalents) of pyridine were added at 0 °C. After stirring at 0 °C for 10 minutes, 4.4 g (42.1 mmol) of cyclopropanecarbonyl chloride was added and then the whole reaction mixture was stirred at room temperature for about 18 hours. For the treatment, the reaction mixture was shaken with 1 M hydrochloric acid. Subsequently, the organic phase was removed, dried and concentrated under reduced pressure. The remaining crude product was purified by column chromatography on a silica gel using a cyclohexane/acetone (gradient) solvent mixture. (3 R )- ( - ) - N - ( IIIb ) pre-purified by isocratic RP column chromatography on palmitic phase of palmar Pak AS-AH [[2-Fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarboxamide Purify again. The solvent (acetonitrile) was decanted under reduced pressure at 40 ° C and the residue was dried at 10 mbar ( mbar) for about 15 minutes. To obtain 1.5g (16.9% of theory, purity: 100%, ee => 99 %) formula (IIIb) of (3 R) - (-) - N - [[2- fluoro-4- [3- (3, 4,5-Trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide. The retention time (R _t ) of (IIIb) on the palmitic Pak AS-AH was 11.09 min.

實驗式：C₂₂H₁₉Cl₃F₄N₂O分子量：509.75g/mol Experimental formula: C ₂₂ H ₁₉ Cl ₃ F ₄ N ₂ O Molecular weight: 509.75 g/mol

LC-MS(ESI正性)：511.0(M+1)；R_t=3.95min logP=4.79 LC-MS (ESI positive): 511.0 (M + 1); R _t = 3.95 min.

旋光度：[α]²⁰=-100.1°(c=1.1；氯仿) Optical rotation: [α] ²⁰ = -100.1 ° (c = 1.1; chloroform)

反應步驟7：Reaction step 7: 式(Id)之(2R,3R)-(-)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之合成(2 R , 3 R )- ( - ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(()) Synthesis of trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide

首先在40ml甲醇中裝填0.6g(0.17mmol)式(IIIb)之(3R)-(-)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺(來自反應步驟6)。此後，在室溫下添加1.8g(7.06mmol,6當量)碘並將反應混合物在60℃下攪拌1小時。隨後，添加1.1g(11.7mmol；10當量)乙酸鉀並將混合物在60℃下再攪拌1小時。 First, 0.6 g (0.17 mmol) of (3 R )- ( - ) - N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl) of formula (IIIb) was charged in 40 ml of methanol. -3-(Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide (from Reaction Step 6). Thereafter, 1.8 g (7.06 mmol, 6 equivalents) of iodine was added at room temperature and the reaction mixture was stirred at 60 ° C for 1 hour. Subsequently, 1.1 g (11.7 mmol; 10 equivalents) of potassium acetate was added and the mixture was further stirred at 60 ° C for 1 hour.

為進行處理，在減壓下放掉甲醇，並將剩餘殘餘物吸收於乙酸乙酯中並用飽和硫代硫酸鈉溶液振盪。然後用1N鹽酸將經去除有機相振盪一次，去除，乾燥且然後在減壓下濃縮。藉助在矽膠上利用環己烷/丙酮(梯度)溶析劑混合物進行管柱層析來純化剩餘粗製產物。獲得344.9mg(理論之52.8%，純度：94.8%)及178.9mg(理論之28.8%)式(Id)之(2R,3R)-(-)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺。對於(Ic)在對掌性Pak AS-AH上之保留時間(R_t)=8.46min。 For the treatment, methanol was taken off under reduced pressure, and the residue was taken up in ethyl acetate and shaken with a saturated sodium thiosulfate solution. The removed organic phase was then shaken once with 1N hydrochloric acid, removed, dried and then concentrated under reduced pressure. The remaining crude product was purified by column chromatography on a silica gel using a cyclohexane/acetone (gradient) solvent mixture. Obtained 344.9 mg (52.8% of theory, purity: 94.8%) and 178.9 mg (28.8% of theory) of (2 R , 3 R )- ( - ) - N -[[2-fluoro-4- [2-Hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide. The retention time (R _t ) of (Ic) on the palmitic Pak AS-AH = 8.46 min.

實驗式：C₂₂H₁₉Cl₃F₄N₂O₂分子量：525.76g/mol Experimental formula: C ₂₂ H ₁₉ Cl ₃ F ₄ N ₂ O ₂ Molecular weight: 525.76 g/mol

LC-MS(ESI正性)：506.9(M-OH)；R_t=1.51 logP=4.04 LC-MS (ESI positive): 506.9 (M-OH); R _t = 1.51.

旋光度：[α]²⁰=-92.4°(c=1.1；氯仿) Optical rotation: [α] ²⁰ = -92.4 ° (c = 1.1; chloroform)

實例3：由主要組份式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(Ib)之(2R,3R)-(-)-非鏡像異構物組成之(2S,3S)-非鏡像異構物富集之混合物之合成Example 3: (2S,3S)-(+)-N-[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl) of the formula (Ia) -(3-Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide and (2R,3R) - ( - ) - non-image isomer composition of formula (Ib) Synthesis of a mixture of (2 S , 3 S )-non-image enantiomers

反應步驟1：Reaction step 1: 由式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶及式(IIb)(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物之合成(3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (IIa) and formula (IIb) (3R) - ( - ) - synthesis of mixtures of enantiomeric enrichment - enantiomer composition of (3 S) - (+)

