CN106083838A - A kind of 2,5 2 replacement 1,3,4 oxadiazole derivative and application thereof - Google Patents

A kind of 2,5 2 replacement 1,3,4 oxadiazole derivative and application thereof Download PDF

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CN106083838A
CN106083838A CN201610378880.5A CN201610378880A CN106083838A CN 106083838 A CN106083838 A CN 106083838A CN 201610378880 A CN201610378880 A CN 201610378880A CN 106083838 A CN106083838 A CN 106083838A
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pyrazoles
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replacement
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CN106083838B (en
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王威
宁斌科
李秉擘
王列平
张晓光
薛超
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Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms

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Abstract

The invention discloses a kind of 2,5 two replacement 1,3,4 oxadiazole derivatives, its formula is I, and in Formulas I, R represents: halogen, hydrogen, nitro, methyl, methoxyl group, trifluoromethyl；R1Represent: methyl, ethyl, hydrogen；R2Represent: trifluoromethyl, chlorine, bromine；R3Represent: halogen, hydrogen.This compounds has significant inhibitory action to mythimna separata, can be used as the effective ingredient of insecticide.

Description

A kind of 2,5-bis-replacement-1,3,4-oxadiazole derivative and application thereof
Technical field
The present invention relates to a kind of 2,5-bis-replacement-1,3,4-oxadiazole derivative and as the activity with insecticidal action Component, for field of pesticides.
Background technology
In recent decades, heterocyclic compound causes the extensive concern of pesticide worker due to its efficient biological activity, Have and much constantly be in the news out containing pyrazoles, the commercialization pesticide of pyridine heterocycle.Such as herbicide azimsulfuron (Azimsulfuron), pyrazolate (Pyrazolate) and pyrrole chlorine grass amine (Nipyraclofen) etc.；Insecticide fenpyroximate (Fenpyroximate), Rynaxypyr (Chlorantraniliprole), nitrile insect amide (Cyantraniliprole) Deng and antibacterial pyrazoles Fluoxastrobin (Pyraclostrobin) etc..Additionally, diazoles heterocyclic compound also tends to have good Good biological activity, has research widely and important application in terms of New pesticides discovery, also has many commercialization pesticide quilts Develop.Such as herbicide oxadiazon and insecticide worm ketone etc..
In view of above-mentioned background, use activity substructure splicing principle, by pyrazoles, pyridine and activity substructure 1,3,4- Diazole heterocycle effectively splices, to obtaining pesticide candidate variety or the guideization with pesticide activity particularly insecticidal activity Compound, one of focus of the most current New pesticides discovery.It should also be noted that long-term a large amount of due to existing insecticide Using, the sensitivity of pesticide is reduced by pest population so that the resistance problem that current a lot of insecticide varieties face is the most prominent Go out, and develop the insecticide variety of more novel structure, just become the important channel solving resistance problem.
Summary of the invention
The technical problem to be solved is the problem existed for prior art, it is provided that one has insecticidal activity 2,5-bis-replacement-1,3,4-oxadiazole derivative and application；This compounds can be as having active group of insecticidal action Point, for field of pesticides, and the present invention enriches 1, the kind of 3,4-diazoles insecticides, can effectively alleviate day by day Serious resistance problems.
The present invention provides one 2,5-bis-replacement-1,3,4-oxadiazole derivatives, and its general structure is as shown in I:
In Formulas I, R represents: halogen, hydrogen, nitro, methyl, methoxyl group, trifluoromethyl；R1Represent: methyl, ethyl, hydrogen；R2Table Show: trifluoromethyl, chlorine, bromine；R3Represent: halogen, hydrogen.
The syntheti c route of the 2,5-bis-replacement-1,3,4-oxadiazole derivative of the present invention is shown below:
In formula, R represents: halogen, hydrogen, nitro, methyl, methoxyl group, trifluoromethyl；R1Represent: methyl, ethyl, hydrogen；R2Table Show: trifluoromethyl, chlorine, bromine；R3Represent: halogen, hydrogen.
