CN104602526A

CN104602526A - Methods of controlling insects

Info

Publication number: CN104602526A
Application number: CN201380044032.5A
Authority: CN
Inventors: M·埃尔卡塞米; J·Y·卡赛雷
Original assignee: Syngenta Participations AG
Current assignee: Syngenta Participations AG
Priority date: 2012-08-24
Filing date: 2013-08-16
Publication date: 2015-05-06
Also published as: WO2014029707A1

Abstract

The present invention provides a method comprising applying to a crop of rice plants, the locus thereof, or propagation material thereof, a compound of formula (I) wherein -B1-Beta2-Beta3- is -C=N-O-, -C=N-CH2-, or -N-CH2-CH2-; providing that when A is A1 -B1-Beta2-Beta3- is -C=N-CH2- or -N-CH2-CH2-, when A is A2 -B1-Beta2-Beta3- is -C=N-O- or -N-CH2-CH2-, and when A is A3 -B1-B2-B3- is -C=N-O-; R1 is trifluoromethyl, difluoromethyl or chlorodifluoromethyl; R2 is group (X) X2 is C-X6 or nitrogen; X1, X3 and X6 are independently hydrogen, halogen or trihalomethyl, wherein at least one of X1, X3 and X 6 : is not hydrogen; A is selected from (A1) to (A5) Y1 is C-R6, CH or nitrogen; Y2 and Y3 are independently CH or nitrogen; wherein no more than two of Y1, Y2 and Y3 are nitrogen and wherein Y2 and Y3 are not both nitrogen; R5 is hydrogen, halogen, cyano, nitro, NH2, C1-C4alkyl, C1-C4haloalkyl, C3-C5cycloalkyl, C3-C5halocycloalkyl, C1-C2alkoxy, or C1-C2haloalkoxy; providing that when A is A3 or A4, R5 is not hydrogen; R6 when present together with R5 forms a -CH=CH-CH=CH- bridge; R7 is C1-C4alkyl; R8 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy(C1-C4)alkyl, C1-C4alkylthio(C1-C4)alkyl, C1-C4alkylsulfmyl(C1-C4)alkyl, C1-C4alkylsulfonyl(C1-C4)alkyl, C3-C6cycloalkyl, C3-C6cycloalkyl(C1-C4)alkyl-, or tetrahydrofuranyl; R9 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkyl-O-CH2-, C1-C4haloalkyl-O-CH2-,C3-C6cycloalkyl, C3- C6cycloalkyl-CH2, C1-C4alkyl-S-CH2-, C1-C4alkyl-S(O)-CH2-, or C1-C4alkyl-S(O)-CH2; each Z is independently halogen, C1-C12alkyl or C1-C12alkyl substituted by one to five R12, nitro, C1-C12alkoxy or C1-C12alkoxy substituted by one to five R12 cyano, C1-C12alkylsulfinyl, C1-C12alkylsulfonyl, C1-C12haloalkylsulfinyl, C1-C12haloalkylsulfonyl, hydroxyl or thiol; each R12 is halogen, cyano, nitro, hydroxy, C1-C8alkoxy-, C1-C8haloalkoxy-, mercapto, C1-C8alkylthio-, or C1-C8haloalkylthio; and k is 0, 1,2 or 3.

Description

Control the method for insect

The present invention relates to a kind of method controlling insect, particularly infect the insect of paddy rice.

By the antagonism of γ-aminobutyric acid (GABA) gate chloride channel activate insecticidal, kill acarid, nematicide and/or kill molluscan, and comprise the compound of the heterocycle (this heterocycle is replaced by a haloalkyl substitution) of a fractional saturation and the ring of one or two aromatic or heteroaromatic be optionally substituted, representative is described in people's " biochemistry and biophysical studies communication " (Biochemical and Biophysical ResearchCommunications) such as such as assistant (Ozoe) difficult to understand, the pesticides of a kind of newtype in 391 (2010) 744-749.Compound from this type is described in WO 2005/085216 (EP 1731512) widely, WO2007/123853, WO 2007/075459, WO 2009/002809, WO 2008/019760, WO2008/122375, WO 2008/128711, WO 2009/097992, WO 2010/072781, WO2010/072781, WO 2008/126665, WO 2007/125984, WO 2008/130651, JP2008110971, JP 2008133273, JP 2009108046, WO 2009/022746, WO2009/022746, WO 2010/032437, WO 2009/080250, WO 2010/020521, WO2010/025998, WO 2010/020522, WO 2010/084067, WO 2010/086225, in WO2010/149506 and WO 2010/108733.

Have been surprisingly found that now that the specific insecticide (being disclosed in such as WO 2009/080250, WO2010/020522, WO 2010/149506, WO 2011/101229 and WO 2012/045700) of γ-aminobutyric acid (GABA) the gate chloride channel antagonists from this newtype is highly effective controlling some pest in paddy rice.

Therefore, these compounds represented for protect useful plant crop particularly rice crop avoid infecting the important new solution of of the insect of rice crop, particularly when these insects have resistance to current method.

In a first aspect of the present invention, provide a kind of method, the method comprises uses a kind of compound with Formula I to the crop of rice plants, its place or its propagating materials

Wherein-B ¹-B ²-B ³-be-C=N-O-,-C=N-CH ₂-or-N-CH ₂-CH ₂-; Its condition is

When A is A1 ,-B ¹-B ²-B ³-be-C=N-CH ₂-or-N-CH ₂-CH ₂-;

When A is A2 ,-B ¹-B ²-B ³-be-C=N-O-or-N-CH ₂-CH ₂-, and

When A is A3 ,-B ¹-B ²-B ³-be-C=N-O-;

R ¹trifluoromethyl, difluoromethyl or chlorodifluoramethyl-;

R ²it is radicals X

X ²c-X ⁶or nitrogen;

X ¹, X ³and X ⁶hydrogen, halogen or trihalomethyl group, wherein X independently ¹, X ³and X ⁶in at least one is not hydrogen;

A is selected from A1 to A5

Y ¹c-R ⁶, CH or nitrogen;

Y ²and Y ³cH or nitrogen independently;

Wherein Y ¹, Y ²and Y ³in no more than two be nitrogen and wherein Y ²and Y ³both inequalities are nitrogen;

R ⁵hydrogen, halogen, cyano group, nitro, NH ₂, C ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₃-C ₅cycloalkyl, C ₃-C ₅halogenated cycloalkyl, C ₁-C ₂alkoxyl or C ₁-C ₂halogenated alkoxy; Its condition is when A is A3 or A4, R ⁵not hydrogen;

R ⁶when it is present with R ⁵form-CH=CH-CH=CH-bridge together;

R ⁷c ₁-C ₄alkyl;

R ⁸c ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkoxyl (C ₁-C ₄) alkyl, C ₁-C ₄alkylthio group (C ₁-C ₄) alkyl, C ₁-C ₄alkyl sulphinyl (C ₁-C ₄) alkyl, C ₁-C ₄alkyl sulphonyl (C ₁-C ₄) alkyl, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl (C ₁-C ₄) alkyl-or tetrahydrofuran base;

R ⁹c ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄haloalkyl-O-CH ₂-, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl-CH ₂-, C ₁-C ₄alkyl-S-CH ₂-, C ₁-C ₄alkyl-S (O)-CH ₂-or C ₁-C ₄alkyl-S (O ₂)-CH ₂;

Each Z is halogen, C independently ₁-C ₁₂alkyl or by one to five R ¹²the C replaced ₁-C ₁₂alkyl, nitro, C ₁-C ₁₂alkoxyl or by one to five R ¹²the C replaced ₁-C ₁₂alkoxyl, cyano group, C ₁-C ₁₂alkyl sulphinyl, C ₁-C ₁₂alkyl sulphonyl, C ₁-C ₁₂alkylsulfinyl, C ₁-C ₁₂halogenated alkyl sulfonyl, hydroxyl or mercaptan;

Each R ¹²halogen, cyano group, nitro, hydroxyl, C ₁-C ₈alkoxyl-, C ₁-C ₈halogenated alkoxy-, sulfydryl, C ₁-C ₈alkylthio group-or C ₁-C ₈halogenated alkylthio; And

K is 0,1,2 or 3.

The method can be the insect for controlling and/or prevent to be selected from lower group, this group is made up of the following: stem borer, tortrix moth (leaffolder), springtail, cecidomyiia, screw thread maggot, rice stinkbug and black stinkbug, preferred springtail and/or stem borer, most preferably springtail and specifically brown plant-hopper.

In one embodiment, the invention provides a kind of control in paddy rice and/or the method for prevention stem borer, the method comprises uses a kind of compound with Formula I to the crop of rice plants, its place or its propagating materials.In one embodiment, the invention provides a kind of compound with Formula I for controlling and/or prevent the purposes of stem borer, particularly in paddy rice.This stem borer can have resistance to other insecticides.The example of stem borer comprises straw borer spp, striped rice borer, top snout moth's larva, goldrimmed moth, white standing grain snout moth's larva genus, positive paddy stem borer, the white snout moth's larva of rice, yellow tail moth standing grain snout moth's larva, moth stem Noctua, pink rice borer.The invention provides in other at one and a kind ofly there are one or more in the compound of Formula I for controlling methods of the supervision approval of the purposes of stem borer (preferably in paddy rice) for obtaining, the method comprise with reference to, submit or depend at least one step in biological data to, the active component described in the display of these biological datas reduces insect pressure.

In one embodiment, the invention provides a kind of control in paddy rice and/or the method for prevention tortrix moth, the method comprises uses a kind of compound with Formula I to the crop of rice plants, its place or its propagating materials.In one embodiment, the invention provides a kind of compound with Formula I for controlling and/or prevent the purposes of tortrix moth, particularly in paddy rice.This tortrix moth can have resistance to other insecticides.The example of tortrix moth comprises leaf roll snout moth's larva and belongs to (Cnaphalocrocis spp.), rice leaf roller, and brush must wild snout moth's larva belongs to (Marasmia spp.), the angle order brush wild snout moth's larva of palpus (Marasmia patnalis), rice shows line brush must wild snout moth's larva (Marasmia exigua).The invention provides in other at one and a kind ofly there are one or more in the compound of Formula I for controlling methods of the supervision approval of the purposes of tortrix moth (preferably in paddy rice) for obtaining, the method comprise with reference to, submit or depend at least one step in biological data to, the active component described in the display of these biological datas reduces insect pressure.

In one embodiment, the invention provides a kind of control in paddy rice and/or the method for prevention springtail, the method comprises uses a kind of compound with Formula I to the crop of rice plants, its place or its propagating materials.In one embodiment, the invention provides a kind of compound with chemical formula for controlling and/or prevent the purposes of springtail, particularly in paddy rice.This springtail can have resistance to other insecticides.The example of springtail comprises rice leafhopper genus, nephotettix bipunctatus, two rice leafhoppers, Malaya rice leafhopper, rice leafhopper, brown plant-hopper, white-backed planthopper, preferred brown plant-hopper.The invention provides in other at one and a kind ofly there are one or more in the compound of Formula I for controlling methods of the supervision approval of the purposes of springtail (preferably in paddy rice) for obtaining, the method comprise with reference to, submit or depend at least one step in biological data to, the active component described in the display of these biological datas reduces insect pressure.

In one embodiment, the invention provides a kind of control in paddy rice and/or the method for prevention cecidomyiia, the method comprises uses a kind of compound with Formula I to the crop of rice plants, its place or its propagating materials.In one embodiment, the invention provides a kind of compound with chemical formula for controlling and/or prevent the purposes of cecidomyiia, particularly in paddy rice.This cecidomyiia can have resistance to other insecticides.Cecidomyiia example comprises cecidomyiia genus, rice gall midge.The invention provides in other at one and a kind ofly there are one or more in the compound of Formula I for controlling methods of the supervision approval of the purposes of cecidomyiia (preferably in paddy rice) for obtaining, the method comprise with reference to, submit or depend at least one step in biological data to, the active component described in the display of these biological datas reduces insect pressure.

In one embodiment, the invention provides a kind of control in paddy rice and/or the method for prevention screw thread maggot, the method comprises uses a kind of compound with Formula I to the crop of rice plants, its place or its propagating materials.In one embodiment, the invention provides a kind of compound with chemical formula for controlling and/or prevent the purposes of screw thread maggot, particularly in paddy rice.This screw thread maggot can have resistance to other elder brother's insecticides.The example of screw thread maggot comprises New records, luxuriant and rich with fragrance island rice hair eye ephydrid.The invention provides in other at one and a kind ofly there are one or more in the compound of Formula I for controlling methods of the supervision approval of the purposes of screw thread maggot (preferably in paddy rice) for obtaining, the method comprise with reference to, submit or depend at least one step in biological data to, the active component described in the display of these biological datas reduces insect pressure.

In one embodiment, the invention provides a kind of control in paddy rice and/or the method for prevention rice stinkbug, the method comprises uses a kind of compound with Formula I to the crop of rice plants, its place or its propagating materials.In one embodiment, the invention provides a kind of compound with chemical formula for controlling and/or prevent the purposes of rice stinkbug, particularly in paddy rice.This rice stinkbug can have resistance to other insecticides.The example of rice stinkbug comprises Leptocorisa spp genus, large Leptocorisa spp, magnificent Leptocorisa spp, standing grain spider edge stinkbug.The invention provides in other at one and a kind ofly there are one or more in the compound of Formula I for controlling methods of the supervision approval of the purposes of rice stinkbug (preferably in paddy rice) for obtaining, the method comprise with reference to, submit or depend at least one step in biological data to, the active component described in the display of these biological datas reduces insect pressure.

In one embodiment, the invention provides and a kind ofly in paddy rice, control and/or prevent the method for black stinkbug, the method comprises uses a kind of compound with Formula I to the crop of rice plants, its place or its propagating materials.In one embodiment, the invention provides a kind of compound with chemical formula for controlling and/or prevent the purposes of black stinkbug, particularly in paddy rice.This black stinkbug can have resistance to other insecticides.The example of black stinkbug comprises black stinkbug and belongs to (Scotinophara sp.), the black stinkbug of Malaya (Scotinophara coarctata), the black stinkbug of rice (Scotinophara lurida), the black stinkbug of wide wing (Scotinophara latiuscula).The invention provides in other at one and a kind ofly there are one or more in the compound of Formula I for controlling methods of the supervision approval of the purposes of black stinkbug (preferably in paddy rice) for obtaining, the method comprise with reference to, submit or depend at least one step in biological data to, the active component described in the display of these biological datas reduces insect pressure.

The present invention preferably relates to and controlling and/or the method for prevention springtail (and particularly brown plant-hopper) and/or stem borer (particularly straw borer spp).Most preferably, the present invention relates to and control and/or prevention springtail and the method for particularly brown plant-hopper.

Compound of the present invention can exist with different geometry or optical isomer or tautomeric form.Present invention encompasses this type of all isomer and dynamic isomer and their mixture being in all proportions, together with isotope form, the compound of such as deuterate.Compound of the present invention can comprise one or more asymmetric carbon atom, and can as enantiomter (or diastereoisomer to) or as this type of mixture and exist.Mentioning salt and N-oxide is also comprised to mentioning of compound of the present invention.

For B ¹, B ², B ³, R ¹, R ², Y ¹, Y ², Y ³, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹², X ¹x ², X ³, X ⁶, Z and k preference as described below with any combination.

Preferably, R ¹trifluoromethyl or chlorodifluoramethyl-, most preferably trifluoromethyl.

Preferably, X ¹, X ³and X ⁶hydrogen, halogen or trifluoromethyl, wherein X independently ¹, X ³and X ⁶in at least two be not hydrogen.More preferably, X ¹, X ³and X ⁶hydrogen, chlorine, bromine or trifluoromethyl, wherein X independently ¹, X ³and X ⁶in at least two be not hydrogen.Preferably, X ¹, X ³and X ⁶in at least two be chlorine, bromine or trifluoromethyl.

In a group of compound, R ²be 3,5-dichlorophenyl-, the chloro-4-fluorophenyl of 3--, the fluoro-4-chlorphenyl of 3--, 3,4-dichlorophenyl-, the chloro-4-bromophenyl of 3--, the chloro-4-fluorophenyl of 3,5-bis--, 3,4,5-trichlorophenyl-, the chloro-4-iodophenyl of 3,5-bis--, 3,4,5-trifluorophenyl-, the chloro-5-bromophenyl of 3--, the chloro-5-fluorophenyl of 3--, the chloro-5-of 3-(trifluoromethyl) phenyl-, the chloro-5-of 3,4-bis-(trifluoromethyl) phenyl-, two (trifluoromethyl) phenyl of 3,5--, two (trifluoromethyl) phenyl of 4-chloro-3,5--, 3-(trifluoromethyl) phenyl-, the chloro-4-pyridine radicals of 2,6-bis--, two (the trifluoromethyl)-4-pyridine radicals of 2,6--, the bromo-5-of 3-(trifluoromethyl) phenyl-, be more preferably the chloro-5-bromophenyl of 3--, the chloro-5-of 3-(trifluoromethyl) phenyl-, the chloro-4-fluorophenyl of 3,5-bis--, 3,4,5-trichlorophenyl-, two (trifluoromethyl) phenyl of 3,5--, 3-(trifluoromethyl) phenyl-, the chloro-4-pyridine radicals of 2,6-bis--, two (the trifluoromethyl)-4-pyridine radicals of 2,6--, the chloro-4-bromophenyl of 3,5-bis--, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyl-, or 3,4-dichlorophenyl-, more preferably R ²3,5-Dichloro-phenyl, 3,5-bis-chloro-4-fluorophenyl-or 3,4,5-trichloro-pheny, most preferably 3,5-Dichloro-phenyl.

Preferably, Y ¹cH, Y ²cH, Y ³cH, or Y ¹n, Y ²cH, Y ³cH, or Y ¹n, Y ²n, Y ³cH, or Y ¹cH, Y ²n, Y ³cH, or Y ¹cH, Y ²cH, Y ³n.Most preferably, Y ¹cH, Y ²cH, and Y ³cH.

Preferably, R ⁵hydrogen, chlorine, bromine, fluorine, trifluoromethyl, methyl, ethyl, methoxyl group, nitro, trifluoromethoxy, cyano group, cyclopropyl, more preferably, R ⁵hydrogen, chlorine, bromine, fluorine, trifluoromethyl, methyl, ethyl, nitro, cyano group, cyclopropyl, most preferably, R ⁵hydrogen, cyano group, chlorine, bromine, fluorine, methyl or trifluoromethyl.

Preferably, R ⁸c ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄haloalkyl-O-CH ₂-, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl-CH ₂-, C ₁-C ₄alkyl-S (O)-CH ₂-, C ₁-C ₄alkyl-S (O ₂)-CH ₂-, more preferably C ₁-C ₄alkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄alkyl-S-CH ₂-, C ₁-C ₄alkyl-SO-CH ₂-, C ₁-C ₄alkyl-SO ₂-CH ₂-, C ₃-C ₄cycloalkyl or C ₃-C ₄cycloalkyl-CH ₂-, most preferably, R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-.

Preferably, R ⁹c ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄haloalkyl-O-CH ₂-, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl-CH ₂-, C ₁-C ₄alkyl-S (O)-CH ₂-, C ₁-C ₄alkyl-S (O ₂)-CH ₂-, more preferably C ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄haloalkyl-O-CH ₂-, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl-CH ₂-, more preferably C ₁-C ₄alkyl, C ₁-C ₄haloalkyl or C ₃-C ₄cycloalkyl, more preferably methyl, ethyl, n-pro-pyl, CF ₃cH ₂-or cyclopropyl, even more preferably ethyl, CF ₃cH ₂-or cyclopropyl.

Preferably, each Z is halogen, cyano group, C independently ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkoxyl or C ₁-C ₄halogenated alkoxy, most preferably, each Z is hydrogen, cyano group, halogen, methyl, halogenated methyl, methoxyl group or halogenated methoxy independently, most preferably cyano group or trifluoromethyl.

Each R ¹²preferably bromine, chlorine, fluorine, methoxyl group or methyl mercapto independently, most preferably chlorine, fluorine or methoxyl group.

Preferably, k is 0 or 1.

In a group of compound ,-B ¹-B ²-B ³-be-C=N-O-.

In another group of compound ,-B ¹-B ²-B ³-be-C=N-CH ₂-.

In another group of compound ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-.

In another group of compound, Y ¹c-R ⁶, and R ⁶and R ⁵form-CH=CH-CH=CH-bridge together.

In one embodiment, the compound with Formula I is the compound with Formula I A

Wherein B ¹, B ², B ³, R ¹, R ², Y ¹, Y ², Y ³, R ⁵and R ⁸be as have Formula I compound define.In the compound with Formula I A, B ¹, B ², B ³, R ¹, R ², Y ¹, Y ², Y ³, R ⁵and R ⁸preferred definition be show as following with any combination.

