A novel polyfluoropyrethroid compound and its synthesis method

Abstract

The present invention discloses a novel polyfluoropyrethroid compound and a preparation method thereof. The polyfluoropyrethroid compound has the structural formula: #imgabs0#, wherein R is one of H, F, and Br. The present invention uses trifluorochlorpyrimidine as the parent compound, introduces a tetrafluorophenyl structure, and then modifies the R group to synthesize a novel polyfluoropyrethroid compound with high anti-mosquito activity and low biological toxicity.

Description

Technical Field

[0001] The present invention relates to the technical field of mosquito control, in particular to a novel polyfluoropyrethroid compound and a synthesis method thereof. Background Art

[0002] Mosquitoes are among the most widespread and deadly creatures in the world, often carrying a variety of viruses that are transmitted to humans and other organisms during their blood-sucking process. Among them, the Aedes albopictus is the primary vector of over 20 diseases, including dengue fever, dengue hemorrhagic fever, and epidemic encephalitis B, posing a serious threat to human health. Currently, the primary means of mosquito control is a combination of environmental management and chemical insecticides. Among chemical control methods, pyrethroid insecticides have long been widely used for mosquito control due to their high efficiency, low toxicity, and low residue levels. However, the problem of mosquito resistance has become increasingly prominent, attracting significant attention.

[0003] Pyrethroid insecticides have long been the preferred mosquito control product. However, due to their extensive and frequent use over a long period of time, mosquitoes have developed a serious resistance to these insecticides. This resistance not only affects the effectiveness and lifespan of insecticides but also contributes to environmental pollution, increasing demand and requirements for new insecticides and making research and development increasingly difficult.

[0004] In 2005, my country established a vector surveillance system to monitor the abundance, species, distribution, and seasonal changes of vectors, including insecticide resistance in mosquitoes. my country has repeatedly reported on insecticide resistance in mosquitoes. In 2011, Liu Silu et al. found that 29% of the 55 surveyed areas showed high resistance to cypermethrin in the Culex pipiens complex; 59% of the 101 surveyed areas showed moderate or higher resistance to deltamethrin; and 20% of the 59 surveyed areas showed high resistance to permethrin. Zhang Xinghua's research demonstrated a serious insecticide resistance problem in wild Aedes albopictus mosquitoes in Guangzhou, with varying levels of resistance to most common insecticides. Cross-resistance between deltamethrin and pyrimethrin was also discovered. Bkhache et al. collected wild Culex pipiens from Morocco and analyzed resistance genes, reporting the first L1014F-kdr mutation in Culex pipiens. Reports of new mutation sites are reported almost every year. This shows that the problem of mosquito resistance can no longer be underestimated, and in the absence of an effective solution, this problem of resistance will become more and more serious.

[0005] The problem of insecticide resistance is often not limited to the use of a single insecticide; cross-resistance exists among a wide variety of insecticides. For example, Li Xiangdong's research found that cypermethrin-resistant varieties of Culex pipiens pallens exhibited high cross-resistance to trichlorfon and deltamethrin. Another example, Kou Jingxuan et al. found that as DDVP-resistant varieties of Culex pipiens pallens gained increased DDVP resistance, their resistance to cypermethrin also continued to increase. By the 39th generation of breeding, DDVP-resistant varieties had reached a high level of cypermethrin resistance, while cypermethrin-resistant varieties showed only a slight increase in DDVP resistance, with little change. Dagg et al. studied cross-resistance in Anopheles arabiensis mosquitoes in Ethiopia and found that wild populations were resistant to malathion (mortality rate: 83%), able to survive exposure to 2, 5, and 10 times the diagnostic doses of deltamethrin and permethrin, and highly resistant to pyrethroid compounds. This suggests that the development of insecticide resistance in mosquitoes is a complex process. Long-term use of the same insecticide can not only lead to severe resistance but can also lead to cross-resistance to different types of insecticides of the same type or with the same mechanism of action. Therefore, there is an urgent need for novel polyfluoropyrethroid compounds with high anti-mosquito activity and low toxicity, as well as methods for their preparation. Summary of the Invention

[0006] In view of this, the present invention provides a novel polyfluoropyrethroid compound with high anti-mosquito activity and low toxicity and a preparation method thereof.

[0007] The purpose of the present invention is achieved through the following technical solutions.

[0008] A novel polyfluoropyrethroid compound, the structural formula of the polyfluoropyrethroid compound is: wherein R is one of H, F and Br.

[0009] The present invention also provides a method for synthesizing a novel polyfluoropyrethroid compound, comprising the following steps:

[0010] S1. Weigh trifluorochlorido chrysanthemic acid BFA, 4-dimethylaminopyridine DMAP, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDCl and the intermediate in a round-bottom flask. The molar ratio of trifluorochlorido chrysanthemic acid BFA, 4-dimethylaminopyridine DMAP, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDCl and the intermediate is:

[0011] 1:2:2:1.5; the structural formula of the intermediate is R is one of H, F and Br;

[0012] S2. Add appropriate amount of dichloromethane to the round-bottom flask, stir, and react at room temperature for 6 hours.

