Preparation and Application of Difluoroalkene Oxime Ether Derivatives

Abstract

The present invention relates to the preparation and application of difluoroalkene oxime ether derivatives. The general structural formula of the difluoroalkene oxime ether derivatives is shown in formula (I):. It has been found through research that the difluoroalkene oxime ether derivatives disclosed in the present invention have good biological activities against common and severely harmful agricultural pests / mites such as Plutella xylostella, Ostrinia furnacalis, Spodoptera frugiperda, and Tetranychus cinnabarinus. Therefore, they can be used as insecticidal / acaricidal candidate substances for the development of new, highly efficient, low-toxic, and environmentally friendly insecticides.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and relates to the application of difluoroalkene oxime ether derivatives in the preparation of novel and highly effective insecticides / acaricides. Background Art

[0002] Oxime ether derivatives are an important class of active compounds in pesticide applications. There have been numerous reports on oxime ether active compounds both at home and abroad, and many commercial products have also emerged. For example, fenpyroximate is an insecticide / acaricide that acts on NADH - coenzyme Q reductase and is mainly used for controlling diamondback moths, rice planthoppers, and various mites. Since oxime ether compounds have good insecticidal (Chin.J.Org.Chem.2017,37,3155), acaricidal (Pesticides,2005,43,196 - 200), bactericidal (Chin.J.Org.Chem.2017,37,1537), herbicidal (Chem.Res.Chin.Univ.2016,32,195) and other biological activities, and most of them have the advantages of high efficiency, low toxicity, and low residue, the oxime ether structure is still an effective active group often selected in the current creation of new pesticides.

[0003] Fluorine atoms have the strongest electronegativity and unique electronic and steric hindrance effects. Fluorine - containing compounds often show characteristics and laws different from those of conventional compounds, so they have unique academic research value. In recent years, more than 50% of the newly developed pesticide molecules contain at least one fluorine atom. Fluorine - containing pesticides have become the theme of current new pesticide creation.

[0004] Due to the special structure of difluoroalkene oxime ether, it has unique value in agrochemistry. For example, in antiviral, insecticidal, and herbicidal aspects. At the same time, these compounds usually have the characteristics of high efficiency, low toxicity, and easy degradation in the environment. Therefore, in the research and development of pesticides, compounds containing the difluoroalkene oxime ether structure play an increasingly important role. Summary of the Invention

[0005] The purpose of the present invention is to provide the preparation and application of difluoroalkene oxime ether derivatives with high insecticidal activity.

[0006] To this end, the chemical structural general formula of the difluoroalkene oxime ether derivatives provided by the present invention is shown as formula (I):

[0007]

[0008] In formula (I): R 1 independently selects from methyl, phenyl, benzyl, pyridyl, pyrazolyl, pyrrolyl, furyl, thiazolyl, benzopyrrolyl, pyridazine, pyrimidine, pyrazine, - CN, - NO 2 , - CH2 CN, -CH 2 CH 2 CN,

[0009] R 2 independently selected from methylphenyl, benzyl, pyridyl, pyrazolyl, pyrrolyl, furyl, thiazolyl, benzopyrrolyl, pyridazine, pyrimidine, pyrazine, -CN, -NO 2 , -CH 2 CN, -CH 2 CH 2 CN,

[0010] R 3 independently selected from one or more of methyl, ethyl, n-butyl, sec-butyl, isobutyl, 3,5-dichlorophenyl, 3,5-dichlorobenzyl, 4-chloropyridyl.

[0011] The preparation route of the difluoroalkene oxime ether derivatives described in the present invention is as follows:

[0012]

[0013] Optionally, the reaction in step (1) is carried out in ethanol (EtOH) and water (H 2 O), while hydroxylamine hydrochloride and sodium acetate are added, and the reaction temperature is 80 °C.

[0014] Optionally, the ketone compound is selected from one of 4-bromoacetophenone, 4-iodoacetophenone, 2,6-difluoroacetophenone, 2-bromo,4-fluoroacetophenone, 3-trifluoromethylacetophenone, 3-methyl-4-fluorophenone, 3-methyl-4-(1,2,4-triazole)acetophenone, 2-furyl methyl ketone, 2-naphthyl methyl ketone, 3,4-(methylenedioxy)acetophenone, 2-acetyl-1-methylpyrrole, 3-phenoxyacetophenone, 2-thienyl methyl ketone.

