CN105218557B - It is a kind of with the substituted thienopyrimidine-4 aminated compounds of pesticide and miticide actility and its application - Google Patents

It is a kind of with the substituted thienopyrimidine-4 aminated compounds of pesticide and miticide actility and its application Download PDF

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CN105218557B
CN105218557B CN201410318199.2A CN201410318199A CN105218557B CN 105218557 B CN105218557 B CN 105218557B CN 201410318199 A CN201410318199 A CN 201410318199A CN 105218557 B CN105218557 B CN 105218557B
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moth
hydrogen
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CN105218557A (en
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柴宝山
张金波
宋玉泉
杨吉春
李轲轲
王立增
孙旭峰
刘长令
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Abstract

The invention discloses a kind of application of the substituted thienopyrimidine-4 aminated compounds as Insecticidal and acaricidal agent as shown in formula I,

Description

A kind of substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility and its Using
Technical field
The invention belongs to agricultural insecticidal, acaricide field.More particularly to a kind of substituted thiophene with pesticide and miticide actility And pyrimidinamine compound and its application.
Background technology
The compound 1 shown in below formula and representation compound KC1 are reported in patent US2007093498 has sterilization Activity, but reported without desinsection, acaricidal activity：
The compound 2 shown in below formula and representation compound KC2, KC3 are reported in patent CN101453895 have and kill Worm activity：
Patent US20060089370 discloses following compound formula and particular compound KC4 (being of numbering in patent Compound 5a), under 200ppm dosage, there is preferable bactericidal activity：
Patent WO2007046809 and US2007093498 also disclose following compound K C5 and KC6, have and preferably kill Bacterium activity：
Although the compound disclosed in the patent has certain similarity with the compounds of this invention, structure or purposes are still In the presence of significant difference.
The content of the invention
It is an object of the invention to provide a kind of substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility and It is applied.
To achieve the above object, the present invention use technical scheme for：
Substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility, as shown in formula I：
In formula：
R1、R2It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C12Alkyl or halo C1-C12Alkyl；
Or R1And R2Saturation or unsaturated 3-6 members carbocyclic ring or heterocycle, the carbon are formed together with the carbon atom being attached thereto It is unsubstituted or optionally by halogen, C on ring or heterocycle1-C12Alkyl, halo C1-C12Alkyl, C1-C12Alkoxy or halo C1-C12Alkane Epoxide substitutes；
R3Selected from hydrogen, halogen, C1-C12Alkyl or halo C1-C12Alkyl；
R4Selected from hydrogen, C1-C12Alkyl or halo C1-C12Alkyl；
R5、R6It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C12Alkyl, halo C1-C12Alkyl, C1-C12Alkoxy, halogen For C1-C12Alkoxy, C3-C12Cycloalkyl, halo C3-C12Cycloalkyl, C1-C12Alkyl amino, halo C1-C12Alkyl amino, C2- C12Dialkyl amido, C1-C12Alkylthio group, halo C1-C12Alkylthio group, C1-C12Alkyl sulphonyl, halo C1-C12Alkyl sulphonyl, C1-C12Alkyl-carbonyl, halo C1-C12Alkyl-carbonyl, C1-C12Alkoxy carbonyl, C1-C12Alkoxy C1-C12Alkyl, halo C1- C12Alkoxy C1-C12Alkyl or C1-C12Alkoxy carbonyl C1-C12Alkyl；
G1Selected from CR7Or N；G2Selected from CR8Or N；G3Selected from CR9Or N；But G1、G2、G3Can not be N simultaneously；
R7、R8、R9It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C12Alkyl, halo C1-C12Alkyl, C1-C12Alkoxy, Halo C1-C12Alkoxy, C3-C12Cycloalkyl, halo C3-C12Cycloalkyl, C1-C12Alkyl amino, halo C1-C12Alkyl amino, C2-C12Dialkyl amido, C1-C12Alkylthio group, halo C1-C12Alkylthio group, C1-C12Alkyl sulphonyl, halo C1-C12Alkyl sulfonyl Base, C1-C12Alkyl-carbonyl, halo C1-C12Alkyl-carbonyl, C1-C12Alkoxy carbonyl, C1-C12Alkoxy C1-C12Alkyl, halo C1-C12Alkoxy C1-C12Alkyl or C1-C12Alkoxy carbonyl C1-C12Alkyl；
Or the salt of compound of Formula I.
More preferably compound is during above-mentioned substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility：Formula In I
R1、R2It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C8Alkyl or halo C1-C8Alkyl；
Or R1And R2Saturation or unsaturated 3-6 members carbocyclic ring or heterocycle, the carbon are formed together with the carbon atom being attached thereto It is unsubstituted or optionally by halogen, C on ring or heterocycle1-C8Alkyl, halo C1-C8Alkyl, C1-C8Alkoxy or halo C1-C8Alcoxyl Base substitutes；
R3Selected from hydrogen, halogen, C1-C8Alkyl or halo C1-C8Alkyl；
R4Selected from hydrogen, C1-C8Alkyl or halo C1-C8Alkyl；
R5、R6It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C8Alkyl, halo C1-C8Alkyl, C1-C8Alkoxy, halo C1-C8Alkoxy, C3-C8Cycloalkyl, halo C3-C8Cycloalkyl, C1-C8Alkyl amino, halo C1-C8Alkyl amino, C2-C8Dioxane Base amino, C1-C8Alkylthio group, halo C1-C8Alkylthio group, C1-C8Alkyl sulphonyl, halo C1-C8Alkyl sulphonyl, C1-C8Alkyl Carbonyl, halo C1-C8Alkyl-carbonyl, C1-C8Alkoxy carbonyl, C1-C8Alkoxy C1-C8Alkyl, halo C1-C8Alkoxy C1-C8 Alkyl or C1-C8Alkoxy carbonyl C1-C8Alkyl；
G1Selected from CR7Or N；G2Selected from CR8Or N；G3Selected from CR9Or N；But G1、G2、G3Can not be N simultaneously；
R7、R8、R9It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C8Alkyl, halo C1-C8Alkyl, C1-C8Alkoxy, halogen For C1-C8Alkoxy, C3-C8Cycloalkyl, halo C3-C8Cycloalkyl, C1-C8Alkyl amino, halo C1-C8Alkyl amino, C2-C8Two Alkyl amino, C1-C8Alkylthio group, halo C1-C8Alkylthio group, C1-C8Alkyl sulphonyl, halo C1-C8Alkyl sulphonyl, C1-C8Alkane Base carbonyl, halo C1-C8Alkyl-carbonyl, C1-C8Alkoxy carbonyl, C1-C8Alkoxy C1-C8Alkyl, halo C1-C8Alkoxy C1- C8Alkyl or C1-C8Alkoxy carbonyl C1-C8Alkyl；
Or the salt of compound of Formula I.
Further preferred compound is during above-mentioned substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility： In formula I
R1、R2It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C4Alkyl or halo C1-C4Alkyl；
Or R1And R2Saturation or unsaturated 3-6 members carbocyclic ring or heterocycle, the carbon are formed together with the carbon atom being attached thereto It is unsubstituted or optionally by halogen, C on ring or heterocycle1-C4Alkyl, halo C1-C4Alkyl, C1-C4Alkoxy or halo C1-C4Alcoxyl Base substitutes；
R3Selected from hydrogen, halogen, C1-C4Alkyl or halo C1-C4Alkyl；
R4Selected from hydrogen, C1-C4Alkyl or halo C1-C4Alkyl；
R5、R6It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C4Alkyl, halo C1-C4Alkyl, C1-C4Alkoxy, halo C1-C4Alkoxy, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl, C1-C4Alkyl amino, halo C1-C4Alkyl amino, C2-C4Dioxane Base amino, C1-C4Alkylthio group, halo C1-C4Alkylthio group, C1-C4Alkyl sulphonyl, halo C1-C4Alkyl sulphonyl, C1-C4Alkyl Carbonyl, halo C1-C4Alkyl-carbonyl, C1-C4Alkoxy carbonyl, C1-C4Alkoxy C1-C4Alkyl, halo C1-C4Alkoxy C1-C4 Alkyl or C1-C4Alkoxy carbonyl C1-C4Alkyl；
G1Selected from CR7Or N；G2Selected from CR8Or N；G3Selected from CR9Or N；But G1、G2、G3Can not be N simultaneously；
R7、R8、R9It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C4Alkyl, halo C1-C4Alkyl, C1-C4Alkoxy, halogen For C1-C4Alkoxy, C3-C6Cycloalkyl, halo C3-C6Cycloalkyl, C1-C4Alkyl amino, halo C1-C4Alkyl amino, C2-C4Two Alkyl amino, C1-C4Alkylthio group, halo C1-C4Alkylthio group, C1-C4Alkyl sulphonyl, halo C1-C4Alkyl sulphonyl, C1-C4Alkane Base carbonyl, halo C1-C4Alkyl-carbonyl, C1-C4Alkoxy carbonyl, C1-C4Alkoxy C1-C4Alkyl, halo C1-C4Alkoxy C1- C4Alkyl or C1-C4Alkoxy carbonyl C1-C4Alkyl；
Or the salt of compound of Formula I.
Compound during above-mentioned substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility still more preferably For：In formula I
R1、R2It is respectively selected from hydrogen, halogen or C1-C4Alkyl；
Or R1And R2Saturation 3-6 member carbocyclic rings are formed together with the carbon atom being attached thereto；
R3Selected from hydrogen；
R4Selected from hydrogen or C1-C4Alkyl；
R5、R6It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C4Alkyl, halo C1-C4Alkyl, C1-C4Alkoxy or halo C1-C4Alkoxy；
G1Selected from CR7Or N；G2Selected from CR8Or N；G3Selected from CR9Or N；But G1、G2、G3Can not be N simultaneously；
R7、R8、R9It is respectively selected from hydrogen, halogen, cyano group, nitro, C1-C4Alkyl, halo C1-C4Alkyl, C1-C4Alkoxy or Halo C1-C4Alkoxy；
Or hydrochloride, sulfate, nitrate, bicarbonate, carbonate, phosphate, formates, the vinegar of compound of Formula I Hydrochlorate, trifluoroacetate, benzene sulfonate, tosilate, metilsulfate, benzoate, citrate, malate, Tartrate, maleate, succinate, ascorbate or oxalates.
Most preferred compound is during above-mentioned substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility：Formula In I
R1Selected from hydrogen, chlorine or methyl；
R2Selected from hydrogen or methyl；
Or R1And R26 yuan of carbocyclic rings of saturation are formed together with the carbon atom being attached thereto；
R3、R4Selected from hydrogen；
R5、R6It is respectively selected from hydrogen, fluorine, chlorine, cyano group, nitro, trifluoromethyl or methoxyl group；
G1Selected from CR7Or N；G2Selected from CR8Or N；G3Selected from CR9Or N；But G1、G2、G3Can not be N simultaneously；
R7Selected from hydrogen, fluorine, chlorine, cyano group, nitro or trifluoromethyl；
R8Selected from hydrogen, chlorine or methoxyl group；
R9Selected from hydrogen, chlorine, bromine, cyano group, nitro, methyl, trifluoromethyl, difluorochloromethyl, seven fluorine isopropyls, Methoxyl group or isopropoxy.
Above-mentioned its desinsection of substituted thienopyrimidine-4 aminated compounds, the activity of mite killing are notable, while following specific chemical combination are not Only desinsection, the activity of mite killing are notable, and the structure of compound is novel, and then make its activity more notable.