[0013] obtaining a reaction product;

[0014] S3. Add saturated salt water and dichloromethane to extract the reaction product, shake well and let stand to separate the layers, and collect the dichloromethane layer after separation;

[0015] S4, evaporate and remove part of the organic solvent in the dichloromethane layer, then add an appropriate amount of crude silica gel,

[0016] The mixture was stirred and purified by silica gel chromatography to obtain a novel polyfluoropyrethroid compound.

[0017] The synthesis reaction equation of the novel polyfluoropyrethroid compound of the present invention is:

[0018]

[0019] Preferably, the synthesis method of the intermediate is as follows: weigh the secondary reactant into the corresponding round-bottom flask, place it in an ice-water bath and cool it to 0°C, slowly add an appropriate amount of anhydrous methanol, stir until completely dissolved, then add sodium borohydride, continue stirring for 10 minutes, remove the ice-water bath, and react at room temperature for 2 hours. The molar ratio of the secondary reactant to sodium borohydride is 1:1.5; after the reaction is completed, place the round-bottom flask in an ice-water bath, slowly add 2 mol / L hydrochloric acid solution to quench the sodium borohydride until no bubbles are generated to obtain a secondary reaction liquid; add saturated brine and ethyl acetate to the secondary reaction liquid for extraction, and collect the ethyl acetate layer; evaporate and remove part of the organic solvent in the ethyl acetate layer, add an appropriate amount of crude silica gel, stir, and purify by silica gel chromatography to obtain the intermediate. Among them, the structural formula of the secondary reactant is R is one of H, F and Br.

[0020] The synthetic reaction equation of the intermediate:

[0021]

[0022] Preferably, the synthesis method of the secondary reactant is as follows: 3-hydroxybenzaldehyde 3-Hydroxybenzaldehyde and cesium carbonate Cs2CO3 are weighed in a dry two-necked round-bottom flask, and under nitrogen protection, an appropriate amount of anhydrous dimethyl sulfoxide DMSO is added to the two-necked round-bottom flask, and the primary reactant is slowly added under stirring, and the reaction is stirred at 25°C for 6 hours to obtain a primary reaction solution; pure water, saturated salt water and dichloromethane are added to the primary reaction solution, and the pH of the primary reaction solution is adjusted to 3-4 with a 2mol / L hydrochloric acid solution, and the dichloromethane layer is collected after shaking and layering, and part of the organic solvent in the dichloromethane layer is evaporated to remove, and an appropriate amount of coarse silica gel is added and stirred, and then purified by silica gel chromatography to obtain a secondary reactant; the molar ratio of 3-hydroxybenzaldehyde, cesium carbonate and primary reactant is 2:3:3; the structural formula of the primary reactant is R is one of H, F and Br.

[0023] The synthesis reaction equation of the secondary reactant is:

[0024]

[0025] Preferably, the trifluoroacetic acid BFA is obtained by adding sodium hydroxide to a 50% ethanol solution of bifenthrin, hydrolyzing at 95° C., and then extracting. The molar ratio of bifenthrin to sodium hydroxide is 1:3.

[0026] The preparation reaction equation of trifluoroacetic acid BFA is:

[0027]

[0028] Preferably, the reaction endpoints of trifluoroacetic acid, secondary reactants, intermediates and novel polyfluoropyrethroid compounds are all detected by thin layer chromatography.

[0029] Preferably, the aqueous phase extracted during the reaction of trifluralin, secondary reactants, intermediates, and novel polyfluoropyrethroid compounds is extracted with a corresponding organic phase solvent and then transferred to a corresponding organic phase layer, thereby improving the recovery rate of the products in each step.

[0030] Preferably, during the reaction of trifluoroacetic acid, secondary reactants, intermediates and novel polyfluoropyrethroid compounds, anhydrous magnesium sulfate is added to the organic phase layer after extraction several times in small amounts to remove residual moisture.

[0031] Beneficial effects of the present invention:

[0032] Using trifluorochlorpyrimidine as the parent compound, a tetrafluorophenyl structure was introduced, and then the R group was improved to synthesize a new type of polyfluoropyrethroid compound with high anti-mosquito activity and low biological toxicity. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is the UV-visible absorption spectrum of cypermethrin methanol solution.

[0034] Figure 2 This is the UV-visible absorption spectrum of bifenthrin methanol solution.

[0035] Figure 3 This is the UV-visible absorption spectrum of BFA-3-1 methanol solution.

[0036] Figure 4 This is the UV-visible absorption spectrum of BFA-3-2 methanol solution.

[0037] Figure 5 This is the UV-visible absorption spectrum of BFA-3-4 methanol solution.