The 2 of the present invention, 5-bis-replacement-1, the preparation method of 3,4-oxadiazole derivatives, comprise the following steps:
(1) 3-replaces the preparation of-1-(substituted pyridines-2-base)-1H-pyrazoles-5-formyl chloride III-1
In three-necked bottle, add 3-replace at-1-(substituted pyridines-2-base)-1H-pyrazoles-5-formic acid III and drying Toluene, thionyl chloride and the DMF of reason, is to slowly warm up to 50～100 DEG C, keeps this thermotonus 3～5h, Solvent is evaporated off and remaining thionyl chloride obtains 3-and replaces-1-(substituted pyridines-2-base)-1H-pyrazoles-5-formyl chloride III-1；Its In, rate of charge is the first that 10mmol3-replaces that-1-(substituted pyridines-2-base)-1H-pyrazoles-5-formyl chloride IV addition 15mL is dried Benzene, 6mL thionyl chloride and the N,N-dimethylformamide of 0.03mL.
(2)N1The preparation of-(3-substituted pyrazolecarboxylic-5-formoxyl)-substituted benzene oxygen alkyl hydrazine IV
In three-necked bottle, add substituted benzene oxygen alkyl hydrazine II, triethylamine and dichloromethane, at 0 DEG C, be slowly added dropwise 3-take The dichloromethane solution of generation-1-(replacing-2-pyridine radicals)-1H-pyrazoles-5-formyl chloride III-1, drips and finishes, allow reactant liquor gradually rise To 40 DEG C, continue reaction 3～5h, have a large amount of solid to separate out, organic solvent is evaporated off, then washs 1～2 through saturated sodium bicarbonate water Secondary, sucking filtration after being neutrality to aqueous solution, gained solid, through ethyl alcohol recrystallization, obtains N1-(3-substituted pyrazolecarboxylic-5-formoxyl)-replacement Benzene oxyalkyl hydrazides IV；Wherein, rate of charge is the substituted benzene oxygen alkyl hydrazine II of 10mmol, add 14mmol triethylamine, 40mL dichloromethane, the 3-of 10.2mmol replace-1-(substituted pyridines-2-base)-1H-pyrazoles-5-formyl chloride III-1 and 50mL bis- Chloromethanes solution.
(3) preparation of 2,5-bis-replacement-1,3,4-diazole I
Three-necked bottle weighs N respectively1-(3-substituted pyrazolecarboxylic-5-formoxyl)-substituted benzene oxygen alkyl hydrazine IV, dichloromethane, Adding triphenylphosphine after stirring, be subsequently adding triethylamine, carbon tetrachloride or hexachlorethane, heating reflux reaction, TLC follows the tracks of reaction To reaction completely, stopped reaction.Slough solvent, obtain 2,5-bis-replacement-1,3,4-diazole I；Wherein, rate of charge is 5mmol's N1-(3-substituted pyrazolecarboxylic-5-formoxyl)-substituted benzene oxygen alkyl hydrazine IV, add 15mL dichloromethane, 10mmol triphenylphosphine, 3.5mL triethylamine and 6.0mL carbon tetrachloride or 0.01mmol hexachlorethane.
The 2 of the present invention, 5-bis-replacement-1, the application of 3,4-oxadiazole derivatives, is to utilize the indoor preliminary virulence of insecticide The method of test, according to the activity rating standard of " pesticide bioactivity evaluates SOP ", treated to mythimna separata 24 hours and 48 hours Rear inspection tries worm death condition, and calculates mortality rate, and result shows that mythimna separata is had by the part of compounds with said structure formula I There is significant inhibitory action, can be used as the effective ingredient of insecticide.
Beneficial effects of the present invention: part 2,5-bis-replacement-1,3,4-oxadiazole derivative of the present invention is to mythimna separata There is A level (A level is 100%-90%) and the insecticidal activity of B level (B level is 90%-70%), can be used as effective one-tenth of insecticide Point, and the present invention enriches 1, the kind of 3,4-diazoles insecticides, can effectively alleviate the most serious Drug resistance and ask Topic.
Detailed description of the invention
Specifically describe the preparation method of the compound of formula I of the present invention below by certain embodiments, these embodiments are only The present invention will be described rather than limits the invention.