Specifically preferable compound is during above-mentioned substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility：It is logical In Formulas I
Work as R1And R2When forming 6 yuan of carbocyclic rings of saturation together with the carbon atom being attached thereto,
R3、R4Selected from hydrogen；
R5、R6It is respectively selected from hydrogen, fluorine, chlorine, cyano group, nitro, trifluoromethyl or methoxyl group；
G1Selected from CR7Or N；G2Selected from CR8Or N；G3Selected from CR9Or N；But G1、G2、G3Can not be N simultaneously；
R7Selected from hydrogen, fluorine, chlorine, cyano group, nitro or trifluoromethyl；
R8Selected from hydrogen, chlorine or methoxyl group；
R9Selected from hydrogen, chlorine, bromine, cyano group, nitro, methyl, trifluoromethyl, difluorochloromethyl, seven fluorine isopropyls, Methoxyl group or isopropoxy；
Work as R1And R2When the carbon atom being attached thereto together is not cyclic,
R1Selected from hydrogen, chlorine or methyl；
R2Selected from hydrogen or methyl；
R3、R4Selected from hydrogen；
R5、R6It is respectively selected from hydrogen, fluorine, chlorine, cyano group, nitro, trifluoromethyl or methoxyl group；
G1Selected from CR7；G2Selected from CR8；G3Selected from CR9；
R7Selected from hydrogen, fluorine, chlorine, cyano group, nitro or trifluoromethyl；
R8Selected from hydrogen, chlorine or methoxyl group；
R9Selected from hydrogen, chlorine, bromine, cyano group, nitro, methyl, trifluoromethyl, difluorochloromethyl, seven fluorine isopropyls, Methoxyl group or isopropoxy.
Specific most preferred chemical combination when in the above-mentioned substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility Thing is：In formula I
R1Selected from hydrogen, chlorine or methyl；
R2Selected from hydrogen or methyl；
Or R1And R26 yuan of carbocyclic rings of saturation are formed together with the carbon atom being attached thereto；
R3、R4Selected from hydrogen；
R5Selected from hydrogen, fluorine or chlorine；
R6Selected from hydrogen；
G1Selected from CR7；G2Selected from CR8；G3Selected from CR9；
R7Selected from hydrogen, fluorine or chlorine；
R8Selected from hydrogen；
R9Selected from hydrogen, chlorine, bromine, cyano group, nitro, methyl, trifluoromethyl, difluorochloromethyl, seven fluorine isopropyls, Methoxyl group or isopropoxy.
A kind of compound of Formula I or its salt are used as preparing Insecticidal and acaricidal agent medicine in agricultural, forestry or health field Purposes.
A kind of insecticidal and acaricidal composition, the active component of insecticidal and acaricidal composition are the compound of the formula I, activity Component is with it in agriculturally acceptable carrier combinations, and then obtain composition；The weight percent of active component contains in composition Measure as 0.1-99%.
In the definition of compound of Formula I given above, collect the following substituent of term general proxy used：
Halogen：Refer to fluorine, chlorine, bromine or iodine.Alkyl：Straight or branched alkyl, such as methyl, ethyl, propyl group, isopropyl, positive fourth Base or the tert-butyl group.Cycloalkyl：Substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopenta or cyclohexyl.Substituent such as first Base, halogen etc..Haloalkyl：Straight or branched alkyl, the hydrogen atom on these alkyl can be partly or entirely by halogen atom institute Substitution, such as chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, seven fluorine isopropyls.Alkoxy： Straight or branched alkyl, through in oxygen atom key connection to structure, such as methoxyl group, ethyoxyl.Halogenated alkoxy：Straight or branched alkane Epoxide, the hydrogen atom on these alkoxies partly or entirely can be substituted by halogen atom.As chloromethane epoxide, dichloro methoxyl group, Trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, trifluoro ethoxy etc..Alkylthio group：Straight chain Or branched alkyl, through in sulphur atom key connection to structure, such as methyl mercapto, ethylmercapto group.Halogenated alkylthio：Straight or branched alkane sulphur Base, the hydrogen atom on these alkyl partly or entirely can be substituted by halogen atom.Such as chloromethane sulfenyl, dichloro methyl mercapto, trichlorine Methyl mercapto, fluorine methyl mercapto, difluoro methyl mercapto, trifluoromethylthio, chlorine fluorine methyl mercapto etc..Alkyl sulphonyl：Straight or branched alkyl Through sulfonyl (- SO2-) be connected in structure, such as methyl sulphonyl.Halogenated alkyl sulfonyl：Straight or branched alkyl sulfonyl, Hydrogen atom on its alkyl partly or entirely can be substituted by halogen atom.Alkyl amino：Straight or branched alkyl, through nitrogen-atoms key It is connected in structure.Haloalkylamino：Straight or branched alkyl amino, the hydrogen atom on these alkyl can be part or all of Substituted by halogen atom.Alkyl-carbonyl：Straight or branched alkyl is connected in structure through carbonyl (- CO-), such as formoxyl.Halo Alkyl-carbonyl：Straight or branched alkyl is connected in structure through carbonyl (- CO-), the hydrogen atom on these alkyl can part or All substituted by halogen atom, such as trifluoro formoxyl.Alkoxy carbonyl：Straight or branched alkoxyl is connected to through carbonyl (- CO-) In structure, such as CH3OCO。
The present invention can be illustrated as the compound of Insecticidal and acaricidal agent by the particular compound listed in table 1-28, but Do not limit the present invention.
Table 1：In 1-1-91 of compound, G1For C-F, G2For CH, G3For C-CN, R1、R2、R3、R4、R5、R6(hereinafter referred to as R1-R6) specifically see the table below.
Table 1
Table 2：In 2-1-91 of compound of Formula I, G1For C-Cl, G2For CH, G3For C-CN, R1-R6Specifically it is shown in Table 1.
Table 3：In 3-1-91 of compound of Formula I, G1For CH, G2For CH, G3For C-CN, R1-R6Specifically it is shown in Table 1.
Table 4：In 4-1-91 of compound of Formula I, G1For C-F, G2For CH, G3For C-CF3, R1-R6Specifically it is shown in Table 1.
Table 5：In 5-1-91 of compound of Formula I, G1For C-Cl, G2For CH, G3For C-CF3, R1-R6Specifically it is shown in Table 1.
Table 6：In 6-1-91 of compound of Formula I, G1For CH, G2For CH, G3For C-CF3, R1-R6Specifically it is shown in Table 1.
Table 7：In 7-1-91 of compound of Formula I, G1For C-F, G2For CH, G3For C-NO2, R1-R6Specifically it is shown in Table 1.
Table 8：In 8-1-91 of compound of Formula I, G1For C-Cl, G2For CH, G3For C-NO2, R1-R6Specifically it is shown in Table 1.
Table 9：In 9-1-91 of compound of Formula I, G1For CH, G2For CH, G3For C-NO2, R1-R6Specifically it is shown in Table 1.
Table 10：In 10-1-91 of compound of Formula I, G1For CH, G2For CH, G3For C-CH3, R1-R6Specifically it is shown in Table 1.
Table 11：In 11-1-91 of compound of Formula I, G1For CH, G2For CH, G3For C-Cl, R1-R6Specifically it is shown in Table 1.
Table 12：In 12-1-91 of compound of Formula I, G1For CH, G2For CH, G3For C-OCH3, R1-R6Specifically it is shown in Table 1.
Table 13：In 13-1-91 of compound of Formula I, G1For CH, G2For CH, G3For C-OCH (CH3)2, R1-R6Specifically it is shown in Table 1。
Table 14：In 14-1-91 of compound of Formula I, G1For N, G2For CH, G3For C-CO2C2H5, R1-R6Specifically it is shown in Table 1.
Table 15：In 15-1-91 of compound of Formula I, G1For C-CN, G2For CH, G3For C-Br, R1-R6Specifically it is shown in Table 1.
Table 16：In 16-1-91 of compound of Formula I, G1For C-NO2, G2For CH, G3For C-CF3, R1-R6Specifically it is shown in Table 1.
Table 17：In 17-1-91 of compound of Formula I, G1For N, G2For CH, G3For C-CONH2, R1-R6Specifically it is shown in Table 1.
Table 18：In 18-1-91 of compound of Formula I, G1For CH, G2For C-Cl, G3For CH, R1-R6Specifically it is shown in Table 1.
Table 19：In 19-1-91 of compound of Formula I, G1For N, G2For CH, G3For CH, R1-R6Specifically it is shown in Table 1.
Table 20：In 20-1-91 of compound of Formula I, G1For N, G2For CH, G3For C-CF3, R1-R6Specifically it is shown in Table 1.
Table 21：In 21-1-91 of compound of Formula I, G1For N, G2For CH, G3For C-CF2Cl, R1-R6Specifically it is shown in Table 1.
Table 22：In 22-1-91 of compound of Formula I, G1For N, G2For CH, G3For C-CN, R1-R6Specifically it is shown in Table 1.
Table 23：In 23-1-91 of compound of Formula I, G1For N, G2For CH, G3For C-Cl, R1-R6Specifically it is shown in Table 1.
Table 24：In 24-1-91 of compound of Formula I, G1For N, G2For N, G3For C-Cl, R1-R6Specifically it is shown in Table 1.
Table 25：In 25-1-91 of compound of Formula I, G1For N, G2For CH, G3For N, R1-R6Specifically it is shown in Table 1.
Table 26：In 26-1-91 of compound of Formula I, G1For CH, G2For CH, G3For CCF (CF3)2, R1-R6Specifically it is shown in Table 1.
Table 27：In 27-1-91 of compound of Formula I, G1For CH, G2For CH, G3ForR1-R6Specifically it is shown in Table 1.
Table 28：In 28-1-91 of compound of Formula I, G1For N, G2For C-Cl, G3For C-Cl, R1-R6Specifically it is shown in Table 1.
The compound of Formula I of the present invention can be prepared in accordance with the following methods, and each group definition is the same in formula：
In formula：Z is selected from halogen atom；R1、R2、R3、R5、R6、G1、G2、G3Respectively as previously described；R4As it was previously stated, but R4≠H。
According to method made above, intermediate II and intermediate III are reacted in suitable solvent and in the basic conditions R in formula I is made4=H compound I-A；
By compound I-A itself and Z-R4Reacted in suitable solvent, you can R in formula I is made4≠ H compound I-B.
Reaction is carried out in suitable solvent, the optional tetrahydrofuran freely of suitable solvent, ethanol, methanol, acetonitrile, dichloro Methane, toluene, dimethylbenzene, benzene, N,N-dimethylformamide or dimethyl sulfoxide etc..
The optional potassium hydroxide freely of suitable alkali, sodium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, triethylamine, pyridine, Sodium hydride, potassium tert-butoxide or sodium tert-butoxide etc..
Above-mentioned preparation method can be in room temperature between solvent boiling point temperature, usually 20-100 DEG C.
The above-mentioned preparation method reaction time is 30 minutes to 20 hours, usual 1-10 hours.
Intermediate II can be made according to known methods by intermediate compound IV or V, specific synthesis can be found in CA2038521, WO2012035423, CN102311448 and US20100069383.
Intermediate compound IV and V can with purchased in market or be made by known method, specific synthesis can be found in US5206375 and US20040142953。
Intermediate III can be made according to known methods by following route, and corresponding raw material is commercially available or reference literature US4895849、JP10036355、EP665225、US20070093498、WO2007046809、US5783522A、 WO02083647A1、CN1927860A、Organic Syntheses,Coll.Vol.10,p.501(2004)；Vol.75,p.61 Or Organic Syntheses, Coll.Vol.10, (1998) p.102 (2004)；Vol.75, p.53 (1998) preparation.
(1) prepared by raw material of Uteramin：
In formula, L is leaving group, is halogen, methanesulfonate ester or p-methyl benzenesulfonic acid ester, (Boc)2O refers to two dimethyl dicarbonates Butyl ester.
(2) prepared by cyano reduction method：
In formula, L is leaving group, is halogen, methanesulfonate ester or p-methyl benzenesulfonic acid ester.