[0038] Figure 6 is the standard curve of deltamethrin.

[0039] Figure 7 is the standard curve of bifenthrin.

[0040] Figure 8 is the standard curve of BFA-3-1.

[0041] Figure 9 is the standard curve of BFA-3-2.

[0042] Figure 10 is the standard curve of BFA-3-4.

[0043] Figure 11 These are the photodegradation curves of deltamethrin, bifenthrin, BFA-3-1, BFA-3-2 and BFA-3-4 under ultraviolet light.

[0044] Figure 12 These are the photodegradation curves of deltamethrin, bifenthrin, BFA-3-1, BFA-3-2 and BFA-3-4 under simulated sunlight.

[0045] Figure 13 This is a linear function graph of the change of -ln([A] / [A]0) of the compound methanol solution under ultraviolet light as a function of time.

[0046] Figure 14 This is a linear function graph of the change of -ln([A] / [A]0) of the compound methanol solution under simulated sunlight as a function of time. DETAILED DESCRIPTION

[0047] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0048] Examples 1-5

[0049] Accurately weigh bifenthrin BFA (10.0 mmol, 1.0 equiv.) into a round-bottom flask. After the flask is properly set, add 25 mL of 50% aqueous ethanol [V (anhydrous ethanol) / V (pure water) = 1 / 1] and stir with a magnetic stirrer. Once fully dissolved, weigh sodium hydroxide (30.0 mmol, 3.0 equiv.) and slowly add it to the reaction mixture. Connect a condenser, fill with condensed water, set the temperature to 95°C, and heat the reaction under reflux overnight. Monitor the reaction endpoint by thin-layer chromatography (TLC) [developing solvent: V (petroleum ether) / V (dichloromethane) = 2 / 1]. After completion of the reaction, transfer the reaction mixture to a separatory funnel and extract with saturated brine and ethyl acetate (EA). After separation, discard the ethyl acetate layer and collect the aqueous phase. The pH of the aqueous phase was adjusted to 1-2 with 2 mol / L HCl solution. After shaking, a large amount of yellow solid precipitated. DCM was added for extraction. After separation, the DCM layer was collected. TLC was used to check for residual compound in the aqueous phase. If residual compound was present, an appropriate amount of DCM was added, and the mixture was shaken and separated. The entire organic phase solution was transferred to a conical flask. Anhydrous magnesium sulfate (MgSO4) was added in small amounts several times to absorb the residual water in the organic phase. The organic solvent in the solution was evaporated using a rotary evaporator. When the solvent volume was only about 10 mL, an appropriate amount of crude silica gel was added and the sample was stirred. The sample was purified by silica gel chromatography (eluent: V(PE) / V(DCM) = 4 / 1) to obtain the intermediate trifluorochlorfenapyric acid (BFA) as a white solid in an 85% yield.

[0050] The synthesis of secondary reactants must be performed under anhydrous and oxygen-free conditions. Pre-dry the clean round-bottom flask, magnetic rod, and needle in a forced-air drying oven for 1-2 hours. Accurately weigh 3-hydroxybenzaldehyde (2.0 mmol, 1.0 equiv.) and cesium carbonate (Cs2CO3) (3.0 mmol, 1.5 equiv.) into the dried round-bottom flask. After weighing, quickly seal the flask with a rubber stopper. Replace the air in the flask with high-purity nitrogen using a double-row tube and insert a nitrogen balloon to maintain a nitrogen atmosphere. After purging, clamp the round-bottom flask onto a metal stand. Using a needle, slowly add 15.0 mL of anhydrous dimethyl sulfoxide (DMSO) to the flasks. Turn on the magnetic stirrer and set the desired speed. The primary reactant (3.0 mmol, 1.5 equiv.) was slowly added with stirring, and the reaction was stirred at room temperature (around 25°C; in winter, if the temperature is too low, it should be heated to 25°C to prevent DMSO from solidifying) for 6 h. The reaction endpoint was monitored by thin-layer chromatography (TLC) [developing solvent: V(PE) / V(EA) = 10 / 1]. After the reaction was completed, the reaction solution was transferred to a separatory funnel, and purified water, saturated brine, and DCM were added. The pH was adjusted to 3-4 with 2 mol / L HCl solution, and the mixture was shaken. After separation, the DCM layer was collected and the aqueous phase was tested for residual compound by TLC. If residual compound was present, an appropriate amount of DCM was added, and the mixture was shaken and separated. The entire organic phase solution was transferred to a conical flask. Anhydrous magnesium sulfate (MgSO4) was added in small amounts several times to absorb the residual water in the organic phase. The organic solvent in the solution was evaporated using a rotary evaporator. When the amount of solvent was only about 10 mL, an appropriate amount of crude silica gel was added in proportion and the sample was mixed. The product was purified by silica gel chromatography [eluent: V(PE) / V(EA)=20 / 1] to obtain the secondary reactant as a white solid.