為進行鏡像異構物富集，首先在600ml甲基第三丁基醚(MTBE)中裝填200g(627.8mmol)式(II)之rac-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶，且在室溫下在5分鐘內逐滴添加溶解於1000ml MTBE中之75g(358.5mmol)式(Va)之(2S)-(+)-2-[(苯基胺基)羰基氧基)丙酸(88.4% ee)。隨後，將反應混合物在室溫下攪拌30分鐘，利用50mg(3R)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶鎓鹽[(IIb)-(Va)]加晶種且在0℃下攪拌另1.5小時。利用抽吸過濾出式(IIb)-(Va)沈澱晶體鹽。此後，利用飽和碳酸鈉水溶液振盪母液。去除有機相且用飽和碳酸氫鈉溶液振盪，然後乾燥並在減壓下濃縮。 For enantiomeric enrichment, first 200 g (627.8 mmol) of rac -3-(3,4,5-trichlorophenyl) of formula (II) was charged in 600 ml of methyl tert-butyl ether (MTBE). -3-(Trifluoromethyl)pyrrolidine, and 75 g (358.5 mmol) of (2 S )-(+)-2 of the formula (Va) dissolved in 1000 ml of MTBE was added dropwise at room temperature over 5 minutes. -[(Phenylamino)carbonyloxy)propionic acid (88.4% ee). Subsequently, the reaction mixture was stirred at room temperature for 30 minutes using 50 mg of ( 3R )- ( + )- 3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidinium. The salt [(IIb)-(Va)] was seeded and stirred at 0 ° C for another 1.5 hours. The crystalline salt of formula (IIb)-(Va) was precipitated by suction. Thereafter, the mother liquor was shaken with a saturated aqueous solution of sodium carbonate. The organic phase was removed and shaken with saturated sodium bicarbonate solution then dried and concentrated under reduced pressure.

獲得87.0g(產率：理論之43.5%，74% ee)以87：13之比率由式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶及式(IIb)之(3R)-(-)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶組成之(S)-(+)-鏡像異構物富集之混合物。 87.0 g (yield: theoretical 43.5%, 74% ee) was obtained from the formula (IIa) of (3S)-(+)-3-(3,4,5-trichlorophenyl) at a ratio of 87:13. -3-(trifluoromethyl)pyrrolidine and (3R)-(-)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (IIb) A mixture of (S) - ( + ) - mirror image isomers.

在Chiracel OD-RH上之保留時間(R_t)為對於(IIa)9.47min及對於(IIb)10.20min。 The retention time (R _t ) on Chiracel OD-RH was 9.47 min for (IIa) and 10.20 min for (IIb).

反應步驟2：Reaction step 2: 由式(VIIa)之(3S)-(+)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲腈及式(VIIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物之合成(3 S )- ( + ) -2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidine of formula (VIIa) Synthesis of a mixture of (3S) - ( + ) -mirroromerisomers consisting of benzonitrile and (3R) - ( - ) -an image isomer of formula (VIIb)

將68.7g(107.8mmol)由式(IIa)之(3S)-(+)-3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶及式(IIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物(來自反應步驟1)在保護氣體氣氛(氬)下溶解於429.6ml N,N-二甲基甲醯胺(DMF)中，且添加43.6g(431.5mmol,4當量)三乙胺及39.0g(280.5mmol)式(VI)之2,4-二氟苯甲腈。此後，將反應混合物在100℃下攪拌約18小時。為進行處理，在70℃下在減壓下濃縮全部反應混合物。將剩餘粗製產品施加至矽藻土並藉助在矽膠上利用環己烷/丙酮(梯度)溶析劑混合物進行管柱層析來純化。獲得66.8g(理論之59%：純度：83.4%；70.6% ee)以85.3：14.7之比率由式(VIIa)之(3S)-(+)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲腈及式(VIIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物。 68.7 g (107.8 mmol) of (3S)-(+)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidine of formula (IIa) and formula (IIb) ) of (3R) - (-) - enantiomer composition of (3 S) - (+) - enantiomer enriched mixtures of (from reaction step 1) under a protective gas atmosphere (argon) dissolved in 429.6 Methyl N,N -dimethylformamide (DMF) with 43.6 g (431.5 mmol, 4 equivalents) of triethylamine and 39.0 g (280.5 mmol) of 2,4-difluorobenzyl of formula (VI) Nitrile. Thereafter, the reaction mixture was stirred at 100 ° C for about 18 hours. For the treatment, the entire reaction mixture was concentrated under reduced pressure at 70 °C. The remaining crude product was applied to diatomaceous earth and purified by column chromatography on a ruthenium gel using a cyclohexane/acetone (gradient) lysing agent mixture. Obtained 66.8 g (59% of theory: purity: 83.4%; 70.6% ee) from (3 S )- ( + ) -2-fluoro-4-[3-(3) of formula (VIIa) at a ratio of 85.3:14.7 , 4,5-trichlorophenyl) -3- (trifluoromethyl) -1-pyrrolidinyl] benzonitrile and of formula (Vllb) of (3R) - (-) - enantiomer of the composition ( 3S) - ( + ) - a mixture of mirror image isomers.

在Chiracel OD-RH上之保留時間(R_t)為對於式(VIIa)之(S)-(+)-鏡像異構物12.22min及對於式(VIIb)之(R)-(-)-鏡像異構物12.66min。 The retention time (R _t ) on Chiracel OD-RH is 12.22 min for (S) - ( + ) - mirror image isomer of formula (VIIa) and (R) - ( - ) - mirror for formula (VIIb) Isomer 12.66 min.

實驗式：C₁₈H₁₁Cl₃F₄N₂分子量：437.64g/mol Experimental formula: C ₁₈ H ₁₁ Cl ₃ F ₄ N ₂ Molecular weight: 437.64 g/mol

LC-MS(ESI正性)：438.9(M+1)；R_t=1.74min logP=5.11；5.15 LC-MS (ESI positive): 438.9 (M + 1); R _t = 1.74 min.