Embodiment 1
Compound I-1::2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(2-chlorobenzene oxygen methylene Base)-1,3,4-diazole
(1) take the bromo-1-of 5.5mmol 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid III, 3mL thionyl chloride and In the three-necked bottle of the 25mL that 7mL toluene is equipped with reflux condensing tube, thermometer, it is warming up to 50～80 DEG C of reactions 4～5h, then Unnecessary thionyl chloride and toluene are evaporated off, i.e. prepare the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formyl chloride III-1, It is directly used in the next step；
(2) in 50mL round-bottomed flask, 5mmol intermediate 4-chlorobenzene oxyalkyl hydrazides II, 3mmol K are added2CO3, 20mL Dichloromethane, is stirred at room temperature the lower dropping bromo-1-of intermediate 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formyl chloride III-1, adds Finishing, TLC follows the tracks of reaction, is stirred at room temperature 0.5～3h, sucking filtration, washes, the mixed solvent recrystallization of ethanol or DMF and ethanol, obtains pure Product N1-[3-replaces-1-(replacing-2-pyridine radicals)-1H-pyrazoles-5-formoxyl]-2-chlorobenzene oxygen acethydrazide IV-1, yield 91%, Fusing point 99～101 DEG C.
(3) three-necked bottle weighs 3mmol N respectively1-[3-replaces-1-(replacing-2-pyridine radicals)-1H-pyrazoles-5-formyl Base]-2-chlorobenzene oxygen acethydrazide IV-1,10mL dichloromethane, add 6mmol triphenylphosphine after stirring, be subsequently adding 2.5mL tri-second Amine, 4mL carbon tetrachloride, heating reflux reaction, TLC follows the tracks of reaction to reaction completely, stopped reaction.Slough solvent, column chromatography (stone Oil ether: ethyl acetate=3:1) 2-[5-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles)]-5-(2-chlorobenzene oxygen is sub- Methyl)-1,3,4-diazole I-1；Yield 65%, fusing point 86～88 DEG C.
Molecular formula: C17H10BrCl2N5O2
Elementary analysis (%), value of calculation: C, 43.71；H,2.16；N,14.99；Measured value: C, 43.68；H,2.15；N, 14.98；
1H NMR(500MHz,CDCl3):δ5.20(s,2H,-CH 2 -),6.86-8.44(m,8H,4H-Pyrazole,3,4, 5H-Py, 3,4,5,6H-Ar)；
MS:m/z 464.94(M+)
Compound I-2～I-6 is all prepared according to the method that compound I-1 is similar.
Compound I-2::2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(2-chlorobenzene oxygen isopropyl Base)-1,3,4-diazole
Yield 62%, fusing point 99～101 DEG C.
Molecular formula: C18H12BrCl2N5O2
Elementary analysis (%), value of calculation: C, 44.93；H,2.51；N,14.56；Measured value: C, 44.94；H,2.54；N, 14.52；
1H NMR(500MHz,CDCl3): δ 1.51 (d, 3H, J=6.5Hz, CH-CH 3 ), 4.93 (q, 1H, J=6.5Hz, CH-CH3),6.85-8.44(m,8H,4H-Pyrazole,3,4,5H-Py,3,4,5,6H-Ar)；
MS:m/z 478.96(M+)
Compound I-3::2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(3-chlorobenzene oxygen methylene Base)-1,3,4-diazole
Yield 59%, fusing point 109～111 DEG C；
Molecular formula: C17H10BrCl2N5O2；
Elementary analysis (%), value of calculation: C, 43.71；H,2.16；N,14.99；Measured value: C, 43.76；H,2.19；N, 14.97；
1H NMR(500MHz,CDCl3):δ5.20(s,2H,-CH 2 -),6.86-8.44(m,8H,4H-Pyrazole,3,4, 5H-Py, 2,4,5,6H-Ar)；
MS:m/z 464.94(M+)
Compound I-4::2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(3-chlorobenzene oxygen isopropyl Base)-1,3,4-diazole
Yield 54%, fusing point 101～103 DEG C；
Molecular formula: C18H12BrCl2N5O2；
Elementary analysis (%), value of calculation: C, 44.93；H,2.51；N,14.56；Measured value: C, 44.89；H,2.51；N, 14.53；
1H NMR(500MHz,CDCl3): δ 1.48 (d, 3H, J=3.25Hz, CH-CH 3 ), 4.87 (q, 1H, J=3.25Hz, CH-CH3),6.91-8.52(m,8H,4H-Pyrazole,3,4,5H-Py,2,4,5,6H-Ar),10.35(1H),10.78(1H)；
MS:m/z 478.96(M+)
Compound I-5:2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(4-chlorobenzene Oxymethylene)- 1,3,4-diazole
Yield 57%, fusing point 119～121 DEG C.