[0051] Synthesis of the intermediate: Accurately weigh the secondary reactant (1.0 mmol, 1.0 equiv.) into a round-bottom flask and clamp the reaction mixture to a metal stand. Fill a small basin 2 / 3 full with ice and add an appropriate amount of water. Place the reaction flask in an ice-water bath to cool to approximately 0°C. Slowly add 10 mL of anhydrous methanol (MeOH) and stir with a magnetic stirrer. Once the compound has completely dissolved and cooled, slowly add sodium borohydride (NaBH4) (1.5 mmol, 1.5 equiv.) to the reaction mixture. Continue stirring in the ice-water bath for 10 minutes after addition. Remove the ice bath and react at room temperature for 2 hours. The reaction endpoint was monitored by thin-layer chromatography (TLC) [developing solvent: V(PE) / V(EA) = 5 / 1]. After completion of the reaction, the reaction flask was placed in an ice-water bath and 2 mol / L HCl solution was slowly added dropwise to quench the excess sodium borohydride. The addition rate was controlled to prevent rapid bubbling and the resulting material rush. The addition was continued until the reaction solution ceased bubbling. The quenched reaction solution was transferred to a separatory funnel and extracted with saturated sodium chloride solution and EA. After separation, the EA layer was collected and the aqueous phase was tested by TLC to determine if any compound remained. If any remained, an appropriate amount of DCM was added, the mixture was shaken well, and the mixture was separated. The entire organic phase solution was transferred to a conical flask. Anhydrous magnesium sulfate (MgSO4) was added in small amounts several times to absorb the residual water in the organic phase. The organic solvent in the solution was evaporated using a rotary evaporator. When the amount of solvent was only about 10 mL, an appropriate amount of crude silica gel was added in proportion and the sample was mixed. The sample was purified by silica gel chromatography [eluent: V(PE) / V(EA)=10 / 1] to obtain an intermediate, a white solid. The polyfluoropyrethroid compound whose R is H is denoted as BFA-3-1, the polyfluoropyrethroid compound whose R is F is denoted as BFA-3-2; the polyfluoropyrethroid compound whose R is Cl is denoted as BFA-3-3, the polyfluoropyrethroid compound whose R is Br is denoted as BFA-3-4; and the polyfluoropyrethroid compound whose R is I is denoted as BFA-3-5. The yields of all the above are higher than 90%.

[0052] Comparative Examples 1-4

[0053] The synthesis method of Comparative Examples 1-4 is similar to that of Examples 1-5, except that R is CH3, CF3, CH=CH2 and CH=CH3, respectively, and the corresponding polyfluoropyrethroid compounds are recorded as BFA-3-6, BFA-3-7, BFA-3-8 and BFA-3-9.

[0054] Comparative Example 5

[0055] The synthesis method of Comparative Example 5 is similar to that of Example 1, except that chrysanthemic acid uses dibromochrysanthemic acid DMA obtained by hydrolysis of deltamethrin, and the corresponding polyfluoropyrethroid compound is recorded as DMA-3-1.

[0056] Comparative Example 6

[0057] The synthesis method of Comparative Example 6 is similar to that of Example 2, except that chrysanthemic acid uses dibromochrysanthemic acid DMA obtained by hydrolysis of deltamethrin, and the corresponding polyfluoropyrethroid compound is recorded as DMA-3-2.

[0058] Comparative Example 7

[0059] The synthesis method of Comparative Example 7 is similar to that of Example 3, except that chrysanthemic acid uses dibromochrysanthemic acid DMA obtained by hydrolysis of deltamethrin, and the corresponding polyfluoropyrethroid compound is recorded as DMA-3-3.

[0060] Comparative Example 8

[0061] The synthesis method of Comparative Example 8 is similar to that of Example 4, except that chrysanthemic acid uses dibromochrysanthemic acid DMA obtained by hydrolysis of deltamethrin, and the corresponding polyfluoropyrethroid compound is recorded as DMA-3-4.

[0062] Comparative Example 9

[0063] The synthesis method of Comparative Example 9 is similar to that of Example 5, except that chrysanthemic acid uses dibromochrysanthemic acid DMA obtained by hydrolysis of deltamethrin, and the corresponding polyfluoropyrethroid compound is recorded as DMA-3-5.

[0064] Comparative Example 10

[0065] The synthesis method of Comparative Example 10 is similar to that of Example 1, except that chrysanthemic acid uses chlorfenapyr acid TFA obtained by hydrolysis of transfluthrin, and the corresponding polyfluoropyrethroid compound is recorded as TFA-3-1.

[0066] Comparative Example 11

[0067] The synthesis method of Comparative Example 11 is similar to that of Example 2, except that chrysanthemic acid uses chlorfenapyr acid TFA obtained by hydrolysis of transfluthrin, and the corresponding polyfluoropyrethroid compound is recorded as TFA-3-2.