[0015] Optionally, the reaction in step (2) is carried out in anhydrous N,N-dimethylformamide (DMF), while cesium carbonate is added, and there is nitrogen protection, and the reaction temperature is 90 °C.

[0016] Optionally, the compound described in step (2) is 1,3-dichloro-5-(1-trifluoromethyl-vinyl)benzene.

[0017] The application of difluoroalkene oxime ether derivatives of the present invention in the preparation of insecticides. And the application of difluoroalkene oxime ether derivatives of the present invention in the preparation of acaricides. The pests include Lepidoptera pests common in agriculture, such as common diamondback moths, fall armyworms, corn borers, etc. The mites refer to mites common in agriculture, such as Tetranychus cinnabarinus, Tetranychus urticae, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 . 1H NMR spectrum of compound 8

[0019] Figure 2 . 1H NMR spectrum of compound 9 DETAILED DESCRIPTION OF THE INVENTION

[0020] Unless otherwise specified, the terms in this article are understood according to the understanding of those of ordinary skill in the relevant art.

[0021] The present invention will be further described in detail below with reference to the drawings and examples.

[0022] In view of the good application value of difluoroalkene oxime ether derivatives, the applicant prepared difluoroalkene oxime ether derivatives and conducted research on insecticidal / acaricidal activities; the results showed that the difluoroalkene oxime ether derivatives had significant insecticidal / acaricidal activities and could be used to prepare insecticides / acaricides. According to the literature search conducted by the applicant, there has been no literature report so far.

[0023] The following are specific examples given by the inventor.

[0024] Example 1: Difluoroalkene oxime ether derivatives Compounds 1-13

[0025] I. Products: Difluoroalkene oxime ether derivatives 1-13 (see Table 1, and the physical and chemical properties of each compound are detailed below)

[0026] Table 1. Substituents and compound structural formulas corresponding to difluoroalkene oxime ether derivatives 1-13 prepared in the present invention

[0027]

[0028]

[0029]

[0030] II. Preparation method of difluoroalkene oxime ether derivatives:

[0031] First, add ketone compounds with different substituents (1.0 eq) dissolved in 75% EtOH aqueous solution to a 25 mL reaction tube, and then add NH 2 OH·HCl (1.6 eq) and CH 3COONa (2.0 eq), react at 80 °C, monitor the completion of the reaction by TLC. After the reaction temperature drops to room temperature, add water until no more precipitation occurs. Filter by suction, wash the filter cake with water, dry it, and perform recrystallization to obtain the oxime compound. Then, dissolve the purified ketoxime (1.0 eq), 1,3-dichloro-5-(1-trifluoromethylvinyl)benzene (1.5 eq), and Cs 2 CO 3 (1.5 eq) in DMF (2.0 mL), react at 90 °C for 12 h under a nitrogen atmosphere. Then, cool the mixture to room temperature, add saturated brine (15 mL), and extract with ethyl acetate (EtOAc) (30 mL × 3). Combine the organic phases, dry over anhydrous Na 2 SO 4 , filter, concentrate under vacuum, and separate by column chromatography to obtain Compounds 1 - 13.

[0032] The reaction general formula is as follows:

[0033]

[0034] Compound 1: (E)-1-(4-bromophenyl)ethan-1-one - O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl)oxime

[0035] The physicochemical properties of this compound are as follows:

[0036] Colorless oil; yield 68%; Structural characterization of this compound: 1 H NMR (600 MHz, CDCl 3 ) δ 7.53 (q, J = 8.7 Hz, 4H), 7.38 (d, J = 1.4 Hz, 2H), 7.35 (s, 1H), 6.05 (s, 1H), 5.77 (s, 1H), 2.24 (s, 3H). HRMS (ESI) calcd for C 17 H 13 BrCl 2 F 2 NO[M + H + + : 433.9520, found 433.9517.

[0037] Compound 2: (E)-1-(4-iodophenyl)ethan-1-one O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl)oxime

[0038] The physicochemical properties of this compound are as follows:

[0039] Colorless oil; yield 70%; Structural characterization of this compound: 1 H NMR (600 MHz, CDCl​3 ) δ 7.73 (d, J = 8.5 Hz, 2H), 7.39 (dd, J = 9.1, 4.9 Hz, 4H), 7.34 (s, 1H), 6.05 (s, 1H), 5.77 (s, 1H), 2.23 (s, 3H). HRMS(ESI) calcd for C 17 H 13 ICl 2 F 2 NO[M + H + + : 481.9381, found 481.9374.