反應步驟3：Reaction step 3: 由式(VIIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]-第三丁基氧基羰基甲醯胺及式(VIIIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物之合成(3 S )- ( + ) - N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)- (3 -Syrrolidyl)phenyl]methyl]-tert-butyloxycarbonylcarboxamide and (3R) - ( - ) -an image isomer of formula (VIIIb) (3S) - ( + ) - Synthesis of a mixture of mirror-isomers

在794ml甲醇及1580ml二噁烷之溶劑混合物中攪拌34.4g(38.1mmol)由式(VIIa)之(3S)-(+)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲腈及式(VIIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物(來自反應步驟2)，且依序添加以下各項：33.3g(152.6mmol；4.0當量)二碳酸二-第三丁基酯及14.8g(114.4mmol；3當量)氯化鎳(II)，且在20分鐘內逐份添加12.7g(335.7mmol)硼氫化鈉(在反應接近結束時顯著發泡)。然後，將反應混合物在0℃下攪拌45分鐘。為進行處理，將全部反應混合物與乙酸乙酯混合，利用1000ml飽和碳酸鈉溶液攪拌並攪拌約15分鐘。隨後，過濾混合物並在旋轉蒸發器上在減壓下將濾液濃縮成水相。用乙酸乙酯振盪水性殘餘物(相分離極差)，添加飽和氯化鈉溶液並使混合物靜置約18小時。去除有機相，經硫酸鎂乾燥並在減壓下濃縮。將剩餘粗製產物施加至矽藻土並藉助在矽膠上利用環己烷/丙酮(梯度)溶析劑混合物進行管柱層析來純化。獲得17.5g(理論之42.5%)由式(VIIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]-第三丁基氧基羰基甲醯胺及式(VIIIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物，其隨後在反應步驟4中進一步轉化。 34.4 g (38.1 mmol) of (3S)- ( + )- 2-fluoro-4-[3-(3,4,5-three) of formula (VIIa) was stirred in a solvent mixture of 794 ml of methanol and 1580 ml of dioxane. (3S) - ( + ) consisting of chlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]benzonitrile and (3R) - ( - ) -an image isomer of formula (VIIb ) a mixture of mirror image isomers (from reaction step 2), and the following were added sequentially: 33.3 g (152.6 mmol; 4.0 equivalents) of di-tert-butyl dicarbonate and 14.8 g (114.4 mmol; 3 Equivalent) nickel (II) chloride, and 12.7 g (335.7 mmol) of sodium borohydride (significantly foamed near the end of the reaction) was added portionwise over 20 minutes. Then, the reaction mixture was stirred at 0 ° C for 45 minutes. For the treatment, the entire reaction mixture was mixed with ethyl acetate, stirred with 1000 ml of a saturated sodium carbonate solution and stirred for about 15 minutes. Subsequently, the mixture was filtered and the filtrate was concentrated to an aqueous phase under reduced pressure on a rotary evaporator. The aqueous residue was shaken with ethyl acetate (very poor phase separation), a saturated sodium chloride solution was added and the mixture was allowed to stand for about 18 hours. The organic phase was removed, dried over magnesium sulfate and evaporated. The remaining crude product was applied to diatomaceous earth and purified by column chromatography on a silica gel using a cyclohexane/acetone (gradient) solvent mixture. Obtain 17.5 g (42.5% of theory) from (3 S )- ( + ) - N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-) of formula (VIIIa) 3-(Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]-t-butyloxycarbonylcarbamidine and (3R) - ( - ) - mirror image isomer of formula (VIIIb) The (3S) - ( + ) -image enrichment-enriched mixture is then further converted in reaction step 4.

反應步驟4：Reaction step 4: 由式(IXa)之(3S)-(+)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲烷氯化銨及式(IXb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡(3 S )- ( + ) -2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidine of formula (IXa) (3S) - ( + ) - mirror composed of ( meth)methane chloride and (3R) - ( - ) - mirror image isomer of formula (IXb) 像異構物富集之混合物之合成Synthesis of a mixture like isomer enrichment

將16.0g(14.7mmol)由式(VIIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]-第三丁基氧基羰基甲醯胺及(3R)-(-)-鏡像異構物(VIIIb)組成之(3S)-(+)-鏡像異構物富集之混合物(來自反應步驟3)在室溫下在於二噁烷中之67ml 4M鹽酸中攪拌約18小時。隨後，在減壓下濃縮反應混合物。獲得14.0g(理論之99.5%)由(3S)-(+)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲烷氯化銨(IXa)及式(IXb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物，其未經進一步純化即用於反應步驟5。 The 16.0g (14.7mmol) of the formula (VIIIa) of (3 S) - (+) - N - [[2- fluoro-4- [3- (3,4,5-trichlorophenyl) -3- (trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]-tert-butyloxycarbonylcarbamidine and (3R) - ( - ) - mirror image isomer (VIIIb) (3S ) - (+) - enantiomer enriched mixtures of (from reaction step 3) in that the stirring of dioxane 67ml 4M hydrochloric acid for about 18 hours at room temperature. Subsequently, the reaction mixture was concentrated under reduced pressure. To obtain 14.0g (99.5% of theory) of (3 S) - (+) -2- fluoro-4- [3- (3,4,5-trichlorophenyl) -3- (trifluoromethyl) - a mixture of (3S) - ( + ) -mirroromeric acid enriched by 1-pyrrolidyl]benzylidene chloride (IXa) and (3R) - ( - ) -an image isomer of formula (IXb) It was used in reaction step 5 without further purification.

反應步驟5：Reaction step 5: 由式(IIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(IIIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物之合成(3S)-(+)-N-[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1 of formula (IIIa) - pyrrolidin-yl] phenyl] methyl] cyclopropanecarboxamide Amides and formula (IIIb) of (3R) - (-) - enantiomer composition of (3 S) - (+) - enantiomer enriched Synthesis of a mixture