[0068] Comparative Example 12

[0069] The synthesis method of Comparative Example 12 is similar to that of Example 3, except that chrysanthemic acid uses chlorfenapyr acid TFA obtained by hydrolysis of transfluthrin, and the corresponding polyfluoropyrethroid compound is recorded as TFA-3-3.

[0070] Comparative Example 13

[0071] The synthesis method of Comparative Example 13 is similar to that of Example 4, except that chrysanthemic acid uses chlorfenapyr acid TFA obtained by hydrolysis of transfluthrin, and the corresponding polyfluoropyrethroid compound is recorded as TFA-3-4.

[0072] Comparative Example 14

[0073] The synthesis method of Comparative Example 14 is similar to that of Example 5, except that chrysanthemic acid uses chlorfenapyr acid TFA obtained by hydrolysis of transfluthrin, and the corresponding polyfluoropyrethroid compound is recorded as TFA-3-5.

[0074] The structures were characterized by nuclear magnetic hydrogen spectrum (1H HMR), carbon spectrum (13C HMR) and high-resolution mass spectrometry (HRMS), and the test data of each polyfluorinated pyrethroid compound were obtained.

[0075]

[0076] 3-(2,3,5,6-tetrafluorophenoxy)benzyl(1S,3S)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate (BFA-3-1, C22H16ClF7O3) is a pale yellow, transparent, oily liquid; yield: 52%. 1H NMR(500MHz,Chloroform-d)δ7.36(t,J=7.9Hz,1H),7.15(d,J=7.6Hz,1H),7.07–6.97(m,2H),6.95(dd,J=8.3,2.6Hz,1 H),6.31(d,J=9.0Hz,1H),5.21–5.06(m,2H),2.09(t,J=8.7Hz,1H),1.94(d,J=8.4Hz,1H),1.28(s,3H),1.28(s,3H).13C NMR(126MHz,Chloroform-d)δ169.88,157.12,147.31,145.35,142.49,140.43,137.92,134.45,129.94, 129.84,123.35,122.56,117.97,115.19,115.06,101.98,65.62,32.70,30.88,28.73,28.13,14.68.19F NMR(471MHz,Chloroform-d)δ-66.72(s,3F),-143.51–-143.61(m,2F),-153.37–-153.49(m,2F).HRMS(ESI)calcdfor C22H16ClF7O3([M+H]+)497.0749; found,497.0744.

[0077]

[0078] 3-(perfluorophenoxy)benzyl(1S,3S)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate (BFA-3-2, C22H15ClF8O3) is a colorless, transparent, oily liquid; yield: 46%. 1H NMR(500MHz,Chloroform-d)δ7.31(t,J=7.9Hz,1H),7.10(dt,J=7.8,1.3Hz,1H),6.99(d,J=2.5Hz,1H),6.98–6.89 (m,3H),5.14–5.02(m,2H),2.18(ddd,J=9.5,8.4,1.1Hz,1H),2.03(d,J=8.3Hz,1H),1.29(s,3H),1.27(s,3H).13C NMR(126MHz,Chloroform-d)δ170.01,157.25,147.49,145.54,142.65,140.52,138.05,134.06,130.07, 129.98,123.48,122.00,117.46,115.32,115.19,102.11,65.75,32.83,31.01,28.86,28.27,14.81.19F NMR(471MHz,Chloroform-d)δ-68.68(s,3F),-153.76–-153.94(m,2F),-159.60(t,J=21.7Hz,1F),-161.78–-162.00(m,2F).HRMS(ESI)calcd for C22H15ClF8O3([M+H]+)514.0582; found,514.0588.

[0079]

[0080] 3-(4-chloro-2,3,5,6-tetrafluorophenoxy)benzyl(1S,3S)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate (BFA-3-3, C22H15Cl2F7O3) is a colorless, transparent, oily liquid; yield: 76%. 1H NMR(500MHz,Chloroform-d)δ7.34(t,J=7.9Hz,1H),7.18–7.11(m,1H),6.99(t,J=2.1Hz,1H),6.91(dd,J=8.3,2.6Hz,1 H),6.77(d,J=8.5Hz,1H),5.14–5.01(m,2H),1.98(t,J=8.5Hz,1H),1.90(d,J=8.4Hz,1H),1.25(s,3H),1.25(s,3H).13C NMR(126MHz,Chloroform-d)δ170.39,157.62,147.68,145.97,143.05,140.99,134.20,130.45,130.35, 123.85,122.11,119.74,117.60,115.70,115.57,102.49,66.13,33.21,31.39,29.24,28.64,15.19.19F NMR(471MHz,Chloroform-d)δ-68.84(s,3F),-138.73–-141.07(m,2F),-152.67–-152.79(m,2F).HRMS(ESI)calcdfor C22H15Cl2F7O3([M+H]+)531.0359; found,531.0351.