[0040] Compound 3: (E)-1-(2,6-difluorophenyl)ethan-1-one O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl)oxime

[0041] The physicochemical properties of this compound are as follows:

[0042] Colorless oil; yield 72%; Structure characterization of this compound: 1 H NMR (600 MHz, CDCl 3 ) δ 7.38 (s, 2H), 7.37–7.31 (m, 2H), 6.94 (t, J = 8.0 Hz, 2H), 6.05 (s, 1H), 5.75 (s, 1H), 2.22 (s, 3H). HRMS(ESI) calcd for C 17 H 11 Cl 2 F 4 NO[M + H + + : 392.0226, found 392.0224.

[0043] Compound 4: (E)-1-(2-bromo-4-fluorophenyl)ethan-1-one O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl)oxime

[0044] The physicochemical properties of this compound are as follows:

[0045] Colorless oil; yield 70%; Structure characterization of this compound: 1 H NMR (600 MHz, CDCl 3 ) δ 7.39 (s, 2H), 7.35 (d, J = 12.5 Hz, 2H), 7.29–7.26 (m, 1H), 7.06 (t, J = 8.2 Hz, 1H), 6.05 (s, 1H), 5.76 (s, 1H), 2.23 (s, 3H). HRMS(ESI) calcd for C​​17 H 11 Cl 2 F 3 NOBr[M+H + + : 451.9425, found 451.9421.

[0046] Compound 5: (E)-1-(3-trifluoromethyl)phenyl ethan-1-one O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl) oxime

[0047] The physicochemical properties of this compound are as follows:

[0048] Colorless oil; yield is 78%; Structure characterization of this compound: 1 H NMR(600MHz, CDCl 3 ) δ 7.92–7.84(m, 2H), 7.69(d, J = 7.7Hz, 1H), 7.53(t, J = 7.8Hz, 1H), 7.39(s, 2H), 7.35(s, 1H), 6.07(s, 1H), 5.79(s, 1H), 2.30(s, 3H). HRMS(ESI) calcd for C 18 H 12 Cl 2 F 5 NO[M+H + + : 424.0288, found 424.0281

[0049] Compound 6: 1-(4-fluoro-3-methylphenyl) ethan-1-one O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl) oxime

[0050] The physicochemical properties of this compound are as follows:

[0051] Colorless oil; yield is 80%; Structure characterization of this compound: 1 H NMR(600MHz, CDCl 3 ) δ 7.52(d, J = 7.2Hz, 1H), 7.45(s, 1H), 7.39(s, 2H), 7.35(d, J = 1.4Hz, 1H), 7.01(t, J = 8.9Hz, 1H), 6.06(s, 1H), 5.77(s, 1H), 2.30(s, 3H), 2.24(s, 3H). HRMS(ESI) calcd for C 18 H 15 Cl 2 F 3 NO[M+H + ​​​+ : 388.0477, found 388.0472.

[0052] Compound 7: (E)-1-(3-methyl-4-(1H-1,2,4-triazol-2-yl)phenyl)but-1-en-1-yl O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl)oxime

[0053] The physical and chemical properties of this compound are as follows: yellow solid; yield is 73%; structural characterization of this compound: 1 H NMR (600 MHz, CDCl 3 ) δ 9.12 (s, 1H), 8.37 (s, 1H), 7.55 (d, J = 7.2 Hz, 1H), 7.43 (s, 1H), 7.37 (s, 2H), 7.33 (d, J = 1.4 Hz, 1H), 7.01 (t, J = 8.9 Hz, 1H), 6.05 (s, 1H), 5.76 (s, 1H), 2.30 (s, 3H), 2.24 (s, 3H). HRMS (ESI) calcd for C 20 H 16 Cl 2 F 2 N 4 O[M + H + + : 437.0742, found 437.0730.

[0054] Compound 8: (E)-1-(furan-2-yl)ethan-1-yl O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl)oxime

[0055] The physical and chemical properties of this compound are as follows:

[0056] Yellow solid; yield is 82%; structural characterization of this compound: 1 H NMR (600 MHz, CDCl 3 ) δ 7.52 (s, 1H), 7.39 (d, J = 1.3 Hz, 2H), 7.34 (d, J = 1.6 Hz, 1H), 6.82 (d, J = 3.3 Hz, 1H), 6.47 (dd, J = 3.2, 1.7 Hz, 1H), 6.06 (s, 1H), 5.77 (s, 1H), 2.19 (s, 3H). HRMS (ESI) calcd for C 15 H 11 Cl 2 F 2 NO 2 [M + H + + ​​: 346.0207, found 346.0211.