In a group of compound, R ²be 3,5-dichlorophenyl-, the chloro-4-fluorophenyl of 3--, the fluoro-4-chlorphenyl of 3--, 3,4-dichlorophenyl-, the chloro-4-bromophenyl of 3--, the chloro-4-fluorophenyl of 3,5-bis--, 3,4,5-trichlorophenyl-, the chloro-4-iodophenyl of 3,5-bis--, 3,4,5-trifluorophenyl-, the chloro-5-bromophenyl of 3--, the chloro-5-fluorophenyl of 3--, the chloro-5-of 3-(trifluoromethyl) phenyl-, the chloro-5-of 3,4-bis-(trifluoromethyl) phenyl-, two (trifluoromethyl) phenyl of 3,5--, two (trifluoromethyl) phenyl of 4-chloro-3,5--, 3-(trifluoromethyl) phenyl-, the chloro-4-pyridine radicals of 2,6-bis--, two (the trifluoromethyl)-4-pyridine radicals of 2,6--, the bromo-5-of 3-(trifluoromethyl) phenyl-, be more preferably the chloro-5-bromophenyl of 3--, the chloro-5-of 3-(trifluoromethyl) phenyl-, the chloro-4-fluorophenyl of 3,5-bis--, 3,4,5-trichlorophenyl-, two (trifluoromethyl) phenyl of 3,5--, 3-(trifluoromethyl) phenyl-, the chloro-4-pyridine radicals of 2,6-bis--, two (the trifluoromethyl)-4-pyridine radicals of 2,6--, the chloro-4-bromophenyl of 3,5-bis--, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyl-, or 3,4-dichlorophenyl-, more preferably R ²3,5-Dichloro-phenyl or 3,4,5-trichloro-pheny, most preferably 3,5-Dichloro-phenyl.

Preferably, R ⁵hydrogen, chlorine, bromine, fluorine, trifluoromethyl, methyl, ethyl, methoxyl group, nitro, trifluoromethoxy, cyano group, cyclopropyl, more preferably, R ⁵hydrogen, chlorine, bromine, fluorine, trifluoromethyl, methyl, ethyl, nitro, cyano group, cyclopropyl, more preferably, R ⁵hydrogen, cyano group, chlorine, bromine, fluorine, methyl or trifluoromethyl, even more preferably hydrogen, chlorine, bromine, methyl or trifluoromethyl, most preferably chlorine, bromine, fluorine or methyl.

Preferably, R ⁸c ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄haloalkyl-O-CH ₂-, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl-CH ₂-, C ₁-C ₄alkyl-S (O)-CH ₂-, C ₁-C ₄alkyl-S (O ₂)-CH ₂-, more preferably C ₁-C ₄alkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄alkyl-S-CH ₂-, C ₁-C ₄alkyl-SO-CH ₂-, C ₁-C ₄alkyl-SO ₂-CH ₂-, C ₃-C ₄cycloalkyl or C ₃-C ₄cycloalkyl-CH ₂-, more preferably, R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, most preferably n-pro-pyl or cyclopropyl.

In a group of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-CH ₂-.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-CH ₂-and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁵chlorine, bromine, fluorine or methyl.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be chlorine, bromine, fluorine or methyl and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be chlorine, bromine, fluorine or methyl and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In a group of compound with Formula I A ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁵chlorine, bromine, fluorine or methyl.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be chlorine, bromine, fluorine or methyl and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound with Formula I A ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵chlorine, bromine, fluorine or methyl, R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In another group of compound with Formula I A, R ⁵be chlorine, bromine, fluorine or methyl and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound with Formula I A, R ⁵chlorine, bromine, fluorine or methyl;

R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl, R ¹cF ₃,-B ¹-B ²-B ³-C=N-O-or-C=N-CH ₂-, Y ¹, Y ²and Y ³cH, and R ⁵chlorine or methyl.

In the other preferred embodiment of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-O-, R ¹trifluoromethyl, Y ¹, Y ²and Y ³cH, R ⁵chlorine, and R ⁸it is n-pro-pyl.

In the other preferred embodiment of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-O-, R ¹trifluoromethyl, R ²the bromo-5-trifluoromethyl of 3-, Y ¹, Y ²and Y ³be CH and R ⁸it is n-pro-pyl.

In the other preferred embodiment of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-O-, R ¹trifluoromethyl, R ²the bromo-5-trifluoromethyl of 3-, Y ¹, Y ²and Y ³be CH and R ⁵chlorine.

In the other preferred embodiment of compound with Formula I A ,-B ¹-B ²-B ³-be-C=N-O-, R ¹trifluoromethyl, R ²the bromo-5-trifluoromethyl of 3-, Y ¹, Y ²and Y ³cH, R ⁵chlorine, and R ⁸it is n-pro-pyl.

In one embodiment, the compound with Formula I is the compound with Formula I B

Wherein B ¹, B ², B ³, R ¹, R ², Y ¹, Y ², Y ³, R ⁷and R ⁸be as have Formula I compound define.In the compound with Formula I B, B ¹, B ², B ³, R ¹, R ², Y ¹, Y ², Y ³, R ⁷and R ⁸preferred definition be show as following with any combination.

Preferably, R ⁷it is methyl.

In a group of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁷it is methyl.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁷be methyl and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁷methyl, R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In a group of compound with Formula I B ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁷it is methyl.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁷be methyl and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound with Formula I B ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁷methyl, R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In another group of compound with Formula I B, R ⁷methyl, and R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl.

In another group of compound with Formula I B, R ⁷methyl, R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-, preferred n-pro-pyl or cyclopropyl, R ¹cF ₃,-B ¹-B ²-B ³-C=N-O-,-C=N-CH ₂-or-N-CH ₂-CH ₂-, and Y ¹, Y ²and Y ³cH.

In the other preferred embodiment of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-, R ¹trifluoromethyl, Y ¹, Y ²and Y ³cH; R ⁵chlorine, R ⁷be methyl and R ⁸it is n-pro-pyl.

In the other preferred embodiment of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-, R ¹trifluoromethyl, R ²the bromo-5-trifluoromethyl of 3-, Y ¹, Y ²and Y ³cH, R ⁷be methyl and R ⁸it is n-pro-pyl.

In the other preferred embodiment of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-, R ¹trifluoromethyl, R ²the bromo-5-trifluoromethyl of 3-, Y ¹, Y ²and Y ³cH, R ⁵be chlorine and R ⁷it is methyl.

In the other preferred embodiment of compound with Formula I B ,-B ¹-B ²-B ³-be-C=N-O-, R ¹trifluoromethyl, R ²the bromo-5-trifluoromethyl of 3-, Y ¹, Y ²and Y ³cH, R ⁵chlorine, R ⁷be methyl and R ⁸it is n-pro-pyl.

In one embodiment, the compound with Formula I is the compound with Formula I C

Wherein B ¹, B ², B ³, R ¹, R ², Y ¹, Y ², Y ³, R ⁵, Z and k be as have Formula I compound define.

In the compound with Formula I C, B ¹, B ², B ³, R ¹, R ², Y ¹, Y ², Y ³, R ⁵, Z and k preferred definition be show as following with any combination.

Preferably, R ⁵chlorine, bromine, fluorine, trifluoromethyl, methyl, ethyl, methoxyl group, nitro, trifluoromethoxy, cyano group, cyclopropyl, more preferably, R ⁵chlorine, bromine, fluorine, trifluoromethyl, methyl, ethyl, nitro, cyano group, cyclopropyl, even more preferably, R ⁵cyano group, chlorine, bromine, fluorine, methyl or trifluoromethyl, most preferably cyano group.

Preferably, each Z is halogen, cyano group, C independently ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkoxyl or C ₁-C ₄halogenated alkoxy, more preferably, each Z is hydrogen, cyano group, halogen, methyl, halogenated methyl, methoxyl group or halogenated methoxy independently, most preferably cyano group or trifluoromethyl.

Preferably, k is 0 or 1.

In a group of compound with Formula I C ,-B ¹-B ²-B ³-be-C=N-O-.

In another group of compound with Formula I C ,-B ¹-B ²-B ³-be-C=N-O-and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I C ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I C ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁵cyano group.

In another group of compound with Formula I C ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and k be 0 or k be 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I C ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I C ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, and Z is cyano group or trifluoromethyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In another group of compound with Formula I C, R ⁵be cyano group, k is 0 or 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I C, R ⁵cyano group, R ¹cF ₃,-B ¹-B ²-B ³-be-C=N-O-, Y ¹, Y ²and Y ³be CH, and k is 0.

In one embodiment, the compound with Formula I is the compound with Formula I D

In the compound with Formula I D, B ¹, B ², B ³, R ¹, R ², Y ¹, Y ², Y ³, R ⁵, Z and k preferred definition be show as following with any combination.

Preferably, k is 0 or 1, more preferably 1.When k is 1, preferably, Z is attached on 4 of imidazole fragment, as follows:

In a group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-O-.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-O-and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁵cyano group.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and k be 0 or k be 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, preferably 1, and Z is cyano group or trifluoromethyl, and when k is 1, Z is attached on 4 of imidazole fragment.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, and Z is cyano group or trifluoromethyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or 1 or k be 1, preferably 1, and Z is cyano group or trifluoromethyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3, two (trifluoromethyl) phenyl of 5--, 3-(trifluoromethyl) phenyl-, 2, the chloro-4-pyridine radicals of 6-bis--, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyl-or 3,4-dichlorophenyl-, and when k is 1, Z is attached on 4 of imidazole fragment.

In a group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-CH ₂-.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-CH ₂-and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁵cyano group.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, and k be 0 or k be 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, preferably 1, and Z is cyano group or trifluoromethyl, and when k is 1, Z is attached on 4 of imidazole fragment.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, and Z is cyano group or trifluoromethyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ₁cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, preferably 1, and Z is cyano group or trifluoromethyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3, two (trifluoromethyl) phenyl of 5--, 3-(trifluoromethyl) phenyl-, 2, the chloro-4-pyridine radicals of 6-bis--, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyl-or 3,4-dichlorophenyl-, and when k is 1, Z is attached on 4 of imidazole fragment.

In a group of compound with Formula I D ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁵cyano group.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, and k be 0 or k be 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, preferably 1, and Z is cyano group or trifluoromethyl, and when k is 1, Z is attached on 4 of imidazole fragment.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, and Z is cyano group or trifluoromethyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In another group of compound with Formula I D ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ₁cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁵be cyano group and k be 0 or k be 1, preferably 1, and Z is cyano group or trifluoromethyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3, two (trifluoromethyl) phenyl of 5--, 3-(trifluoromethyl) phenyl-, 2, the chloro-4-pyridine radicals of 6-bis--, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyl-or 3,4-dichlorophenyl-, and when k is 1, Z is attached on 4 of imidazole fragment.

In another group of compound with Formula I D, R ⁵be cyano group, k is 0 or 1, and Z is cyano group or trifluoromethyl.

In another group of compound with Formula I D, R ⁵be cyano group, k is 0 or 1, preferably 1, and Z is cyano group or trifluoromethyl, and when k is 1, Z is attached on 4 of imidazole fragment.

In another group of compound with Formula I D, R ⁵be cyano group, k is 0 or 1, and Z is cyano group or trifluoromethyl, R ¹cF ₃,-B ¹-B ²-B ³-be-C=N-O-or-C=N-CH ₂-, Y ¹, Y ²and Y ³cH.

In another group of compound with Formula I D, R ⁵be cyano group, k is 0 or 1, preferably 1, and Z is cyano group or trifluoromethyl, R ¹cF ₃,-B ¹-B ²-B ³-be-C=N-O-or-C=N-CH ₂-, Y ¹, Y ²and Y ³be CH, and when k is 1, Z is attached on 4 of imidazole fragment.

Preferably there is the group of the compound of Formula I D, wherein-B ¹-B ²-B ³-be-C=N-O-.

In one embodiment, the compound with Formula I is the compound with Formula I E

Wherein B ¹, B ², B ³, R ¹, R ², R ⁹, Y ¹, Y ², and Y ³be as have Formula I compound define

In the compound with Formula I E, B ¹, B ², B ³, R ¹, R ², R ⁹, Y ¹, Y ², Y ³preferred definition be show as following with any combination.

Preferably, R ⁹c ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄haloalkyl-O-CH ₂-, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl-CH ₂-, C ₁-C ₄alkyl-S (O)-CH ₂-, C ₁-C ₄alkyl-S (O ₂)-CH ₂-, more preferably C ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄haloalkyl-O-CH ₂-, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl-CH ₂-, more preferably C ₁-C ₄alkyl, C ₁-C ₄haloalkyl or C ₃-C ₄cycloalkyl, more preferably methyl, ethyl, propyl group, CF ₃cH ₂-or cyclopropyl, even more preferably ethyl, CF ₃cH ₂-or cyclopropyl.

In a group of compound, R ⁹ethyl or CF ₃cH ₂-.

Preferably, Y ¹cH, Y ²cH, Y ³cH, or Y ¹n, Y ²cH, Y ³cH, or Y ¹n, Y ²n, Y ³cH, or Y ¹cH, Y ²n, Y ³cH, or Y ¹cH, Y ²cH, Y ³n.Preferably, Y ¹cH, Y ²cH, and Y ³cH.

In a group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-O-.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-O-and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁹c ₁-C ₄alkyl.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, and R ⁹c ₁-C ₄haloalkyl.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁹c ₃-C ₄cycloalkyl.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-O-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁹c ₁-C ₄alkyl, C ₁-C ₄haloalkyl or C ₃-C ₄cycloalkyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In a group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-CH ₂-.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-CH ₂-and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁹c ₁-C ₄alkyl.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁹c ₁-C ₄haloalkyl.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁹c ₃-C ₄cycloalkyl.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-C=N-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁹c ₁-C ₄alkyl, C ₁-C ₄haloalkyl or C ₃-C ₄cycloalkyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

In a group of compound with Formula I E ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, and Y ¹cH, Y ²cH, Y ³cH.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be--N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³be CH and R ¹cF ₃.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃and R ⁹c ₁-C ₄alkyl.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, and R ⁹c ₁-C ₄haloalkyl.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁹c ₃-C ₄cycloalkyl.

In another group of compound with Formula I E ,-B ¹-B ²-B ³-be-N-CH ₂-CH ₂-, Y ¹cH, Y ²cH, Y ³cH, R ¹cF ₃, R ⁹c ₁-C ₄alkyl, C ₁-C ₄haloalkyl or C ₃-C ₄cycloalkyl, and R ²be 3-chloro-5-bromophenyl-, the chloro-5-of 3-(trifluoromethyl) phenyl-, 3, the chloro-4-fluorophenyl of 5-bis--, 3,4,5-trichlorophenyl-, 3,5-two (trifluoromethyl) phenyl-, 3-(trifluoromethyl) phenyl-, 2,6-bis-chloro-4-pyridine radicals-, 2, two (the trifluoromethyl)-4-pyridine radicals of 6--, 3,5-bis-chloro-4-bromophenyl-, the bromo-5-of 3-(trifluoromethyl) phenyl-, 3,5-dibromo phenyls-or 3,4-dichlorophenyl-.

Below there is Formula I-1, the compound of I-2 and I-3 illustrates ought-B ¹-B ²-B ³-be-C=N-O-,-C=N-CH respectively ₂-or-N-CH ₂-CH ₂in-time, has the compound of Formula I.

Compound of the present invention is illustrated with following table 1 to table 28.

table 1

Table 1 provides the compound that 304 kinds have Formula I a, and wherein R5 is hydrogen, and B1-B2-B3 is C=N-O, and R2 and R8 as table P in define.

table 2

Table 2 provides the compound that 304 kinds have Formula I a, and wherein R5 is methyl, and B1-B2-B3 is C=N-O, and R2 and R8 as table P in define.

table 3

Table 3 provides the compound that 304 kinds have Formula I a, and wherein R5 is trifluoromethyl, and B1-B2-B3 is C=N-O, and R2 and R8 as table P in define.

table 4

Table 4 provides the compound that 304 kinds have Formula I a, and wherein R5 is chlorine, and B1-B2-B3 is C=N-O, and R2 and R8 as table P in define.

table 5

Table 5 provides the compound that 304 kinds have Formula I a, and wherein R5 is bromine, and B1-B2-B3 is C=N-O, and R2 and R8 as table P in define.

table 6

Table 6 provides the compound that 304 kinds have Formula I a, and wherein R5 is hydrogen, and B1-B2-B3 is C=N-CH2, and R2 and R8 as table P in define.

table 7

Table 7 provides the compound that 304 kinds have Formula I a, and wherein R5 is methyl, and B1-B2-B3 is C=N-CH2, and R2 and R8 as table P in define.

table 8

Table 8 provides the compound that 304 kinds have Formula I a, and wherein R5 is trifluoromethyl, and B1-B2-B3 is C=N-CH2, and R2 and R8 as table P in define.

table 9

Table 9 provides the compound that 304 kinds have Formula I a, and wherein R5 is chlorine, and B1-B2-B3 is C=N-CH2, and R2 and R8 as table P in define.

table 10

Table 10 provides the compound that 304 kinds have Formula I a, and wherein R5 is bromine, and B1-B2-B3 is C=N-CH2, and R2 and R8 as table P in define.

table 11

Table 11 provides the compound that 304 kinds have Formula I a, and wherein R5 is hydrogen, and B1-B2-B3 is N-CH2-CH2, and R2 and R8 as table P in define.

table 12

Table 12 provides the compound that 304 kinds have Formula I a, and wherein R5 is methyl, and B1-B2-B3 is N-CH2-CH2, and R2 and R8 as table P in define.

table 13

Table 13 provides the compound that 304 kinds have Formula I a, and wherein R5 is trifluoromethyl, and B1-B2-B3 is N-CH2-CH2, and R2 and R8 as table P in define.

table 14

Table 14 provides the compound that 304 kinds have Formula I a, and wherein R5 is chlorine, and B1-B2-B3 is N-CH2-CH2, and R2 and R8 as table P in define.

table 15

Table 15 provides the compound that 304 kinds have Formula I a, and wherein R5 is bromine, and B1-B2-B3 is N-CH2-CH2, and R2 and R8 as table P in define.

table P

table 16

Table 16 provides the compound that 304 kinds have Formula I b, and wherein B1-B2-B3 is C=N-O, and R2 and R8 as table P in define.

table 17

Table 17 provides the compound that 304 kinds have Formula I b, and wherein B1-B2-B3 is C=N-CH2, and R2 and R8 as table P in define.

table 18

Table 18 provides the compound that 304 kinds have Formula I b, and wherein B1-B2-B3 is N-CH2-CH2, and R2 and R8 as table P in define.

table 19

Table 19 provides the compound that 19 kinds have Formula I c, and wherein B1-B2-B3 is C=N-O, and R2 as table Q in define.

table 20

Table 20 provides the compound that 19 kinds have Formula I c, and wherein B1-B2-B3 is C=N-CH2, and R2 as table Q in define.

table 21

Table 21 provides the compound that 19 kinds have Formula I c, and wherein B1-B2-B3 is N-CH2-CH2, and R2 as table Q in define.

table 22

Table 22 provides the compound that 19 kinds have Formula I d, wherein B1-B2-B3 be C=N-O and R2 be as table Q in define.

table 23

Table 23 provides the compound that 19 kinds have Formula I d, wherein k be CF3, B1-B2-B3 be C=N-O and R2 be as table Q in define.

table 24

Table 24 provides the compound that 19 kinds have Formula I d, wherein k be CN, B1-B2-B3 be C=N-CH2 and R2 be as table Q in define.

table 25

Table 25 provides the compound that 19 kinds have Formula I d, wherein k be CF3, B1-B2-B3 be C=N-CH2 and R2 be as table Q in define.

table 26

Table 26 provides the compound that 19 kinds have Formula I d, wherein k be CN, B1-B2-B3 be N-CH2-CH2 and R2 be as table Q in define.

table 27

Table 27 provides the compound that 19 kinds have Formula I d, wherein k be CF3, B1-B2-B3 be N-CH2-CH2 and R2 be as table Q in define.

table Q

table 28

Table 28 provides the compound that 114 kinds have Formula I e, and wherein B1-B2-B3 is C=N-O, and R2 and R9 as table S in define.

table 29

Table 29 provides the compound that 114 kinds have Formula I e, and wherein B1-B2-B3 is C=N-CH2, and R2 and R9 as table S in define.

table 30

Table 30 provides the compound that 114 kinds have Formula I e, and wherein B1-B2-B3 is N-CH2-CH2, and R2 and R9 as table S in define.

table S

The compound with Formula I comprises at least one chiral centre and can exist as the compound with Formula I * or the compound with Formula I * *.If do not have other chiral centre or other epimer, Compound I * and Compound I * * is enantiomter.

Generally, the compound with Formula I * * has more biologically active than the compound with Formula I *.The present invention includes Compound I * and Compound I * * with the mixture of any ratio such as its mol ratio for 1:99 to 99:1, such as 10:1 to 1:10, the mol ratio of such as 50:50 substantially.In the mixture of Formula I * * being rich in enantiomter (or epimer), compared with the total amount of two kinds of enantiomters (or epimer), the molar ratio of Compound I * * is such as greater than 50%, such as at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98% or at least 99%.Similarly, in the mixture of Formula I * being rich in enantiomter (or epimer), compared with the total amount of two kinds of enantiomters (or epimer), the molar ratio of Compound I * is such as greater than 50%, such as at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98% or at least 99%.The mixture being rich in the Formula I * * of enantiomter (or epimer) is preferred.The disclosure of a kind of compound of often kind of compounds represented according to the compound of Formula I * disclosed in table 1 to table 30 and a kind of compound of the compound according to Formula I * *.

Similarly, group A2 can be group A2* or A2**.