首先在509ml二氯甲烷中裝填15.9g(16.6mmol)由式(IXa)之(3S)-(+)-2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯甲烷氯化銨及式(IXb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物(來自反應步驟4)，並在0℃下添加5.8g(73.1mmol；4當量)吡啶。在0℃下攪拌10分鐘之後，添加4.2g(39.9mmol)環丙烷羰基氯且然後將全部反應混合物在室溫下攪拌約18小時。為進行處理， 用1M鹽酸振盪反應混合物。隨後，去除有機相，乾燥並在減壓下濃縮。藉助在矽膠上利用環己烷/丙酮(梯度)溶析劑混合物進行管柱層析來純化剩餘粗製產物。獲得10.2g(理論之54.1%，純度：89.9%；76.4% ee)以88.2：11.8之比率由式(IIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(IIIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物。 First charged 15.9g (16.6mmol) in 509ml dichloromethane by formula (IXa) of (3 S) - 3- (3,4,5- trichlorophenyl) (+) - 2-fluoro-4- [ (3S) - ( + ) - mirror image of -3-(trifluoromethyl)-1-pyrrolidinyl]phenylmethane chloride and (3R)-(-)-mirromer of formula (IXb) The isomer-rich mixture (from reaction step 4) was added 5.8 g (73.1 mmol; 4 equivalents) of pyridine at 0 °C. After stirring at 0 °C for 10 minutes, 4.2 g (39.9 mmol) of cyclopropanecarbonyl chloride was added and then the entire reaction mixture was stirred at room temperature for about 18 hours. For the treatment, the reaction mixture was shaken with 1 M hydrochloric acid. Subsequently, the organic phase was removed, dried and concentrated under reduced pressure. The remaining crude product was purified by column chromatography on a silica gel using a cyclohexane/acetone (gradient) solvent mixture. Obtained 10.2 g (54.1% of theory, purity: 89.9%; 76.4% ee) from (3S)-(+)-N-[[2-fluoro-4-[3) of formula (IIIa) at a ratio of 88.2:11.8 -(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide and (3R) of formula (IIIb) ( - ) - a mixture of ( 3S )- ( + ) -mirrromeromers enriched in the image isomer.

在Chiracel OD-RH上之保留時間(R_t)為對於式(IIIa)之(S)-(+)-鏡像異構物11.40min及對於式(IIIb)之(R)-(-)-鏡像異構物10.97min。 The retention time (R _t ) on Chiracel OD-RH is 11.40 min for (S) - ( + ) - mirror image isomer of formula (IIIa) and (R) - ( - ) - mirror for formula (IIIb) Isomer 10.97 min.

實驗式：C₂₂H₁₉Cl₃F₄N₂O 分子量：509.75g/mol Experimental formula: C ₂₂ H ₁₉ Cl ₃ F ₄ N ₂ O Molecular weight: 509.75 g/mol

LC-MS(ESI正性)：511.0(M+1)；R_t=3.95min logP=4.8 LC-MS (ESI positive): 511.0 (M + 1); R _t = 3.95 min.

反應步驟6：Reaction step 6: 由主要組份式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(Id)之(2R,3R)-非鏡像異構物組成之(2S,3S)-(+)-非鏡像異構物富集之混合物之合成(2S,3S)-(+)-N-[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3) of the formula (Ia) -(Trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamamine and (2R,3R)-non -image isomer of formula (Id) (2 S ,3 S )- ( + ) - Synthesis of a mixture of non-image isomers

首先在530ml甲醇中裝填8.8g(8.7mmol)由式(IIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(IIIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物(來自反應步驟5)。此後，在室溫下逐份添加13.2g(52.1mmol,6當量)碘並將反應混合物在60℃下攪拌1小時。隨後，添加8.5g(86.8mmol；10當量)乙酸鉀並將混合物在60℃下再攪拌1小時。冷卻後，將飽和二硫亞磺酸鈉溶液逐滴添加至反應混合物中直至褪色為止。為進行處理，在減壓下去除甲醇，並將剩餘殘餘物吸收於乙酸乙酯中並用飽和硫代硫酸鈉溶液振盪。然後用1N鹽酸將經去除有機相振盪一次，去除，乾燥且然後在減壓下濃縮。藉助在矽膠上利 用環己烷/丙酮(梯度)溶析劑混合物進行管柱層析來純化剩餘粗製產物。獲得4.6g(理論之46.3%，純度：90.6%)及2.75g(理論之28.8%；純度：95.6%)式(Id)化合物作為流份1。 First, 8.8 g (8.7 mmol) of (3S)-(+)-N-[[2-fluoro-4-[3-(3,4,5-trichlorophenyl) of formula (IIIa) was charged in 530 ml of methanol. (3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamamine and (3R) - ( - ) -mirrible isomer of formula (IIIb) (3) S )- ( + ) - a mixture of mirror image isomers (from reaction step 5). Thereafter, 13.2 g (52.1 mmol, 6 equivalents) of iodine was added portionwise at room temperature and the reaction mixture was stirred at 60 ° C for 1 hour. Subsequently, 8.5 g (86.8 mmol; 10 equivalents) of potassium acetate was added and the mixture was further stirred at 60 ° C for 1 hour. After cooling, a saturated sodium disulfoxide solution was added dropwise to the reaction mixture until fading. For the treatment, methanol was removed under reduced pressure, and the residue was taken up in ethyl acetate and shaken with saturated sodium sulfate. The removed organic phase was then shaken once with 1N hydrochloric acid, removed, dried and then concentrated under reduced pressure. The remaining crude product was purified by column chromatography on a silica gel using a cyclohexane/acetone (gradient) solvent mixture. 4.6 g (46.3% of theory, purity: 90.6%) and 2.75 g (28.8% of theory; purity: 95.6%) of the compound of formula (Id) were obtained as fraction 1.

作為流份2，獲得以87.3：12.7之比率由主要組份式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺(74：6% ee)及式(Id)之(2R,3R)-非鏡像異構物組成之(2S,3S)-(+)-非鏡像異構物富集之混合物。在對掌性Pak IC上之保留時間(R_t)為對於(Ia)3.95min及對於(Id)4.34min。 As fraction 2, (2S,3S)-(+)-N-[[2-fluoro-4-[2-hydroxy-3-(3) was obtained from the main component of formula (Ia) at a ratio of 87.3:12.7. ,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide (74:6% ee) and formula (Id) (2R, 3R) - diastereomers composition of (2 S, 3 S) - (+) - enriched mixtures of diastereomers. The retention time (R _t ) on the palmitic Pak IC was 3.95 min for (Ia) and 4.34 min for (Id).

流份1與具有小於95%純度之其他流份一起自乙腈重結晶。為進行乾燥，將產物溶解於丙酮中並在減壓下濃縮。此程序重複兩次。隨後，在高真空下在60℃下將產物乾燥5天。 Fraction 1 was recrystallized from acetonitrile with other fractions having less than 95% purity. For drying, the product was dissolved in acetone and concentrated under reduced pressure. This procedure is repeated twice. Subsequently, the product was dried at 60 ° C for 5 days under high vacuum.