Compound of Formula I all shows that high desinsection (mite) is living to the insect (mite) in agriculture, civilian and zoo technical field Property.Therefore, technical scheme is related to compound of Formula I and is used as preparing desinsection (mite) agent in agricultural and other field Purposes.
Compound of Formula I can be used for preventing and treating following insect：
Coleoptera (Coleoptera) (beetle)：Bean weevil category kind (Acanthoscelides spp.) (curculionid), acanthoscelides obtectus (Acanthoscelides obtectus) (common pea weevil), Emerald ash borer (Agrilus planipennis) (Fraxinus rhynchophylla Narrow lucky fourth), acupuncture needle Eimeria kind (Agriotes spp.) (wireworm), anoplophora glabripennis (Anoplophora Glabripennis) (Asia psacotheahilaris), Anthonomusgrandis category kind (Anthonomus spp.) (Culculionidae), Mexico's Anthonomusgrandis (Anthonomus grandis) (bollworm), cocoon honeybee category kind of (an Aphidius spp.), weevil category kind (an Apion spp.) (as Worm), sugarcane cockchafer category kind of (Apogonia spp.) (grub), black suede cockchafer (Atacnius sprctulus) (black suede cockchafer Son), Atomaria linearis (Atomaria linearis) (small beet beetle (pygmy mangold beetle), cucumber beetle category kind (Aulacophore spp.), beet are as (Bothynoderes punctiventris) (beet root curculionid), bean weevil category kind (Bruchus spp.) (curculionid), pea weevil (Bruchus pisorum) (pea weevil), Cacoesia category kind (Cacoesia Spp.), Callosobruchus maculatus (Callosobruchus maculatus) (southern cowpea curculionid), pineapple bug (Carpophilus Hemipteras) (dried-frait beetle), beet tortoise beetle (Cassida vittata), day Bos kind (Ccrostcrna spp.), Ccrotoma category kind (Ccrotoma spp.) (chrysomonad (chrysomcids)), beans are chrysomelid (Cerotoma trifur cata) (the chrysomelid worm of beans), ceutorhynchus kind (Ceutorhynchus spp.) (curculionid), Chinese cabbage seed tortoise are as (Ceutorhynchus Assimilis) (Chinese cabbage weevil (cabbage seedpod weevil)), turnip tortoise are as (Ceutorhynchus napi) (cabbage curculionid (cabbage curculio)), phyllotreta kind (Chaetocnema spp.) (chrysomonad), Colaspis category Kind (Colaspis spp.) (native beetle), Conoderus scalaris, Conoderus stigmosus, Li Xiang (Conotrachelus nenuphar) (plum bores weevil), Cotinus nitidis (Green june beetle (Green June Beetle)), asparagus scotellaris (Crioceris asparagi) (asparagus beetle), rusty grain beetle (Cryptolestes Ferrugincus) (rust paddy beetle (rusty grainbeetle)), Cryptolestes pusillus (Cryptolestes pusillus) (flat ostomatid), Cryptolestes turcicus Grouville (Cryptolestes turcicus) (Turkey paddy beetle (Turkish grain Beetle)), Ctenicera category kind (Ctenicera spp.) (nematode), Curculio kind (Curculio spp.) (curculionid), circle Head rhinoceros cockchafer category kind (Cyclocephala spp.) (grub), close withe are as (Cylindrocpturus adspersus) (sunflower grass curculionid (sunflower stem weevil)), as (Deporaus marginatus), (mango is cut for mango leaf-cutting Leaf curculionid (mango leaf-cutting weevil)), it is lader beetle stupid (Dermestes lardarius) (lader beetle is stupid), white Abdomen skin stupid (Dermestes maculates) (white abdomen skin is stupid), chrysomelid category kind (Diabrotica spp.) (chrysomelid), Mexico Epilachna spp (Epilachna varivcstis) (Mexico beans beetle), moth stem weevil (raustinus cubae), pale neck As (Hylobius pales) (pales weevil (pales weevil)), Phytonomus kind (Hypera spp.) (curculionid), alfalfa Leaf is as (Hypera postica) (alfalfa weevil), Hyperdoes category kind (Hyperdoes spp.) (Argentinian stem weevils (Hyperodes weevil)), the small stupid category kind of coffee berry small stupid (Hypothenemus hampei) (coffee berry beetle), tooth (Ips spp.) (spine shin is small stupid (engravers)), lasioderma serricorne (Lasioderma serricorne) (cigarette beetle), Ma Ling Potato beetle (Leptinotarsa decemlineata) (Colorado potato beetle), Liogenys fuscus, The stupid category kind of Liogenys suturalis, rice water weevil (Lissorhoptrus oryzophilus) (rice water weevil), powder (Lyctus spp.) (the stupid stupid beetle of moth/powder (powder post beetles) of wood), Maecolaspis joliveti, Megascelis category kind (Megascelis spp.), corn click beetle (Melanotus communis), nitidulid category kind (Meligethes spp.), rape nitidulid (Meligethes aeneus) (brevitarsis (blossom beetle)), May Chafer (Melolontha melolontha) (typical European chafer), Oberea brevis, linear cylinder longicorn (Oberea Linearis), coconut palm moth rhinoceros cockchafer (Oryctes rhinoceros) (date palm beetle (date palm beetle)), trade saw paddy Steal (Oryzaephilus mercator) (market saw-toothed grain beetle (merchant grain beetle)), saw-toothed grain beetle (Oryzaephilus surinamensis) (sawtooth paddy beetle (sawtoothcd grain bcctlc)), beak weevil category kind (Otiorhynchus spp.) (curculionid), black angle scotellaris (Oulema melanopus) (cereal leaf beetle (cereal Leafbeetle)), Oulema oryzae (Oulema oryzae), the short beak of rose as category kind of (Pantomorus spp.) (curculionid), Phyllobranchia cockchafer category kind (a Phyllophaga spp.) (May/June chafer) is eaten, Phvllophaga cuyabana, yellow bar are jumped First category kind (Phyllotreta spp.) (chrysomonad), apple tiger are as category kind (Phynchites spp.), Japan popillia flavosellata fairmaire (large space between muscles length is stupid for (Popillia japonica) (Japanese beetle), large space between muscles stupid (Prostephanus truncates) (larger grain borer)), paddy stupid (Rhizopertha dominica) (the small moth of paddy (lesser grain Borer)), root gill cockchafer category kind (Rhizotrogus spp.) (European chafer (Eurpoean chafer)), Rhynchophorus Kind (Rhynchophorus spp.) (curculionid), small stupid category kind (a Scolytus spp.) (the stupid moth of wood), Shenophorus category kinds (Shenophorus spp.) (grain weevil), pea leaf are as (Sitona lincatus) (pealeaf weevil (pca leaf Weevil)), Sitophilus kind (Sitophilus spp.) (grain weevil first), grain weevil (Sitophilus granaries) (paddy worm (granary weevil)), rice weevil (Sitophilus oryzae) (rice weevil first (rice weevil)), medicinal material ostomatid (Stegobium paniceum) (Stegobium paniceum (drugstore beetle)), Tribolium kind (Tribolium spp.) (face Curculionid), red flour beetle (Tribolium castaneum) (red flour beetle (red flour beetle)), it is miscellaneous plan paddy moisten (Tribolium confusum) (confused flour beetle (confused flour beetle)), the stupid (Trogoderma of piebald skin Variabile) (warehouse skin is stupid (warehouse beetle)) and Zabrus tenebioides.
Dermaptera (Dcrmaptcra) (earwig).
Neuroptera (Dictyoptera) (cockroach)：Groton bug (Blattella germanica) (Groton bug (German cockroach)), oriental cockroach (Blatta orientalis) (oriental cockoach), Pennsylvania wood Lian (Parcoblatta pennylvanica), American cockroach (Periplaneta americana) (America roach consumptive disease (American Cockroach)), Australian cockroach (Periplaneta australoasiae) (Australian cockroach (Australian Cockroach)), periplaneta brunnea (Pcriplancta brunnca) (periplaneta brunnea (brown cockroach)), smoke Perilpaneta americana (Periplaneta fuliginosa) (Peroplaneta fluligginosa (smokybrown cockroach)), the green blattaria (Pyncoselus of sugarcane Suninamensis) (sugarcane Lian (Surinam cockroach)) and long hair blattaria (Supella longipalpa) (brown band blattaria (brownbanded cockroach))。
Diptera (Diptera) (fly)：Latent fly (the Agromyza of Aedes kind (Aedes spp.) (mosquito), alfalfa Frontella) ((Agromyza spp.) is (latent for (alfalfa dive fly (alfalfa blotch leafminer)), Hippelates kind Leaf fly), (add by trypetid (Anastrepha suspensa) by Anastrepha kind (Anastrepha spp.) (drosophila), Caribbean Strangle ratio press trypetid (Caribbean fruit fly)), Anopheles kind (Anopheles spp.) (mosquito), Bactrocera kind (Batrocera spp.) (drosophila), melonfly (Bactrocera cucurbitae) (melon fly), citrus fruit fly (Bactrocera dorsalis) (oriental fruit fly), small bar Anastrepha kind (Ceratitis spp.) (drosophila), the small bar in Mediterranean are real Fly (Ceratitis capitata) (medfly), Chrysops kind (Chrysops spp.) (deer horsefly), Callitroga's kind (Cochliomyia spp.) (screw worm fly larva), Ying uranotaenia kind (Contarinia spp.) (Ying mosquitos), Culex kind (Culex Spp.) (mosquito), Ye Ying uranotaenias kind (Dasineura spp.) (Ying mosquitos), You Cai Ye Ying mosquitos (Dasineura brassicae) (volume Xin Cai Ying mosquitos), Delia kind (Delia spp.), delia platura (Delia platura) (root maggot (seedcorn Maggot)), Drosophila kind (Drosophila spp.) (vinegar fly), Fannia kind (Fannia spp.) (housefly), anthomyia canicularis (Fannia canicularis) (Fannia canicularis (little house fly)), anthomyia scalaris (Fannia scalaris) (grey abdomen Latrine fly), big horse botfly (Gasterophilus intestinalis) (horse botfly), Gracillia perseae, Haematobia irritans (Haematobia irritans) (horn fly), Hylemyia kind (Hylemyia spp.) (root maggot (root maggot)), heel fly (Hypoderma lineatum) (common heel fly (common cattle grub)), Liriomyza kind (Liriomyza Spp.) (Liriomyza), wild cabbage liriomyza bryoniae (Liriomyza brassica) (snake Liriomyza (serpentine Leafminer)), sheep hippoboscid (Melophagus ovinus) (sheepked), fly category kind (Musca spp.) (housefly (muscid fly)), face fly (Musca autumnalis) (face fly (face fly)), housefly (Vusca Domestica) (housefly (house fly)), Oestrus ovis (Oestrus ovis) (sheep nose fly (sheep bot fly)), Europe Frit fly (Oscinella frit) (Oscinella frit), beet spring fly (Pegomyia betae) (spinach leaf miner (beet Leafminer)), wheat fly category kind (Phorbia spp.), carrot fly (Psila rosae) (carrot rust fly (carrotrust fly)), cherry fruit fly (Rhagoletis cerasi) (cherry fruit fly (cherry fruit fly)), apple Fruit fly (Rhagoletis pomonella) (apple maggots (apple maggot)), wheat midge (Sitodiplosis Mosellana) (orange wheat flower mosquito (orange wheat blossom midge)), tatukira (stomoxys Calcitruns) (tatukira (stable fly)), gadfly category kind (Tahanus spp.) (horse botfly) and big uranotaenia kind (Tipula Spp.) (daddy-longlegs).