The present invention includes the mixture with the compound of Formula I that wherein A2 is A2* and A2**, both is in any ratio, and such as mol ratio is 1:99 to 99:1, such as 10:1 to 1:10, the mol ratio of such as 50:50 substantially.Wherein A2 be the Formula I of A2* be rich in the mixture of enantiomter (or epimer), compared with the total amount of two kinds of enantiomters (or epimer), wherein A2 is the molar ratio of the Formula I of A2* is such as be greater than 50%, such as at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98% or at least 99%.Similarly, wherein A2 be the Formula I of A2** be rich in the mixture of enantiomter (or epimer), compared with the total amount of two kinds of enantiomters (or epimer), wherein A2 is the molar ratio of the compound of the Formula I of A2** is such as be greater than 50%, such as at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98% or at least 99%.Wherein A2 is the mixture being rich in enantiomter (or epimer) of the Formula I of A2** is preferred.

Often kind of compounds represented disclosed in table 16 to table 18 wherein A2 be A2* I and wherein A2 be the disclosure of the Compound I of A2**.Often kind of compounds represented disclosed in table 16 to table 18 is the disclosure of the compound of the Formula I * of A2* according to wherein A2.Often kind of compounds represented disclosed in table 16 to table 18 is the disclosure of the compound of the Formula I * * of A2* according to wherein A2.Often kind of compounds represented disclosed in table 16 to table 18 is the disclosure of the compound of the Formula I * of A2** according to wherein A2.Often kind of compounds represented disclosed in table 16 to table 18 is the disclosure of the compound of the Formula I * * of A2** according to wherein A2.Wherein A2 is the mixture being rich in enantiomter (or epimer) of the Formula I * * of A2** is preferred.

Similarly, group A5 can be group A5* or A5**

The present invention includes the mixture with the compound of Formula I that wherein A5 is A5* and A5**, both is in any ratio, and such as mol ratio is 1:99 to 99:1, such as 10:1 to 1:10, the mol ratio of such as 50:50 substantially.Wherein A5 be the Formula I of A5* be rich in the mixture of enantiomter (or epimer), compared with the total amount of two kinds of enantiomters (or epimer), wherein A5 is the molar ratio of the Formula I of A5* is such as be greater than 50%, such as at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98% or at least 99%.Similarly, wherein A5 be the Formula I of A5** be rich in the mixture of enantiomter (or epimer), compared with the total amount of two kinds of enantiomters (or epimer), wherein A5 is the molar ratio of the compound of the Formula I of A5** is such as be greater than 50%, such as at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98% or at least 99%.The compound with chemical formula A5* is preferred.

Often kind of compounds represented disclosed in table 28 to table 30 wherein A5 be A5* I and wherein A5 be the disclosure of the Compound I of A5**.Often kind of compounds represented disclosed in table 28 to table 30 is the disclosure of the compound of the Formula I * of A5* according to wherein A5.Often kind of compounds represented disclosed in table 28 to table 30 is the disclosure of the compound of the Formula I * * of A5* according to wherein A5.Often kind of compounds represented disclosed in table 28 to table 30 is the disclosure of the compound of the Formula I * of A5** according to wherein A5.Often kind of compounds represented disclosed in table 28 to table 30 is the disclosure of the compound of the Formula I * * of A5* according to wherein A5.

Mentioning salt and N-oxide is also comprised to mentioning of compound of the present invention.

The compound with Formula I can as being described in WO 2008/128711, preparing in WO 2010/043315, the compound with Formula I can as being described in WO 2008/128711, WO2010/043315, WO 2011/051455, WO 2007/105814, WO 2008/122375, WO2009/035004, WO 2009/045999, WO 2009/072621, WO 2009/097992, WO2010/133336, WO 2010/043315, WO 2011/051455, WO 2011/080211, JP2010235590, JP 2011037817, JP 2011178724, CN 102210317, CN102246777, WO 2009/07261, WO 2009/097992, preparing in WO 2009/051956, each document above is combined in this by reference.

In one embodiment, the invention provides a kind of compound being selected from table 1 to 15, for resisting paddy rice pest.

In one embodiment, the invention provides a kind of compound being selected from table 16 to 18, for resisting paddy rice pest.

In one embodiment, the invention provides a kind of compound being selected from table 19 to 21, for resisting paddy rice pest.

In one embodiment, the invention provides a kind of compound being selected from table 22 to 27, for resisting paddy rice pest.

In one embodiment, the invention provides a kind of compound being selected from table 28 to 30, for resisting paddy rice pest.

In one embodiment, the invention provides a kind of compound being selected from table 1 to 15, for resisting stem borer, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 16 to 18, for resisting stem borer, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 19 to 21, for resisting stem borer, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 22 to 27, for resisting stem borer, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 28 to 30, for resisting stem borer, particularly in paddy rice.

The example of stem borer comprises straw borer spp, striped rice borer, top snout moth's larva, goldrimmed moth, white standing grain snout moth's larva genus, positive paddy stem borer, the white snout moth's larva of rice, yellow tail moth standing grain snout moth's larva, moth stem Noctua, pink rice borer.

In one embodiment, the invention provides a kind of compound being selected from table 1 to 15, for resisting tortrix moth, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 16 to 18, for resisting tortrix moth, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 19 to 21, for resisting tortrix moth, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 22 to 28, for resisting tortrix moth, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 28 to 30, for resisting tortrix moth, particularly in paddy rice.

The example of tortrix moth comprises leaf roll snout moth's larva and belongs to (Cnaphalocrocis spp.), rice leaf roller, and brush must wild snout moth's larva belongs to (Marasmia spp.), the angle order brush wild snout moth's larva of palpus (Marasmia patnalis), rice shows line brush must wild snout moth's larva (Marasmia exigua).

In one embodiment, the invention provides a kind of compound being selected from table 1 to 15, for resisting springtail, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 16 to 18, for resisting springtail, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 19 to 21, for resisting springtail, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 22 to 27, for resisting springtail, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 28 to 30, for resisting springtail, particularly in paddy rice.

The example of springtail comprises rice leafhopper genus, nephotettix bipunctatus, two rice leafhoppers, Malaya rice leafhopper, rice leafhopper, brown plant-hopper, white-backed planthopper.

In one embodiment, the invention provides a kind of compound being selected from table 1 to 15, for resisting cecidomyiia, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 16 to 18, for resisting cecidomyiia, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 19 to 21, for resisting cecidomyiia, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 22 to 27, for resisting cecidomyiia, particularly in paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 28 to 30, for resisting cecidomyiia, particularly in paddy rice.

Cecidomyiia example comprises cecidomyiia genus, rice gall midge.

In one embodiment, the invention provides a kind of compound being selected from table 1 to 15, for resisting in screw thread maggot, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 16 to 18, for resisting in screw thread maggot, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 19 to 21, for resisting in screw thread maggot, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 22 to 28, for resisting in screw thread maggot, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 28 to 30, for resisting in screw thread maggot, particularly paddy rice.

The example of screw thread maggot comprises New records, luxuriant and rich with fragrance island rice hair eye ephydrid.

In one embodiment, the invention provides a kind of compound being selected from table 1 to 15, for resisting in rice stinkbug, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 16 to 18, for resisting in rice stinkbug, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 19 to 21, for resisting in rice stinkbug, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 22 to 27, for resisting in rice stinkbug, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 29 to 30, for resisting in rice stinkbug, particularly paddy rice.

The example of rice stinkbug comprises Leptocorisa spp genus, large Leptocorisa spp, magnificent Leptocorisa spp, standing grain spider edge stinkbug.

In one embodiment, the invention provides a kind of compound being selected from table 1 to 15, for resisting in black stinkbug, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 16 to 18, for resisting in black stinkbug, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 19 to 21, for resisting in black stinkbug, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 22 to 27, for resisting in black stinkbug, particularly paddy rice.

In one embodiment, the invention provides a kind of compound being selected from table 28 to 30, for resisting in black stinkbug, particularly paddy rice.

The example of black stinkbug comprises black stinkbug and belongs to (Scotinophara sp.), the black stinkbug of Malaya (Scotinophara coarctata), the black stinkbug of rice (Scotinophara lurida), the black stinkbug of wide wing (Scotinophara latiuscula).

As used herein, " place " of term useful plant is intended to comprise the place that these useful plants grow thereon, is sowed at the plant propagation material of these these useful plants local or will be placed in soil at the plant propagation material of these these useful plants local.An example in such place is the field that crop plants grows thereon.

Term " plant propagation material " is appreciated that the reproductive part representing this plant, and such as seed, these parts may be used for the breeding of this plant, and trophism material, such as cutting or stem tuber (such as potato).Can mention, such as the part of seed (in a strict sense), root, fruit, stem tuber, bulb, rhizome and plant.Can also mention transplanted germination plant and young plant after germination or after breaking ground.These young plants can be processed wholly or in part by dipping and protect before transplanting.Preferably, " plant propagation material " it should be understood that seed.

Using can be carry out before infecting or when pest exists.Using of compound of the present invention can be carried out according to any common method of application (such as foliage applying, spray are used, soil application, furrow irrigation use etc.).But usually realized the control of Mexico cotton boll elephant by foliage applying, foliage applying is according to preferred method of application of the present invention.

The using of compound of the present invention is preferably carried out to the crop of vegetable lamb, its place or its propagating materials.

Compound of the present invention can be applied to plant parts.Plant part should be understood to mean that more than all ground and following plant part and plant organ, such as bud, leaf, Hua Hegen, the example that can mention is leaf, needle, bar, stem, flower, fruit body, fruit, seed, root, stem tuber and rhizome.Plant part also comprises the material of results, and growth with generative propagation material, such as cutting, stem tuber, rhizome, branch and seed.The process of use reactive compound according to the present invention to plant and plant part directly can be carried out or allow compound effects to its surrounding environment, site, memory space by the processing method (such as by embathing, spraying, evaporate, be atomized, disperse, smear, inject) that use is conventional, and when propagating materials, particularly when seed, also by using one or more dressings to carry out.

Compound of the present invention is adapted at the upper use of any plant (preferred vegetable lamb), comprise genetically modified and have resistance to active component (such as weed killer herbicide), or producing those that can control bioactive compound that plant-pest infects.

Term as used herein " plant " comprises seedling, shrub and tree.Crop should be understood to also comprise by conventional breeding or those crops being endowed weed killer herbicide (such as ALS-, GS-, EPSPS-, PPO-and HPPD-inhibitor) tolerance to weed killer herbicide or plurality of classes by engineered method.The example having been given the crop of its tolerance to imidazolone type (such as, imazamox) by the breeding method of routine is summer rape (Corolla (canola)).The example being given the crop of the tolerance to weed killer herbicide by gene engineering method comprises the corn variety of such as glyphosate and careless fourth phosphine resistance, and these corn varieties exist with commercially available under trade (brand) name.

The compound with Formula I can be used to by engineered method and/or the genetically modified plants (comprising cultivar) by the acquisition of conventional method.These are understood to imply the plant with novel characteristics (" proterties "), and these novel characteristics (" proterties ") are by conventional breeding, obtain by mutagenesis or by recombinant DNA technology.Depend on the species of plant or Plant cultivars, their position and growth conditions (soil, weather, vegetative period, nutrition), treatment in accordance with the present invention can also cause superadditivity (" working in coordination with ") effect.

Therefore, such as according to the activity using ratio and/or the activity profile widened and/or increase of the reduction of the operable material of the present invention and composition, better plant growth, the tolerance to high or low temperature increased, increase to arid, or the tolerance of water or soil salt content, the performance of blooming increased, easier harvesting, the maturation accelerated, higher crop, the higher quality of results product and/or higher nutritive value, better storage stability and/or the processability of results product are possible, this has exceeded the effect be in fact expected.

Have pending preferred genetically modified plants or Plant cultivars to comprise all plants utilizing genetic modification to have received genetic material according to the present invention, this material gives these plants particularly advantageous useful proterties.The example of this type of proterties be plant growth better, the tolerance of high or low temperature is improved, to arid or water or soil salt content tolerance increases, performance of blooming improves, more easily gather in, ripely accelerate, harvesting output is higher, the quality of results product is higher and/or nutritive value is higher, gather in the crops better storage stability and/or the machinability of product.

In addition and the example of this type of proterties ben be these plants against animal and multiple-microorganism pest, such as better to the defence of various insects, mite, plant pathogenic fungi, bacterium and/or virus, and increase the tolerance of these plants to some herbicidal activity compound.

The example of the genetically modified plants that can mention is important crop plants, such as cereal (wheat, paddy rice), corn, soybean, potato, beet, tomato, pea and other vegetable varieties, cotton, tobacco, rape and also have fruit plant (apple, pears, citrus fruit and grape).Transgene cotton is interested especially.

The compound with Formula I can be used to produce the genetically modified plants that one or more kill pest protein, and these albumen give the tolerance of these genetically modified plants to pest (such as insect pest, nematode pests and analog) or resistance.This type of kills the Cry albumen that pest protein includes but not limited to from bacillus thuringiensis, Cry1Ab, Cry1Ac, Cry1F, Cry2Ab, Cry2Ae, Cry3A, Cry3Bb or Cry9C; Engineered protein, the Cry3A such as modified (United States Patent (USP) 7,030,295) or Cry1A.105; Or Vegetative Insecticidal Proteins, such as Vip1, Vip2 or Vip3.Find in the B. thuringiensis Toxin nomenclature database that Bt Cry albumen useful in the present invention and the complete list of VIP can be safeguarded in University of Sussex (University of Sussex) in WWW (also see, people (1998) " microbial molecules biology summary " (Microbiol.Mol.Biol.Rev.) 62:807-813 such as Ke Like mole (Crickmore)).Its homicide pest protein useful in the present invention comprises, the bacterium of the nematode that lives away from home, the albumen of such as Photorhabdus or Xenorhabdus; The toxin produced by animal, as scorpion toxin, spider toxin, wasp toxin or other insect-specific neurotoxins; By mycetogenetic toxin, as streptomycete toxin; Phytolectin (lectin), as pisum sativum agglutinin or barley lectin element; Agglutinin (agglutinin) class; Protease inhibitors, as trypsin inhibitor, serpin, potato storage protein (patatin), cystatin or antipain; Ribosome inactivating protein (RIP), as ricin, corn-RIP, abrin, Luffin, sapotoxin fibroin or red bryony toxalbumin; Steroid metabolism enzyme, as 3-hydroxy steroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidase, moulting hormone inhibitor or HMG-CoA-reductase; Ion channel blocking agent, as sodium channel or calcium channel blocker, juvenile hormone esterase; Diuretic hormone acceptor (cotton bollworm kassinin kinin (helicokinin) acceptor); Stilbene (stilben) synthase, bibenzyl synthases, chitinase or dextranase.This kind kills other examples that pest protein maybe can synthesize the genetically modified plants of this kind of albumen and is disclosed in, such as, in EP-A 374753, WO 93/007278, WO 95/34656, EP-A427529, EP-A 451878, WO 03/18810 and WO 03/52073.Known for the production of the method for these type of genetically modified plants generally for those of ordinary skill in the art and some of them are commercially available, such as (P1) (corn, produce Cry1Ab), rW (P2) (corn produces mCry3A), viptera (P3) (corn hybridization body, the Vip3Aa of generation); Agrisure300GT (P4) (corn hybridization body produces Cry1Ab and mCry3A); (P5) (corn hybridization body, produce Cry1Ab albumen), plus (P6) (corn hybridization body produces Cry1Ab and Cry3Bb1), (P7) (there is the corn hybridization body of following item: Cry1A.105, Cry2Ab2, Cry1F, Cry34/35, Cry3Bb); i (P8) (corn hybridization body, produce Cry1Fa) and rW (P9) (corn hybridization body produces Cry34Ab1, Cry35Ab1 and enzyme grass fourth phosphine-N-acetyl-transferase [PAT]); 33B (P10) (cotton cultivar produces Cry1Ac), (P11) (cotton cultivar, produce Cry1Ac), iI (P12) (cotton cultivar, produce Cry1Ac and Cry2Ab2) and (P13) (cotton cultivar produces Vip3Aa).The soybean of the Cyst of resistance to soybean nematode ( syngenta (P14)) and have aphid tolerance trait soybean ( (P15) be also) significant.

Other examples of these type of genetically modified crops are:

1.Bt11 corn, from (France of Xian Zhengda seeds company (Syngenta Seeds SAS), Sheng Suoweier (St.Sauveur) F-31790, Chemin de l'Hobit 27), registration number C/FR/96/05/10 (P16).The maize of genetic modification, by CryIA (b) toxin of transgene expression brachymemma, makes it the invasion and attack of resisting European corn borer (corn borer and powder stem snout moth's larva).Bt11 corn also transgenosis ground expresses PAT enzyme to reach the tolerance to weed killer herbicide grass fourth phosphine ammonium salt.

2.Bt176 corn, from Xian Zhengda seeds company (France, Sheng Suoweier F-31790, Chemin de l'Hobit 27), registration number C/FR/96/05/10 (P17).The maize of genetic modification, by transgene expression CryIA (b) toxin, makes it the invasion and attack of resisting European corn borer (corn borer and powder stem snout moth's larva).Bt176 corn also transgenosis ground expresses PAT enzyme to reach the tolerance to weed killer herbicide grass fourth phosphine ammonium salt.

3.MIR 604 corn, from Xian Zhengda seeds company (France, Sheng Suoweier F-31790, Chemin de l'Hobit 27), registration number C/FR/96/05/10 (P18).The CryIIIA toxin modified by transgene expression and be endowed the corn of insect-resistant.This toxin is the Cry3A055 modified by inserting a cathepsin-D-protease recognition sequence.The preparation of this type of rotaring gene corn plant is described in WO03/018810.

4.MON 863 corn, from Meng Shan all (Belgium of European Company (Monsanto Europe S.A.), Brussels B-1150, De Tewenrui street (Avenue de Tervuren) 270-272), registration number C/DE/02/9 (P19).MON 863 expresses CryIIIB (b1) toxin, and has resistance to some coleopteron.

5.IPC 531 cotton, from Meng Shan all European Company 270-272 Te Fulun main roads, B-1150 Brussels, Belgium, number of registration C/ES/96/02.(P20)

6.1507 corns, from pioneer overseas company (Pioneer Overseas Corporation), Tedesco main road (Avenue Tedesco), 7B-1160 Brussels, Belgium, number of registration C/NL/00/10.(P21) genetically altered corn, marking protein CrylF to obtain the resistance to some lepidopterous insects, and expresses PAT protein to obtain the tolerance to weed killer herbicide grass fourth phosphine ammonium salt.

7.NK603 × MON 810 corn, from Meng Shan all European Company (Monsanto EuropeS.A.), 270-272 De Tewenrui street, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.By the kind NK 603 of genetic modification and MON 810 is hybridized, be made up of the hybrid corn variety of conventional breeding.NK 603 × MON 810 corn gene expresses the CP4EPSPS protein obtained by Agrobacterium strains CP4, makes it herbicide-resistant (containing glyphosate), and CryIA (b) toxin obtained by B. thuringiensis subspecies, make it some lepidopterous insects resistance to, comprise European corn borer.

Genetically modified plants other and the example with very large meaning are those of the proterties of carrying the tolerance given for following item: 2.4D (such as, ) (such as WO2011066384), glyphosate (such as Roundup (P24), Roundup Ready 2 (P25)), sulfonyl urea (such as, ) (P26), careless fourth phosphine (such as, Liberty (P27), (P28)), dicamba (P29) (Monsanto Company (Monsanto)), HPPD tolerance (P30) (such as isoxazole humulone weed killer herbicide) (Bayer scientific company (Bayer CropScience), Syngenta Co., Ltd (Syngenta)).Dual or triple superposition of any proterties described here is also significant, comprises glyphosate and sulfonyl urea tolerance (such as, Optimum ) (P31), have and Roundup (P32) plant superposed or have with Roundup Ready 2 (P33) plant superposed), dicamba and glyphosate tolerant (P34) (Monsanto Company).The special bean plant that meaningfully carry the proterties imparted following resistance: 2.4D (such as ), glyphosate (such as Roundup roundup Ready 2 ), sulfonyl urea (such as, ), careless fourth phosphine (such as Liberty ), dicamba (Monsanto Company (Monsanto)), HPPD tolerance (such as isoxazole humulone weed killer herbicide) (Bayer scientific company (Bayer CropScience), Syngenta Co., Ltd (Syngenta)).

The genetically modified crops of the plant of anti-insect are also described in BATS (bio-safety and sustainable development center (Zentrum f ü r Biosicherheit und Nachhaltigkeit), BATS center (ZentrumBATS), Peter Krass Cui She (Clarastrasse) 13, Basel (Basel) 4058, Switzerland) report 2003 ( http:// bats.ch) in.