實驗式：C₂₂H₁₉Cl₃F₄N₂O₂分子量：525.76g/mol Experimental formula: C ₂₂ H ₁₉ Cl ₃ F ₄ N ₂ O ₂ Molecular weight: 525.76 g/mol

LC-MS(ESI正性)：509.1(M-OH)；R_t=3.57min logP=4.05 LC-MS (ESI positive): 509.1 (M-OH); R _t = 3.57 min.

實例4：式(Ib)之(2R,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺Example 4: (2 R , 3 S )- ( + ) - N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-) of formula (Ib) 3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide

首先在400ml甲醇中裝填6.7g(6.5mmol)由式(IIIa)之(3S)-(+)-N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺及式(IIIb)之(3R)-(-)-鏡像異構物組成之(3S)-(+)-鏡像異構物富集之混合物(其係根據實例3反應步驟5獲得)。此後，在室溫下逐份添加9.9g(39.3mmol,6當量)碘並將反應混合物在60℃下攪拌1小時。隨後，添加6.4g(65.5mmol；10當量)乙酸鉀並將混合物在60℃下再攪拌1小時。冷卻後，在減壓下放掉甲醇，將剩餘殘餘物吸收於 乙酸乙酯中並將反應混合物與飽和二硫亞磺酸鈉溶液混合並振盪。用1N鹽酸將有機相振盪一次，去除並在減壓下濃縮。首先藉助在矽膠上利用環己烷/丙酮(梯度)溶析劑混合物進行管柱層析且然後藉助製備型HPLC純化剩餘粗製產物。可分離1.2g(理論之36.2%，純度：98.6%)式(Ib)之(2R,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺作為流份1，且獲得已自實例1得知之化合物(Ia)作為流份2。 First, 6.7 g (6.5 mmol) of (3S)-(+)-N-[[2-fluoro-4-[3-(3,4,5-trichlorophenyl) of formula (IIIa) was charged in 400 ml of methanol. (3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamamine and (3R) - ( - ) -mirrible isomer of formula (IIIb) (3) S )- ( + ) -Image enantiomerically enriched mixture (obtained according to reaction step 5 of Example 3). Thereafter, 9.9 g (39.3 mmol, 6 equivalents) of iodine was added portionwise at room temperature and the reaction mixture was stirred at 60 ° C for 1 hour. Subsequently, 6.4 g (65.5 mmol; 10 equivalents) of potassium acetate was added and the mixture was further stirred at 60 ° C for 1 hour. After cooling, methanol was taken off under reduced pressure, and the residue was taken up in ethyl acetate and mixture was stirred and sat. The organic phase was shaken once with 1N hydrochloric acid, removed and concentrated under reduced pressure. The column chromatography was first performed by means of a cyclohexane/acetone (gradient) solvent mixture on a silica gel and then the remaining crude product was purified by preparative HPLC. Can be isolated 1.2g (36.2% of theory, purity: 98.6%) of (2 R , 3 S )- ( + ) - N -[[2-fluoro-4-[2-hydroxy-3-() 3,4,5-Trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide as fraction 1, and obtained from Example 1 The compound (Ia) is known as the fraction 2.

實驗式：C₂₂H₁₉Cl₃F₄N₂O₂分子量：525.76g/mol Experimental formula: C ₂₂ H ₁₉ Cl ₃ F ₄ N ₂ O ₂ Molecular weight: 525.76 g/mol

HPLC/MS(ESI正性)：508.9(M-OH)；R_t=1.52min logP=4.06 HPLC/MS (ESI positive): 508.9 (M-OH); R _t = 1.52 min.

旋光度：[α]²⁰=+174.8°(c=1.1；氯仿) Optical rotation: [α] ²⁰ = +174.8 ° (c = 1.1; chloroform)

¹³C NMR(600MHz,DMSO-d₆,ppm)δ=6.6(2×CH₂，環丙基)；14.2(CH，環丙基)；25.2(CH₂，吡咯啶基)；36.8(CH₂-NH)；45.2(CH₂-N，吡咯啶基)；59.8(C-CF₃,)；86.7(C-OH，反式)；100.3；109.2；131.4(C-H，芳基)；162.0(C-F，芳基)；115.1(C-CH₂，芳基)；126.4(CF₃)；129.6(2×C-H，芳基)；129.6(C-Cl，芳基)；134.6(2×C-Cl，芳基)ppm。 ¹³ C NMR (600 MHz, DMSO-d ₆ , ppm) δ = 6.6 (2 × C H ₂ , cyclopropyl); 14.2 ( C H, cyclopropyl); 25.2 ( C H ₂ , pyrrolidinyl); ( C H ₂ -NH); 45.2 ( C H ₂ -N, pyrrolidinyl); 59.8 ( C- CF ₃ ,); 86.7 ( C- OH, trans); 100.3; 109.2; 131.4 ( C- H, aryl group); 162.0 (C -F, aryl); 115.1 (C -CH _{2, aryl); 126.4 (C F 3)} ; 129.6 (2 × C -H, aryl); 129.6 (C -Cl, Aryl); 134.6 (2 x C- Cl, aryl) ppm.

生物實例Biological instance 辣根猿葉甲噴霧測試(PHAECO)Horseradish 猿 leaf spray test (PHAECO)

溶劑：7重量份數二甲基甲醯胺 Solvent: 7 parts by weight of dimethylformamide

乳化劑：烷基芳基聚二醇醚 Emulsifier: alkyl aryl polyglycol ether

為產生適當的活性成分調配物，用所述重量份數的由含有1000ppm乳化劑濃度之水製得之溶劑溶解1重量份數活性成分，直至達到期望濃度為止。為產生其他測試濃度，用含有乳化劑之水稀釋該製備。若需要添加銨鹽或/及滲透劑，將該等各自以1000ppm之濃度添加至調配物溶液中。 To produce a suitable active ingredient formulation, one part by weight of the active ingredient is dissolved in a solvent prepared from water containing 1000 ppm of emulsifier concentration until the desired concentration is reached. To produce other test concentrations, the preparation was diluted with water containing an emulsifier. If it is desired to add an ammonium salt or/and a penetrant, each of these is added to the formulation solution at a concentration of 1000 ppm.