Molecular formula: C17H10BrCl2N5O2；
Elementary analysis (%), value of calculation: C, 43.71；H,2.16；N,14.99；Measured value: C, 43.73；H,2.14；N, 14.97；
1H NMR(500MHz,CDCl3):δ5.20(s,2H,-CH2-), 6.88 (d, 2H, J=9.0Hz,2and 6H- Phenyl),7.12(s,1H,4H-Pyrazole), 7.25 (d, 2H, J=9.0Hz,3and 5H-Phenyl),7.44(1H),7.90 (1H),8.44(1H)；
13C NMR(125MHz,CDCl3):δ59.87,112.49,116.17,126.58,127.30,128.27, 128.87,129.14,129.64,129.89,130.45,132.15,139.31,147.11,155.72,162.11；
MS:m/z 464.94(M+)
Compound I-6:2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(4-chlorobenzene oxygen isopropyl)- 1,3,4-diazole
Yield 60%, fusing point 106～108 DEG C；
Molecular formula: C18H12BrCl2N5O2；
Elementary analysis (%), value of calculation: C, 44.93；H,2.51；N,14.56；Measured value: C, 44.90；H,2.55；N, 14.61；
1H NMR(500MHz,CDCl3): δ 1.43 (d, 3H, J=6.5Hz, CH-CH 3 ), 4.82 (q, 1H, J=7.0Hz, CH-CH3), 6.88 (d, 2H, J=9.0Hz,2 and 6H-Phenyl),7.12(s,1H,4H-Pyrazole), 7.25 (d, 2H, J= 4.5Hz,3 and5H-Phenyl),7.44(1H),7.90(1H),8.44(1H)；
MS:m/z 478.96(M+)
Embodiment 2
Compound I-7:2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(2,4 dichloro benzene oxygen methylene Base)-1,3,4-diazole
(1) take the bromo-1-of 5.5mmol 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formic acid III, 3mL thionyl chloride and In the three-necked bottle of the 25mL that 7mL toluene is equipped with reflux condensing tube, thermometer, it is warming up to 50～80 DEG C of reactions 4～5h, then Remaining thionyl chloride and toluene are evaporated off, i.e. prepare the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formyl chloride III-1, It is directly used in the next step；
(2) in 50mL round-bottomed flask, 5mmol intermediate 2,4-Dichlorophenoxy alkyl hydrazine II, 3mmol K are added2CO3, 20mL dichloromethane, is stirred at room temperature the lower dropping bromo-1-of intermediate 3-(3-chloropyridine-2-base)-1H-pyrazoles-5-formyl chloride III- 1, finish, TLC follows the tracks of reaction, is stirred at room temperature 0.5～3h, sucking filtration, washing, the mixed solvent recrystallization of ethanol or DMF and ethanol, Obtain sterling N1-[3-replaces-1-(replacing-2-pyridine radicals)-1H-pyrazoles-5-formoxyl]-2,4-Dichlorophenoxy acethydrazide IV-7, Yield 92%, fusing point 118～120 DEG C.
(3) three-necked bottle weighs 3mmol N respectively1-[3-replaces-1-(replacing-2-pyridine radicals)-1H-pyrazoles-5-formyl Base]-2,4-Dichlorophenoxy acethydrazide IV-7,10mL dichloromethane, add 6mmol triphenylphosphine after stirring, be subsequently adding 2.5mL Triethylamine, or 0.005mmol hexachlorethane, heating reflux reaction, TLC follows the tracks of reaction to reaction completely, stopped reaction.Slough molten Agent, column chromatography (petroleum ether: ethyl acetate=3:1) 2-[5-(the bromo-1-of 3-(3-chloropyridine-2-base)-1H-pyrazoles)]- 5-(2-chlorobenzene Oxymethylene)-1,3,4-diazole I-1；Yield 71%, fusing point 116～118 DEG C.