The example of cotton transgenic event comprise MON 531/757/1076 ( – Meng Shan is (Monsanto)), MON1445 (Roundup ready – Meng Shan is), MON531xMON1445 (Bollgard I+ – Meng Shan is), MON15985 (Genuity Bollgard II – Meng Shan is), MON88913 (Genuity RR FLEX – Meng Shan is), MON15985x MON1445 (Genuity Bollgard II+RR FELX – Meng Shan is), MON15983x MON88913 (Genuity Bollgard II+RR FLEX meng Shan is), MON15985 (FibreMax Bollgard II – Meng Shan is), LL25 (FibreMax LL – BCS Stoneville), GHB614 (FibreMax GlyTol – BCS Stoneville), LL25x MON15985 (FibreMax LL Bollgard II – BCS Stoneville/ Meng Shan is), GHB614x LL25 (FibreMax LL GlyTol – BCS Stoneville), GHB614x LL25x MON15985 (FibreMax RR GlyTol Bollgard II – BCSStoneville), MON88913x MON15985 (FibreMax LL GlyTol Bollgard II – Meng Shan is), MON88913 (FibreMax RR Flex – Meng Shan is), GHB119+T304-40 ( – BCS Stoneville), GHB119+T304-40x LL25x GHB614 (Twinlink LL bCS Stoneville), 3006-210-23x 281-24-236 (PhytoGenWidestrike Insect – Tao Shi (Dow), 3006-210-23x 281-24-236xMON88913 (PhytoGen Widestrike Insect Protection+RR dow/ Meng Shan is), 3006-210-23x 281-24-236x MON1445 ((PhytoGen Widestrike InsectProtection+ – Dow/ Meng Shan is), MON1445 (PhytoGen Roundup – Meng Shan all, MON88913 (PhytoGen Roundup Ready – Meng Shan is), COT102x COT67B ( – first just reaches), COT102x COT67B x MON88913 (VipcotRR first just reach (Syngenta)/Meng Shandou), 281-24-236 (Tao Shi (Dow)), 3006-210-23 (Tao Shi), COT102 (first just reaching), COT67B (first just reaching), T304-40 (BCS Stoneville).

The example of soybean transgenic event comprises MON87701x MON89788 (Genuity Roundupready2Yield – Meng Shan is (Monsanto)), MON89788 (Roundup – Meng Shan is), MON87708 (Meng Shandou), 40-3-2 (Roundup – Meng Shan is), MON87701 (Meng Shandou), DAS-68416 (Enlist Weed Control – Tao Shi (Dow)), DP356043 (Optimum – pioneer (Pioneer)), A5547-127 (LibertyLink – Bayer Cropscience (Bayercropscience))), A2704-12 (Bayer Cropscience), GU262 (Bayer Cropscience), W62W98 (Bayer Cropscience), CRV127 ( – BASF/EMBRAPA), SYHT0H2 (WO 2012/082548).

The example of corn gene event comprise T25 ( – Bayer Cropscience (Bayerscropscience)), DHT-1 (Tao Shi (Dow)), TC1507 ( – Tao Shi), DAS59122-7 (Herculex – Tao Shi), TC1507+DAS59122-7 – Herculex – Tao Shi), TC1507x DAS-59122-7x NK603 (Herculex Xtra+ – Tao Shi),TC1507x DAS-59122-x MON88017x MON89034 (GenuitySmartstax Genuity Smartstax RIB – Meng Shan is (Monsanto)/Tao Shi), MON89034x NK603 (Genuity VT double – Meng Shan is), MON89034+MON88017 (Genuity VT Triple – Meng Shan is), NK603 (Roundup Ready – Meng Shan is),MON810 (YieldGard Yieldgard – Meng Shan is), MON810x NK603 (YieldGard corn borer RR corn – Monasnto), MON810x MON863 (YieldGard – Meng Shan is), MON863x MON810x NK603 (YieldGard Plus+RR corn RR – Meng Shan is), MON863x NK603 (YieldGard Rotworm+RR – Meng Shan is), MON863 (YieldBard – Meng Shan is), MON89034 (YieldGard – Meng Shan is), MON88017 (YieldGard VT – Meng Shan is),MON810+MON88017 (YieldGard VT – Meng Shan is), MON88017+MON89034 (YieldGard VTTriple – Meng Shan is), Bt11+MIR604+GA21 (Agrisure – first just reaches (Syngenta)), Bt11+TC1507+MIR604+5307+GA21 (first just reaching), Bt11+TC1507+MIR604+DAS59122+GA21 (Agrisure – first just reaches), BT11 (Agrisure – first just reaches),GA21 – (Agrisure – first just reaches), MIR604 (Agrisure – first just reaches), Bt11+MIR162 (Agrisure TL – first just reaches), BT11+MIR162+GA21 (Agrisure Viptra – first just reaches), BT11+MIR162+MIR604 (Agrisure – first just reaches), Event3272+BT11+MIR604+GA21 (first just reaching),BT11+MIR1692+MIR604+GA21 (Agrisure Viptera – first just reaches), BT11+MIR162+TC1507+GA21 (Agrisure Viptera – first just reaches), BT11+MIR162+TC1507+MIR604+5307+GA21 (Agrisure Viptera – first just reaches), MIR162 (first just reaching), BT11+GA21+MIR162+MIR604+5307 (first just reaching), 5307 (first just reaching).

The plant (plant with usual manner breeding for herbicide-tolerant) of the antiweed that can mention is included in title the kind of selling under (such as corn).

These illustrate also be applicable to will exploitation in future and/or introduce to the market, the Plant cultivars with these genetic character or still untapped genetic character.

Compound of the present invention is adapted at any vegetable lamb uses, comprise genetically modified and have resistance to active component (such as weed killer herbicide), or produce those that can control bioactive compound that plant-pest infects, such as BT cotton.

Compound of the present invention can with fertilizer (such as nitrogenous-, potassium-or phosphorus-fertilizer) used in combination.Suitable preparation type comprises fertiliser granulates.These mixtures preferably comprise up to by weight 25% compound of the present invention.

Therefore, present invention also offers a kind of Ru 2006101161 comprising a kind of fertilizer and a kind of compound of the present invention.

What composition of the present invention can comprise other has bioactive compound, such as micronutrient, or the compound with Fungicidally active, or has coordinate plant growth, weeding, the compound that kills insect, kill nematode or acaricidal activity.

The compound with chemical formula (I) can be the independent active component of said composition or it can be other with one or more active component, such as pesticides, such as insecticide, fungicide or weed killer herbicide, or mix with synergist or plant growth substance in a suitable case.Other active component can be provided in a kind of composition that a place has the retention time of wider activity profile or increase; Synergy or supplement this activity (such as by increasing action speed or overcome repellency) with the compound of chemical formula (I); Or help the development overcoming or prevent the resistance to single component.Concrete other active component will depend on the application desired by said composition.The example of suitable pesticides comprises the following:

A) pyrethroid, such as permethrin, cypermethrin, sumicidin, esfenvalerate, decis, Cyhalothrin (particularly λ-Cyhalothrin and γ Cyhalothrin), Biphenthrin, fenpropathrin, cyfloxylate, tefluthrin, pyrethroid (such as ether chrysanthemum ester), natural pyrethrin, tetramethrin, S-bioallethrin, Fenfluthrin, d-prallethrin, fluorine ester chrysanthemum ester, ether chrysanthemum ester or 5-benzyl-3-furfuryl to fish safety-( e)-(1R, 3S)-2,2-dimethyl-3-(2-oxo tiacyclopentane-3-ylidenylmethyl) cyclopropanecarboxylcompound;

B) organophosphorus compounds, as Profenofos, sulprofos, orthene, parathion-methyl, gusathion m-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, nuvacron, Profenofos, Hostathion, acephatemet, Rogor, phosphamidon, malathion, chlopyrifos, Phosalone, Terbufos, fensulfothion, Dyfonate, thimet, phoxim, Actellic-methyl, Actellic-ethyl, sumithion, thiazolone phosphorus or diazinon;

C) carbamates (comprising aryl-carbamate), as Aphox, triaguron, cloethocarb, carbofuran, furathiocarb, ethiofencarb, Aldicarb, thiofanox, fourth sulphur gram hundred Cheng, Evil worm prestige, Bassa, unden, Methomyl or oxamyls;

D) benzoyl area kind, as grand in diflubenzuron, desinsection, HEXAFLUMURON, flufenoxuron, methamidophos, Lufenuron (lufeneron), Rimon, noviflumuron or UC 62644;

E) organo-tin compound, as plictran, fenbutatin oxide or azacyclotin;

F) pyrazoles, as tebufenpyrad, Tolfenpyrad, second worm nitrile, Pi Ruipu (pyriprole), ethiprole and azoles Qiu ester;

G) macrolides, as Avermectin or milbemycin class, such as abamectin, according to mark's butylbenzene formates, ivermectin, milbemycin, pleocidin, nimbin, milbemycin, thunder cuticulin or ethyl pleocidin;

H) hormone or pheromones;

I) organochlorine compound, as 5a,6,9,9a-hexahydro-6,9-methano-2,4 (particularly α-5a,6,9,9a-hexahydro-6,9-methano-2,4), lindane, DDT, Niran or dieldrin;

J) amidine class, such as galecron or Amitraz;

K) fumigant, as chloropicrin, dichloropropane, methyl bromide or metham-sodium;

L) anabasine compound, as Imidacloprid, thiacloprid, Acetamiprid, Nitenpyram, MTI-446, Diacloden, clothianidin or Nithiazine;

M) two hydrazides classes, as worm hydrazides, ring worm hydrazides or methoxyfenozide;

N) diphenyl ether, as difenolan or pyriproxyfen;

O) urea, as indoxacarb or metaflumizone;

P) ketone enol class, as spiral shell worm ethyl ester, spiral shell mite ester or Spiromesifen;

Q) diamide, as Flubendiamide, chlorantraniliprole or cyanogen insect amide;

R) volatile oil, as -(PlantImpact); Or

S) a kind ofly following compound is selected from: Buprofezin (buprofezine), flonicamid, acequinocyl, Bifenazate, azoles mite cyanogen, cyflumetofen, second mite azoles, flometoquin, fluacrypyrim, fluorine thiophene worm sulfone (fluensulfone), phonetic worm amine, flupyradifuone, positive Knagzhuang extract (harpin), iodomethane, 12 allenic alcohols (dodecadienol), pyridaben, pyridalyl, pyrimidifen, flupyradifurone, 4-[(the chloro-pyridin-3-yl methyl of 6-)-(2, 2-Difluoro-ethyl)-amino]-5H-furans-2-ketone (DE 102006015467), CAS:915972-17-7 (WO 2006129714, WO2011/147953, WO 2011/147952), CAS:26914-55-8 (WO 2007020986), chlorfenapyr, pyrrole first piperazine, fluorine pyridine worm amine nitrile and pyrifluqinazon.

Except chemical pesticides kind mainly listed above, if be applicable to the desired use of said composition, other pesticides with particular target can be adopted in the composition.Such as the selectivity insecticide of concrete crop, stem borer (stemborer) specificity insecticide (such as cartap) or springtail animal specificity insecticide (such as Buprofezin) that such as use in paddy rice can be adopted.Alternately, also can be included in these compositions (such as other insecticides of concrete caste/phase specificity or miticide, kill the ovicidal larva agent (ovolarvicides) of mite, such as clofentezine, fluorine mite thiophene, Hexythiazox or tetradiphon; Kill the motilicides of mite, such as kelthane or propargite; Miticide, such as Xiu Man Du (bromopropylate) or chlorobenzilate; Or growth regulator, such as hydramethylnon, match are gone out clean, methoprene, UC 62644 or diflubenzuron).

The example that can comprise Fungicidal compounds be in the compositions of the present invention ( e)-N-methyl-2-[2-(2,5-Dimethylphenoxymethyl) phenyl]-2-methoxyl group-imino group acetamide (SSF-129), the bromo-2-cyano group of 4--N, N-dimethyl 6 trifluoro methyl benzimidazole-1-sulfonamide, α-[N-(chloro-2, the 6-xylyls of 3-)-2-methoxyacetamido] gamma butyrolactone, the chloro-2-cyano group of 4--N, the p-tolylimidazol of N-dimethyl-5--1-sulfonamide (IKF-916, cyanogen azoles flusulfamide), the chloro-N-of 3-5-bis-(the chloro-1-ethyl of 3--1-methyl-2-oxopropyl)-4-methyl benzamide (RH-7281, zoxamide), N-pi-allyl-4,5 ,-dimethyl-2-trimethyl silyl thiophene-3-formamide (MON65500), N-(1-cyano group-1,2-dimethyl propyl)-2-(2,4-dichlorophenoxy) propionamide (AC382042), N-(2-methoxyl group-5-pyridine radicals) cyclopropane carboxamide, thiadiazoles element (CGA245704) (such as I acid benzene-S-methyl), alanycarb, allethrin, anilazine, oxygen ring azoles, Fluoxastrobin, M 9834, benomyl, benzene metsulfovax, Bitertanol (biloxazol), bitertanol, biphenyl pyrrole bacterium amine, blasticidin-S S, Boscalid, bromuconazole, bupirimate, difoltan, captan, carbendazim, carbendazim hydrochloride, carboxin, add general amine, carvol, CGA41396, CGA41397, chinomethionat, tpn, chlozolinate, carat health (clozylacon), copper-containing compound (such as COPPER OXYCHLORIDE 37,5, phenoxyl quinoline copper, copper sulphate, copper resinate and Bordeaux mixture), cyflufenamid (cyclufenamid), frost urea cyanogen, cyproconazole, cyprodinil, debacarb, two-2-pyridyl disulfide 1,1'-dioxide, dichlofluanid, diclomezine, botran, the mould prestige of second, Difenoconazole, difenzoquat, difluoro woods, O, O-diisopropyl-S-dibenzylsulfide substituted phosphate, the U.S. good fortune azoles (dimefluazole) in ground, ground Miconazole (dimetconazole), dimethomorph, dimethirimol, olefin conversion, karathane, Delan, dodecyl dimethyl ammonium chloride, dodemorph, dodine, dodine, edifenphos, epoxiconazole, the phonetic phenol of second, ( z)-N-benzyl-N-([methyl (methyl-sulfo-ethyleneimino oxygen base carbonyl) is amino] sulfenyl)-Beta-alanine ethyl ester, Grandox fumigant, Famoxate, Fenamidone (RPA407213), Fenarimol, RH-7592, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin, butadiene morpholine, fentin acetate, triphenyl tin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, the holder of fluorine U.S., fluorine pyrrole bacterium acid amides, fluoxastrobin, azoles furan grass, Fluquinconazole, Flusilazole, flutolanil, Flutriafol, fluorine azoles bacterium acid amides, folpet, furidazol, furalaxyl, good fortune Lapie, iminoctadine, own azoles alcohol, hydoxyisoxazole, dislike mould spirit, imazalil, glyoxalin, iminoctadine, iminoctadine triacetate, plant bacterium azoles, iprobenfos, iprodione, third gloomy pungent (SZX0722), isopropyl butyl carbamate, Isoprothiolane, isopyrazam, kasugarnycin, kresoxim-methyl-methyl, LY186054, LY211795, LY248908, mancozeb, mandipropamid, maneb, Metalaxyl-M, metalaxyl, mepanipyrim, mebenil, metalaxyl, metconazole, Carbatene, Carbatene zinc, SSF 126, nitrile bacterium azoles, neoasozin, Methyl disulfide generation-carbamic acid nickel ester, nitrothalisopropyl (nitrothalisopropyl), nuarimol, ofurace, organomercurial compound class, the spirit of Evil frost, oxasulfuron, oxolinic acid, Ou Baike azoles (oxpoconazole), oxycarboxin, pefurazoate, penconazole, Pencycuron, penta benzene pyrrole bacterium amine, pyrrole metsulfovax, phenazine oxide, Yimeiling Al, phosphoric acid class, phthalide, ZEN 90160 (ZA1963), polyoxin D, Carbatene (polyram), probenazole, Prochloraz, procymidone, Propamocarb, propiconazole, Propineb, propionic acid, prothioconazoles, Ppyrazophos, pyrifenox, phonetic mould amine, pyraclostrobin, pyroquilon, chlorine pyrrole furan ether, pyrrolnitrin, quaternary ammonium compounds, chinomethionat, quinoxyfen, ring benzene pyrrole bacterium amine (sedaxane), west gram azoles (sipconazole) (F-155), penta sodium pentachlorophenate, volution bacterium amine, streptomycin, sulphur, Tebuconazole, tecloftalam, tecnazene, fluorine ether azoles, probenazole, thiophene methuroxam, 2-(thiocyanomethylthio) benzothiazole, thiophanate-methyl, plug logical sequence, glyoxalin (timibenconazole), vertical withered phosphorus methyl, tolyfluanid, triazolone, Triadimenol, fourth triazole, triazoxide, tricyclazole, tridemorph, oxime bacterium ester (CGA279202), triforine, fluorine bacterium azoles, triticonazole, jinggangmycin A, prestige hundred, vinclozolin, zineb and ziram, N-[9-(dichloromethylene)-1,2,3,4-tetrahydrochysenes-Isosorbide-5-Nitrae-methanonaphthalene-5-base]-3-(difluoromethyl)-1-methyl isophthalic acid H-pyrazole-4-carboxamide [1072957-71-1], 1-methyl-3-difluoromethyl-1H-pyrazoles-4-carboxylic acid (2-dichloromethylene-3-ethyl-1-methyl-dihydro indenes-4-base)-acid amides, and 1-methyl-3-difluoromethyl-4H-pyrazoles-4-carboxylic acid [2-(2,4-Dichloro-phenyl)-2-methoxyl group-1-methyl-ethyl]-acid amides.

In addition, biological agent such as bacillus can be comprised in the compositions of the present invention, such as bacillus firmus, Bacillus cercus, bacillus subtilis, and Pasteurella such as puncture pasteurella and plan Si Zhawa Pasteurella (Pasteuria nishizawae).A kind of suitable bacillus firmus bacterial strain is as BioNem ^tMcommercially available bacterial strain CNCM I-1582.A kind of suitable bacillus cereus strain is bacterial strain CNCM I-1562.At US 6,406, the more details about two kinds of Bacillus strains can be found in 690.Other biologic artifacts that can be included in these compositions of the present invention are bacterium (such as streptomyces such as Avid kyowamycins), and fungi (such as Pu Qiniya Pseudomonas thick wall spore Pu Keniya bacterium).What also have meaning is Metarhizium such as Metarhizium anisopliae; Pu Puqiniya Pseudomonas (such as thick wall spore Pu Keniya bacterium).

Compound of the present invention can be mixed for protective plant with soil, mud coal or other rooting media and resist seed-Sheng, soil-Sheng or leaf fungal disease.

Example for the suitable synergist used in these compositions comprises piperonyl butoxide, sesoxane, Safroxane and dodecyl imidazole.

In order to be included in suitable weed killer herbicide in these compositions and plant growth regulator will depend on intended object and required effect.

The example of the rice selective herbicide that can be included is Stam F-34.Example for the plant growth regulator used in cotton is PIX ^tM.

Some mixtures can comprise various active composition, and these active components have significantly different physics, chemistry or biological nature thus make them be not easy the preparation type making self for same routine.In these cases, other preparation type can be prepared.Such as, when another kind is water-insoluble liquid when a kind of active component is water-insoluble solid, still likely this liquid actives is carried out disperseing (preparation method that use is similar to EW) as a kind of emulsion by this solid active agent is carried out disperseing (preparation method that use is similar to SC) as a kind of suspension thus often kind of active component is distributed in same continuous print liquid phase.The composition produced is a kind of suspension emulsion (SE) preparation.

Unless otherwise specified, the weight ratio of the compound and a kind of other active component with I can be between 1000:1 and 1:1000 usually.In other examples, the weight ratio of the compound and other active component with Formula I can between 500:1 to 1:500, such as between 100:1 to 1:100, such as between 1:50 to 50:1, such as between 1:20 to 20:1, such as between 1:10 to 10:1, such as, between 1:5 to 5:1.Such as 1:1,1:2,1:3,1:4,1:5,2:1,3:1,4:1 or 5:1.

Interested especially for the present invention with the mixture of pyrethroid particularly pyrrole first piperazine.

Composition of the present invention comprises by premixed before using, such as namely prepare with mixture or tank mixture as a kind of those, or by use to plant simultaneously or prepared by continuous administration those.

In order to compound of the present invention be applied as pest, pest place or be subject to the insecticide of plant of pest infestation, acarus-killing, nematocide or invertebrate poison, usually compound of the present invention is mixed with a kind of composition, said composition comprises a kind of applicable inert diluent or carrier and optionally a kind of surfactant (SFA) in addition to the compounds of the invention.SFA is can by reducing interfacial tension amendment interface (such as liquid/solid, liquid/gas or liquid/liquid interface) characteristic and the chemicals that changes of other characteristics that cause thus (such as disperse, emulsification and moistening).Preferably, all composition (solid and liquid formulations both) comprises by weight 0.0001% to 95%, is more preferably 1% to 85%, the compound of the present invention of such as 5% to 60%.Said composition is normally used for controlling pest, compound of the present invention like this with per hectare 0.1g to 10kg, preferably from per hectare 1g to 6kg, be more preferably and use from the ratio of per hectare 1g to 1kg.

In one embodiment, compound of the present invention controls with the pest of 1:500g/ha (such as 10g/ha-70g/ha) on cotton.But, should note because Mexico's cotton boll resembles very injurious effects (quality and quantity to output), spraying be often strongly and be in low-down threshold level and almost zero tolerance can be dropped to.

When using in a kind of seed dressing, compound of the present invention is with every kilogram of seed 0.0001g to 10g (such as 0.001g or 0.05g), and preferably 0.005g to 10g, the ratio being more preferably 0.005g to 4g uses.

The composition comprising a kind of compound of the present invention can be selected from multiple preparation type, comprising can dust formation pulvis (DP), soluble powder (SP), water-soluble particle (SG), the dispersible particle of water (WG), wetting powder (WP), particle (GR) (releasing slowly or soon), solvable concentrate (SL), the miscible liquid of oil (OL), ultralow volume of liquid (UL), emulsible concentrate (EC), dispersible concentrate (DC), emulsion (oil-in-water (EW) and Water-In-Oil (EO) both), microemulsion (ME), suspending concentrate (SC), aerosol, mist/cigarette preparation, capsule suspension liquid (CS) and seed treatment preparation.Under any circumstance, selected preparation type will depend on physics, the chemistry and biology characteristic of intended specific purposes and compound of the present invention.