Semiptera (Hemiptera) (stinkbug)：Intend acrosternumhilare (Acrosternum hilare) (acrosternumhilare (green stink Bug)), america valley cinchbug (Blissus leucopterus) (chinch bug (chinch bug)), potato person of outstanding talent fleahopper (Calocoris norvegicus) (potato fleahopper (potato mirid)), cimex hemipterus (Cimex hemipterus) (cimex hemipterus (tropical bed bug)), bedbug (Cimex lectularius) (bedbug (bed hug)), Daghertus The black wing red stinkbug of fasciatus, Dichelops furcatus, cotton (Dysdercus suturellus) (red cotton bug (cotton Stainer)), Edessa meditabunda, Europe Eurygasterspp (Eurygaster maura) (paddy worm (cereal bug)), Euschistus heros, brown smelly stinkbug (Euschistus servus) (brown stinkbug (brown stink bug)), iS-One angle fleahopper (Helopeltis antonii), tea angle fleahopper (Helopeltis theivora) (tea blight plantbug), stinkbug category Kind (Lagynotomus spp.) (stinkbug), big Leptocorisa spp (Leptocorisa oratorius), different Leptocorisa spp (Leptocorisa Varicornis), Lygus Hahn kind (Lygus spp.) (fleahopper (plant bug)), lygushesperus (Lygus Hesperus) (western tarnished plant bug), the graceful powder stinkbug of the rose of Sharon (Maconellicoccus hirsutus), Neurocolpus longirostris, green rice bug (Nezara viridula) (southern green stink bug), plant Fleahopper belongs to kind of (PhyLocoris spp.) (fleahopper), fleahopper (Phytocoris californicus) is planted in California, Phytocoris relativus, Piezodorus guildingi, four line fleahoppers (Poecilocapsus lineatus) (fourlined plant bug)、Psallus vaccinicola、Pseudacysta perseae、Scaptocoris Castanea and Triatoma kind (Triatoma spp.) (cone nose worm (bloodsuckingconenose bug) of sucking blood/hunt stinkbug (kissing bug))。
Homoptera (Homoptera) (aphid, a red-spotted lizard, aleyrodid, leafhopper)：Acyrthosiphum pisim (Acrythosiphonpisum) (pea Aphid (pea aphid)), adelgid kind (Adelges spp.) (adelgids), wild cabbage aleyrodid (Aleurodes Proletella) (cabbage aleyrodid), Aleurodicus dispersus (Aleurodicus disperses), velvet aleyrodid (Aleurothrixus flccosus) (whitefly in bt cotton (woolly whitefly)), white wheel armored scale category kind (Aluacaspis Spp.), Amrasca bigutella bigutella, froghopper category kind (Aphrophora spp.) (leafhopper (leafhopper)), California red scale (Aonidiella aurantii) (California red a red-spotted lizard (California red Scale)), Aphis kind (Aphis spp.) (aphid), cotten aphid (Aphis gossypii) (cotton aphid), apple aphid (Aphis pomi) (apple aphid), eggplant are without net aphid (Aulacorthitm solani) (digitalis aphid (foxglove Aphid)), Aleyrodes kind (Bemisia spp.) (aleyrodid), Bemisia argentifolii (Bemisia argentifolii), sweet potato whitefly (Bemisia tabaci) (sweetpotato whitefly), Diuraphis noxia (Brachycolus noxius) (Russian aphid (Russian aphid)), asparagus tubule aphid (Brachycorynclia asparagi) (asparagus aphid (asparagus Aphid)), Brevennia rehi, brevicoryne brassicae (Brevicoryne brassicae) (cabbage aphid), lecanium category kind (Ceroplastes spp.) (a red-spotted lizard), ceroplastes rubens (Ceroplastes rubens) (red wax scale), snow armored scale category kind (Chionaspis spp.) (a red-spotted lizard), Aspidiotus category kind (Chrysomphalus spp.) (a red-spotted lizard), soft wax a red-spotted lizard category kind (Coccus Spp.) (a red-spotted lizard), the pink bad aphid (Dysaphis plantaginea) (rosy apple aphid) of apple, green jassids category kind (Empoasca spp.) (leafhopper), apple aphid (Eriosoma lanigerum) (woolly apple aphid), blow cotton a red-spotted lizard (Icerya purchasi) (cottony cushion scale), mango yellow line leafhopper (Idioscopus nitidulus) (mango leafhopper), small brown rice planthopper (Laodelphax striatellus) (smaller brown planthopper), Lepidosaphes shimer kind (Lepidosaphes spp.), long tube Aphis kind (Macrosiphum spp.), root of Beijing euphorbia Macrosiphus spp (Macrosiphum euphorbiae) (potato aphid (potato aphid)), grain aphid (Macrosiphum Granarium) (Britain's wheat aphid (English grain aphid)), rose aphid (Macrosiphum rosae) (rose Aphid (rose aphid)), four line leafhopper (Macrosteles quadrilineatus) (Aster tataricus leafhopper (aster Leafhopper)), Mahanarva frimbiolata, Acyrthosiphon dirhodum (Metopolophium dirhodum) (rose Wheat aphid (rose grain aphid)), Midis longicornis, black peach aphid (Myzus persicae) (black peach aphid (green Peach aphid)), rice green leafhopper category kind of (Nephotettix spp.) (leafhopper), rice green leafhopper (Nephotettix Cinctipes) (greenery cicada (green leafhopper)), brown paddy plant hopper (Nilaparvata lugens) (brown Planthopper), chaff piece armored scale (Parlatoria pergandii) (chaff scale), ebony armored scale (Parlatoria Ziziphi) (ebony scale), popcorn wing plant hopper (Peregrinus maidis) (corn delphacid), froghopper category Kind (Philaenus spp.) (spittle insects), grape phylloxera (Phylloxera vitifoliae) (grape Phylloxera), Physokermes piceae (Physokermes piceae) (spruce bud scale), stern line mealybug category kind (Planococcus spp.) (mealybug), mealybug category kind (Pseudococcus spp.) (mealybug), the clean mealybug of pineapple (Pscudococcus brcvipcs) (pinc apple mcalybug), theatre armored scale (Quadraspidiotus Perniciosus) (san jose scale (San Jose scale)), aphid a red-spotted lizard category kind (Rhapalosiphum spp.) (aphid), jade Rice tree louse (Rhapalosiphum maida) (corn leaf aphids (corn leaf aphid)), rhopalosiphum padi (Rhapalosiphum Padi) (oatbird-cherry aphid), pearl lecanium category kind (Saissetia spp.) (a red-spotted lizard), olive pearl lecanium (Saissetia Oleae) (black a red-spotted lizard), green bugs (Schizaphis graminum) (green bugs (gr eenbug)), grain aphid (Sitobion avenge) (Britain's wheat aphid), white backed planthopper (Sogatella furcifera) (white-backed Planthopper), variegation Aphis kind (Therioaphis spp.) (aphid), line lecanium category kind (Toumeyella spp.) (a red-spotted lizard), sound Aphis kind (Toxoptera spp.) (aphid), white powder Pediculus kind (Trialeurodes spp.) (aleyrodid), greenhouse Trialeurodes vaporariorum (Trialeurodes vaporariorum) (greenhouse whitefly (greenhouse whitefly)), knot wing trialeurodes vaporariorum (Trialeurodes abutiloneus) (bandedwing whitefly), sharp armored scale category kind (Unaspis spp.) (a red-spotted lizard), Swear sharp clam (Unaspis yanonensis) (arrow a red-spotted lizard (arrowhead scale)) and Zulia entreriana.
Hymenoptera (Hymenoptera) (ant, wasp and honeybee)：It is Myrmecina kind (Acromyrrmex spp.), new Boundary cabbage sawfly (Athalia rosae), leaf ant category kind (Atta spp.) (Ieafcutting ants), black ant category kind (Camponotus spp.) (carpented ant (carpenter ant)), Diprion kind (Diprion spp.) (sawfly (sawfly)), ant category kind (Formica spp.) (ant), Argentine ant (Iridomyrmex humilis) (Argentineant), Monomorium subspecies (Monomorium ssp.), MonomoriumMayr (Monomorium minumum) (little Black ant), kitchen ant (Monomorium pharaonis) (little red ant (Pharaoh ant)), Neodiprion kind (Neodiprion spp.) (sawfly), Pogonomyrmex kind (Pogonomyrmex spp.) (harvester ant), hornet category kind (Polistes spp.) (wasp (paper wasp)), Solenopsis kind (Solenopsis spp.) (fiery ant), odorous antenna (Tapoinoma sessile) (odorous antenna (odorous house ant)), Tetramorium kind (Tetranomorium spp.) (Pavement Ant (pavement ant)), Vespula kind (Vespula spp.) (yellow jacket (yellow jacket)) and carpenter bee Category kind (Xylocopa spp.) (carpenter bee (carpenter bee)).
Isoptera (Isoptera) (termite)：Formosanes category kind (Coptotcrmcs spp.), bent jaw termite (Coptotermes curvignathus), French termite (Coptotermes frenchii), coptotermes formosanus (Coptotermes Formosanus) (Formosan subterranean termite), angle Cryptotermes kind (Cornitermes spp.) (proboscis Termite (nasute termite)), sand Cryptotermes kind (Cryptotermes spp.) (dry-wood termite), different Cryptotermes kind (Heterotermes spp.) (desert Soil termites (desert subterranean termite)), golden yellow different termite ((IIeterotermes aureus), kalotermitid category kind (Kalotermes spp.) (dry-wood termite), principal columns of a hall Cryptotermes kind (Incistitermes spp.) (dry-wood termite), Macrotermes kind (Macrotermes spp.) (cultivation termite (fungus Growing termite)), edge kalotermitid category kind ((Marginitermes spp.) (dry-wood termite), saw a Cryptotermes kind (Microcerotermes spp.) (careless termite (harvester termite)), the small termite (Microtermes of rice wheat Obesi), former angle Cryptotermes kind (Procornitermes spp.), Reticulitermes kind (Reticulitermes spp.) (dwell by soil Termite), Reticulitermes banyulensis, meadow reticulitermes flavipe (Reticulitermes grassei), yellow limb dissipate it is white Ant (Reticulitermes flavipes) (east Soil termites), beautiful little Huang reticulitermes flavipes (Reticulitermes Hageni), west reticulitermes flavipe (Reticulitermes hesperus) (west Soil termites), Sang Te reticulitermes flavipes (Reticulitermes santonensis), the northern reticulitermes flavipe that dwells (Reticulitermes speratus), U.S. black shin reticulitermes flavipe (Reticulitermes tibialis), U.S. small black reticulitermes flavipe (Reticulitermes virginicus), proboscis reticulitermes flavipe Category kind (Schedorhinotermes spp.) and ancient Cryptotermes kind (Zootermopsis spp.) (rotten wood termite).