Molecular formula: C17H9BrCl3N5O2
Elementary analysis (%), value of calculation: C, 40.71；H,1.81；N,13.96；Measured value: C, 40.72；H,1.80；N, 13.99；
1H NMR(500MHz,CDCl3):δ5.27(s,2H,-CH2-), 6.96 (d, 1H, J=4.5Hz,6H-Phenyl), 7.14(s,1H,4H-Pyrazole), 7.16～7.18 (q, 1H), 7.39 (d, 1H), 7.43～7.46 (q, 1H), 8.43～ 8.45(q,1H)；
13C NMR(125MHz,CDCl3):δ61.04,112.63,115.69,124.68,126.59,127.91, 128.19,128.94,129.32,129.81,130.56,139.64,147.22,137.78,151.78,156.68,161.63；
MS:m/z 498.9(M+)
Compound I-8～I-14 is all prepared according to the method that compound I-7 is similar.
Compound I-8:2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(2,4 dichloro benzene oxygen isopropyl Base)-1,3,4-diazole
Yield 65%, fusing point 110～112 DEG C.
Molecular formula: C18H11BrCl3N5O2
Elementary analysis (%), value of calculation: C, 41.93；H,2.15；N,13.58；Measured value: C, 41.96；H,2.20；N, 13.62；
1H NMR(500MHz,CDCl3): δ 1.45 (d, 3H, J=6.5Hz, CH-CH 3 ), 4.86 (q, 1H, J=7.0Hz, CH-CH3), 6.96 (d, 1H, J=9.0Hz,6H-Phenyl),7.14(s,1H,4H-Pyrazole), 7.16～7.18 (q, 1H), 7.39 (d, 1H), 7.43～7.46 (q, 1H), 8.43～8.45 (q, 1H)；
MS:m/z 512.92(M+)
Compound I-9:2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(2-fluorobenzene Oxymethylene)- 1,3,4-diazole
Yield 59%, fusing point 89～91 DEG C；
Molecular formula: C17H10BrClFN5O2；
Elementary analysis (%), value of calculation: C, 45.31；H,2.24；N,15.54；Measured value: C, 45.33；H,2.27；N, 15.51；
1H NMR(500MHz,CDCl3):δ4.72(s,2H,-CH 2 -),6.95-8.52(m,8H,4H-Pyrazole,3,4, 5H-Py, 3,4,5,6H-Ar)；
MS:m/z 448.97(M+)
Compound I-10:2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(2-fluorobenzene oxygen isopropyl Base)-1,3,4-diazole
Yield 59%, fusing point 100～102 DEG C；
Molecular formula: C18H12BrClFN5O2；
Elementary analysis (%), value of calculation: C, 46.53；H,2.60；N,15.07；Measured value: C, 46.52；H,2.61；N, 15.11；
1H NMR(500MHz,CDCl3): δ 1.46 (d, 3H, J=6.5Hz, CH-CH 3 ), 4.83 (q, 1H, J=6.5Hz, CH-CH3),6.95-8.52(m,8H,4H-Pyrazole,3,4,5H-Py,3,4,5,6H-Ar)；
MS:m/z 462.98(M+)
Compound I-11:2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(4-fluorobenzene oxygen methylene Base)-1,3,4-diazole
Yield 68%, fusing point 91～93 DEG C；
Molecular formula: C17H10BrClFN5O2；
Elementary analysis (%), value of calculation: C, 45.31；H,2.24；N,15.54；Measured value: C, 45.29；H,2.20；N, 15.51；
1H NMR(500MHz,CDCl3):δ4.58(s,2H,-CH 2 -),6.97-8.52(m,8H,4H-Pyrazole,3,4, 5H-Py, 2,3,5,6H-Ar)；
MS:m/z 448.97(M+)
Compound I-12:2-[5-(the bromo-1-of 3-(3-chloro-pyridine-2-base)-1H-pyrazoles)]-5-(4-fluorobenzene oxygen isopropyl Base)-1,3,4-diazole
Yield 81%, fusing point 97～99 DEG C；
Molecular formula: C18H12BrClFN5O2；
Elementary analysis (%), value of calculation: C, 46.53；H,2.60；N,15.07；Measured value: C, 46.55；H,2.61；N, 15.09；
1H NMR(500MHz,CDCl3): δ 1.43 (d, 3H, J=6.5Hz, CH-CH 3 ), 4.78 (q, 1H, J=6.5Hz, CH-CH3),6.94-8.52(m,8H,4H-Pyrazole,3,4,5H-Py,2,3,5,6H-Ar)；
MS:m/z 462.98(M+)
Compound I-13:2-[5-(3-Trifluoromethyl-1-(pyridine-2-base)-1H-pyrazoles)]-5-(4-chlorobenzene oxygen methylene Base)-1,3,4-diazole
Yield 72%, fusing point 118～120 DEG C；
Molecular formula: C18H11ClF3N5O2；
Elementary analysis (%), value of calculation: C, 51.26；H,2.63；N,16.61；Measured value: C, 51.23；H,2.64；N, 16.62；
1H NMR(500MHz,CDCl3):δ4.52(s,2H,-CH 2 -),6.98-8.52(m,8H,4H-Pyrazole,3,4, 5H-Py, 2,3,5,6H-Ar)；
MS:m/z 421.06(M+)
Compound I-14:2-[5-(the bromo-1-of 3-(pyridine-2-base)-1H-pyrazoles)]-5-(4-chlorobenzene Oxymethylene)-1,3, 4-diazole