Can the pulvis (DP) of dust formation can by a kind of compound of the present invention and one or more solid diluents (such as, natural clay, kaolin, pyrophyllite, bentonite, aluminium oxide, montmorillonite, diatomite (kieselguhr), chalky soil, diatomite (diatomaceous earths), calcium phosphate, calcium carbonate and magnesium carbonate, sulphur, lime, flour, talcum and other organic and inorganic solid carriers) be mixed and this mixture are mechanically milled into fine powder to prepare.

Soluble powder (SP) can by by compound of the present invention and one or more water-soluble inorganic salt (as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (as polysaccharide) and optionally one or more wetting agents, one or more dispersants or as described in the mixture of reagent carry out mixing and prepare to improve water dispersible/water-soluble.Then this mixture is ground to form fine powder.Also can by similar composition grain to form water-soluble granular formulation (SG).

Wetting powder (WP) can by being prepared as follows, by compound of the present invention and one or more solid diluents or carrier, one or more wetting agents and preferably one or more dispersants and optionally one or more suspending agents mix, to promote dispersion in a liquid.Then this mixture is ground to form fine powder.Also can by similar composition grain to form water-dispersible granular material agent (WG).

Granule (GR) can be formed like this: by being formed by the mixture pelleting of compound of the present invention and one or more powdered solid diluents or carrier, or by compound of the present invention (or its solution) in a kind of applicable reagent is absorbed into honeycombed grain material (such as float stone, Concave-convex clay rod, bleaching earth, diatomite (kieselguhr), diatomite (diatomaceous earths) or maize cob meal), or it is (such as husky by compound of the present invention (or its solution) in the reagent be applicable to is adsorbed onto hard core material, silicate, mineral carbonic acid salt, sulphate or phosphate) and if the words of upper necessity carry out drying, the preformed blank granules of cause is formed.Generally comprise solvent (as aliphatic and aromatic petroleum solvent, alcohol, ether, ketone and ester) and sticker (as polyvinyl acetate, polyvinyl alcohol, dextrin, sugar and vegetable oil) with the reagent of helping absorb or adsorb.Also one or more other additives (such as emulsifier, wetting agent or dispersant) can be comprised at particle.

Dispersible concentrate (DC) can be prepared by being dissolved in by compound of the present invention in water or organic solvent (such as ketone, alcohol or glycol ether).These solvents can comprise surfactant (being such as used for improving water-thinned or prevent crystallization in spray cistern).

Emulsible concentrate (EC) or O/w emulsion (EW) can be prepared by compound of the present invention being dissolved in a kind of organic solvent (optionally comprising the mixture of one or more wetting agents, one or more emulsifier or described reagent).The organic solvent be applicable to used in EC comprises aromatic hydrocarbon (such as alkylbenzene or Fluhyzon, such as SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is registration mark), ketone (such as cyclohexanone or methyl cyclohexanone) and alcohol (such as phenmethylol, furfuryl alcohol or butanols), N-alkyl pyrrolidone (such as 1-METHYLPYRROLIDONE or NOP), fatty acid dimethylformamide (such as C ₈-C ₁₀fatty acid dimethylamides) and chlorinated hydrocabon.EC product can the spontaneously emulsification when being added in water, produces and have enough stability to allow to spray by suitable equipment the emulsion used.The preparation of EW relates to acquisition as a kind of liquid (if it is not at room temperature liquid, then it can be melted under typically lower than the reasonable temperature of 70 DEG C) or be in the compound of the present invention of (by it being dissolved in suitable solvent) in solution, then under high shear gained liquid or emulsifying soln are entered to comprise in the water of one or more SFA, to produce emulsion.The solvent be applicable to used in EW comprise vegetable oil, chlorinated hydrocabon (as chlorobenzene), aromatic solvent (as alkylbenzene or Fluhyzon) and other there is the suitable organic solvent of low solubility in water.

Microemulsion (ME) can be prepared by mix by the admixture of water and one or more solvents and one or more SFA, spontaneously to produce the thermodynamically stable isotropic liquid formulations of one.Originally compound of the present invention is present in water or solvent/SFA blend.The solvent being applicable to ME comprises the above for those in EC or EW.ME can be oil-in-water system or water-in-oil system (there is which kind of system to be determined by conductivity measurement) and can be suitable in identical preparation, mix water miscible and oil-soluble pesticides.ME is suitable for dilution and enters in water, remains microemulsion or forms conventional O/w emulsion.

Suspension-concentrates (SC) can comprise the moisture of the insoluble solids particle of the fine dispersion of compound of the present invention or without water slurry.SC can optionally use one or more dispersants to grind solid chemical compound of the present invention to prepare, to produce the fine grained suspension of this compound by ball milling or pearl in the medium be applicable to.One or more wetting agents can be comprised in the composition, and suspending agent can be comprised to reduce the settling velocity of particle.Alternately, can to dry grind compound of the present invention be added in the water comprising previously described reagent, to produce desired final products.

Aerosol formulations comprises compound of the present invention and a kind of applicable propellant (such as normal butane).Also compound of the present invention can be dissolved in or be scattered in a kind of applicable medium (such as water or can be miscible with water liquid, as normal propyl alcohol) in be provided in the composition used in non-pressurised hand spray pump.

Compound of the present invention can mix with firework mixture to form a kind of composition being suitable for producing in enclosure space the smog comprising this compound in the dry state.

Capsule suspension liquid (CS) can be prepared by a kind of method of preparation of the EW of being similar to preparation, but there is other polymerization stage, thus obtain the aqueous liquid dispersion of oil droplet, wherein each oil droplet is comprised compound of the present invention and optionally a kind of carrier of this compound or thinner by a kind of polymer shell packing.This polymer shell can be reacted by interfacial polycondensation or be produced by cohesion program.These compositions can provide the controlled release of compound of the present invention and they may be used for seed treatment.Compound of the present invention can also be formulated in Biodegradable polymeric matrix with provide this compound slowly, controlled release.

Composition can comprise one or more additives to improve the biology performance of said composition (such as by the wettability on improvement surface, reservation or distribution; Rain proofness on the surface processed; Or the absorption of compound of the present invention or animal migration).Such additive comprises surfactant, spray additives based on oil, such as some mineral oil or crude vegetal (such as soybean and rapeseed oil), and the blend of these and other biological reinforcing aids (can help or modify the composition of the effect of compound of the present invention).

Compound of the present invention can also be formulated as seed treatment, such as a kind of powder composition, comprise a kind of pulvis for dry seeds process (DS), a kind of water solube powder (SS) or a kind of water-dispersible pulvis (WS) for slurry treatment, or as a kind of fluid composition, comprise one and can to flow concentrate (FS), a kind of solution (LS) or a kind of capsule suspension liquid (CS).The preparation of DS, SS, WS, FS and LS composition is very similar with those of DP, SP, WP, SC and DC composition described above respectively.Composition for the treatment of seed can comprise a kind of for assisting said composition to be attached to reagent (such as a kind of mineral oil or a kind of film forming obstacle) on this seed.

Wetting agent, dispersant and emulsifier can be the surperficial SFA of cation, anion, both sexes or non-ionic type.

Suitable cationic SFA comprises quaternary ammonium compound (such as softex kw), imidazoline and amine salt.

The SFA of suitable anion comprises the alkali metal salt of fatty acid, the salt of sulfated fatty race monoesters (such as, NaLS), the salt of the aromatic compound of sulfonation (such as, neopelex, calcium dodecyl benzene sulfonate, the mixture of butyl naphthalene sulfonate and diisopropyl sodium naphthalene sulfonate and triisopropyl sodium naphthalene sulfonate), ether sulfate, ether alcohol sulfate (such as, laureth-3-sodium sulphate), ether carboxylate (such as laureth-3-carboxylic acid sodium), phosphate (the product that one or more fatty alcohols and phosphoric acid (mainly monoesters) or phosphorus pentoxide (mainly diester) react, reaction such as between lauryl alcohol and four phosphoric acid, in addition these products can be ethoxylations), sulphosuccinamate, paraffin or alkene sulfonates, taurate and lignosulphonates.

The SFA of the amphoteric type be applicable to comprises betain, propionate and glycinate.

The SFA of this non-ionic type be applicable to comprises alkylene oxides (as oxirane, expoxy propane, epoxy butane or its mixture) and aliphatic alcohols (as oleyl alcohol or cetanol) or the condensation product with induced by alkyl hydroxybenzene (as octyl phenol, nonyl phenol or octyl cresol); The partial ester of derivation of self-long chain fatty acid or hexitan; The condensation product of described partial ester and oxirane; Block polymer (comprising oxirane and expoxy propane); Alkanolamide; Monoesters (such as fatty acid polyethylene glycol ester); Amine oxide (such as lauryl dimethyl amine oxide); And lecithin.

The suspending agent be applicable to comprises hydrophilic colloid (such as polysaccharide, polyvinylpyrrolidone or sodium carboxymethylcellulose) and expansive clay (such as bentonite or attapulgite).

Compound of the present invention can be used by any means of killing pest compound of using that oneself knows.Such as, it (preparation or do not prepare) can directly be applied to (the habitat of such as these pests, place, place of these pests or these pests, or be subject to the planting plants of pest infection), or be applied to any part of plant, comprise leaf, stem, branch or root, be applied to the seed before plantation, or be applied to plant and growing or by by other media (such as soil in root week of planting, normal soil, the planting system that paddy field water either or water are planted), or it can be sprayed, dusting, used by dipping, use as butterfat or paste preparation, to use as steam or by by composition (such as particulate composition or the composition that wraps in water-soluble bag) distribution or and use in burying or in water environment.

Compound of the present invention can also to be injected in plant or to use electrodynamic spraying techniques or other low capacity methods to be sprayed on plant, or is irrigated by soil or aerial irrigation systems is used.

Composition as aqueous formulation (aqueous solution or dispersion) provides with the form of the concentrate containing a high proportion of active component generally, and this concentrate is added to the water before the use.These concentrates (can comprise DC, SC, EC, EW, ME, SG, SP, WP, WG and CS) are often required to stand long-term storage and can be added to the water to form aqueous formulation after this kind stores, and said preparation keeps the homogeneous state sufficiently long time to use by the spraying apparatus of routine to make them.This type of aqueous formulation can comprise the compound of the present invention (such as, by weight 0.0001% to 10%) of variable quantity, and this depends on the object using them to do.

These examples show but do not limit the present invention below.

example 1:N-[(1S)-1-[4-[3-[two (trifluoromethyl) phenyl of 3,5-]-3-(trifluoromethyl) pyrrolidin-1-yl] phenyl] ethyl] preparation of cyclopropane carboxamide

To the 3-[3 under argon gas through stirring, two (trifluoromethyl) phenyl of 5-]-3-(trifluoromethyl) pyrrolidines (0.15g, 0.4271mmol, as being described in preparing of WO 2008/128711) and N-[(1S)-1-(4-bromophenyl) ethyl] cyclopropane carboxamide (0.134g, 0.4997mmol, as being described in preparing of WO 2012/001107) add three (dibenzylideneacetone) two palladium (0) (9mg) in solution in toluene (6.03mL), 4, two (diphenylphosphino)-9 of 5-, 9-dimethyl xanthene (18mg) and sodium tert-butoxide (96mg).This mixture is heated 15min in microwave at 130 DEG C.Then by this reaction ethyl acetate and water dilution, then with salt solution dilution, and then this mixture is extracted with ethyl acetate.Organic layer is merged, and through dried over mgso, filter, then under reduced pressure carry out concentrated to provide a kind of yellow oil, this yellow oil is carried out purifying with product (172mg) desired by providing in white foam by column chromatography (cyclohexane/EtOAc is as solvent).

¹H NMR(CDCl3,400MHz)：d＝7.92(s,1H),7.86(s,2H),7.27(m,2H),6.63(d,J＝8.4Hz,2H),5.74(d,J＝7.7Hz,1H),5.09(t,J＝7.3Hz,1H),4.16(d,J＝10.3Hz,1H),3.85(d,J＝10.3Hz,1H),3.60(d,J＝8.1Hz,1H),3.51(d,J＝2.9Hz,1H),2.91-3.03(m,1H),2.61(d,J＝13.6Hz,1H),1.50(d,J＝7.0Hz,3H),1.17-1.34(m,1H),0.90-1.04(m,2H),0.63-0.80ppm(m,2H)

example 2:N-[(1S)-1-[4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidin-1-yl] phenyl] ethyl] ring the preparation of propane carboxylic acid amides

Under an argon, by three (dibenzylideneacetone) two palladium (0) (32mg), 4, two (diphenylphosphino)-9 of 5-, 9-dimethyl xanthene (61mg) and sodium tert-butoxide (190mg) are added into 3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidines (520mg, as being described in preparing of WO 2008/128711) and the solution of N-[(1S)-1-(4-bromophenyl) ethyl] cyclopropane carboxamide (as being described in preparing of WO 2012/001107,520mg) in toluene (15mL) in.This mixture is heated 30min in microwave at 130 DEG C.Then by this reaction ethyl acetate and water dilution, then with salt solution dilution, and then this mixture is extracted with ethyl acetate.Organic layer is merged, and through dried over sodium sulfate, filter, then under reduced pressure carry out concentrated to provide a kind of yellow oil, this yellow oil is carried out purifying with product (650mg) desired by providing in white foam by column chromatography (heptane/EtOAc is as solvent (10/0 to 0/10)). ¹H NMR(CDCl3,400MHz)：d＝7.40(s,1H),7.31(s,2H),7.26(m,2H),6.62(d,2H),5.73(d,1H),5.09(t,1H),4.06(d,1H),3.85(d,1H),3.57(m,1H),3.50(m,1H),2.84(m,1H),2.56(m,1H),1.50(d,3H),1.2(m,1H),0.99(m,2H),0.72ppm(m,2H)

example 3:N-[(1S)-1-[4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazole-3-base] phenyl] second base] preparation of acetamide

Step 1:

To N-[(1S)-1-(4-acetylphenyl) ethyl] acetamide (3g) and 1-(3; 5-dichlorophenyl)-2; 2; triethylamine (0.2mL) and potash (1g) is added in the suspension of 2-trifluoro-ethanone (3.6g) in 1,2-dichloroethane (40mL).This solution is stirred at 80 DEG C.After 40 minutes, more potash (1g) is added.This solution is heated other 20 minutes at 80 DEG C, then adds more potash (1g), and by this suspension returning 16 hours.Then this mixture is cooled to room temperature, and adds water.By this mixture dichloromethane extraction, then use salt water washing.Organic layer is merged, and through dried over mgso, filter, then under reduced pressure carry out concentrated to provide a kind of yellow oil, this yellow oil is carried out purifying with product (5g) desired by providing in yellow oil by column chromatography (heptane/EtOAc is as solvent (1/0 to 3/7)).

1H NMR(CDCl3,400MHz)：d＝7.78-7.87(m,2H),7.42-7.40(m,2H),7.33(m,1H),7.16(d,2H),5.69(d,1H),5.02-5.26(m,1H),2.02(s,3H),1.48-1.51ppm(d,3H)

Step 2:

At room temperature; to N-[(1S)-1-[4-[3-(3; 5-dichlorophenyl)-4; 4; the fluoro-but-2-ene acyl group of 4-tri-] phenyl] ethyl] acetamide (100mg) is in 1; TBuA hydrobromide (40mg), azanol (0.03mL, 50% in water) and sodium hydroxide (0.46mL, 1M) is added in solution in 2-dichloroethane (4mL).This solution is at room temperature stirred 6 hours, then adds the solution of saturated ammonium chloride.This mixture DCM is extracted, then uses salt water washing.Organic layer is merged, and through dried over mgso, filter, then under reduced pressure carry out concentrated to provide a kind of yellow oil, this yellow oil is carried out purifying with product (77mg) desired by providing in yellow oil by column chromatography (heptane/EtOAc is as solvent (1/0 to 1/1)).

¹H NMR(CDCl3,400MHz)：d＝7.59-7.69(m,2H),7.49-7.57(m,2H),7.43(t,J＝1.8Hz,1H),7.34-7.41(m,J＝8.4Hz,2H),5.65(d,J＝7.3Hz,1H),5.15(t,J＝7.2Hz,1H),4.01-4.13(m,1H),3.68(d,J＝17.2Hz,1H),2.01(s,3H),1.50(d,J＝7.0Hz,3H),1.27ppm(t,J＝7.2Hz,1H)。

example 4:2-(1,2,4-triazol-1-yl)-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin- 5-yl] preparation of benzonitrile

The preparation of the fluoro-N-of the bromo-4-of step 1:3-(trimethylsilyl methyl) benzamide

To the fluoro-benzoic acid (500mg of the bromo-4-of 3-, N is added in solution 2.2830mmol) in carrene (15mL), N-lutidines-4-amine (28mg, 0.22830mmol), EDCI HCl (570mg, 2.9679mmol).In this, add trimethysilylmethylamine (260mg, 2.5113mmol), and this reaction is stirred under nitrogen atmosphere in room temperature spend the night and monitored by TLC.This reactive material use water (10ml) is diluted, and extracts with DCM (3 × 50mL).The organic layer of merging is concentrated under vacuo through dried over sodium sulfate.The bromo-4-of 3-fluoro-N-(trimethylsilyl methyl) benzamide (550mg) is provided by chromatography (hexane/ethyl acetate) purifying.

¹h NMR (400MHz, CDCl3): 7.94 (dd, 1H); (7.65 m, 1H); (7.15 t, 1H); (5.9 brs, 1H); (2.94 d, 2H); 0.12 (s, 9H), LCMS (methyl alcohol, ESI): the time of staying=2.06, m/z=302.0 (M-H)

The preparation of the fluoro-N-of step 2:3-cyano group-4-(trimethylsilyl methyl) benzamide

To have collected at N, the bromo-4-of 3-fluoro-N-(trimethylsilyl methyl) benzamide (10g in dinethylformamide (60mL), zinc formonitrile HCN (7.85g is added in the sealed tube of solution 32.870mmol), 65.740mmol), then add four (triphenylphosphines) and close palladium (0) (7.61g, 6.5740mmol).By degassed for this reaction and with nitrogen purge and at 100 DEG C, stir 4-5 hour.This reaction use water (100mL) is diluted, extracts with ethyl acetate (3x 100mL), and wash with sodium bicarbonate (50mL).The organic layer of merging is concentrated under vacuo through dried over sodium sulfate.3-cyano group-4-fluoro-N-(trimethylsilyl methyl) benzamide (6.7g) is provided by chromatography (hexane/ethyl acetate) purifying

¹H NMR(400MHz,CDCl3)：7.98-8.02(m,2H)；7.3(m,1H)；5.94(brs,1H)；2.95-2.98(m,2H)；0.13(s,9H)。LCMS (methyl alcohol, APCI): the time of staying=4.11, m/z=249.09 (M-H)

The preparation of the fluoro-N-of step 3:3-cyano group-4-(trimethylsilyl methyl) thiobenzamide

By 3-cyano group-4-fluoro-N-(trimethylsilyl methyl) benzamide (6.5g, 26mmol) He 2, two (the 4-methoxyphenyl)-2 of 4-, 4-bis-sulphur oxo-1,3, the solution return of 2,4-bis-thiophene two phosphorus heterocycle butane (11g, 26mmol) in oxolane (75mL) 2 hours.This reactive material is carried out concentrated to remove THF, with water (50ml) dilution, and extract with ethyl acetate (3 × 100mL).The organic layer of merging is concentrated under vacuo through dried over sodium sulfate.3-cyano group-4-fluoro-N-(trimethylsilyl methyl) thiobenzamide (4.8g) is provided by chromatography (hexane/ethyl acetate) purifying.

¹h NMR (400MHz, CDCl3): 8.2 (m, 1H); 7.93-7.99 (m, 1H); 7.64 (brs, 1H); 7.22 (m, 1H); 3.52 (d, 2H); 0.18 (s, 9H), LCMS (methyl alcohol, APCI): the time of staying=4.55, m/z=265.45 (M-H).

The preparation of the fluoro-5-of step 4:2-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] benzonitrile

To 3-cyano group-4-fluoro-N-(trimethylsilyl methyl) thiobenzamide (4g, 15.02mmol) in N, dipotassium carbonate (5.26g, 37.54mmol) is added in solution in dinethylformamide (40mL).Iodomethane (21.31g, 150.2mmol) is added in this.This reactive material is monitored by TLC stirring at room temperature 3 hours.By this reactive material use water (10ml) cancellation, and extract with ethyl acetate (3 × 50mL).The organic layer of merging is through dried over sodium sulfate and under vacuo concentrated to provide methyl-3-cyano group-4-fluoro-N-(trimethylsilyl methyl) thio phenyl azomethine acyl ester.