利用期望濃度之活性成分調配物噴霧甘藍葉(甘藍(Brassica oleracea))並利用芥菜甲蟲(辣根猿葉甲)之幼蟲進行繁殖。 The cabbage leaves ( Brassis oleracea) are sprayed with the desired concentration of the active ingredient formulation and propagated using the larvae of the mustard beetle (horse root).

在期望時間後，測定殺死率(%)。100%意味著所有甲蟲幼蟲皆殺死；0%意味著甲蟲幼蟲均未殺死。 After the desired time, the kill rate (%) was determined. 100% means that all beetle larvae are killed; 0% means that the beetle larvae are not killed.

在此測試中，達成表中所列示之結果。 In this test, the results listed in the table are achieved.

小菜蛾噴霧測試(PLUTMA)Plutella xylostella spray test (PLUTMA)

溶劑：7重量份數二甲基甲醯胺 Solvent: 7 parts by weight of dimethylformamide

乳化劑：烷基芳基聚二醇醚 Emulsifier: alkyl aryl polyglycol ether

為產生適當的活性成分調配物，用所述重量份數的由含有1000ppm乳化劑濃度之水製得之溶劑溶解1重量份數活性成分，直至達到期望濃度為止。為產生其他測試濃度，用含有乳化劑之水稀釋該製備。若需要添加銨鹽或/及滲透劑，將該等各自以1000ppm之濃度添加至調配物溶液中。 To produce a suitable active ingredient formulation, one part by weight of the active ingredient is dissolved in a solvent prepared from water containing 1000 ppm of emulsifier concentration until the desired concentration is reached. To produce other test concentrations, the preparation was diluted with water containing an emulsifier. If it is desired to add an ammonium salt or/and a penetrant, each of these is added to the formulation solution at a concentration of 1000 ppm.

利用期望濃度之活性成分調配物噴霧甘藍葉(甘藍)並利用小菜蛾(diamondback moth)(小菜蛾(Plutella xylostella))之幼蟲進行繁殖。 The cabbage leaves (cabbage) are sprayed with the desired concentration of the active ingredient formulation and propagated using the larvae of the diamondback moth ( Plutella xylostella ).

在期望時間後，測定殺死率(%)。100%意味著所有毛蟲皆殺死；0%意味著毛蟲均未殺死。 After the desired time, the kill rate (%) was determined. 100% means that all caterpillars are killed; 0% means that none of the caterpillars are killed.

在此測試中，達成表中所列示之結果。 In this test, the results listed in the table are achieved.

草地灰翅夜蛾噴霧測試(SPODFR)Grasshopper Spodoptera litura spray test (SPODFR)

溶劑：7重量份數二甲基甲醯胺 Solvent: 7 parts by weight of dimethylformamide

乳化劑：烷基芳基聚二醇醚 Emulsifier: alkyl aryl polyglycol ether

為產生適當的活性成分調配物，用所述重量份數的由含有1000ppm乳化劑濃度之水製得之溶劑溶解1重量份數活性成分，直至達到期望濃度為止。為產生其他測試濃度，用含有乳化劑之水稀釋該製備。若需要添加銨鹽或/及滲透劑，將該等各自以1000ppm之濃度添加至調配物溶液中。 To produce a suitable active ingredient formulation, one part by weight of the active ingredient is dissolved in a solvent prepared from water containing 1000 ppm of emulsifier concentration until the desired concentration is reached. To produce other test concentrations, the preparation was diluted with water containing an emulsifier. If it is desired to add an ammonium salt or/and a penetrant, each of these is added to the formulation solution at a concentration of 1000 ppm.

利用期望濃度之活性成分調配物噴霧棉花葉(陸地棉(Gossypium hirsutum))並用夜盜蛾(草地灰翅夜蛾)之毛蟲進行繁殖。 The cotton leaves ( Gossypium hirsutum ) are sprayed with the desired concentration of the active ingredient formulation and propagated with the caterpillars of the night moth (Sphingidae).

在期望時間後，測定殺死率(%)。100%意味著所有毛蟲皆殺死；0%意味著毛蟲均未殺死。 After the desired time, the kill rate (%) was determined. 100% means that all caterpillars are killed; 0% means that none of the caterpillars are killed.

在此測試中，達成表中所列示之結果。 In this test, the results listed in the table are achieved.

二點葉蟎噴霧測試；OP抗性(TETRUR)Two-point leafhopper spray test; OP resistance (TETRUR)

溶劑：7重量份數二甲基甲醯胺 Solvent: 7 parts by weight of dimethylformamide

乳化劑：烷基芳基聚二醇醚 Emulsifier: alkyl aryl polyglycol ether

為產生適當的活性成分調配物，用所述重量份數的由含有1000ppm乳化劑濃度之水製得之溶劑溶解1重量份數活性成分，直至達到期望濃度為止。為產生其他測試濃度，用含有乳化劑之水稀釋該製備。若需要添加銨鹽或/及滲透劑，將該等各自以1000ppm之濃度添加至調配物溶液中。 To produce a suitable active ingredient formulation, one part by weight of the active ingredient is dissolved in a solvent prepared from water containing 1000 ppm of emulsifier concentration until the desired concentration is reached. To produce other test concentrations, the preparation was diluted with water containing an emulsifier. If it is desired to add an ammonium salt or/and a penetrant, each of these is added to the formulation solution at a concentration of 1000 ppm.

利用期望濃度之活性成分調配物噴霧嚴重滋生所有階段之溫室紅葉蟎(二點葉蟎)之菜豆植物(菜豆(Phaseolus vulgaris))。 The use of the active ingredient formulation at the desired concentration sprays the bean bean plant ( phaseolus vulgaris ), which is a serious breeding ground for all stages of greenhouse red leafhopper (two-leaf leafhopper ).

在期望時間段後，測定功效(%)。100%意味著所有紅葉蟎皆殺死；0%意味著紅葉蟎均未殺死。 After a desired period of time, the efficacy (%) was determined. 100% means that all red leafhoppers are killed; 0% means that none of the red leafhoppers are killed.