Yield 78%, fusing point 103～105 DEG C；
Molecular formula: C17H11BrClN5O2；
Elementary analysis (%), value of calculation: C, 47.19；H,2.56；N,16.19；Measured value: C, 47.16；H,2.61；N, 16.21；
1H NMR(500MHz,CDCl3):δ4.62(s,2H,-CH 2 -),6.98-8.52(m,8H,4H-Pyrazole,3,4, 5H-Py, 2,3,5,6H-Ar)；
MS:m/z 430.98(M+)
The 2,5-bis-replacement-1,3,4-oxadiazole derivative insecticidal activity experiment of the present invention:
(1) for examination target and condition of culture:
Mythimna separata is placed in culture dish in indoor process, in temperature 22 ± 3 DEG C, humidity 60～80% insectary put Put.
(2) instrument and equipment and experimental concentration:
Electronic balance (sensibility reciprocal ten thousand/), 100ml beaker, graduated cylinder, culture dish, para film, sponge, filter paper, pipet, Tweezers, brush pen etc..
Former medicine: weigh aequum with ten thousand/electronic balance；Solvent: DMF, 0.2%；Emulsifying agent: tween 80, 0.2%；Add clear water and be diluted to desired concn.
Experimental concentration:
It is standby that load poison leaf dish method uses sample accurately to prepare 5% test sample acetone soln.
It is standby that nebulization uses sample accurately to prepare 500mg/L.
(3) test method and activity rating:
With reference to " pesticide bioactivity evaluates SOP ".
Dip method: choose the examination worm that Individual Size is basically identical, healthy, often process 4 times and repeat, often repeat 10 cephalonts.Will Leaching worm cage leaching equipped with examination worm is into the liquid, through taking-up in 5 seconds with absorbent paper absorption polypide surface and around medicinal liquid, and set Corresponding organic solvent without medicament processes as comparison.
Carry poison leaf dish method: use and carry poison leaf dish method.I.e. with 0.01%Tritonix 100 aqueous solution, medicament to be measured is diluted 5 Individual concentration, breaks into disk by the card punch of cabbage leaves diameter 1cm, drops on blade with 1 μ L micro intravenous drip device point respectively, viscous Worm use 1% acetone soln to treat solvent volatilization is dry, put in 24 orifice plates, 1, every hole, access 3 instar larvae 1.Often process 10 Examination worm, 4 repetitions, compare drop equivalent acetone treatment blade, be placed in moisturizing under the temperature conditions of 25 DEG C and cultivate, after 24h, 48h Check each process death toll, calculate corrected mortality.
The insecticidal activity data of table 1 compound I-1～I-14
24h and 48h mortality levels in table: A level is 100%-90%；
B level is 90%-70%；C level is 70%-50%；D level is 50%-0%；
aNT represents and does not tests.

Claims (2)

1. one kind 2,5-bis-replacement-1,3,4-oxadiazole derivatives, it is characterized in that there is the structural formula represented by formula I:
In Formulas I, R represents: halogen, hydrogen, nitro, methyl, methoxyl group, trifluoromethyl；R1Represent: methyl, ethyl, hydrogen；R2Represent: Trifluoromethyl, chlorine, bromine；R3Represent: halogen, hydrogen.
2. 2 described in claim 1,5-bis-replacement-1, the application of 3,4-oxadiazole derivatives, it is characterized in that having as to mythimna separata There is significant inhibitory action, can be used as the effective ingredient of insecticide.
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