Lepidoptera (Lepidoptera) (moth and butterfly)：Achoea janata, Adoxophyessp kind (Adoxophyes Spp.), adoxophyes moth (Adoxophyes orana), tiger category kind of (Agrotis spp.) (cutworm), small cutworm ((Agrotis ipsilon) (black cutworm), cotton leaf ripple noctuid (Alabama argillacea) (cotton leafworm (cotton leafworm))、Amorbia cuneana,Amyelosis transitella(navel orangeworm)、 Anacamptodes defectaria, sliver gelechiid (Anarsia lineatella) (peach twig borer), jute bridge Night high (Anomis sabulijera) (jute looper), Anticarsia (Anticarsia gemmatalis) (velvetbean caterpillar), fruittree leafroller (Archips argyrospila) (fruit tree Leafroller), rose leaf roller (Archips rosana) (rose leaf roller), volume moth category kind (Ar Gyrotaenia spp.) (tortricid moths), tangerine Argyrotaenia spp (Argyrotaenia citrana) (citrus leaf-roller (orange tortrix)), Autographa gamma, Bonagota cranaodcs, rice leaf roller (Borbo Cinnara) (rice leaf folder), cotton leaf lyonetid (Bucculatrix thurberiella) (cotton Leafperforator), thin moth category kind (Caloptilia spp.) (leaf miner), Capua reticulana, peach fruit moth (Carposina niponensis) (peach fruit moth (peach fruit moth)), straw borer spp kind (Chilo spp.), mango Chlumetia transversa (Chlumetia transversa) (mango shoot borer), rose Choristoneura spp (Choristoneura Rosaceana) (oblique banded leaf roller), Noctua kind (Chrysodeixis spp.), cnaphalocrocis are wild Snout moth's larva (Cnaphalocerus medinalis) (meadow leaf roller (grass leafroller)), beans Pier kind (Colias Spp.), lichee litchi (Conpomorpha cramerella), the stupid moth (Cossus cossus) of fragrance wood (the stupid moth of wood), Crambus Fabricius kind (Crambus spp.) (Sod webworms), Lee's Grapholita spp (Cydia funebrana) (Li Guoe (plum Fruit moth)), oriental fruit months (Cydia molesta) (east heart-eating worm (oriental fruit moth)), pea Eat into pod high (Cydia nignicana) (pea moth), the stupid moth of apple (Cydia pomonella) (codling moth (codling moth)), Darna diducta, Diaphania kind (Diaphania spp.) (stem borer (stem borer)), Snout moth's larva category kind (Diatr aea spp.) (stem borer (stalk bor er)), small sugarcane borer (Diatraea saccharalis) (sugarcane borer), Diatraea grandiosella (Diatraea graniosella) (southwester corn Borer), Earias kind (Earias spp.) (bollworm), earias insulana (Earias insulata) (Egyptian Bollworm), earias fabia (Earias vit.ella) (rough northern bollworm), Ecdytopopha Aurantianum, South America maize seedling phycitid (Elasmopalpus lignosellus) (lesser cornstalk borer), Shallow brown apple moth (Epiphysias postruttana) (light brown apple moth), meal moth category kind (Ephestia spp.) (powder snout moth's larva), meal moth (Ephestia cautella) (almond moth), tobacco powder sp (Ephestia elutella) (tobacco snout moth's larva (tobbaco moth)), Mediterranean flour moth (Ephestia kuehniella) (Mediterranean flour moth), Epimeces category kind (Epimeces spp.), night steinernema (Epinotia Aporema), Erionota thorax (Linne) (Erionota thrax) (banana skipper), ligustrum fine tortricidae (Eupoecilia Ambiguella) (grape berry moth (grape berry moth)), former cutworm (Euxoa auxiliaris) (army Cutworm), Agrotis kind (Feltia spp.) (cutworm), angle sword Noctua kind (Gortyna spp.) (stem borer), East moth fruit moth (Grapholita molesta) (peach (apricot) sub- heart-eating worm (oriental fruit moth)), treble cut snout moth (Hedylepta indicata) (bean pyralid (bean leaf webber)), blue or green Eimeria kind (Helicoverpa spp.) (noctuid), bollworm (Helicoverpa armigera) (cotton bollworm), paddy reality noctuid (Helicoverpa Zea) (corn borer ridge (snout moth's larva ridge worm/bollworm)), Heliothis kind (Heliothis spp.) (noctuid), tobacco budworm (Heliothis virescens) (tobacco budworm), Hellula undalis (Hellula undalis) (cabbage Webworm), Indarbela category kind (Indarbela spp.) (root moth), the stupid moth (Keiferia of tomato Lycopersicella) (tomato pinworm), the white wing open country snout moth's larva of eggplant (Leucinodes orbonalis) (eggplant Fruit borer), pear leaf blister moth (Leucoptera malifoliella), thin moth category kind of (a Lithocollectis spp.), Grape olethreutid (Lobesia botrana) (grape fruit moth), Loxagrotis category kind (Loxagrotis Spp.) (noctuid), beans white line cutworm (Loxagrotis albicosta) (western bean cutworm), gypsymoth (Lymantria dispar) (gypsy moth), apple leaf miner (Lyonetiaclerkella) (apple leaf miner (apple Leafminer)), oil palm bag moth (Mahasena corbetti) (oil palm bagworm), Malacosoma kind (Malacosoma spp.) (tent caterpillars), lopper worm (Mamestra brassicae) (dish march moth (cabbage armyworm)), beanpod open country snout moth's larva (Maruca testulalis) (beans open country snout moth's larva), bag moth (Metisa plana) (knot Grass-and-insect painting), Mythimna unipuncta (true armyworm), Neoleucinodes elegantalis (small tomato moths (small tomato borer)), 3 water snout moth's larva (Nymphula depunctalis) (rice leaf roller (rice Caseworm)), winter looper (Operophthera brumata) (winter moth), European corn borer (Ostrinia Nubilalis) (European corn borer (European corn borer)), Oxydia vesulia, the brown volume moth (Pandemis of boundary Cerasana) (common glucose leaf roller (common currant tortrix)), apple brown bortrix (Pandemis heparana) (brown apple tortrix), African Bodhidharma swallowtail butterfly (Papilio demodocus), Pectinophora gossypiella (Pectinophora Gossypiella) (pink bollworm (pink bollworm)), boundary Noctua kind (Peridroma spp.) (cutworm), variegated Tiger (Peridroma saucia) (variegated cutworm), coffee leafminer (Perileucoptera Coffeella) (white coffee leafminer), phthorimaea operculella (Phthorimaea operculella) (potato tuber moth), citrus leaf lyonetid (Phyllocnisitis citrella), thin moth category kind (Phyllonorycter spp.) (leaf miner), cabbage butterfly (Pieris rapae) (external cabbage caterpillar (imported Cabbageworm)), head is by green noctuid (Plathypena scabra), India paddy spot moth (Plodia interpunctella) (Indian meal moth), diamond-back moth (Plutella xylostella) (diamondback moth), grape berry moth (Polychrosis viteana) (grape berry moth), tangerine fruit ermine moth (Prays endocarps), olive ermine moth (Prsys oleae) (olive moth), mythimna separata category kind (Pseudaletia spp.) (noctuid), Pseudaletia Unipunctata (armyworm), soybean noctuid (Pseudoplusia includens) (soybean looper), looper (Rachiplusia nu), yellow rice borer (Scirpophaga incertulas), moth stem night high category kind (Sesamia spp.) (moth Stem worm), Sesamia inferens (Sesamia inferens) (pink rice stemborer), powder stem snout moth's larva (Sesamia Nonagrioides), the brown slug moth of copper stain (Setora nitens), gelechiid (Sitotroga cerealella) (Angoumois Grain moth), pilleriana (Sparganothis pilleriana), Spodoptera kind (Spodoptera Spp.) night is coveted on (armyworm), beet armyworm (Spodoptera exigua) (beet armyworm (beet armyworm)), meadow Moth (Spodoptcra fugipcrda) (autumn armyworm (fall armyworm)), southern spodoptera (Spodoptera Oridania) (root is eaten into for (southern armyworm (southern armyworm)), emerging Noctua kind (Synanthedon spp.) Worm), Thecla basilides, Thermisia gemmatalis, casemaking clothes moth (Tineola bisselliella) (webbing Clothes moth), cabbage looper (Trichoplusia ni) (cabbage looper), Liriomyza brponiae (Tuts Absoluta), Yponomeuta kind (Yponomeuta spp.), the stupid moth of coffee leopard (Zeuzeracoffeae) (red branch ) and Zeuzera pyrina (the stupid moth of pears leopard (leopard moth)) borer.
Mallophaga ((Mallophaga) poultry louse (chewing lice))：Sheep poultry louse (Bovicola ovis) (sheep Biting louse), fiery menopon gallinae (Menacanthus stramineus) (chick poultry louse (chicken body )) and shaft louse (Menopon gallinea) (common hen house (common hen house)) louse.
Orthoptera (Orthoptera) (grasshopper, locust and cricket)：Blackspot arna Zhong (Anabrus simplex) (Mo Men Katydid (Mormon cricket)), mole cricket (Gryllotalpidae) (mole cricket (mole cricket)), Asiatic migrotory locust (Locusta migratoria), grasshopper category kind (Melanoplus spp.) (grasshopper), guiding principle wing spinelet Zhong (Microcentrum Retinerve) (angle wing katydid (angular winged katydid)), Pterophylla category kind (Pterophylla Spp.) (katydid), chistocerca gregaria, fork-tail katydid (Scudderia furcata) (fork-tail shrubbery tree Zhong (fork tailed bush katydid)) and black angle oncus locust (Valanga nigricorni).
Anoplura (Phthiraptera) (sucks lice (sucking louse))：Pediculus of sucking blood kind (Haematopinus Spp.) (ox louse and pig lice), sheep jaw lice (Linognathus ovillus) (sheep lice (sheep louse)), head louse (Pediculus humanus capitis) (body louse), pediculus humanus corporis (Pediculus humanus humanus) (body louse) and the moon Lice (Pthirus pubis) (crab louse (crab louse)).
Siphonaptera (Siphonaptera) (flea)：Ctenocephalides canis (Ctenocephal ides canis) (dog flea), Ctenocephalides felis (Ctenocephalides felis) (cat flea) and Pulex irritans (Pulex irritans) (human flea).
Thysanoptera (thrips)：Cigarette brown thrip (Frankliniella fusca) (tobacco thrip), western classical architecture (Frankliniella occidentalis) (western flower thrips), Frankliniella shultzei, prestige Lian Si flower thrips (Frankliniella williamsi) (corn thrips (corn thrip)), greenhouse thrips (IIeliothrips haemorrhaidalis)(greenhouse thrip)、Riphiphorothrips cruentatus、 Hard Thrips kind (Scirtothrips spp), balloonflower root thrips (Scirtothrips cirri) (citrus thrip), tea are yellow Thrips (Scirtothrips dorsalis) (yellow tea thrips), Taeniothrips rhopalantennalis With Thrips kind (Thrips spp.).
Thysanoptera (Thysanura) (moth (bristletail))：Silverfish category kind (Lepisma spp.) (stupid worm (silverfish)) belong to kind of (Thermobia spp.) (a special mess fish) with special mess silverfish.
Acarina (Acarina) (mite (mite) and cicada (tick))：Wu Shi honeybee shields mite (Acarapsis woodi) (honeybee gas Pipe endoparasitism mite (tracheal mite of honeybee)), Tyroglyphus kind (Acarus spp.) (food mites), Acarus siro (Acarus siro) (paddy mite (grain mite)), mango bud mite (Aceria mangiferae) (mango bud mite), Peronium Eriophyes kind (Aculops spp.), Aculops lycopersici (Aculops lycopersici) (tomato russet Mite), Aculops pelekasi, tangerine peronium goitre mite (Aculus pelekassi), Si Shi thorn goitre mites (Aculus Schlechtendali) (apple thorn goitre mite (apple rust mite)), lone star tick (Amblyomma amcricanum) (lone star tick), Boophilus kind (Boophilus spp.) (tick), avette short hairs tick (Brevipalpus Obovatus) (privet mite), purplish red short hairs mite (Brevipalpus phoenicis) (red and black flat Mite), fat tick category kind (Demodex spp.) (mange mites), Dermacentor kind (Dermacentorspp.) (hard tick), U.S. Continent dog tick (Dermacentor variabilis) (american dog tick), dermatophagoides pteronyssinus (Dermatophagoides Pteronyssinus) (house dust mite), Eotetranychus kind (Eotetranycus spp.), Eotetranychus carpini (Eotetranychus carpini) (yellow spider mite (yellow spider mite)), Epitrimerus kind (Epitimerus Spp.), Eriophyes kind (Eriophyes spp.), Isodesspp kind (work；Odes spp.) (tick), Panonychus citri category kind ((Metatetranycus spp.), notoedres cati (Notoedres cati), Oligonychus kind (Oligonychus spp.), coffee Coffee unguiculus mite (Oligonychus coffee), ilex Oligonychus (Oligonychus ilicus) (southernred Mite), Panonychus citri category kind (Panonychus spp.), Jie-Li enzyme-SQ (Panonychus cirri) (orange spider (citrus Red mite)), panonychus ulmi (Panonychus ulmi) (European red spider (European red mite)), tangerine wrinkle leaf Pierce goitre (Phyllocoptruta oleivora) (citrus rust mite), Polyphagotarsonemus latus Banks (Polyphagotarsonemun latus) (broad mite (broad mite)), brown dog tick (Rhipicephalus Sanguineus) (brown dog tick (brown dog tick)), root mite category kind (Rhizoglyphus spp.) (root mite (bulb Mite)), itch mite (Sarcoptes scabiei) (itch mite), avocado apical cap goitre mite (Tegolophus Perseaflorae), Tetranychus kind (Tetranychus spp.), T.urticae Koch (Tetranychus urticae) (2 spiders Spider mite (twospotted spider mite)) and Di Shi watts of mite (Varroa destructor) (honeybee mite).