[0057] Compound 9: (E)-1-(naphthalen-2-yl)ethan-1-one O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl)oxime

[0058] The physicochemical properties of this compound are as follows:

[0059] Yellow solid; yield is 76%; Structure characterization of this compound: 1 H NMR (600 MHz, cdcl 3 ) δ 8.07 (s, 1H), 7.88 (d, J = 8.0 Hz, 2H), 7.84 (d, J = 7.1 Hz, 2H), 7.56–7.49 (m, 2H), 7.43 (s, 2H), 7.36 (s, 1H), 6.09 (s, 1H), 5.80 (s, 1H), 2.39 (s, 3H). HRMS (ESI) calcd for C 21 H 15 Cl 2 F 2 NO[M + H + + : 406.0571, found 406.0563.

[0060] Compound 10: (E)-1-(benzo[d][1,3]dioxol-5-yl)ethyl-1-1-O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl)oxime

[0061] The physicochemical properties of this compound are as follows:

[0062] White solid; yield is 83%; Structure characterization of this compound: 1 H NMR (600 MHz, cdcl 3 ) δ 7.39 (s, 2H), 7.34 (s, 1H), 7.22 (s, 1H), 7.15 (d, J = 8.1 Hz, 1H), 6.81 (d, J = 8.1 Hz, 1H), 6.05 (s, 1H), 5.99 (s, 2H), 5.76 (s, 1H), 2.22 (s, 3H). HRMS (ESI) calcd for C 18 H 13 Cl 2 F 2 NO 3 [M + H + + : 400.0313, found 400.0311.

[0063] ​​Compound 11: (E)-1-(1-methyl-1H-pyrrol-2-yl)-1-O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl) oxime

[0064] The physical and chemical properties of this compound are as follows:

[0065] Yellow solid; yield is 73%; structural characterization of this compound: 1 H NMR (600 MHz, CDCl 3 ) δ 7.38 (d, J = 1.4 Hz, 2H), 7.33 (s, 1H), 7.14 (d, J = 6.4 Hz, 1H), 6.62 (d, J = 8.6 Hz, 1H), 6.20 (m, 1H), 6.04 (s, 1H), 5.77 (s, 1H), 2.24 (s, 3H). HRMS (ESI) calcd for C 16 H 16 Cl 2 F 2 N 2 O[M + H + + : 359.0524, found 359.0522.

[0066] Compound 12: (E)-1-(4-phenoxy)-1-O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl) oxime

[0067] The physical and chemical properties of this compound are as follows:

[0068] Colorless liquid; yield is 72%; structural characterization of this compound: 1 H NMR (600 MHz, CDCl 3 ) δ 7.87 (d, J = 8.8 Hz, 2H), 7.49 (s, 1H), 7.42 (d, J = 6.4 Hz, 2H), 7.12 - 7.01 (m, 7H), 6.04 (s, 1H), 5.75 (s, 1H), 2.24 (s, 3H). HRMS (ESI) calcd for C 23 H 18 Cl 2 F 2 NO 2 [M + H + + : 448.0677, found 448.0673.

[0069] Compound 13: (E)-1-(thiophen-2-yl)-1-O-(2-(3,5-dichlorophenyl)-1,1-difluoroallyl) oxime

[0070] ​​Colorless liquid; yield: 58%; structural characterization of the compound: 1 H NMR(600MHz,CDCl 3 )δ7.52(m,3H),7.22(d,J=7.4Hz,2H),7.12(t,J=8.9Hz,1H),6.01(s,1H),5.73(s,1H),2.24(s,3H).HRMS(ESI)calcd for C 23 H 19 Cl 2 F 2 NO 2 [M+H + + :361.9979,found361.9972.

[0071] The second technical problem to be solved by the present invention is to provide the use of the above compound in the preparation of agricultural insecticides.

[0072] Activity test example 1: Determination of the activity of the target compound against Plutella xylostella indoors.