To methyl-3-cyano group-4-fluoro-N-(trimethylsilyl methyl) iodobenzene azomethine acyl ester (4g, 14.27mmol) and 1,2, the chloro-5-of 3-tri-[1-(trifluoromethyl) vinyl] benzene (3.97g., TBuA hydrofluoride (7.13mL is added lentamente in the cooling solution of-5 DEG C 14.41mmol) in oxolane (5mL), 7.133mmol, 1mol/L).This reaction is stirred 30min at-5 DEG C, then allows to reach room temperature, and stir 2 hours under nitrogen atmosphere in room temperature.This reaction use water (50mL) is diluted and extracts with ethyl acetate (3x 100mL).The organic layer of merging is concentrated under vacuo through dried over sodium sulfate.The fluoro-5-of 2-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] benzonitrile (2.5g) is provided by chromatography (hexane/ethyl acetate) purifying.

¹h NMR (400MHz, CDCl ₃): 8.04-8.13 (m, 2H); 7.37 (s, 2H); 7.35 (m, 1H); 4.82 (dd, 1H); 4.36 (d, 1H); 3.7 (dd, 1H); 3.35 (d, 1H), LCMS (methyl alcohol, APCI): the time of staying=5.05, m/z=434.88 (M+H)

The preparation of step 5:2-(1,2,4-triazol-1-yl)-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] benzonitrile

By fluoro-for 2-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] benzonitrile (1.0g, 2.3mmol), dipotassium carbonate (390mg, 2.8mmol) and 1H-1,2,4-triazole (190mg, 2.8mmol) is heated 2-3 hour and is monitored by TLC at 120 DEG C.This reaction use water (10mL) is diluted and extracts with ethyl acetate (3x 30mL).The organic layer of merging is concentrated under vacuo through dried over sodium sulfate.The 2-(1 in solid is provided by chromatography (hexane/ethyl acetate) purifying, 2,4-triazol-1-yl)-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] benzonitrile (950mg).Fusing point: 162 DEG C-164 DEG C.

¹h NMR (400MHz, CDCl ₃): 8.9 (s, 1H), 8.29-8.34 (m, 2H); 8.21 (s, 1H); 7.93 (d, 1H); 7.40 (s, 2H); 4.94 (d, 1H); 4.51 (d, 1H); 3.84 (d, 1H); 3.54 (d, 1H); , LCMS (methyl alcohol, APCI): the time of staying=4.96, m/z=483.94 (M+H)

example 5:N-[(1S)-1-[4-[5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-3-base] phenyl] ethyl] preparation of cyclopropane carboxamide

the preparation of step 1:N-[(1S)-1-(4-bromophenyl) ethyl] t-butyl carbamate

Through the time period of 20min, tertbutyloxycarbonyl tert-butyl carbonate (50mmol) is added in the solution carrying out stirring of compound (1S)-1-(4-bromophenyl) ethamine (50mmol) in 50mL round-bottomed flask, and continue to stir tempestuously, after 5min, solid is out precipitated from reactive material, thus obtained precipitation is carried out filtering and dry under vacuo with hexanes wash.Weight: 13g

¹H-NMR(400MHz,CDCl ₃)：7.45(2H,d),7.18(2H,d),4.74(1H,m),1.40-1.48(12H,m)。

Step 2:4-[(1S)-1-(tertbutyloxycarbonylamino) ethyl] benzoic preparation

Under nitrogen atmosphere, to compound N-[(1S)-1-(4-bromophenyl) ethyl] t-butyl carbamate (1g, lithium methide (5.33mmol is dropwise added in the solution carrying out stirring 3.331mmol) in the THF (30mL) being cooled to-78 DEG C, 1.6eq.), and stir and continue 15min, dropwise add butyl lithium (5.33mmol, 1.6eq.) subsequently, and continue to stir 30min.Add dry carbonic acid gas and at-70 DEG C, continue stirring 1 little of room temperature.By this reactive material water (50mL) cancellation and by this compound ethyl acetate (30mL x 2) extraction to remove debrominate compound.Water layer ammonium chloride is carried out acidifying and extracts with ethyl acetate (30mL x 2).By the organic layers with sodium sulfate of merging, dry and vaporising under vacuum falls and dry under vacuo.Weight: 0.61g

¹H-NMR(400MHz,CDCl ₃)：7.86(2H,d),7.37(2H,d),4.64(1H,m),1.28-1.31(12H,m)。LC-MS (methyl alcohol, ESI): m/z=264 (M-H), RT 1.95-2.07.

The preparation of step 3:N-[(1S)-1-[4-(trimethylsilyl methyl carbamoyl) phenyl] ethyl] t-butyl carbamate

To 4-[(1S)-1-(tertbutyloxycarbonylamino) ethyl] benzoic acid (1g, 3.769mmol), I-hydroxybenzotriazole hydrate (542mg, in the solution carrying out stirring 3.5mmol) in DMF (5mL), in DCM (30mL), trimethysilylmethylamine (0.38g, 3.7mmol), trimethysilylmethylamine (0.38g, 3.7mmol) and by reactive material be cooled to 0 DEG C and add 3-(ethylimino methene amido)-N, N-dimethyl-propane-1-amine hydrochlorate (848mg, 4.4234mmol), and this reaction is stirred to ambient temperature overnight at 0 DEG C.TCL illustrates that this reaction completes.By this reactive material water (30mL) cancellation and with DCM (35mL x 2) extraction and by merge organic layers with water (20mL x 2) washing and by dried over sodium sulfate and vapourisation under reduced pressure fall and by combiflash, compound purified.Weight: 0.93g

¹H-NMR(400MHz,CDCl ₃)：7.68(2H,d),7.34(2H,d),5.93(1H,m)。4.81(2H,d),2.95(2H,d),1.40-1.45(12H,m)。LC-MS (methyl alcohol, ESI): m/z=349 (M-H), RT 1.95-2.07.

The preparation of step 4:N-[(1S)-1-[4-(trimethylsilyl methyl thiocarbamoyl) phenyl] ethyl] t-butyl carbamate

To N-[(1S)-1-[4-(trimethylsilyl methyl carbamoyl) phenyl] ethyl] t-butyl carbamate (1g; 2 are added in solution 2.853mmol) in THF (25mL); two (the 4-methoxyphenyl)-1 of 4-; 3; 2,4-bis-thiophene two phosphorus heterocycle butane-2,4-disulphide (1eq; 2.853mmol), and reactive material is stirred 4 hours at 65 DEG C.TCL illustrates that this reaction completes.On the rotary evaporator solvent is removed from reactive material, and the reactive material diluted ethyl acetate of gained is washed with water (twice).Organic layer is carried out drying through anhydrous sodium sulfate and under reduced pressure concentrates.Thus obtained thick material is carried out purifying by combiflash (silica gel).Weight: 0.8g

¹H-NMR(400MHz,CDCl ₃)：7.65(2H,d),7.51-7.52(1H,m),7.30(2H,d),4.76-4.81(2H,m),3.51(2H,d),1.40-1.45(12H,m)。LC-MS (methyl alcohol, ESI): m/z=365 (M-H), RT 2.51-2.57.

The preparation of step 5:N-[(1S)-1-[4-[5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-3-base] phenyl] ethyl] t-butyl carbamate

To compound N-[(1S)-1-[4-(trimethyl silyl thiocarbamoyl) phenyl] ethyl] t-butyl carbamate (0.5g; potash (2eq. is added in the solution carrying out stirring 1mmol) in DMF (25mL); 2mmol); with after add iodomethane (10eq., 10mmol) and continue stirring 3 hours through the time period of 1 hour.After reaction completes (being monitored by TLC), by this reactive material diluted ethyl acetate and with water (20mL x 3) washing and by dried over sodium sulfate and vaporising under vacuum fall.The reactive material of acquisition put into THF (25mL) and add the chloro-5-of 1,2,3-tri-[1-(trifluoromethyl) vinyl] benzene (1eq., 1mmol) wherein.This mixture is cooled to 0 DEG C, adds TBAF (1eq, 1mmol) and at room temperature continue stirring 3 hours.After reaction completes (being monitored by TLC), solvent vaporising under vacuum is fallen and by this reactive material diluted ethyl acetate and with water (30mL x 2) washing and by dried over sodium sulfate and vaporising under vacuum fall.Compound is carried out purifying by combiflash (25%-30%EtOAC-hexane).Weight: 0.11g

¹H-NMR(400MHz,CDCl ₃)：7.97(2H,d),7.33-7.56(4H,m),4.85-4.92(2H,m),4.50(1H,dd),3.91(1H,dd),3.58(1H,dd),1.40-1.45(12H,m)。LC-MS (methyl alcohol, ESI): m/z=533 (M-H), RT 2.51-2.57.

The preparation of step 6:N-[(1S)-1-[4-[5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-3-base] phenyl] ethyl] cyclopropane carboxamide

To N-[(1S)-1-[4-[5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-3-base] phenyl] ethyl] add 2 in the solution of t-butyl carbamate (0.35g) in DCM (20mL), 2,2-trifluoroacetic acid (3eq.), and this reactive material is at room temperature stirred 5 hours.After the reaction was completed, solvent is removed under vacuo, and thus obtained compound is directly used in next step.By (1S)-1-[4-[5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-3-base] phenyl] solution of ethamine tfa salt (0.3g, 0.7mmol) in DCM (20mL) cools at 0 DEG C.In the mixture of this cooling, add triethylamine (2.2eq, 1.54mmol), with after dropwise add cyclopropane-carboxylic acid chloride (1eq., 0.7mmol) through the time period of 5min and continue stirring and spend the night.After this reaction completes (being monitored by TLC), this reactive material is diluted with DCM (20mL) and washs with water (20mL).Then by organic layer through anhydrous sodium sulfate drying, and solvent to be removed under vacuo.Compound is carried out purifying by Combiflash (35%EtOAC-hexane).Weight: 0.2g, fusing point: 80 DEG C-82 DEG C.

¹H-NMR(400MHz,CDCl ₃)：7.82(2H,d),7.35-7.41(4H,m),6.05(1H,m),5.13(1H,m),4.86(1H,dd),4.42(1H,dd),3.78(1H,dd),3.45(1H,dd)。1.46-1.50 (4H, m), 0.93-0.96 (2H, m), 0.72-0.731 (2H, m) LC-MS (methyl alcohol, ESI): m/z=501 (M-H), RT 2.23-2.30.

the bromo-4-of example 6:N-{2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-benzyl } the preparation of acetamide.

The bromination of the bromo-4-methyl benzoic acid of step 1:3-.

Bromo-for 3-4-methyl benzoic acid (10g, 46.72mmol), NBS (8.7g, 49.15mmol) and benzoyl peroxide (0.5g, 2mmol) are suspended in CCl ₄in, and be then heated to backflow lasting 5 hours.After reaction completes (TLC monitoring), in this reactant mixture, add water.Be separated organic layer, through dried over sodium sulfate, and concentrate in a vacuum.The crude mixture of bromo-for the thus obtained 3-of comprising 4-bromo methyl acid and 3-bromo-4-xylylene bromide formic acid is directly used in next step.

LC-MS (methyl alcohol, ESI): m/z=291 (M-H) and 368 (M-H)

The preparation of the bromo-4-of step 2:3-(two bromomethyls)-N-[(trimethyl silyl) methyl] benzamide.

By bromo-for 3-4-(bromomethyl)-N-[(trimethyl silyl) methyl] benzamide and the bromo-4-of 3-(two bromomethyls)-N-[(trimethyl silyl) methyl] benzamide (19g, 51mmol), 1-(trimethyl silyl) methylamine (5.78g, 56mmol), N, N-dimethyl aminopyridine (0.1g) and N-(3-dimethylaminopropyl)-N '-ethyl carbodiimide HCl (12.74g, 66mmol) to be dissolved in tetrahydrofuran solvent and at room temperature to stir 1 hour.After this reaction completes (TLC monitoring), on the rotary evaporator this reactant mixture is concentrated.In this reactant mixture, add water, be extracted with ethyl acetate subsequently.Organic layer is separated and uses dried over sodium sulfate.Residue is carried out purifying to obtain the bromo-4-of 3-(two bromomethyls)-N-[(trimethyl silyl) methyl] benzamide (16g) by silica gel chromatography.

LC-MS (methyl alcohol, ESI): m/z=456 (M+H).

1H-NMR(400MHz,CDCl3)：8.01(1H,dd),7.87(1H,d),7.04(1H,dd),6.13(1H,bs),3.51(2H,d),0.17(9H,s)。

The preparation of the bromo-4-formoxyl of step 3:3--N-[(trimethyl silyl) methyl] benzamide.

Bromo-for 3-4-(two bromomethyls)-N-[(trimethyl silyl) methyl] benzamide (0.25g, 0.69mmol) is placed in acetone (5mL) and water (2.5mL).Silver nitrate (0.3g, 1.7mmol) is added in this reactant mixture.This reaction is at room temperature stirred 6 hours.Then this reactive material concentrated and be extracted with ethyl acetate.Organic layer is separated and uses dried over sodium sulfate.Organic layer is carried out concentrated to obtain the bromo-4-formoxyl of product 3--N-[(trimethyl silyl) methyl] benzamide.(0.15g)。

LC-MS (methyl alcohol, ESI): m/z=314 (M+H).

1H-NMR(400MHz,CDCl3)：10.33(1H,s),7.90(1H,m),7.60(1H,dd),7.56(1H,m),5.99(1H,s),2.99(2H,d),0.17(9H,s)。

The preparation of the bromo-4-hydroxymethyl of step 4:3--N-[trimethylsilyl methyl] benzamide.

Bromo-for 3-4-formoxyl-N-[(trimethyl silyl) methyl] benzamide (0.1g, 0.3mmol) to be dissolved in methyl alcohol and to adding NaBH in this ₄(0.014g, 0.38mmol).This reaction is at room temperature stirred 1 hour.Remove methyl alcohol under vacuo and add water in reactive material, then making to be extracted with ethyl acetate this reactive material.Organic layer is separated and uses dried over sodium sulfate concentrated to obtain the bromo-4-hydroxymethyl of product 3--N-[trimethylsilyl methyl] benzamide (0.05g) subsequently.

LC-MS (methyl alcohol, ESI): m/z=316 (M+H).

1H-NMR(400MHz,CDCl3)：7.90(1H,m),7.60(1H,m),7.53(1H,m),6.02(1H,s),4.75(2H,s),2.99(2H,s),0.17(9H,s)。

Step 5: the preparation of the bromo-4-of acetic acid 2-(TMS methyl-cabanaoyl)-benzyl ester.

By bromo-for 3-4-hydroxymethyl-N-[trimethylsilyl methyl] benzamide (0.25g, 0.7mmol) be dissolved in DMF solvent, at room temperature in this reactant mixture, add triethylamine (0.159g, 1.5mmol) with chloroacetic chloride (0.061g, 0.8mmol).This reaction is at room temperature stirred 30min.Add water and then this reactive material be extracted with ethyl acetate.Organic layer is separated, uses dried over sodium sulfate and concentrate to obtain product: the bromo-4-of acetic acid 2-(TMS methyl-cabanaoyl)-benzyl ester (0.15g).

LC-MS (methyl alcohol): m/z=358 (M+H).

¹H-NMR(400MHz,CDCl3)：7.90(1H,m),7.60(1H,m),7.38(1H,m),6.14(1H,bs),5.11(2H,s),2.99(2H,d),2.15(3H,s),0.17(9H,s)。

The preparation of the bromo-4-of step 6:3-(2-oxo-propyll)-N-trimethyl silane ylmethyl-thiobenzamide.

Bromo-for acetic acid 2-4-(TMS methyl-cabanaoyl)-Benzyl ester (2.4g, 7.6mmol) and Lao Weisen reagent (2.7g, 6.6mmol) are suspended in THF.This mixture is heated to backflow and continues 3 hours, concentrated, wash with water and be extracted with ethyl acetate.Organic layer is separated and uses dried over sodium sulfate.Residue is carried out purifying to obtain the bromo-4-of 3-(2-oxo-propyll)-N-trimethyl silane ylmethyl-thiobenzamide (1.8g) by silica gel chromatography.

LC-MS (methyl alcohol, ESI): m/z=374 (M+H).

¹H-NMR(400MHz,CDCl3)：7.90(1H,m),7.60(1H,m),7.38(1H,m),6.01(1H,br s),5.11(2H,d),2.99(2H,d),2.15(3H,s),0.17(9H,s)

Step 7: the preparation of the bromo-4-of acetic acid 2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-Benzyl ester.

By methiodide (0.69g, 4.8mmol), potash (0.80g, the solution through mixing 5.7mmol) with the bromo-4-of 3-(2-oxo-propyll)-N-trimethyl silane ylmethyl-thiobenzamide (1.8g, 5.4mmol) in DMF (25mL) stirs 4 hours at 0 DEG C.This reactant mixture to be poured in icy water and to be extracted with ethyl acetate.Organic layer is separated; use dried over sodium sulfate and concentrated to obtain the bromo-4{ methyl sulphonyl of thick acetic acid 2--[(E)-TMS methyl-imino]-methyl }-benzyl ester (0.95g), to be dissolved in THF and to be cooled to 0 DEG C under nitrogen atmosphere.The solution of TBAF (1.0M is in THF) (0.56mL) is added into wherein gradually, and this reactant mixture is at room temperature stirred 8 hours.Then this reactive material concentrated and be extracted with ethyl acetate.Organic layer is separated and uses dried over sodium sulfate.Then the mixture of this generation is carried out purifying to obtain the bromo-4-of acetic acid 2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-Benzyl ester (1.1g) by silica gel column chromatography.

LC-MS (methyl alcohol, ESI): m/z=508 (M+H).

¹H-NMR(400MHz,CDCl3)：8.07(1H,m),7.71(1H,m),7.47(1H,m),7.38(1H,m),7.24(2H,m),5.23(2H,s),4.90(1H,m),4.43(1H,d),3.75(1H,m),3.43(1H,d),2.17(3H,s)。

The preparation of the bromo-4-of step 8:2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-phenvl-methanol.

To the bromo-4-of acetic acid 2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-Benzyl ester (1.1g, sodium methoxide (0.1g is added in solution 2.1mmol) in methyl alcohol (20mL), 1.85mmol), and this solution is at room temperature stirred 1 hour.Then this reactive material concentrated and be extracted with ethyl acetate.Organic layer is separated and uses dried over sodium sulfate.Then the mixture of this generation is carried out purifying to obtain the bromo-4-of 2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-phenvl-methanol (0.95g) by silica gel column chromatography.

LC-MS (methyl alcohol, ESI): m/z=466 (M+H).

¹H-NMR(400MHz,CDCl3)：8.07(1H,m),7.78(1H,m),7.59(1H,m),7.38(3H,m),4.90(3H,d),4.43(1H,d),3.75(1H,m),3.43(1H,d)。

Step 9: the preparation of the bromo-4-of methanesulfonic acid-2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-Benzyl ester.

To the bromo-4-of 2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-phenvl-methanol (0.95g, 2mmol) with triethylamine (0.4g, mesyl chloride (0.35g, 3.0mmol) is added gradually in solution 4.0mmol) in THF.This mixture is at room temperature stirred 1 hour.Reactant mixture is washed with water.Organic layer is separated and uses dried over sodium sulfate.Organic layer is carried out evaporate to obtain the bromo-4-of solid chemical compound methanesulfonic acid-2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-Benzyl ester (0.9g).

LC-MS (methyl alcohol, ESI): m/z=544 (M+H).

¹H-NMR(400MHz,CDCl3)：8.13(1H,m),7.81(1H,m),7.58(1H,m),7.38(1H,m),7.24(2H,m),5.36(2H,s),4.90(1H,m),4.43(1H,d),3.75(1H,m),3.43(1H,d),3.04(3H,s)。

The preparation of the bromo-4-of step 10:2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-benzylamine.

To the bromo-4-of methanesulfonic acid-2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-Benzyl ester (1.0g, dropwise add ammoniacal liquor (30%) the solution 30mL through mixing in solution 1.8mmol) in THF (30mL) and MeOH (30mL), and this reaction is at room temperature stirred 12 hours.Then this reactive material concentrated and be extracted with ethyl acetate.Organic layer is separated and uses dried over sodium sulfate.By organic layer evaporation with the bromo-4-of compound 2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 the base]-benzylamine providing viscosity.

LC-MS (methyl alcohol, ESI): m/z=467 (M+H).

¹H-NMR(400MHz,CDCl3)：8.07(1H,m),7.71(1H,m),7.59(1H,m),7.38(1H,m),7.24(2H,m),4.90(1H,d),4.43(3H,m),3.75(1H,m),3.43(1H,d)。

The bromo-4-of step 11:N-{2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-benzyl } preparation of acetamide.

To the bromo-4-of 2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-benzylamine (0.15g, acetic anhydride (0.04g is added in solution 0.32mmol) in THF, 0.39mmol), and this mixture is at room temperature stirred 1 hour.Then this reactive material under reduced pressure carried out concentrated and be extracted with ethyl acetate.Organic layer is separated and uses dried over sodium sulfate.Then the mixture of this generation is carried out purifying to obtain the bromo-4-of N-{2-[4-(3,5-dichlorophenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrroles-2 base]-benzyl by silica gel column chromatography } acetamide.

LC-MS (methyl alcohol, ESI): m/z=509 (M+H).

¹H-NMR(400MHz,CDCl3)：8.07(1H,m),7.71(1H,m),7.47(1H,m),7.38(1H,m),7.24(2H,m),5.98(1H,s),4.90(1H,d),4.43(3H,m),3.75(1H,m),3.43(1H,d),2.04(3H,s)。

example 7:N-{4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidines 1-yl]-2-Methyl-benzvl) acetamide preparation.