在此測試中，達成表中所列示之結果。 In this test, the results listed in the table are achieved.

西花薊馬噴霧測試(FRANOC)West Flower Hummer Spray Test (FRANOC)

溶劑：7重量份數二甲基甲醯胺 Solvent: 7 parts by weight of dimethylformamide

乳化劑：烷基芳基聚二醇醚 Emulsifier: alkyl aryl polyglycol ether

為產生適當的活性成分調配物，用所述重量份數的由含有1000ppm乳化劑濃度之水製得之溶劑溶解1重量份數活性成分，直至達到期望濃度為止。為產生其他測試濃度，用含有乳化劑之水稀釋該製備。若需要添加銨鹽或/及滲透劑，將該等各自以1000ppm之濃度添加至調配物溶液中。 To produce a suitable active ingredient formulation, one part by weight of the active ingredient is dissolved in a solvent prepared from water containing 1000 ppm of emulsifier concentration until the desired concentration is reached. To produce other test concentrations, the preparation was diluted with water containing an emulsifier. If it is desired to add an ammonium salt or/and a penetrant, each of these is added to the formulation solution at a concentration of 1000 ppm.

用期望濃度之活性成分調配物噴霧叢狀菜豆植物(菜豆)。在乾燥 後，用混合薊馬群體(西花薊馬)感染經處理植物。 Spray the plexiform bean plant ( cabbage ) with the active ingredient of the desired concentration. After drying, the treated plants were infected with a mixed thrips population ( Western Thrips ) .

在期望時間段後，測定植物保護功效(%)。100%意味著損害不明顯；0%意味著對經處理植物之損害對應於未經處理對照之損害。 Plant protection efficacy (%) was determined after a desired period of time. 100% means that the damage is not obvious; 0% means that the damage to the treated plants corresponds to the damage of the untreated control.

在此測試中，達成表中所列示之結果。 In this test, the results listed in the table are achieved.

褐飛虱測試(NILALU)Brown planthopper test (NILALU)

溶劑：14重量份數二甲基甲醯胺 Solvent: 14 parts by weight of dimethylformamide

乳化劑：2重量份數之烷基芳基聚二醇醚 Emulsifier: 2 parts by weight of alkyl aryl polyglycol ether

為產生適當的活性成分調配物，用所述重量份數溶劑及乳化劑溶解1重量份數活性成分，直至達成期望濃度為止。為產生其他測試濃度，使用水進行稀釋。在需要添加銨鹽或/及滲透劑(菜籽油甲基酯)之情形下，在已稀釋經製成調配物溶液後，各自以1000ppm之濃度對該等添加劑進行移液。 To produce a suitable active ingredient formulation, 1 part by weight of the active ingredient is dissolved with the parts by weight of solvent and emulsifier until the desired concentration is achieved. To produce additional test concentrations, use water for dilution. In the case where it is necessary to add an ammonium salt or/and a penetrating agent (rice oil methyl ester), after the diluted preparation solution is prepared, the additives are each pipetted at a concentration of 1000 ppm.

藉由利用活性成分調配物以期望濃度進行噴霧處理水稻植物(巴利拉水稻變種(Oryza sativa,var.Balilla))，且然後利用褐飛虱(brown planthopper)(褐飛虱(Nilaparvata lugens))之L3幼蟲進行繁殖。 The rice plant ( Oryza sativa, var. Balilla ) is spray-treated at a desired concentration by using the active ingredient formulation, and then the brown planthopper ( Nilaparvata lugens ) is utilized. The L3 larvae are propagated.

在期望時間後，測定殺死率(%)。100%意味著所有飛虱皆殺死；0%意味著飛虱均未殺死。 After the desired time, the kill rate (%) was determined. 100% means that all the locusts are killed; 0% means that the locusts are not killed.

在此測試中，達成表中所列示之結果。 In this test, the results listed in the table are achieved.

微小牛尾壁蝨(Boophilus microplus)浸漬測試(BOOPMI DIP)Boophilus microplus impregnation test (BOOPMI DIP)

測試動物：牛蜱(微小牛尾壁蝨)帕克斯特品系(Parkhurst strain)，SP抗性 Test animals: Burdock (Micro oxtail tick) Parkhurst strain, SP resistance

溶劑：二甲基亞碸 Solvent: dimethyl hydrazine

將10mg活性成分溶解於0.5ml二甲基亞碸中。為產生適宜調配物，在每一情形下用水將活性成分溶液稀釋至期望濃度。 10 mg of the active ingredient was dissolved in 0.5 ml of dimethyl hydrazine. To produce a suitable formulation, the active ingredient solution is diluted with water to the desired concentration in each case.

將此活性成分調配物移液至管中。將8隻至10隻飽食的雌性牛蜱成蟲(微小牛尾壁蝨)轉移至具有洞之另一管中。將管浸沒至活性成分 調配物中，且使所有蜱完全潤濕。在耗盡液體後，將蜱轉移於濾盤上至塑膠盤中並儲存在氣候受控之室中。 The active ingredient formulation is pipetted into the tube. Transfer 8 to 10 satiety female calves (micro-burrock tick) into another tube with a hole. Immerse the tube to the active ingredient In the formulation, and all the mashes are completely wetted. After depleting the liquid, the crucible is transferred to a filter tray to a plastic tray and stored in a climate controlled chamber.

在期望時間後藉由可孕卵之產生評價活性。將不明顯可孕之卵儲存在氣候受控之櫃中直至在約42天後幼蟲孵出為止。100%之功效意味著蜱均未產生任何可孕卵；0%意味著所有卵皆可孕。 Activity was evaluated by the production of fertile eggs after the desired time. Eggs that are not significantly fertile are stored in climate controlled cabinets until the larvae hatch after about 42 days. 100% efficacy means that no eggs produce any fertile eggs; 0% means that all eggs are fertile.

在此測試中，達成表中所列示之結果。 In this test, the results listed in the table are achieved.