Nematoda (nematode)：Aphelenchoides kind (Aphelenchoides spp.) (bud and leaf and pine wood nematode (bud And leaf＆pine wood nematode)), thorn Turbatrix kind (Belonolaimus spp.) (sting nematodes), Small loop wire Eimeria kind (Criconemella spp.) (ring nematodes), heart worm (Dirofilaria immitis) (dog heartworm), Ditylenchus kind (Ditylenchus spp.) (stem and bulb eelworm), spine rubber-insulated wire Eimeria kind (Heterodera spp.) (cyst nematode), corn SCN (Heterodera zeae) (corn cyst Nematode), Hirschmanniella kind (Hirschmanniella spp.) (root nematodes), tie Turbatrix kind (Hoplolaimus spp.) (lance nematodes), Meloidogyne kind (Meloidogyne spp.) (root-knot nematode), Meloidogyne incognita ((Meloidogyne incognita) (root-knot nematode), Onchocerca caecutiens (Onchocerca Volvulus) (hook-tail worm), Pratylenchus kind (PraLylenchus spp.) (rotten nematode (lesion Nematode)), perforation line Eimeria kind (Radopholus spp.) (similes thorne (burrowing nematode)) and banana Reniform nematode (Rotylenchus reniformis) (kidney-shaped nematode).
Symphyla (comprehensive insects)：Kahikatea worm (Scutigerella immaculata).
Especially, to black peach aphid, diamondback moth, mythimna separata, Tetranychus cinnabarinus, still there is good prevention effect at lower doses.
Due to its positive characteristic, above-claimed cpd is advantageously used for protection agricultural and the important crop of horticulture, family Poultry and breeding stock, and the environment that the mankind often go is from there is the injury of insect, mite.
To obtain ideal effect, the dosage of compound changes because of various factors, such as compound used therefor, the work to be protected Thing, the type of harmful organism, gradient of infection, weather conditions, application method, the formulation used.
The compound of Formula I dosage of 10 grams -5 kilograms of per hectare can provide sufficient prevention effect.
Another object of the present invention is further related to by using compound of Formula I, preventing and treating agricultural and the important crop of horticulture And/or the method for the worm mite in the environment that often goes of domestic animal and breeding stock and/or the mankind.Especially, the dosage of compound is in per hectare Change in 10 grams -5 kilograms.
The use of the composition containing one or more compound of Formula I is typically beneficial to be applied to agricultural.
Therefore, another technical scheme of the invention also includes a kind of insecticide acaricide composition, containing as activearm Point compound of Formula I and agriculturally acceptable carrier, the weight percentage of active component is 0.1-99% in composition.
The type of service of composition can be dry powder, wettable powder, missible oil, microemulsion, paste, granule, solution, outstanding Floating agent etc.：The selection of types of compositions depends on specific application.
Composition is prepared in a known way, such as optionally in the presence of surfactant, by using solvent medium And/or solid diluent or dissolving active material.
Available solid diluent or carrier are for example：Silica, kaolin, bentonite, talcum, diatomite, white clouds Stone, calcium carbonate, magnesia, chalk, clay, synthetic silicate, Attagel, sepiolite.
Than water, available liquid diluent is such as aromatic organic solvent (mixture of dimethylbenzene or alkylbenzene, chlorine Benzene etc.), paraffin (petroleum distillate), alcohols (methanol, propyl alcohol, butanol, octanol, glycerine), esters (ethyl acetate, isobutyl acetate Deng), ketone (cyclohexanone, acetone, acetophenone, isophorone, ethyl pentyl group ketone etc.), amide-type (DMF, N- Methyl pyrrolidone etc.).
Available surfactant be alkylsulfonate, alkylaryl sulfonates, polyoxyethylene alkylphenol, sorbierite it is poly- Sodium, calcium, triethylamine or the triethanolamine salt of oxygen vinyl acetate, lignosulfonates etc..
Composition can also contain special additive and be used for specific purpose, for example, adhesive for example Arabic gum, polyvinyl alcohol, Polyvinylpyrrolidone etc..
The concentration of active component can be according to active component, its application target, environmental condition and use in above-mentioned composition Preparation type and change in relative broad range.Generally, the concentration range of active component is 1-90%, preferably 5-60%.
If desired, other active components that can be compatible with compound of Formula I can be added into composition, such as other Insecticidal/acaricidal agent, bactericide, plant growth regulator, antibiotic, herbicide, fertilizer etc..
The compound method of several formulations is exemplified below：
The preparation of suspending agent：Active component content is 5%-35% in common prescription.Using water as medium, by active compound, disperse Agent, suspending agent and antifreeze etc. are added in sand mill, are ground, suspending agent is made.
The preparation of aqueous emulsion：Active compound, solvent and emulsifying agent are added together, make to be dissolved into homogeneous oil phase.By water, antifreeze Etc. being mixed, turn into homogeneous aqueous phase.Under high velocity agitation, aqueous phase is added to oil phase or oil phase is added to aqueous phase, formed The aqueous emulsion of favorable dispersibility.The aqueous emulsion active component content of the present invention is generally 5%-15%.To prepare emulsifiable concentrate, this hair Bright compound is dissolvable in water one or several kinds of mixed solvents, adds emulsifying agent to strengthen scattered effect of the compound in water Fruit.
The preparation of wettable powder：It is by recipe requirements, active compound, various surfactants and solid diluent etc. is fully mixed Close, after ultra-fine pulverizer disintegrating, that is, obtain the wettable powder product of predetermined content (such as 10%-40%).It is suitable to prepare In the wettable powder of sprinkling, compound of the invention can be with finely ground solid powder such as clay, inorganic silicate, carbonic acid Salt and wetting agent, adhesive and/or dispersant composition mixture.
The preparation of water-dispersible granules：Active compound and powdered solid diluents, wetting spreader-sticker and adhesive etc. are mixed Close and crush, after adding water kneading, add in the comminutor equipped with 10 to 100 eye mesh screens and be granulated, then again through drying, screening (pressing screen cloth scope).Also active compound, dispersant, disintegrant and wetting agent and solid diluent can be added in sand mill, using water as Medium milling, suspending agent is made, then carries out spray drying granulation, it is 20%-30% granular products to be typically formulated content.
Embodiment
Specific examples below is used for further illustrating the present invention, but the present invention is only limitted to absolutely not these examples.(original used Expect commercially available)
Synthetic example
Embodiment 1：The preparation of intermediate 4- (4- cyano group -2- fluorophenoxies) phenethylamine hydrochloride
(1) preparation of N-Boc-4- hydroxyphenethylamines
11.3g (0.1mol) 4- hydroxyphenethylamines are dissolved in 80ml tetrahydrofurans, sequentially add 10.08g (0.12mol) Sodium acid carbonate, 50ml water, lower dropwise addition 21.80g (0.1mol) di-tert-butyl dicarbonate is stirred at room temperature, drop finishes, and continues to react 4-10 Hour, TLC is monitored after completion of the reaction, removes solvent under reduced pressure, adds the extraction of (3 × 50ml) ethyl acetate, and organic phase is eaten with saturation Salt solution 50ml is washed, and depressurizes precipitation, and (eluant, eluent is ethyl acetate and petroleum ether (60-90 DEG C of boiling range) to residue column chromatography, volume Than for 1:4) white solid 17.15g, yield 81%, 48-49 DEG C of fusing point are separated to obtain.
(2) preparation of 4- (4- cyano group -2- fluorophenoxies) benzene ethylamino t-butyl formate
2.37g (0.01mol) N-Boc-4- hydroxyphenethylamines and 1.39g (0.01mol) 3,4- difluorophenyls are added In 50ml butanone, 2.76g (0.02mol) potassium carbonate is added, is heated to flowing back under stirring, reacted 8 hours, TLC monitoring reactions After, remove solvent under reduced pressure, add the extraction of (3 × 50ml) ethyl acetate, organic phase is washed with saturated aqueous common salt 50ml, is depressurized Precipitation, (eluant, eluent is ethyl acetate and petroleum ether (60-90 DEG C of boiling range) to residue column chromatography, volume ratio 1:5) obtain white solid Body 2.85g, yield 80%.
(3) preparation of 4- (4- cyano group -2- fluorophenoxies) phenethylamine hydrochloride
3.56g (0.01mol) 4- (4- cyano group -2- fluorophenoxies) benzene ethylamino t-butyl formate is added into 50ml acetic acid second In ester, lower dropwise addition 15ml concentrated hydrochloric acids are stirred at room temperature, solid dissolving, there are a large amount of solids to separate out after continuing stirring 4 hours, filter, filter Cake washs to obtain 2.81g white solids, yield 96%, 245-246 DEG C of fusing point with 10ml ethyl acetate.
Embodiment 2：The preparation of intermediate 4,5- dichloro-thiophenes simultaneously [2,3-d] pyrimidine
Take 2- Amino 3 cyano -4- epoxide -4,5- dihydro-thiophenes and 250ml POCl3s (POCl3) in reaction bulb, 38ml dimethylformamides (DMF) are slowly added dropwise at room temperature, are added dropwise within about 30 minutes.Room temperature reaction 1 hour, then it is warming up to 75 DEG C reaction 3 hours.After being down to room temperature, reaction solution is poured into trash ice, dark gray solid 89.1g is filtered to obtain, yield 86.9%, melts 160-161 DEG C of point.
Embodiment 3：Compound table 1-2 preparation
Take 2.05g (0.01mol) 4,5- dichloro-thiophenes simultaneously [2,3-d] pyrimidine and 2.93g (0.01mol) 4- (4- cyano group -2- Fluorophenoxy) phenethylamine hydrochloride in 50ml ethanol, is stirred at room temperature lower addition 3.03g (0.03mol) triethylamine, is heated to back Stream, react 5 hours, TLC is monitored after completion of the reaction, removes solvent under reduced pressure, adds the extraction of (3 × 50ml) ethyl acetate, organic phase Washed with saturated aqueous common salt 50ml, depressurize precipitation, (eluant, eluent is ethyl acetate and petroleum ether (boiling range 60-90 to residue column chromatography DEG C), volume ratio 1:3) white solid 3.56g, yield 83.8%, 135~136 DEG C of fusing point are obtained.
Nuclear magnetic data1H-NMR (300MHz, internal standard TMS, solvent C DCl3) as follows：δ(ppm):8.48(s,1H),7.49(d, 1H),7.38(d,1H),7.32(d,2H),7.05(s,1H),7.04(d,2H),6.92(d,1H),6.52(m,1H),3.91(m, 2H),3.02(m,2H).