The preparation of step 1:1-benzyl-3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidines.

To 1,3-bis-chloro-5 (1-trifluoromethyl) vinyl) benzene (0.5g, 2.0mmol) with N-benzyl-1-methoxyl group-N-9 trimethyl silyl) methyl) methylamine (0.4g, the solution of TFA (0.024g, 0.2mmol) in DCM (1mL) is dropwise added in cooling solution 2.0mmol) in DCM (10mL).This reactant mixture is at room temperature stirred 3 hours.This organic layers with water (2x 10mL) and 10% water-based sodium carbonate liquor (10mL) are washed.Organic layer is separated, under reduced pressure concentrates by dried over sodium sulfate.Residue is carried out purifying to produce 1-benzyl-3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidines (0.5g) by silica gel chromatography.

LC-MS (methyl alcohol, ESI): m/z=374 (M+H).

¹H-NMR(400MHz,CDCl3)：7.36(4H,m),7.30(2H,m),7.23(2H,m),3.67(2H,s),3.08(2H,dd),2.69(2H,m),2.53(1H,m),2.27(1H,m)。

The preparation of step 2:3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidines.

By 1-benzyl-3-(-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidines (0.22g, 0.59mmol) carry out adding hot reflux with the solution of 1-chloroethyl chloromethyl ester (0.17g, 1.2mmol) in DCM and continue 3 hours.This mixture be cooled to room temperature and under reduced pressure concentrate.Methyl alcohol is added into residue, then this residue is heated at 60 DEG C and continue 3 hours with stirring.This mixture is concentrated and water is added into wherein.Residue with ethyl acetate (20mL x 3) is extracted, uses salt water washing, under reduced pressure concentrate through dried over sodium sulfate.Carry out purifying through silica gel and produce 3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidines (4.2g).

LC-MS (methyl alcohol, ESI): m/z=284 (M+H).

¹H-NMR(400MHz,CDCl3)：7.35(1H,t),7.25(2H,d),3.74(1H,d),3.19(2H,m),2.97(1H,m),2.53(1H,m),2.27(1H,m)。

The preparation of step 3:N-(the bromo-2-Methyl-benzvl of 4-) acetamide.

Bromo-for 4-2-methyl benzonitrile (2.0g, 0.01mol) is placed in methyl alcohol and NiCl ₂in (2.41g, 0.01mol).In identical tank, take acetic anhydride (2.0g, 0.020mol).This reaction is cooled to 0 DEG C.Add NaBH lentamente ₄(2.7g, 0.07mol), in this reaction, stirs 1 hour simultaneously at that same temperature.This reactant mixture under reduced pressure carried out concentrated and be extracted with ethyl acetate.Isolate organic layer, use dried over sodium sulfate and under reduced pressure concentrate.Thus obtained residue is carried out purifying to produce N-(the bromo-2-Methyl-benzvl of 4-) acetamide (1.1g) by silica gel chromatography.

LC-MS (methyl alcohol, ESI): m/z=242 (M+H).

1H-NMR(400MHz,CDCl3):7.71(1H,m),7.47(1H,m),7.38(1H,m),5.98(1H,s),3.75(1H,m),3.43(1H,d),2.31(3H,s),2.04(3H,s)。

Step 4:N-{4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidines 1-yl]-2-Methyl-benzvl) preparation of acetamide.

Under nitrogen atmosphere, to 3-(3,5-dichlorophenyl)-3-(trifluoromethyl) pyrrolidines (0.25g, 0.88mmol) with N-(the bromo-2-Methyl-benzvl of 4-) acetamide (0.8g, interpolation three (dibenzylideneacetone) two palladium (0.02g in mixture 0.7mmol) in dry toluene, 0.02mmol) with part 4, the two diphenylphosphine-9 of 5-, 9-dimethyl xanthene (xanthphos) (0.03g, 0.053mmol), add sodium tert-butoxide (0.127g, 1.3mmol) subsequently.Reactant mixture is heated 3 hours at 80 DEG C.After this reaction completes (TLC monitoring), this reactive material is filtered through diatomite.Filtrate is concentrated and uses column chromatography to carry out purifying.

LC-MS (methyl alcohol, ESI): m/z=445 (M+H).

1H-NMR(400MHz,CDCl3)：7.37(1H,d),7.29(2H,m),7.11(1H,d),6.41(2H,m),5.45(1H,b s),4.35(2H,s),4.01(1H,d),3.75(1H,d),3.43(2H,m),2.81(1H,d),2.51(1H,d),2.31(3H,s),1.97(3H,s)。

Prepare following instance according to the method being described in US 2009/0156643 and analyzed by following described LCMS method.

Method A:

From this ZQ mass spectrograph (single quadrupole mass spectrometer) of water

Instrument parameter:

Ionization method: electrojet

Polarity: cation and anion

Capillary: 3.00kV

Taper hole: 30.00V

Extractor: 2.00V

Source temperature: 100 DEG C,

Desolvation temperature: 250 DEG C

Taper hole blowback air-flow: 50L/Hr

Desolvation gas flow: 400L/Hr

Mass range: 100 to 900Da

HP 1100HPLC from Agilent company (Agilent):

Solvent degasser, quaternary pump, heating tube column compartment and diode array detector.

Post type: Féraud door company (Phenomenex) Gemini C18; Column length: 30mm; Column internal diameter: 3mm; Particle size: 3 microns; Temperature: 60 DEG C.

DAD wave-length coverage (nm): 210 to 500

Solvent Gradient:

A＝H2O+5％MeOH+0.05％HCOOH

B=acetonitrile+0.05%HCOOH

Method B:

From the ACQUITY SQD mass spectrograph (single quadrupole mass spectrometer) of Waters (Waters)

Ionization method: electrojet

Polarity: cation

Capillary (kV) 3.00, taper hole (V) 20.00, extractor (V) 3.00, source temperature (DEG C) 150, desolvation temperature (DEG C) 400, taper hole blowback air-flow (L/Hr) 60, desolvation air-flow (L/Hr) 700

Mass range: 100 to 800Da

DAD wave-length coverage (nm): 210 to 400

Method: this (Waters) ACQUITY UPLC of water using following HPLC gradient condition

(solvent orange 2 A: water/methyl alcohol 9:1, the formic acid of 0.1%, and solvent B: acetonitrile, 0.1% formic acid)

Post type: this (Waters) ACQUITY UPLC BEH C18 of water; Column length: 50mm; Column internal diameter: 2.1mm; Particle size: 1.7 microns; Temperature: 60 DEG C.

example 8:

Method A, time of staying 2.17min, MH+511

example 9:

Method A, time of staying 2.19min, MH+493

example 10:

Method B, time of staying 1.98min, MH+479

Following instance is prepared according to the method being described in WO 2008/150393.

example 11:

Method A, time of staying 2.1min, MH+470

Following instance is prepared according to the method being described in WO 2009/051956.

example 12:

1H NMR (in CDCl3): 3.73ppm (d, 1H), 4.12ppm (d, 1H), 7.58ppm (d, 2H), 7.93 (m, 1H), 8.07-8.12 (m, 3H), 8.62 (s, 1H)

the preparation of the bromo-N-hydroxy indene of example 13:5--1-imines:

By 5-bromine indan-1-one (10.0g, solution hydroxylamine hydrochloride (3.65g 47.38mmol) in methyl alcohol (50mL), 52.17mmol) process with sodium acetate (4.27g, 52.17mmol) and at room temperature stir 20 hours.Solvent is evaporated, and residue with water (25mL) is processed and extracts with ethyl acetate (2x 50mL).By the organic layer of merging through dried over sodium sulfate, and carry out concentrated to provide the bromo-N-hydroxy indene of 5--1-imines (10g). ¹H-NMR(400MHz,CDCl ₃)：7.65(1H d),7.5(1H,s),7.4(1H,d),3.05(2H,m),3.10(2H,m)。LC-MS (methyl alcohol, ESI): m/z=227 (M+H, the time of staying=1.75).

bromo-2, the 3-dihydro-1H-indenes-1-bases of example 14:(5-) preparation of t-butyl carbamate:

By bromo-for 5-N-hydroxy indene-1-imines (16g, 70.77mmol) in methyl alcohol, (400mL) is with solution two-te lambdat-butyl dicarbonate (31g in diox (200mL), 141.55mmol) with nickel chloride (4.68g, 35.39mmol) process.This reactant mixture is cooled to-20 DEG C, adds sodium borohydride (10.7g, 283.1mmol) lentamente and stir 1 hour.Then by diethylenetriamines (16mL) process of this reactant mixture, and 30min is stirred.This reactant mixture being diluted by adding water, being extracted with ethyl acetate.By the organic layer of merging through dried over sodium sulfate, concentrate and carry out purifying to provide (bromo-2, the 3-dihydro-1H-indenes-1-bases of 5-) t-butyl carbamate (10.5g) by column chromatography (hexane/ethyl acetate 1:9 is as eluent). ¹H-NMR(400MHz,CDCl ₃)：7.1(1H,d),7.2(1H,s),7.3(1H,d),5.15(1H,m),4.7(1H,m),2.9(1H,m),2.8(1H,m),2.5(1H,m),1.8(1H,m),1.45(s,9H)。

the preparation of example 15:1-(tertbutyloxycarbonylamino) indane-5-carboxylic acid:

By (5-bromo-2,3-dihydro-1H-indenes-1-base) t-butyl carbamate (10g, solution 32mmol) in oxolane (200mL) is cooled to-78 DEG C, dropwise use lithium methide (16mL, 48mmol) process and stir 10min, add n-BuLi (29mL, 64mmol) subsequently and stir 1 hour further.This reactant mixture dry ice is processed lentamente and stirs 30min.Then used the cancellation of ammonium chloride saturated solution and extracted with ethyl acetate (2x 50mL).By the organic layer of merging through dried over sodium sulfate, under reduced pressure concentrated to provide thick solid material, and then grind to provide pure 1-(tertbutyloxycarbonylamino indane-5-carboxylic acid (3.8g) with hexane/diethyl ether. ¹H-NMR(400MHz,DMSO)：7.8(1H,s),7.3(1H,m),7.2(1H,m),5.00(1H,m),2.9(1H,m),2.8(1H,m),2.31(1H,m),1.8(1H,m),1.45(s,9H)。LC-MS (methyl alcohol, ESI): m/z=276 (M-H, the time of staying=1.74).

example 16:N-[5-(trimethylsilyl methyl carbamoyl) indane-1-base] t-butyl carbamate preparation:

By 1-(tertbutyloxycarbonylamino indane-5-carboxylic acid (2.1g, solution trimethysilylmethylamine (0.88g 7.6mmol) in carrene (20mL), 8.3mmol), EDCI (1.4g, 9.1mmol) and the DMAP (0.09g of catalytic amount, 0.76mmol) process, and stir 20 hours.Then this reactant mixture use water (10mL) is processed, and extract with carrene (2x 25mL).By the organic layer of merging through dried over sodium sulfate; concentrated, and carry out purifying to provide N-[5-(trimethylsilyl methyl carbamoyl) indane-1-base] t-butyl carbamate (1.9g) by column chromatography (hexane/ethyl acetate is as eluent). ¹H-NMR(400MHz,CDCl3)：7.6(1H,s),7.53(1H,d),7.33(1H,d),6.00(1H,m),5.2(1H,m),4.8(1H,m),3.0(1H,m),2.9(2H,d),2.8(1H,m),2.6(1H,m),1.8(1H,m),1.45(s,9H),0.2(s,9H)。LC-MS (methyl alcohol, ESI): m/z=363 (M+H, the time of staying=2.05).

example 17:N-[5-(trimethylsilyl methyl thiocarbamoyl) indane-1-base] t-butyl carbamate preparation:

By N-[5-(trimethylsilyl methyl carbamoyl) indane-1-base] t-butyl carbamate (2.2g; solution 6.1mmol) in toluene (25mL) processes with Lao Weisen reagent (2.8g, 6.7mmol) and heats 2 hours at 120 DEG C.By toluene evaporates, and residue with water (25mL) is processed and extracts with ethyl acetate (25mL).By the organic layer of merging through dried over sodium sulfate; concentrated, and carry out purifying to provide N-[5-(trimethylsilyl methyl thiocarbamoyl) indane-1-base] t-butyl carbamate (1.8g) by column chromatography (hexane/ethyl acetate is as eluent). ¹H-NMR(400MHz,CDCl3)：7.6(1H,s),7.53(1H,brs),7.45(1H,d),7.30(1H,d),5.2(1H,brs),4.7(1H,brs),3.5(2H,d),3.00(1H,m),2.8(1H,m),2.6(1H,m),1.8(1H,m),1.45(s,9H)0.2(s,9H)。LC-MS (methyl alcohol, ESI): m/z=379 (M+H, the time of staying=2.27).

example 18:N-[5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] indane-1-base] ammonia the preparation of base t-butyl formate:

At 0 DEG C; by N-[5-(trimethylsilyl methyl thiocarbamoyl) indane-1-base] carbamate (1.2g; solution potash (0.9g 3.2mmol) in dimethyl formamide (10mL); 6.3mmol) process; methyl iodide (4.5g is added with three parts; 32mmol), and stir 3 hours.In this reactant mixture, add water (10mL), use ethyl acetate (2x 25mL) to extract subsequently.By the organic layer of merging through dried over sodium sulfate, concentrated to provide roughage.By oxolane (20mL) dilution of this roughage, cool at 0 DEG C, with the chloro-5-of 1,3-bis-[1-(trifluoromethyl) vinyl] benzene and TBAB process, and stir 20 hours.Oxolane is under reduced pressure removed, with water (25mL) dilution, and extracts with ethyl acetate (2x 25mL).By dry for the organic layers with sodium sulfate merged, carry out concentrating and carrying out purifying by column chromatography (hexane/ethyl acetate) providing N-[5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] indane-1-base] t-butyl carbamate (0.7g). ¹H-NMR(400MHz,CDCl3)：7.8(2H,s),7.7(1H,m),7.35(2H,s),7.25(1H,d),5.9(1H,brs),5.6(1H,brs),4.9(1H,d),4.4(1H,d),4.8(1H,d),3.40(1H,d),3.00(1H,m),2.90(1H,m),2.6(1H,m),2.00(1H,m),1.45(s,9H)。LC-MS (methyl alcohol, ESI): m/z=513 (M+H, the time of staying=2.50).

example 19: for preparation N-[5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] indenes full-1-base] general program of acid amides: (a) R=Me, (b) R=Et, (c) R=cPr, (d)=CF ₃

By N-[5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] indane-1-base] TFA (4eq.) process of the solution of t-butyl carbamate (1mmol) in carrene (5mL), and stir 5 hours.This reactant mixture is under reduced pressure concentrated, dilute with carrene (5mL), and process with triethylamine (5eq.) and suitable carboxylic acid chloride (1.1eq.), and stir 16 hours reactant mixture is concentrated and by column chromatography (hexane/ethyl acetate) purifying to provide:

(a) N-[5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] indane-1-base] acetamide: 0.12g, ¹h-NMR (400MHz, CDCl3): 7.8 (1H, m), 7.7 (1H, m), 7.30 (1H, m), 7.20 (1H, m), 6.1 (1H, m), 5.5 (1H, m), 4.8 (1H, d), 4.4 (1H, d), 3.8 (1H, d), 3.45 (1H, d), 3.00 (1H, m), 2.90 (1H, m), 2.6 (1H, m), 2.00 (3H, s), 1.8 (1H, m).LC-MS (methyl alcohol, ESI): m/z=455 (M+H, the time of staying=2.11).

(b) N-[5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] indane-1-base] propionamide: 0.12g, ¹h-NMR (400MHz, CDCl3): 7.9 (1H, m), 7.8 (1H, m), 7.40 (2H, m), 7.30 (2H, m), 5.70 (1H, m), 5.50 (1H, m), 4.90 (1H, d), 4.50 (1H, d), 3.90 (1H, d), 3.60 (1H, d), 3.00 (1H, m), 2.90 (1H, m), 2.6 (1H, m), 2.3 (2H, d), 1.8 (1H, m).1.2 (3H, t) LC-MS (methyl alcohol, ESI): m/z=469 (M+H, the time of staying=2.17).

(c) N-[5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] indane-1-base] cyclopropane carboxamide: 70mg, ¹h-NMR (400MHz, CDCl3): 7.8 (1H, m), 7.77 (1H, m), 7.40 (2H, m), 7.30 (2H, m), 5.90 (1H, m), 5.50 (1H, m), 4.90 (1H, d), 4.45 (1H, d), 3.85 (1H, d), 3.50 (1H, d), 3.00 (1H, m), 2.90 (1H, m), 2.6 (1H, m), 1.8 (1H, m).1.0 (2H, m), 0.8 (2H, m), LC-MS (methyl alcohol, ESI): m/z=481 (M+H, the time of staying=2.22)

(d) N-[5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-2,4-pyrrolin-5-base] indane-1-base]-2,2,2-trifluoro-acetamide: 120mg, ¹h-NMR (400MHz, CDCl3): 7.9 (1H, m), 7.8 (1H, m), 7.35 (2H, m), 7.25 (2H, m), 6.60 (1H, m), 5.50 (1H, m), 4.90 (1H, d), 4.50 (1H, d), 3.80 (1H, d), 3.50 (1H, d), 3.10 (1H, m), 3.00 (1H, m), 2.70 (1H, m), 2.00 (1H, m), LC-MS (methyl alcohol, ESI): m/z=509 (M+H, the time of staying=2.37)

the system of example 20:5-[3-[two (trifluoromethyl) phenyl of 3,5-]-3-(trifluoromethyl) pyrrolidin-1-yl] indane-1-amine standby

To the 3-[3 under argon gas through stirring, two (trifluoromethyl) phenyl of 5-]-3-(trifluoromethyl) pyrrolidines (0.260g, as being described in preparing of WO 2008/128711) and N-(the 5-bromine indane-1-base) solution of t-butyl carbamate (0.231g) in toluene (5.2mL) in add three (dibenzylideneacetone) two palladium (0) (13.6mg), 4,5-two (diphenylphosphino)-9,9-dimethyl xanthene (22.1mg) and sodium tert-butoxide (147mg).

This mixture is heated 15min in microwave at 130 DEG C.Then by this reaction ethyl acetate and water dilution, then with salt solution dilution, and then this mixture is extracted with ethyl acetate.Organic layer is merged, and through dried over mgso, filter, then under reduced pressure carry out concentrated to provide a kind of brown oil, this brown oil is carried out purifying with product (245mg) desired by providing in white foam by column chromatography (cyclohexane/EtOAc is as solvent).1H NMR(CDCl3,400MHz)：d＝7.92(s,1H),7.86(s,2H),7.27(m,1H),6.47-6.58(m,2H),4.35(m,1H),4.05-4.23(m,1H),3.85(m,1H),3.60(m,1H),3.51(m,1H),2.90-3.03(m,2H),2.71-2.86(m,1H),2.55-2.66(m,1H),2.50(dt,J＝7.2,4.3Hz,1H),1.83-2.13(m,2H),1.72ppm(dd,J＝12.5,8.1Hz,1H)

example 21:N-[5-[3-[two (trifluoromethyl) phenyl of 3,5-]-3-(trifluoromethyl) pyrrolidin-1-yl] indane-1-base] the preparation of propionamide

To the 5-[3-[3 at room temperature through stirring, two (trifluoromethyl) phenyl of 5-]-3-(trifluoromethyl) pyrrolidin-1-yl] add propionyl chloride (0.027mL) in the solution of indane-1-amine (100mg) in carrene (3.0mL) and triethylamine (0.088mL), and this solution is stirred 3 hours.Then by this reaction ethyl acetate and water dilution, and then this mixture is extracted with ethyl acetate.Organic layer is merged, and through dried over mgso, filter, then under reduced pressure carry out concentrated to provide a kind of yellow solid, this yellow solid is carried out purifying with product (87mg) desired by providing in beige solid by column chromatography (cyclohexane/EtOAc is as solvent).1H NMR(CDCl3,400MHz)：d＝7.92(s,1H),7.86(s,2H),7.21(d,J＝8.1Hz,1H),6.45-6.58(m,2H),5.56(d,J＝8.1Hz,1H),5.37-5.49(m,1H),4.16(d,J＝9.2Hz,1H),3.85(d,J＝10.6Hz,1H),3.46-3.60(m,2H),2.91-3.04(m,2H),2.78-2.91(m,1H),2.52-2.70(m,2H),2.24(q,J＝7.7Hz,2H),1.76-1.87(m,1H),1.13-1.24ppm(m,3H)

example 22

These synthesis as described in WO 2009/112275.