[0081]

[0082] 3-(4-bromo-2,3,5,6-tetrafluorophenoxy)benzyl(1S,3S)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate (BFA-3-4, C22H15BrClF7O3) is a colorless, transparent, oily liquid; yield: 64%. 1H NMR(500MHz,Chloroform-d)δ7.36(td,J=7.9,2.6Hz,1H),7.22–7.11(m,1H),7.05–6.92(m,3H) ,5.18–5.06(m,2H),2.22(t,J=8.9Hz,1H),2.07(d,J=8.4Hz,1H),1.33(s,3H),1.31(s,3H).13C NMR(126MHz,Chloroform-d)δ170.00,157.24,146.96,145.00,142.74,140.63,138.04,133.56,130.07, 129.97,123.48,121.11,119.35,115.33,115.20,102.12,65.76,32.83,31.02,28.86,28.28,14.82.19F NMR(471MHz,Chloroform-d)δ-68.71(s,3F),-132.57–-132.81(m,1F),-138.49–-1 38.58(m,1F),-152.19–-152.37(m,1F),-153.93–-154.01(m,1F).HRMS(ESI)calcd for C22H15BrClF7O3([M+H]+)573.9781; found,573.9789.

[0083]

[0084] 3-(2,3,5,6-tetrafluoro-4-iodophenoxy)benzyl(1S,3S)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclanopropane-1-carboxylate (BFA-3-5, C22H15ClF7IO3) is a colorless, transparent, oily liquid; yield: 57%. 1H NMR(500MHz,Chloroform-d)δ7.36(t,J=7.9Hz,1H),7.15(dt,J=7.8,1.3Hz,1H),7.03(m,1H),6.99–6.9 3(m,2H),5.18–5.06(m,2H),2.23(t,J=8.9Hz,1H),2.07(d,J=8.3Hz,1H),1.33(s,3H),1.31(s,3H).13C NMR(126MHz,Chloroform-d)δ170.01,157.25,147.47,145.55,142.47,140.52,138.05,134.00,130.07, 129.98,123.48,121.82,119.36,115.32,115.19,102.11,65.75,32.83,31.01,28.86,28.27,14.81.19F NMR(471MHz,Chloroform-d)δ-68.72(s,3F),-138.49–-138.61(m,2F),-153.94–-154.05(m,2F).HRMS(ESI)calcd for C22H15ClF7IO3([M+Na]+)644.9535; found,644.9520.

[0085]

[0086] 3-(2,3,5,6-Tetrafluoro-4-methylphenoxy)benzyl (1S,3S)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate (BFA-3-6, C23H18ClF7O3) is a colorless transparent oily liquid; yield: 69%. 1H NMR (500 MHz, Chloroform-d) δ 7.31 (t, J = 7.9 Hz, 1H), 7.14–7.06 (m, 1H), 6.98 (t, J = 2.0 Hz, 1H), 6.90 (dd, J = 8.3, 2.6 Hz, 1H), 6.78 (d, J = ८.5 Hz, 1H), 5.14–4.99 (m, 2H), 2.29 (t, J = 2.1 Hz, 3H), 1.98 (t, J = 8.5 Hz, 1H), 1.91 (d, J = 8.4 Hz, 1H), 1.25 (s, 3H), 1.24 (s, 3H). 13C NMR (126 MHz, Chloroform-d) δ 170.20, 157.51, 146.47, 144.55, 142.41, 140.39, 137.97, 134.30, 131.96, 129.37, 128.14, 126.96, 125.66, 123.28, 121.66, 115.20, 65.40, 51.67, 32.95, 30.98, 28.33, 16.18, 14.95. 19F NMR (471 MHz, Chloroform-d) δ -68.62–-68.66 (m, 3F), -143.34–-143.45 (m, 2F), -155.67–-155.77 (m, 2F). HRMS (ESI) calcd for C23H18ClF7O3 ([M+Na]+) 533.0728; found, 533.0713.

[0087]

[0088] 3-(2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenoxy)benzy l(1S,3S)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate (BFA-3-7, C23H15ClF10O3) is a colorless, transparent, oily liquid; yield: 69%. 1H NMR(500MHz,Chloroform-d)δ7.39(t,J=8.0Hz,1H),7.20(dd,J=7.8,1.3Hz,1H),7.06(t,J=2.1Hz,1H),6.97(dd,J=8.3,2. 6Hz,1H),6.94(d,J=9.4Hz,1H),5.20–5.06(m,2H),2.27–2.19(m,1H),2.07(d,J=8.4Hz,1H),1.33(s,3H),1.31(s,3H).13C NMR(126MHz,Chloroform-d)δ169.97,156.62,146.15,143.92,142.77,140.70,138.30,137.23,130.24,129 .86,124.22,121.81,119.32,118.46,115.75,115.58,105.77,65.61,32.80,31.04,28.88,28.30,14.83.19F NMR(471MHz,Chloroform-d)δ-55.89(t,J=22.0Hz,3F),-68.77(s,3F),-140.05–-140.22(m,2F),-151.75–-151.85(m,2F).HRMS(ESI)calcd for C23H15ClF10O3([M+Na]+)587.0446; found,587.0446.