Embodiment 4：The preparation of intermediate 2- (4- (5- trifluoromethyl pyridine -2- epoxides) phenyl) ethamine
(1) preparation of 2- (4- (5- (trifluoromethyl) pyridine -2- epoxides) phenyl) acetonitrile
18.15g (0.1mol) 2- chloro-5-trifluoromethylpyridines and 15.96g (0.12mol) p-hydroxybenzylcyanide are added In 200ml butanone, 27.60g (0.2mol) potassium carbonate is added, is heated to flowing back under stirring, reacted 10 hours, TLC monitoring reactions After, remove solvent under reduced pressure, add the extraction of 300ml ethyl acetate, organic phase is successively with 5% sodium hydrate aqueous solution, saturation Each 50ml of saline solution washings, depressurize precipitation, residue column chromatography (eluant, eluent is ethyl acetate and petroleum ether (60-90 DEG C of boiling range), Volume ratio is 1:5) white solid 22.50g, yield 81%, 48-49 DEG C of fusing point are obtained.
(2) preparation of 2- (4- (5- trifluoromethyl pyridine -2- epoxides) phenyl) ethamine
By 2.78g (0.01mol) 2- (4- (5- trifluoromethyl pyridine -2- epoxides) phenyl) acetonitrile, Raney nickel (1.0g), The mixture of 10ml25% ammoniacal liquor and 50ml ethanol composition is in hydrogen atmosphere, at room temperature stirring reaction 3-15 hours, TLC monitoring reactions After, Raney nickel is filtered out, solvent is removed under reduced pressure and obtains viscous liquid, white solid 2.20g is obtained after cooling, yield 78%, is melted 82-83 DEG C of point.
Embodiment 5：The preparation of the chloro- 5,6- thioxenes of intermediate 4- simultaneously [2,3-d] pyrimidine
(1) preparation of 5,6- thioxenes simultaneously [2,3-d] pyrimidine -4 (3H) -one
19.9g (0.1mol) 2- amino -4,5- thioxene -3- Ethyl formates are taken to be heated up back in 100ml formamides Stream reaction 6 hours, TLC are monitored after completion of the reaction, and reaction solution is down to room temperature, adds 100ml water, continues stirring 1 hour, filters Field gray solid 15.3g, yield 85%, 274-275 DEG C of fusing point.
(2) preparation of the chloro- 5,6- thioxenes of 4- simultaneously [2,3-d] pyrimidine
Take 1.8g (0.01mol) 5,6- thioxenes simultaneously [2,3-d] pyrimidine -4 (3H) -one in 10ml thionyl chlorides, A drop dimethylformamide (DMF) is added, temperature rising reflux is reacted 3 hours, and TLC is monitored after completion of the reaction, removes solvent under reduced pressure Obtain dark gray solid 1.8g, yield 90.6%, 112-113 DEG C of fusing point.
Embodiment 6：Compound table 20-19 preparation
Take the chloro- 5,6- thioxenes of 0.3g (1.5mmol) 4- simultaneously [2,3-d] pyrimidine and 0.42g (1.5mmol) 2- (4- (5- trifluoromethyl pyridine -2- epoxides) phenyl) in 50ml ethanol, lower addition 0.5g (5mmol) triethylamine is stirred at room temperature in ethamine, It is heated to flowing back, reacts 5 hours, TLC is monitored after completion of the reaction, removes solvent under reduced pressure, adds (3 × 50ml) ethyl acetate extraction Take, organic phase is washed with saturated aqueous common salt 50ml, depressurizes precipitation, (eluant, eluent is ethyl acetate and petroleum ether to residue column chromatography (60-90 DEG C of boiling range), volume ratio 1:3) white solid 0.33g, yield 50%, 109~110 DEG C of fusing point are obtained.
Nuclear magnetic data1H-NMR (300MHz, internal standard TMS, solvent C DCl3) as follows：δ(ppm):8.42(s,1H),8.41(s, 1H),7.89(d,1H),7.31(d,2H),7.12(d,2H),7.01(d,1H),5.44(br s,1H),3.89(m,2H),3.02 (m,2H),2.38(s,3H),2.25(s,3H)。
The preparation of other compounds of the invention can refer to above example.
Part of compounds physical data and nuclear magnetic data (1HNMR, 300MHz, internal standard TMS, solvent C DCl3) as follows：
Compound table 1-1：Clear yellow viscous.δ(ppm):8.52(s,1H),7.50(d,1H),7.38(d,1H),7.28(d, 2H),7.04(d,2H),6.94(m,1H),5.29(br s,1H),3.86(m,2H),3.00(t,2H),2.80(s,2H),2.68 (s,2H),1.86(m,4H)。
Compound table 1-23：146-147 DEG C of fusing point.δ(ppm):8.40(s,1H),7.48(d,1H),7.57(d,1H), 7.34(d,2H),7.04(s,1H),7.04(d,2H),6.98(d,1H),6.66(br s,1H),3.75(m,2H),2.95(t, 2H),2.51(s,3H)。
Compound table 2-2：109-110 DEG C of fusing point.δ(ppm):8.48(s,1H),7.32(d,1H),7.13(d,1H), 7.06(d,2H),7.04(s,1H),7.04(d,2H),6.82(d,1H),6.53(s,1H),3.86(m,2H),2.93(t,2H)。
Compound table 5-2：104-105 DEG C of fusing point.δ(ppm):8.49(s,1H),7.29(d,1H),6.98-7.09(m, 4H),6.81-6.85(m,2H),6.57(s,1H),3.91(m,2H),3.02(m,2H)。
Compound table 6-2：119-120 DEG C of fusing point.δ(ppm):8.48(s,1H),7.56(d,2H),7.30(d,2H), 7.26(s,1H),7.04(d,2H),7.01(d,2H),6.48(s,1H),3.91(m,2H),3.02(t,2H)。
Compound table 8-53：181-182 DEG C of fusing point.δ(ppm):8.47(s,1H),8.32(m,2H),7.22(d,2H), 7.04(s,1H),6.80(d,2H),6.50(s,1H),6.53(s,1H,NH),3.89(m,2H),2.98(t,2H)。
Compound table 10-2：84-85 DEG C of fusing point.δ(ppm):8.47(s,1H),7.20(d,2H),7.13(d,2H),7.03 (s,1H),6.94(d,2H),6.88(d,2H),6.52(m,1H),3.88(m,2H),2.97(t,2H),2.33(s,3H)。
Compound table 11-2：107-108 DEG C of fusing point.δ(ppm):8.47(s,1H),7.25(m,4H),7.02(s,1H), 6.96(d,2H),6.90(d,2H),6.52(s,1H),3.88(m,2H),2.98(t,2H)。
Compound table 12-2：111-112 DEG C of fusing point.δ(ppm):8.47(s,1H),7.20(d,2H),7.03(s,1H), 6.97(d,2H),6.95(d,2H),6.88(d,2H),6.53(m,1H),3.87(m,2H),3.81(s,3H),2.97(t,2H)。
Compound table 13-2：Brown oil.δ(ppm):8.47(s,1H),7.19(d,2H),7.03(s,1H,),6.94 (d,2H,Ph-2,6-H),6.92(d,2H),6.88(d,2H),6.53(m,1H),4.48(q,1H),3.87(m,2H),3.81 (s,3H),2.96(t,2H),1.33(d,6H)。
Compound table 14-2：102-103 DEG C of fusing point.δ(ppm):8.82(d,1H),8.48(s,1H),8.26(d,1H), 7.34(d,2H),7.14(d,2H),7.04(s,1H),6.92(d,1H),6.57(s,1H),4.38(q,2H),3.93(q,2H), 3.04(t,2H),1.37(t,3H)。
Compound table 14-53：154-155 DEG C of fusing point.δ(ppm):8.63(d,1H),8.48(s,1H),8.34(d,1H), 7.33(d,2H),7.12(t,2H),7.04(s,1H),6.57(s,1H),4.38(q,2H),3.93(q,2H),3.03(t,2H), 1.39(t,3H)。
Compound table 15-2：144-145 DEG C of fusing point.δ(ppm):8.48(s,1H),7.75(s,1H),7.55(d,1H), 7.31(d,2H),7.05(s,1H),7.03(d,2H),6.68(d,1H),6.56(m,1H),3.91(m,2H),3.02(t,2H)。
Compound table 16-2：124-125 DEG C of fusing point.δ(ppm):8.48(s,1H),7.85(s,1H),7.65(d,1H), 7.31(d,2H),7.05(s,1H),7.03(d,2H),6.78(d,1H),6.56(br s,1H),3.91(m,2H),3.02(t, 2H)。
Compound table 17-53：125-126 DEG C of fusing point.δ(ppm):8.48(s,1H),8.39(d,1H),8.25(d,1H), 7.35(d,2H),7.14(d,2H),7.04(s,1H),3.93(q,2H),3.04(t,2H)。
Compound table 18-73：141-142 DEG C of fusing point.δ(ppm):8.49(s,1H),7.29(d,2H),6.98-7.09(m, 4H),6.81-6.85(q,2H),6.57(s,1H),3.91(m,2H),3.02(t,2H)。
Compound table 19-1：118-119 DEG C of fusing point.δ(ppm):8.53(s,1H),8.43(s,1H),7.90(q,1H), 7.27(q,3H),7.09(d,3H),7.01(d,1H),5.58(d,1H),3.92(q,2H),3.02(t,2H)。
Compound table 19-5：Oil.δ(ppm):8.44(d,2H),7.90(d,1H),7.31(d,2H),7.12(d,2H), 7.01(d,1H),5.44(s,1H),3.92(q,2H),3.04(t,2H),2.39(s,3H)。
Compound table 19-68：Yellow oil.δ(ppm):8.48(s,1H),8.28(d,1H),8.28(d,1H),7.32 (d,2H),7.26(s,1H),7.13(d,2H),7.03(d,1H),6.57(m,1H),3.92(m,2H),3.02(t,2H)。
Compound table 20-52：144-145 DEG C of fusing point.δ(ppm):8.53(s,1H),8.26(s,1H),7.98(d,1H), 7.27(m,3H),7.12(m,3H),5.66(d,1H),3.92(q,2H),3.04(t,2H)。
Compound table 20-53：Oil.δ(ppm):8.48(s,1H),8.26(d,1H),7.98(d,1H),7.35(d,2H), 7.14(d,2H),7.04(s,1H),6.55(q,1H),3.93(q,2H),3.04(t,2H)。
Compound table 20-54：Oil.δ(ppm):8.45(s,1H),8.25(d,1H),7.98(d,1H),7.30(t,2H), 7.15(t,2H),6.78(s,1H),5.45(s,1H),3.92(q,2H),3.04(t,2H),2.38(s,3H)。
Compound table 20-56：It is sticky.δ(ppm):8.40(s,1H),8.25(d,1H),7.98(d,1H),7.31(d, 2H),7.12(d,2H),5.28(br s,1H),3.87(m,2H),3.02(t,2H),2.77(br s,2H),2.67(br s, 2H),1.85(m,4H)。
Compound table 21-53：It is sticky.δ(ppm):8.49(s,1H),8.27(m,1H),7.99(d,1H),7.35(d, 2H),7.14(d,2H),7.04(d,1H),6.56(s,1H),3.93(m,2H),3.04(t,2H)。
Compound table 22-2：108-109 DEG C of fusing point.δ(ppm):8.46(t,2H),7.91(q,1H),7.34(d,2H), 7.11(d,2H),7.02(d,2H),6.55(s,1H),3.93(q,2H),3.03(t,2H)。
Compound table 22-53：154-155 DEG C of fusing point.δ(ppm):8.48(s,1H),7.49(s,1H),7.99(s,1H), 7.36(d,2H),7.13(d,2H),7.05(s,1H),6.58(s,1H),3.93(m,2H),3.04(t,2H)。
Compound table 24-2：It is sticky.δ(ppm):8.48(s,1H),7.47(d,1H),7.32(d,2H),7.17(d,1H), 7.13(d,2H),7.03(s,1H),6.52(m,1H),3.91(m,2H),3.02(t,2H)。
Compound table 25-78：134-135 DEG C of fusing point.δ(ppm):8.48(s,1H),8.39(s,1H),7.36(d,2H), 7.13(d,2H),7.05(s,1H),6.55(m,1H),3.93(m,2H),3.05(t,2H)。
Compound table 28-53：It is sticky.δ(ppm):8.49(s,1H),7.85(s,1H),7.26(s,1H),7.12(d, 2H),7.04(s,1H),3.93(m,2H),3.04(m,2H)。
Part of compounds physical data and nuclear magnetic data (1HNMR, 300MHz, internal standard TMS, solvent DMSO) it is as follows：
Compound table 1-5：116-117 DEG C of fusing point.δ(ppm):8.24(s,1H),7.88(d,1H),7.57(d,1H), 7.34(d,2H),7.04(s,1H),7.04(d,2H),6.98(d,1H),6.66(br s,1H),3.75(m,2H),2.95(t, 2H),2.51(s,3H)。
Compound table 1-19：171-172 DEG C of fusing point.δ(ppm):8.19(s,1H),7.85(d,1H),7.57(d,1H), 7.33(d,2H),7.02(d,2H),7.01(d,1H),6.61(br s,1H),3.74(m,2H),2.95(t,2H),2.50(s, 6H)。
Compound table 5-53：168-169 DEG C of fusing point.δ(ppm):8.36(s,1H),8.05(s,2H),7.57(s,1H), 7.23(s,2H),7.18(s,1H),6.78(d,2H),3.68(m,2H),2.89(t,2H)。
Example of formulations (each component addition is weight percentage, and reactive compound folding hundred is post-dised)
Embodiment 7：30% compound table 1-2 wettable powders
Above-claimed cpd table 1-2 and other components are sufficiently mixed, after ultra-fine pulverizer disintegrating, that is, obtain 30% can WP product.