微小牛尾壁蝨注射測試(BOOPMI INJ)Tiny oxtail tick injection test (BOOPMI INJ)

溶劑：二甲基亞碸 Solvent: dimethyl hydrazine

為產生適宜的活性成分調配物，將10mg活性成分與0.5ml溶劑混合並用溶劑將濃縮物稀釋至期望濃度。 To produce a suitable active ingredient formulation, 10 mg of the active ingredient is mixed with 0.5 ml of solvent and the concentrate is diluted to the desired concentration with a solvent.

將1μl活性成分溶液注射至5隻飽食的雌性牛蜱成蟲(微小牛尾壁蝨)之腹部中。將該等動物轉移至盤中並保存在氣候受控之室中。 1 μl of the active ingredient solution was injected into the abdomen of five satiety female burdock adults ( micro oxtail tick ) . The animals were transferred to a pan and stored in a climate controlled chamber.

在期望時間後藉由可孕卵之產生評價活性。將不明顯可孕之卵儲存在氣候受控之櫃中直至在約42天後幼蟲孵出為止。100%之功效意味著蜱均未產生任何可孕卵；0%意味著所有卵皆可孕。 Activity was evaluated by the production of fertile eggs after the desired time. Eggs that are not significantly fertile are stored in climate controlled cabinets until the larvae hatch after about 42 days. 100% efficacy means that no eggs produce any fertile eggs; 0% means that all eggs are fertile.

在此測試中，達成表中所列示之結果。 In this test, the results listed in the table are achieved.

Claims (12)

一種製備鏡像異構物富集之式(I)之N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之方法， 其中立體異構源碳原子係由*標識，其特徵在於，在第一步驟中，式(II)之外消旋3-(3,4,5-三氯苯基)-3-(三氟甲基)吡咯啶 其中立體異構源碳原子係由*標識，由適宜的鏡像異構純酸之助分離成式(IIa)及(IIb)之鏡像異構物 及然後，在第二反應步驟中，使該式(IIa)化合物在觸媒存在下與式(IV)之N-[(4-溴-2-氟苯基)甲基]環丙烷甲醯胺反應， 得到化合物式(IIIa)之N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之(S)-鏡像異構物 及然後在第三反應步驟中在適宜氧化劑存在下將該(S)-鏡像異構物羥基化，獲得式(Ia)之(2S,3S)-(+)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺作為主要組份 或使該式(IIb)化合物在觸媒存在下與式(IV)之N-[(4-溴-2-氟苯基)甲基]環丙烷甲醯胺反應， 得到化合物式(IIIb)之N-[[2-氟-4-[3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺之(R)-鏡像異構物 及然後在第三反應步驟中在適宜氧化劑存在下將該(R)-鏡像異構物羥基化，獲得式(Id)之(2R,3R)-(-)-N-[[2-氟-4-[2-羥基-3-(3,4,5-三氯苯基)-3-(三氟甲基)-1-吡咯啶基]苯基]甲基]環丙烷甲醯胺作為主要組份 N -[[2-fluoro-4-[2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl) of formula (I) prepared by enrichment of mirror image isomer a method of ethyl-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamamine, Wherein the stereogenic source carbon atom is identified by *, characterized in that in the first step, racemic 3-(3,4,5-trichlorophenyl)-3-(trifluoro) is of formula (II) Methyl pyrrolidine The stereogenic source carbon atom is identified by * and is separated into the mirror image isomers of formula (IIa) and (IIb) by the appropriate mirror image isomerized pure acid. And then, in the second reaction step, the compound of the formula (IIa) is reacted with N-[(4-bromo-2-fluorophenyl)methyl]cyclopropanecarbamamine of the formula (IV) in the presence of a catalyst. reaction, The N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl group of the formula (IIIa) is obtained. (S)-Spiegelmer of methyl]cyclopropanecarbamamine And then hydroxylating the (S)-mirromeric isomer in the presence of a suitable oxidizing agent in a third reaction step to obtain (2S,3S)-(+)-N-[[2-fluoro-) of formula (Ia) 4-[2-Hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide as the main Component Or reacting the compound of the formula (IIb) with N-[(4-bromo-2-fluorophenyl)methyl]cyclopropanecarbamamine of the formula (IV) in the presence of a catalyst, The N -[[2-fluoro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl group of the formula (IIIb) is obtained. (R)-Spiegelmer of methyl]cyclopropanecarbamamine And then hydroxylating the (R)-mirromeric isomer in the presence of a suitable oxidizing agent in a third reaction step to obtain (2R,3R)-(-)-N-[[2-fluoro-) of formula (Id) 4-[2-Hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-1-pyrrolidinyl]phenyl]methyl]cyclopropanecarbamide as the main Component 一種製備式(Ia)化合物之方法， 其特徵在於將式(IIIa)化合物 在適宜氧化劑存在下羥基化。 A method of preparing a compound of formula (Ia), Characterized by a compound of formula (IIIa) Hydroxylation in the presence of a suitable oxidizing agent. 一種製備式(Id)化合物之方法， 其特徵在於將式(IIIb)化合物 在適宜氧化劑存在下羥基化。 A method of preparing a compound of formula (Id), Characterized by the compound of formula (IIIb) Hydroxylation in the presence of a suitable oxidizing agent. 如請求項1、2或3之方法，其中該羥基化係用碘在乙酸鉀及適宜氧來源存在下進行。 The method of claim 1, 2 or 3 wherein the hydroxylation is carried out with iodine in the presence of potassium acetate and a suitable source of oxygen. 一種式(Ia)化合物 a compound of formula (Ia) 一種式(Ib)化合物 a compound of formula (Ib) 一種式(Ic)化合物 a compound of formula (Ic) 一種式(Id)化合物 a compound of formula (Id) 一種式(IIIa)化合物 a compound of formula (IIIa) 一種式(IIIb)化合物 a compound of formula (IIIb) 一種式(Ia)化合物之用途，其用於控制動物有害生物。 Use of a compound of formula (Ia) for controlling animal pests. 一種式(Ib)化合物之用途，其用於控制動物有害生物。 Use of a compound of formula (Ib) for controlling animal pests.