Fusing point: 103 DEG C-105 DEG C

LC-MS: the time of staying=1.95, (M ⁺h) ⁺=471 (measurement) (method B)

example 23

To 1-[the chloro-phenyl of 4-(bromomethyl)-3-] ethyl ketone (1g, 4.04mmol) in N, (1,3-dioxoisoindolin-2-base) potassium (823mg, 4.44mmol) is added in solution in dinethylformamide.By this reaction mixture refluxed 5-6 hour, monitored by thin-layer chromatography (TLC) simultaneously.Then this reactant mixture use water (20mL) is processed, extract with ethyl acetate (3 × 30mL).By the organic layer of merging through dried over sodium sulfate, then under reduced pressure concentrate.By the residue of acquisition by column chromatography purification to provide desired product 2-[(the chloro-phenyl of 4-acetyl group-2-) methyl] isoindoline-1,3-diketone (870mg)

ESI-MS:m/z＝313.9[M+H] ⁺。

¹H NMR(400MHz,CDCl ₃)：δ7.85-7.90(m,1H),7.80-7.85(m,1H),7.68-7.71(m,4H),7.21-7.23(m,1H),4.96(s,2H),2.50(s,3H)

To 2-[(the chloro-phenyl of 4-acetyl group-2-) methyl] isoindoline-1; 3-diketone (670mg; 2.13mmol) with 1-[the bromo-5-of 3-(trifluoromethyl) phenyl]-2; 2; 2-trifluoro-ethanone (685mg; potash (150mg, 1.06mmol) is added in solution 2.13mmol) in acetonitrile (10mL).This reactant mixture is flow through night next time at 120 DEG C.Then water (10mL) is used to dilute and extract with ethyl acetate (3 × 30mL).By the organic layer of merging through dried over sodium sulfate, then under reduced pressure concentrate.By the residue of acquisition by column chromatography purification to provide desired product 2-[[4-[(Z)-3-[the bromo-5-of 3-(trifluoromethyl) phenyl]-4; 4; 4-tri-fluoro-but-2-ene acyl group] the chloro-phenyl of-2-] methyl] isoindoline-1,3-diketone (550mg)

ESI-MS:m/z＝614.76[M-H] ⁺。

¹H NMR(400MHz,CDCl ₃)：δ7.87-7.93(m,3H),7.73-7.83(m,4H),7.52-7.65(m,2H),7.38-7.42(m,1H),7.27-7.31(m,1H),5.00-5.02(d,2H)

To 2-[[4-[(Z)-3-[the bromo-5-of 3-(trifluoromethyl) phenyl]-4; 4; 4-tri-fluoro-but-2-ene acyl group] the chloro-phenyl of-2-] methyl] isoindoline-1; 3-diketone (500mg; sodium hydroxide (98mg is added in solution 0.813mmol) in isopropyl alcohol (5mL); solution 2.44mmol) in water (2mL), then adds 50% hydroxylamine solution (322mg, 4.88mmol).By this reaction mixture refluxed 6-7 hour, monitored by TLC simultaneously.This reactant mixture is under reduced pressure concentrated, with water (10ml) dilution, and extracts with ethyl acetate (3 × 30mL).By the organic layer of merging through dried over sodium sulfate, then under reduced pressure concentrate.By the residue of acquisition by column chromatography purification to provide desired product [4-[5-[the bromo-5-of 3-(trifluoromethyl) phenyl]-5-(trifluoromethyl)-4H-isoxazole-3-base] the chloro-phenyl of-2-] methylamine (170mg)

ESI-MS:m/z＝500.84[M+H] ⁺。

At 0 DEG C, to [4-[5-[the bromo-5-of 3-(trifluoromethyl) phenyl]-5-(trifluoromethyl)-4H-isoxazole-3-base] the chloro-phenyl of-2-] methylamine (100mg, triethylamine (0.05mL is added in solution 0.2mmol) in carrene (4mL), 0.3mmol), then butyl chloride (32mg, 0.3mmol) is added.This reactant mixture is at room temperature stirred 1 hour.Then water (5mL) is used to dilute and extract with carrene (3 × 20mL).By the organic layer of merging through dried over sodium sulfate, then under reduced pressure concentrate.By the residue of acquisition by column chromatography purification to provide desired product N-[[4-[5-[the bromo-5-of 3-(trifluoromethyl) phenyl]-5-(trifluoromethyl)-4H-isoxazole-3-base] the chloro-phenyl of-2-] methyl] butyramide (50mg)

ESI-MS:m/z＝570.88[M+H] ⁺。

¹H NMR(400MHz,CDCl ₃)：δ7.88(m,1H),7.77(m,1H),7.72(m,1H),7.62-7.63(m,1H),7.38-7.46(m,2H),5.89(br s,1H),4.46-4.48(d,2H),4.01-4.05(d,1H),3.60-3.64(d,1H),2.12-2.15(m,2H),1.57-1.65(m,2H),0.85-0.89(m,3H)

biological example

table A

Table A provides the compound with Formula I a, wherein B ¹, B ², B ³, R ², R ⁵and R ⁸as described below

	B1-B2-B3	R2	R5	R8
					A1	C＝N-O	3,5-dichlorophenyl	Chlorine	Methylsulfanyl methyl
A2	C＝N-O	3,5-dichlorophenyl	Chlorine	Isopropyl
					A3	C＝N-O	3,5-dichlorophenyl	Chlorine	Ethyl
A4	N-CH ₂-CH ₂	3,5-dichlorophenyl	Methyl	Methyl
					A5	C＝N-CH ₂	3,5-dichlorophenyl	Bromine	Methyl
A6	C＝N-CH ₂	3,5-dichlorophenyl	Bromine	Ethyl
					A7	C＝N-CH ₂	3,5-dichlorophenyl	Bromine	Cyclopropyl
A8	C＝N-O	3,5-dichlorophenyl	Methyl	Methyl
					A9	C＝N-O	3,5-dichlorophenyl	Methyl	Isopropyl

A10	C＝N-O	3,5-dichlorophenyl	Methyl	Methylsulfanyl methyl
					A11	C＝N-O	3,5-dichlorophenyl	Methyl	Oxolane-2-base
A12	C＝N-O	3,5-dichlorophenyl	Hydrogen	Isopropyl
					A13	C＝N-O	3,5-dichlorophenyl	Hydrogen	Methylsulfanyl methyl
A14	C＝N-O	3,5-dichlorophenyl	Chlorine	1-N-Propyl Bromide-1-base
					A15	C＝N-O	3,5-dichlorophenyl	Chlorine	Oxolane-2-base
A16	C＝N-O	3,5-dichlorophenyl	Hydrogen	Ethyl
					A17	C＝N-O	3,5-dichlorophenyl	Hydrogen	1-N-Propyl Bromide-1-base
A18	C＝N-O	3,5-dichlorophenyl	Hydrogen	Oxolane-2-base
					A19	C＝N-O	3,5-dichlorophenyl	Chlorine	Sulfonyloxy methyl ylmethyl
A20	C＝N-O	3,5-dichlorophenyl	Chlorine	Methylsulphinylmethyl
					A21	C＝N-O	The bromo-5-trifluorophenyl of 3-	Chlorine	N-pro-pyl

table B

Table B provide the compound with Formula I b*, wherein B ¹, B ², B ³, R ²and R ⁸as described below

	B1-B2-B3	R2	R8
				B1	N-CH ₂-CH ₂	3,5-dichlorophenyl	Cyclopropyl
B2	C＝N-O	3,5-dichlorophenyl	-CH ₃
				B3	C＝N-CH ₂	3,4,5-trichlorophenyl	Cyclopropyl
B4	N-CH ₂-CH ₂	3,5-di-trifluoromethyl phenyl	Cyclopropyl

table C

Table C provide the compound with Formula I c, wherein B ¹, B ², B ³, R ²and R ⁵as described below

	B1-B2-B3	R2	R5
				C1	N-CH ₂-CH ₂	3,5-dichlorophenyl	Cyano group
C2	C＝N-CH ₂	3,4,5-trichlorophenyl	Cyano group
				C3	C＝N-O	The chloro-4-fluorophenyl of 3,5-bis-	Cyano group
C4	C＝N-O	3,5-dichlorophenyl	Cyano group
				C5	C＝N-O	3,5-dichlorophenyl	Methyl
C6	C＝N-O	3,4,5-trichlorophenyl	Cyano group
				C7	C＝N-O	3,5-dichlorophenyl	Cyano group

table D

Table D provide the compound with Formula I d, wherein B ¹, B ², B ³, R ², R ⁵, Z ¹, Z ²and Z ³as described below

B1-B2-B3

R2

R5

Z1

Z2

Z3

D1

C＝N-O

The chloro-4-fluorophenyl of 3,5-bis-

Cyano group

H

Cyano group

H

D2

C＝N-O

The chloro-4-fluorophenyl of 3,5-bis-

Cyano group

H

F

H

D3

C＝N-O

3,5-dichlorophenyl

Cyano group

H

D4

C＝N-O

3,5-dichlorophenyl

Amino

H

D5

C＝N-O

3,5-dichlorophenyl

Methyl

H

D6

C＝N-O

The chloro-4-fluorophenyl of 3,5-bis-

Cyano group

H

Chlorine

H

D7

C＝N-O

The chloro-4-fluorophenyl of 3,5-bis-

Cyano group

H

Bromine

H

D8

C＝N-O

The chloro-4-fluorophenyl of 3,5-bis-

Cyano group

H

Iodine

H

D9

C＝N-O

The chloro-4-fluorophenyl of 3,5-bis-

Cyano group

H

Nitro

H

D10

C＝N-O

The chloro-4-fluorophenyl of 3,5-bis-

Cyano group

CF3

H

CF3

D11

C＝N-O

The chloro-4-fluorophenyl of 3,5-bis-

Cyano group

CF3

H

table E

Table E provide the compound with Formula I e, wherein B ¹, B ², B ³, R ²and R ⁹as described below

	B ¹-B ²-B ³	R ²	R ⁹
				E1	C＝N-O	3,5-dichlorophenyl	Ethyl
E2	C＝N-CH ₂	3,5-dichlorophenyl	Methyl
				E3	C＝N-CH ₂	3,5-dichlorophenyl	Ethyl
E4	C＝N-CH ₂	3,5-dichlorophenyl	Cyclopropyl
				E5	C＝N-CH ₂	3,5-dichlorophenyl	Trifluoromethyl
E6	N-CH ₂-CH ₂	Two (trifluoromethyl) phenyl of 3,5-	Ethyl
				E7	C＝N-O	3,5-dichlorophenyl	2,2,2-trifluoroethyl
E8	C＝N-O	3,5-dichlorophenyl	N-propyl chloride-1-base

Brown plant-hopper (brown planthopper)

With the test solution of these dilutions, rice seedlings is processed in spray chamber.After drying, with 20 N ₃phase, nymph infected (2 repetitions) plant.After this process 6 to 12 days, for lethality, sample is checked.

Compound

A1, A2, A3, A4, A5, A6, A7, A19, A20, B1, B2, B3, B4, C1, C2, C3, C4, D1, E1, E2, E3, E4, E4, E5, E6, E7 are tested, and following compound provides the control of at least 80% at 200ppm or less place: A1, A19*, A20*, B1*, B3*, B4*, C2*, C3*, C4*, D1*, E1*, E7*.

*=to provide at 50ppm place at least 80% control

comparison example

According to above method test compounds.It is the activity being significantly higher than structurally similar compounds that these results demonstrate compound of the present invention for brown plant-hopper (brown planthopper), when particularly using with low ratio.

Contrast table 1

Compound of the present invention and reference compound are compound 3-6 and 3-643 from WO 2009/112275 respectively.

Contrast table 2

Compound of the present invention and reference compound are the compound 42 and 9 from WO 2007/075459 respectively.

Claims

1. one kind comprises and uses a kind of method with the compound of Formula I C to the crop of rice plants, its place or its propagating materials

Wherein-B ¹-B ²-B ³-be-C=N-O-;

R ¹trifluoromethyl, difluoromethyl or chlorodifluoramethyl-;

R ²it is radicals X

X ²c-X ⁶or nitrogen;

Y ¹c-R ⁶, CH or nitrogen;

Y ²and Y ³cH or nitrogen independently;

R ⁵halogen, cyano group, nitro, NH ₂, C ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₃-C ₅cycloalkyl, C ₃-C ₅halogenated cycloalkyl, C ₁-C ₂alkoxyl or C ₁-C ₂halogenated alkoxy;

R ⁶when it is present with R ⁵form-CH=CH-CH=CH-bridge together;

K is 0,1,2 or 3.

2. method according to claim 1, wherein

R ⁵cyano group;

K is 0 or 1; And

Z is cyano group or trifluoromethyl.

3. according to method according to claim 1 or claim 2, wherein

R ¹cF ₃;

Y ¹, Y ²and Y ³cH; And

K is 0.

4. one kind comprises and uses a kind of method with the compound of Formula I D to the crop of rice plants, its place or its propagating materials

Wherein-B ¹-B ²-B ³-be-C=N-O-,-C=N-CH ₂-or-N-CH ₂-CH ₂-, preferably-C=N-O-;

R ¹trifluoromethyl, difluoromethyl or chlorodifluoramethyl-;

R ²it is radicals X

X ²c-X ⁶or nitrogen;

Y ¹c-R ⁶, CH or nitrogen;

Y ²and Y ³cH or nitrogen independently;

R ⁶when it is present with R ⁵form-CH=CH-CH=CH-bridge together;

K is 0,1,2 or 3.

5. method according to claim 4, wherein

Wherein

R ⁵cyano group;

K is 0 or 1; And

Z is cyano group or trifluoromethyl;

And preferably, when k is 1, Z is attached on 4 of imidazole fragment.

6. according to claim 4 or method according to claim 5, wherein

R ¹cF ₃;

-B ¹-B ²-B ³-be-C=N-O-or-C=N-CH ₂-, preferably-C=N-O-;

Y ¹, Y ²and Y ³cH;

K is 1; And

Z is cyano group or trifluoromethyl;

And preferably, Z is attached on 4 of imidazole fragment.

7. one kind comprises and uses a kind of method with the compound of Formula I E to the crop of rice plants, its place or its propagating materials

Wherein-B ¹-B ²-B ³-be-C=N-O-,-C=N-CH ₂-or-N-CH ₂-CH ₂-;

R ¹trifluoromethyl, difluoromethyl or chlorodifluoramethyl-;

R ²it is radicals X

X ²c-X ⁶or nitrogen;

Y ¹cH or nitrogen;

Y ²and Y ³cH or nitrogen independently;

Wherein Y ¹, Y ²and Y ³in no more than two be nitrogen and wherein Y ²and Y ³both inequalities are nitrogen; And

R ⁹c ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkyl-O-CH ₂-, C ₁-C ₄haloalkyl-O-CH ₂-, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl-CH ₂-, C ₁-C ₄alkyl-S-CH ₂-, C ₁-C ₄alkyl-S (O)-CH ₂-or C ₁-C ₄alkyl-S (O ₂)-CH ₂.

8. method according to claim 7, wherein R ⁹methyl, ethyl, propyl group, CF ₃cH ₂-or cyclopropyl, preferred ethyl or CF ₃cH ₂-.

9. according to claim 7 or method according to claim 8, wherein

R ¹cF ₃;

-B ¹-B ²-B ³-be-C=N-O-or-C=N-CH ₂-; And

Y ¹, Y ²and Y ³cH.

10. one kind comprises and uses a kind of method with the compound of Formula I A to the crop of rice plants, its place or its propagating materials

Wherein-B ¹-B ²-B ³-be-C=N-CH ₂-or-N-CH ₂-CH ₂-;

R ¹trifluoromethyl, difluoromethyl or chlorodifluoramethyl-;

R ²it is radicals X

X ²c-X ⁶or nitrogen;

Y ¹c-R ⁶, CH or nitrogen;

Y ²and Y ³cH or nitrogen independently;

R ⁵hydrogen, halogen, cyano group, nitro, NH ₂, C ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₃-C ₅cycloalkyl, C ₃-C ₅halogenated cycloalkyl, C ₁-C ₂alkoxyl or C ₁-C ₂halogenated alkoxy;

R ⁶when it is present with R ⁵form one-CH=CH-CH=CH-bridge together; And

R ⁸c ₁-C ₄alkyl, C ₁-C ₄haloalkyl, C ₁-C ₄alkoxyl (C ₁-C ₄) alkyl, C ₁-C ₄alkylthio group (C ₁-C ₄) alkyl, C ₁-C ₄alkyl sulphinyl (C ₁-C ₄) alkyl, C ₁-C ₄alkyl sulphonyl (C ₁-C ₄) alkyl, C ₃-C ₆cycloalkyl, C ₃-C ₆cycloalkyl (C ₁-C ₄) alkyl-or tetrahydrofuran base.

11. methods according to claim 10, wherein

R ⁵chlorine, bromine, fluorine or methyl; And

R ⁸methyl, ethyl, n-pro-pyl, isopropyl, CH ₃-O-CH ₂-, CH ₃-S-CH ₂-, CH ₃-S (O)-CH ₂-, CH ₃-SO ₂-CH ₂-, cyclobutyl, cyclopropyl or cyclopropyl-CH ₂-.

12. according to claim 10 or method according to claim 11, wherein

R ¹cF ₃;

-B ¹-B ²-B ³-be-C=N-O-or-C=N-CH ₂-;

Y ¹, Y ²and Y ³cH; And

R ⁵chlorine or methyl.

13. method according to claim 10 or purposes, wherein

-B ¹-B ²-B ³-be-C=N-O-, R ¹trifluoromethyl, R ²the bromo-5-trifluoromethyl of 3-, Y ¹, Y ²and Y ³cH; R ⁵chlorine, and R ⁸it is n-pro-pyl.

14. 1 kinds comprise and use a kind of method with the compound of Formula I B to the crop of rice plants, its place or its propagating materials

Wherein-B ¹-B ²-B ³-be-C=N-O-or-N-CH ₂-CH ₂-;

R ¹trifluoromethyl, difluoromethyl or chlorodifluoramethyl-;

R ²it is radicals X

X ²c-X ⁶or nitrogen;

Y ¹cH or nitrogen;

Y ²and Y ³cH or nitrogen independently;

R ⁷c ₁-C ₄alkyl; And

15. methods according to claim 14, wherein

R ⁷it is methyl; And

16. according to claim 14 or method according to claim 15, wherein

R ¹cF ₃;

-B ¹-B ²-B ³-be-C=N-O-,-C=N-CH ₂-or-N-CH ₂-CH ₂-; And

Y ¹, Y ²and Y ³cH.

17. methods according to any one of claim 1 to 16 or purposes, wherein R ²be 3,5-dichlorophenyl-, 3,5-bis-chloro-4-fluorophenyls-, two (trifluoromethyl) phenyl of 3,4,5-trichlorophenyl-or 3,5-.

18. methods according to any one of claim 1 to 17, wherein the method is a kind of control in paddy rice and/or the method infected of prevention stem borer, the method comprise to the crop of rice plants, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

19. 1 kinds control and/or the methods infected of prevention stem borers in the crop of useful plant, the method comprise to the crop of useful plant, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

20. methods according to any one of claim 1 to 17, wherein the method is a kind of control in paddy rice and/or the method infected of prevention tortrix moth, the method comprise to the crop of rice plants, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

21. 1 kinds control and/or the methods infected of prevention tortrix moths in the crop of useful plant, the method comprise to the crop of useful plant, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

22. methods according to any one of claim 1 to 17, wherein the method is a kind of control in paddy rice and/or the method infected of prevention springtail, the method comprise to the crop of rice plants, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

23. 1 kinds control and/or the methods infected of prevention springtails in the crop of useful plant, the method comprise to the crop of useful plant, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

24. methods according to any one of claim 1 to 17, wherein the method is a kind of control in paddy rice and/or the method infected of prevention cecidomyiia, the method comprise to the crop of rice plants, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

25. 1 kinds control and/or the methods infected of prevention cecidomyiias in the crop of useful plant, the method comprise to the crop of useful plant, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

26. methods according to any one of claim 1 to 17, wherein the method is a kind of control in paddy rice and/or the method infected of prevention screw thread maggot, the method comprise to the crop of rice plants, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

27. 1 kinds control and/or the methods infected of prevention screw thread maggots in the crop of useful plant, the method comprise to the crop of useful plant, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

28. methods according to any one of claim 1 to 17, wherein the method is a kind of control in paddy rice and/or the method infected of prevention rice stinkbug, the method comprise to the crop of rice plants, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

29. 1 kinds control and/or the methods infected of prevention rice stinkbugs in the crop of useful plant, the method comprise to the crop of useful plant, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

30. methods according to any one of claim 1 to 17, wherein the method a kind ofly in paddy rice, controls and/or prevent the method infected of black stinkbug, the method comprise to the crop of rice plants, its place or its propagating materials to use any one of claim 1 to 17 the compound with Formula I that defines.

31. 1 kinds control and/or prevent the methods infected of black stinkbug in the crop of useful plant, the method comprise to the crop of useful plant, its place or its propagating materials use as one of claim 1 to 17 the compound with Formula I that defines.

32. methods with the compound of Formula I according to any one of claims 1 to 31 or purposes, wherein this compound with Formula I has the compound of Formula I * and has the mixture of compound of Formula I * *

Wherein A represents A1, A2, A3A4 or A5

And remaining substituting group any one of claim 1 to 17 define, its condition is when A represents A2, R ⁵be hydrogen, and wherein said mixture is rich in the compound with Formula I * *.

33. methods according to any one of claim 7 to 9 and 17 to 32 or purposes, wherein this compound with Formula I E is the mixture of Compound I E-a and IE-b

Wherein compare with the total amount of IE-a with IE-b, the molar ratio of Compound I E-a is greater than 50%.

34. 1 kinds for obtain as any one of claims 1 to 33 define have in the compound of Formula I one or more for control the purposes of the insect being selected from lower group supervision approval methods, this group is made up of the following: stem borer, tortrix moth, springtail, cecidomyiia, screw thread maggot, rice stinkbug and black stinkbug, at least one step that the method comprises reference, submits to or depend in biological data, these biological datas show described active component and reduce insect pressure.