Embodiment 8：40% compound table 1-2 suspension concentrates
Compound table 1-2 and other components are sufficiently mixed, thus obtained suspension concentrates, and gained suspending agent is diluted with water can Obtain the dilution of any required concentration.
Embodiment 9：60% compound table 20-19 water-dispersible granules
By compound table 20-19 and other components co-grinding, after adding water kneading, the granulation of 10-100 eye mesh screens is added It is granulated in machine, then again through drying, screening (pressing screen cloth scope).
Biological activity determination example
The insecticidal activity assay of embodiment 10
With the compounds of this invention sample to having carried out insecticidal activity assay experiment to several insects.The method of experiment is as follows：
Testing compound acetone/methanol (1：1) after mixed solvent dissolving, with the water containing 0.1% (wt) Tween 80 It is diluted to required concentration.
Using diamondback moth, mythimna separata, black peach aphid and Tetranychus cinnabarinus as target, insecticidal activity survey is carried out using airbrush spray-on processes It is fixed.
(1) to the determination of activity of diamondback moth
Assay method：Cabbage leaves are broken into diameter 2cm leaf dish with card punch, the pressure of airbrush spraying treatments is 10psi (is roughly equal to 0.7kg/cm2), per the spraying of leaf dish positive and negative, spouting liquid 0.5ml.The first 2 age examination of often processing access 10 after drying in the shade Worm, often handle 3 repetitions.25 DEG C are put into after processing, is cultivated in the observation ward of relative humidity 60~70%, survival is investigated after 72 hours Borer population, calculate the death rate.
It is as follows to the partial test result of diamondback moth：
When liquor strength is 600ppm, to the fatal rate of diamondback moth more than 80% have compound table 1-1,1-2,1-5, 5-2,10-2,11-2,12-2,13-2,19-1,19-5,19-68,20-2,20-19,20-53,24-2 etc.；Wherein compound table 1-2,1-5,10-2,11-2,12-2,13-2,19-68,20-53,24-2 fatal rate are 100%；Control compound KC1 and KC3 is 67% and 50% to the fatal rate of diamondback moth under 600ppm.
When liquor strength is 100ppm, 11-2 is 100% to the fatal rate of diamondback moth；1-1,1-2,1-5,12-2 are to pickles The fatal rate of moth is more than 70%；Control compound KC2 is 27% to the fatal rate of diamondback moth under 100ppm.
(2) to the determination of activity of mythimna separata：
Assay method：Maize leaf is cut into long 2cm leaf section, the pressure of airbrush spraying treatments (is roughly equal to for 10psi 0.7kg/cm2), per the spraying of leaf section positive and negative, spouting liquid 0.5ml.10 first 2 age test worms of often processing access, often handle 3 after drying in the shade Secondary repetition.25 DEG C are put into after processing, is cultivated in the observation ward of relative humidity 60~70%, investigation survival borer population, is calculated after 72 hours The death rate.
It is as follows to the partial test result of mythimna separata：
When liquor strength is 600ppm, to the fatal rate of mythimna separata more than 80% have 1-1,1-2,1-5,1-19,1-23, 10-2,11-2,19-5,19-68,20-2,20-53,24-2 etc.；Wherein 1-1,1-19,11-2,20-53 fatal rate is 100%.Control compound KC1, KC2 and KC4 are respectively 14%, 0% and 29% to the fatal rate of mythimna separata under 600ppm.
(3) to the determination of activity of black peach aphid：
Assay method：Diameter 6cm culture dishes are taken, one layer of filter paper is covered at ware bottom, and appropriate running water moisturizing is added dropwise.From culture peach Clip suitable size (diameter about 3cm) and with the cabbage leaves of 15~30 aphids on the cabbage plant of aphid, removes alatae And the aphid of face of blade, blade back are placed in culture dish upwards.The pressure of airbrush spraying treatments is that 10psi (is roughly equal to 0.7kg/cm2), spouting liquid 0.5ml, 3 repetitions are often handled.25 DEG C, the observation ward of relative humidity 60~70% are put into after processing Interior culture, investigation survival borer population, calculates the death rate after 48 hours.
It is as follows to the partial test result of black peach aphid：
When liquor strength is 600ppm, to the fatal rate of black peach aphid more than 80% have 1-1,1-2,1-5,1-19,1-23, 5-2、6-2、10-2、11-2、12-2、13-2、14-2、14-53、18-73、19-1、19-5、19-68、20-2、20-19、20- 52nd, 20-53,20-54,21-53,22-2,24-2 etc.；Wherein 1-1,1-2,1-5,1-19,1-23,5-2,6-2,10-2,11-2, 12-2,13-2,14-2,19-1,19-5,19-68,20-2,20-19,20-53,21-53,22-2,24-2 fatal rate is 100%；
When liquor strength is 100ppm, to the fatal rate of black peach aphid more than 80% have 1-1,1-2,1-5,1-19,1-23, 5-2、6-2、10-2、11-2、12-2、13-2、14-2、18-73、19-1、19-5、19-68、20-2、20-19、20-52、20- 53rd, 20-54,21-53,22-2,24-2 etc.；Wherein 1-1,1-2,1-5,1-19,5-2,6-2,10-2,13-2,14-2,19-1, 19-5,19-68,20-2,20-19,20-52,20-53,20-54,24-2 fatal rate are 100%；
When liquor strength is 10ppm, to the fatal rate of black peach aphid more than 80% have 1-1,1-2,1-5,1-19,6-2, 10-2,11-2,12-2,13-2,14-2,19-1,19-5,19-68,20-2,20-19,20-52,20-54,22-2,24-2 etc.； Wherein 1-1,6-2,10-2,14-2,19-1,19-5,19-68,24-2 fatal rate are 100%.Control compound KC1, KC2 and KC3 is respectively 21%, 53% and 68% to the fatal rate of black peach aphid under 10ppm.
(4) Tetranychus cinnabarinus is determined：
Assay method：Two panels true leaf Kidney bean seedling is taken, after connecting Tetranychus cinnabarinus into mite and investigating radix, is sprayed with airbrush Device carries out whole strain processing, and pressure is that 10psi (is roughly equal to 0.7kg/cm2), spouting liquid 0.5ml.3 repetitions are often handled, after processing Standard sight room is placed in, investigation survival mite number, calculates the death rate after 72 hours.
It is as follows to the partial test result of Tetranychus cinnabarinus：
When liquor strength is 600ppm, to the fatal rate of Tetranychus cinnabarinus more than 80% have 1-1,1-2,1-5,1-23, 5-2、5-53、6-2、10-2、11-2、12-2、13-2、14-2、19-1、19-5、19-68、20-2、20-19、20-53、20-54、 20-56,21-53,22-2,24-2 etc.；Wherein 1-1,1-2,1-5,1-23,5-2,6-2,10-2,11-2,12-2,13-2,19- 1st, 19-5,19-68,20-2,20-19,20-53,21-53,22-2,24-2 fatal rate are 100%；Control compound KC2 exists It is 76% to the fatal rate of Tetranychus cinnabarinus under 600ppm.
When liquor strength is 100ppm, to the fatal rate of Tetranychus cinnabarinus more than 80% have 1-2,5-2,6-2,10-2, 11-2,12-2,13-2,19-1,19-5,19-68,20-2,20-19,20-54,22-2,24-2 etc.；Wherein 1-2,5-2,6-2, 10-2,11-2,19-1,19-5,20-19,20-54 fatal rate are 100%；
When liquor strength is 10ppm, wherein 1-2,6-2,13-2,19-1,19-5,20-19,20-54 etc. are to Tetranychus cinnabarinus Fatal rate be more than 90%.Control compound KC1, KC3 and KC4 be 42% to the fatal rate of Tetranychus cinnabarinus under 10ppm, 35% and 17%.

Claims (3)

  1. A kind of 1. substituted thienopyrimidine-4 aminated compounds with pesticide and miticide actility, it is characterised in that:Compound structure is such as Shown in formula I：
    Formulas I
    In formula：
    R1Selected from hydrogen, chlorine or methyl；
    R2Selected from hydrogen or methyl；
    R3、R4It is respectively selected from hydrogen；
    R5Selected from hydrogen, fluorine or chlorine；
    R6Selected from hydrogen；
    G1Selected from CR7；G2Selected from CR8；G3Selected from CR9；
    R7Selected from hydrogen, fluorine or chlorine；
    R8Selected from hydrogen；
    R9Selected from hydrogen, chlorine, bromine, cyano group, methyl, difluorochloromethyl, seven fluorine isopropyls,, methoxyl group or isopropoxy.
  2. 2. a kind of compound of Formula I according to claim 1 or its salt be used as preparing in agricultural, field of forestry desinsection, The purposes of acaricide medicine.
  3. A kind of 3. insecticidal and acaricidal composition, it is characterised in that：The active component of insecticidal and acaricidal composition is such as claim 1 institute State the compound of formula I, the weight percentage of active component is 0.1-99% in composition.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0459611A2 (en) * 1990-03-30 1991-12-04 Dowelanco Furopyrimidine derivatives
US20070093498A1 (en) * 2005-10-21 2007-04-26 Brewster William K Thieno-pyrimidine compounds having fungicidal activity
WO2007046809A1 (en) * 2005-10-21 2007-04-26 Dow Agrosciences Llc Thieno-pyrimidine compounds having fungicidal activity
CN101453895A (en) * 2006-05-22 2009-06-10 巴斯夫欧洲公司 Insecticidal methods using 4-amino-5-chloro-thieno[2,3-d]-pyrimidine compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0459611A2 (en) * 1990-03-30 1991-12-04 Dowelanco Furopyrimidine derivatives
US20070093498A1 (en) * 2005-10-21 2007-04-26 Brewster William K Thieno-pyrimidine compounds having fungicidal activity
WO2007046809A1 (en) * 2005-10-21 2007-04-26 Dow Agrosciences Llc Thieno-pyrimidine compounds having fungicidal activity
CN101453895A (en) * 2006-05-22 2009-06-10 巴斯夫欧洲公司 Insecticidal methods using 4-amino-5-chloro-thieno[2,3-d]-pyrimidine compounds

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