[0073] The leaf-dipping method was adopted: The target compound was dissolved in DMSO. The test insects were the 2nd instar larvae of Plutella xylostella, which were a normal population reared indoors. The cabbage leaves were dipped into the prepared solution with forceps for 10 - 15 seconds, taken out and air-dried naturally. After the liquid medicine was dry, they were put into a petri dish with a diameter of 10 cm lined with filter paper, and 20 2nd instar larvae of Plutella xylostella were introduced into each dish. Then the lid was covered, and it was placed in an incubator at a temperature of 26 °C and a relative humidity of 75%. After 48 hours, the test results were observed, and three parallels were set for each liquid medicine.

[0074] After 48 hours, the death situation of Plutella xylostella in the experimental group and the control group was observed and counted. Gently touching the insect body with a brush, no obvious reaction was regarded as death.

[0075] According to the following formula, the mortality rate (%) and corrected mortality rate (%) of the test insects after 48 h were calculated.

[0076]

[0077] Activity test example 2: Determination of the activity of the target compound against Ostrinia furnacalis indoors.

[0078] ​Using the artificial diet mixed with poison method: Dissolve the target compound in DMSO to obtain a liquid medicine with a concentration of 1 mg / mL for later use. Take 2 mL of the liquid medicine and add it to the prepared 18 g of feed, stir well, pour it into a sterilized petri dish, and use a knife to cut the middle of the feed in a "well" shape. Pick up the square feed formed in the center of the feed to facilitate the feeding and inhabitation of the corn borer larvae. Select 3rd instar larvae of the same size and introduce them into the "well", with 20 larvae in each dish. The control is to add an equal amount of solvent to the feed. Repeat 3 times. Seal it with plastic wrap and place it in an incubator at a temperature of 26 °C and a relative humidity of 75%. Check the number of dead and live insects after 48 h and 72 h respectively (touch the insect body with the tip of a writing brush, and those that do not move are dead). Calculate the mortality rate (%) and corrected mortality rate (%) of the test insects at 48 h according to the following formula.

[0079]

[0080]

[0081] Activity test example 3: Determination of the activity of the target compound against Spodoptera frugiperda indoors.

[0082] Using the artificial diet mixed with poison method: Dissolve the target compound in DMSO to obtain a liquid medicine with a concentration of 1 mg / mL for later use. Take 2 mL of the liquid medicine and add it to the prepared 18 g of feed, stir well, and evenly add it to a sterilized 24-well plate, with one insect in each well. 12 insects are used as one treatment, and each treatment is repeated 3 times. The control is to add an equal amount of solvent to the feed. Seal it with plastic wrap and place it in an incubator at a temperature of 26 °C and a relative humidity of 75%. Check the number of live insects after 48 h (touch the insect body with the tip of a writing brush, and those that do not move are dead). Calculate the mortality rate (%) and corrected mortality rate (%) of the test insects at 48 h according to the following formula.

[0083]

[0084] Activity test example 4: Determination of the activity of the target compound against Tetranychus cinnabarinus indoors.

[0085] The slide immersion method was adopted: 2 mg of the test compound was weighed, dissolved with 200 μL acetone, and then fixed to 4 mL with 1‰ Tween 80, that is, a 500 μg / mL solution was prepared for standby use. A 1 cm wide double-sided tape was attached to one end of the slide, and healthy and active female adult mites of the same age of cinnabarinus spider mites were selected with a No. 0 brush, and their backs were carefully and neatly attached to the double-sided tape. About 30 mites were attached to each slide, arranged in 2 rows, and the slide with the test mites was placed on an iron plate with a moist sponge, and the iron plate was placed in a light incubator under the conditions of 26±1℃, relative humidity of 60% to 80%, and light L:D=14h:10h. After 4 hours, it was checked with a stereo microscope, and dead and inactive individuals were removed, and the number of live mites on each slide was recorded. The end of the glass slide with the mite stuck to it was shaken and immersed in the test solution for 5 seconds, then taken out. The excess solution was carefully absorbed with a small filter paper strip and returned to the iron plate. It was placed in a light incubator under the same breeding conditions. One glass slide was one treatment, and each treatment was repeated 3 times. 1‰ Tween 80 solution was used as a blank control. After 24 hours of drug treatment, the glass slide was taken out and the results were checked under a stereomicroscope. During the inspection, the mite body was lightly touched with the tip of a brush. Those whose chelicerae did not move were considered dead, and the number of dead individuals was recorded; continuous observation and recording was performed for 72 hours. The mortality rate (%) and corrected mortality rate (%) of the test mite at 48 hours and 72 hours were calculated according to the following formula.