[0089]

[0090] 3-(2,3,5,6-tetrafluoro-4-vinylphenoxy)benzyl(1S,3S)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate (BFA-3-8, C24H18ClF7O3) is a colorless, transparent, oily liquid; yield: 57%. 1H NMR(500MHz,Chloroform-d)δ7.33(t,J=7.9Hz,1H),7.12(dt,J=7.6,1.2Hz,1H),7.00(t,J=2.1Hz,1H),6.96–6.90(m,2H),6.69(dd,J=18.0,11.9Hz,1H), 6.12(d,J=18.0Hz,1H),5.73(d,J=11.9Hz,1H),5.15–5.03(m,2H),2.19(ddd ,J=9.6,8.4,1.1Hz,1H),2.04(d,J=8.3Hz,1H),1.30(s,3H),1.28(s,3H).13C NMR(126MHz,Chloroform-d)δ170.00,157.33,146.26,144.76,142.59,140.64,138.00,131.93,130.07,129.95, 123.59,123.45,121.87,121.83,119.35,115.31,115.23,113.38,65.78,32.83,31.02,28.86,28.31,14.84.19F NMR(471MHz,Chloroform-d)δ-68.70(s,3F),-143.62–-143.72(m,2F),-155.33–-155.43(m,2F).HRMS(ESI)calcdfor C24H18ClF7O3([M+Na]+)545.0729; found,545.0714.

[0091]

[0092] 3-(4-ethyl-2,3,5,6-tetrafluorophenoxy)benzyl(1S,3S)-3-((Z)-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane-1-carboxylate (BFA-3-9, C24H20ClF7O3) is a colorless, transparent, oily liquid; yield: 66%. 1H NMR(500MHz,Chloroform-d)δ7.35(t,J=8.0Hz,1H),7.14(dt,J=7.7,1.2Hz,1H),7.04(t,J=2.1Hz,1H),6.99(dd,J=9.4,1.1Hz,1H),6.95(dd,J=8.3,2.6 Hz,1H),5.19–5.07(m,2H),2.82(qt,J=7.6,1.6Hz,2H),2.23(t,J=9.1Hz,1H ),2.09(d,J=8.4Hz,1H),1.33(s,3H),1.32(s,3H),1.30(t,J=7.6Hz,3H).13C NMR(126MHz,Chloroform-d)δ170.01,157.49,146.24,144.29,142.34,140.43,137.99,131.02,130.06,129.99 ,123.22,121.87,119.38,118.42,115.22,115.09,65.78,32.84,31.00,28.82,28.19,16.17,14.76,13.89.19F NMR(471MHz,Chloroform-d)δ-68.74(s,3F),-145.53–-145.64(m,2F),-155.39–-155.52(m,2F).HRMS(ESI)calcd forC24H20ClF7O3([M+Na]+)547.0885; found,547.0870.

[0093]

[0094] 3-(2,3,5,6-tetrafluorophenoxy)benzyl(1S,3S)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylate (DMA-3-1, C21H16Br2F4O3) is a colorless, transparent, oily liquid; yield: 66%. 1H NMR(500MHz,Chloroform-d)δ7.33(t,J=7.9Hz,1H),7.12(d,J=7.5Hz,1H),6.99(s,2H),6.91(dd,J=8.3,2.7Hz,1H), 6.78(d,J=8.5Hz,1H),5.14–5.01(m,2H),1.98(t,J=8.5Hz,1H),1.91(d,J=8.4Hz,1H),1.26(s,3H),1.25(s,3H).13C NMR(126MHz,Chloroform-d)δ170.21,157.22,147.41,145.48,142.57,140.53,138.21,134.06,133 .38,130.06,123.45,115.28,115.13,102.13,89.49,65.59,35.79,31.79,28.34,27.77,15.01.19F NMR(471MHz,Chloroform-d)δ-137.72–-138.93(m,2F),-153.37–-154.31(m,2F).HRMS(ESI)calcd for C21H16Br2F4O3([M+H]+)550.9475; found,550.9468.