[0086]

[0087] in conclusion

[0088] Activity tests showed that at a concentration of 100 μg / mL, compounds 1-4, 6-8 and 10-12 showed 100% mortality to Plutella xylostella, compounds 1, 3, 4, 7, 11, 13 showed 100% mortality to Ostrinia furnacalis, and compound 7 showed 100% mortality to Spodoptera frugiperda.

[0089] The lethality of compounds 7 and 12 at 10 μg / mL was 100% to Plutella xylostella, 100% and 80% to Ostrinia nubilalis, and 100% and 45% to Spodoptera frugiperda.

[0090] The insecticidal activity of difluoroolefin ether compounds 1-12 against Tetranychus cinnabarinus at a concentration of 500 μg / mL was greater than 80%.

[0091] In view of this, the difluoroolefin oxime ether derivative disclosed in the present invention has significant insecticidal / mite activity and is expected to be used in the preparation of new and highly effective insecticidal / mite agents in the future.

[0092] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Any simple modifications, equivalent changes and decorations made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. Difluoroalkene oxime ether derivatives, characterized in that, The general structural formula of this series of derivatives is shown in formula (I): Formula (I) R 1 is methyl; R 2 is selected from phenyl, pyridyl, pyrazolyl, pyrrolyl, furyl, thiazolyl, benzopyrrolyl, R 3 is selected from phenyl.

2. Difluoroalkene oxime ether derivatives, and the general structural formula of this series of derivatives is shown in formula (I): characterized in that selected from the following specific compounds: (1)R 1 = methyl, R 2 = 4 - bromophenyl, R 3 = 3,5 - dichlorophenyl; (2)R 1 = methyl, R 2 = 4-iodophenyl, R 3 = 3,5-dichlorophenyl; (3)R 1 = methyl, R 2 = 2,6-difluorophenyl, R 3 = 3,5-dichlorophenyl; (4)R 1 = methyl, R 2 = 2-bromo, 4-fluorophenyl, R 3 = 3,5-dichlorophenyl; (5)R 1 = methyl, R 2 = 3-trifluoromethylphenyl, R 3 = 3,5-dichlorophenyl; (6)R 1 = methyl, R 2 = 3-methyl-4-fluorophenyl, R 3 = 3,5-dichlorophenyl; (7)R 1 = methyl, R 2 = 3-methyl-4(1,2,4-triazole)phenyl, R 3 = 3,5-dichlorophenyl; (8)R 1 = methyl, R 2 = α - furyl, R 3 = 3,5 - dichlorophenyl; (9)R 1 = methyl, R 2 = β-naphthyl, R 3 = 3,5-dichlorophenyl; (10)R 1 = methyl, R 2 = 3,4-(methylenedioxy)phenyl, R 3 = 3,5-dichlorophenyl; (11)R 1 = methyl, R 2 = 2-(1-methyl)pyrrolyl, R 3 = 3,5-dichlorophenyl; (12)R 1 = methyl, R 2 = 3 - phenoxyphenyl, R 3 = 3,5 - dichlorophenyl; (13)R 1 = methyl, R 2 = 2 - thienyl, R 3 = 3,5 - dichlorophenyl.

3. The preparation method of the difluoroalkene oxime ether derivative according to claim 1, characterized in that comprising the following steps: Step (1): Using a series of ketone compounds as raw materials, reacting with hydroxylamine hydrochloride to obtain an oxime intermediate Step (2), a series of oxime intermediates react with trifluoromethyl olefin compounds to prepare the compound shown in formula (I).

4. The preparation method of the difluoroalkene oxime ether derivative according to claim 3, characterized in that, In step (1), the reaction solvent is selected from one or more of N,N-dimethylformamide, N,N-diethylformamide, 1,4-dioxane, tetrahydrofuran, toluene, ethyl acetate, dimethyl sulfoxide, methanol, ethanol, acetonitrile, acetone, and water, and the reaction temperature is 25-80 °C.

5. The preparation method of the difluoroalkene oxime ether derivative according to claim 3, characterized in that, In step (2), the reaction solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, toluene, and xylene, and the reaction temperature is 60-120 °C.

6. The application of the difluoroalkene oxime ether derivative prepared by the preparation method of the difluoroalkene oxime ether derivative according to claims 3-5 in the preparation of insecticides.

7. The application of the difluoroalkene oxime ether derivative prepared by the preparation method of the difluoroalkene oxime ether derivative according to claims 3-5 in the preparation of acaricides.

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