[0095]

[0096] 3-(perfluorophenoxy)benzyl(1S,3S)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylate (DMA-3-2, C21H15Br2F5O3) is a colorless, transparent, oily liquid; yield: 63%. 1H NMR(500MHz,Chloroform-d)δ7.36(t,J=7.9Hz,1H),7.16(d,J=7.8Hz,1H),7.01(t,J=2.0Hz,1H),6.92(dd,J=8.3,2.6Hz, 1H),6.80(d,J=8.6Hz,1H),5.15–5.06(m,2H),2.01(t,J=8.5Hz,1H),1.94(d,J=8.4Hz,1H),1.29(s,3H),1.28(s,3H).13C NMR(126MHz,Chloroform-d)δ170.19,157.22,143.11,141.10,139.89,138.19,138.34,137.88,133 .37,130.13,129.47,123.59,115.15,114.96,89.50,65.54,35.81,31.77,28.32,27.78,14.99.19F NMR(471MHz,Chloroform-d)δ-153.67–-153.78(m,2F),-159.51(t,J=21.9Hz,1F),-161.70–-161.86(m,2F).HRMS(ESI)calcd for C21H15Br2F5O3([M+H]+)568.9381; found,568.9375.

[0097]

[0098] 3-(4-chloro-2,3,5,6-tetrafluorophenoxy)benzyl(1S,3S)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylate (DMA-3-3, C21H15Br2ClF4O3) is a colorless, transparent, oily liquid; yield: 71%. 1H NMR(500MHz,Chloroform-d)δ7.36(t,J=7.9Hz,1H),7.18–7.13(m,1H),7.01(t,J=2.1Hz,1H),6.94(dd,J=8.4,2.6Hz,1 H),6.79(d,J=8.5Hz,1H),5.16–5.05(m,2H),2.01(t,J=8.5Hz,1H),1.93(d,J=8.4Hz,1H),1.28(s,3H),1.27(s,3H).13C NMR(126MHz,Chloroform-d)δ170.33,157.34,147.52,145.59,142.68,140.64,138.33,134.17,133 .50,130.18,123.56,115.40,115.24,102.24,89.60,65.71,35.90,31.90,28.46,27.89,15.13.19F NMR(471MHz,Chloroform-d)δ-142.37–-142.48(m,2F),-152.19–-152.30(m,2F).HRMS(ESI)calcd for C21H15Br2ClF4O3([M+H]+)584.9085; found,584.9079.

[0099]

[0100] 3-(4-bromo-2,3,5,6-tetrafluorophenoxy)benzyl(1S,3S)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylate (DMA-3-4, C21H15Br3F4O3) is a pale yellow, transparent, oily liquid; yield: 70%. 1H NMR(500MHz,Chloroform-d)δ7.36(t,J=7.9Hz,1H),7.16(d,J=8.0Hz,1H),7.01(t,J=2.1Hz,1H),6.94(dd,J=8.4,2.6Hz, 1H),6.79(d,J=8.5Hz,1H),5.16–5.05(m,2H),2.01(t,J=8.5Hz,1H),1.93(d,J=8.4Hz,1H),1.28(s,3H),1.27(s,3H).13C NMR(126MHz,Chloroform-d)δ169.87,156.90,142.82,140.83,139.15,137.59,136.99,133.06,129 .81,129.19,123.28,114.83,114.64,101.56,89.19,65.22,35.49,31.45,28.00,27.47,14.67.19F NMR(471MHz,Chloroform-d)δ-140.39–-140.51(m,2F),-152.72–-152.84(m,2F).HRMS(ESI)calcd for C21H15Br3F4O3([M+H]+)628.8580; found,628.8573.

[0101]

[0102] 3-(2,3,5,6-tetrafluoro-4-iodophenoxy)benzyl(1S,3S)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylate (DMA-3-5, C21H15Br2F4IO3) is a pale yellow, transparent, oily liquid; yield: 56%. 1HNMR(500MHz,Chloroform-d)δ7.36(t,J=7.9Hz,1H),7.15(dt,J=7.7,1.3Hz,1H),7.03–7.02(m,1H),6.94(dd,J=8.3,2.7H z,1H),6.81(d,J=8.5Hz,1H),5.17–5.05(m,2H),2.01(t,J=8.5Hz,1H),1.94(d,J=8.4Hz,1H),1.28(s,3H),1.28(s,3H).13C NMR(126MHz,Chloroform-d)δ170.19,157.04,146.42,144.42,143.93,141.91,138.32,133.35,132 .99,130.13,130.06,123.67,115.30,115.16,89.53,65.54,35.80,31.78,28.35,27.78,15.01.19F NMR(471MHz,Chloroform-d)δ-138.36–-138.48(m,2F),-153.77–-153.89(m,2F).HRMS(ESI)calcd for C21H15Br2F4IO3([M+H]+)676.8444; found,676.8444.

[0103]

[0104] 3-(2,3,5,6-tetrafluorophenoxy)benzyl(1S,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate (TFA-3-1, C21H16Cl2F4O3) is a colorless, transparent, oily liquid; yield: 43%. 1H NMR(500MHz,Chloroform-d)δ7.36(t,J=7.9Hz,1H),7.15(d,J=7.6Hz,1H),7.07–6.99(m,2H),6.95(dd,J=8.3 ,2.6Hz,1H),6.31(d,J=9.0Hz,1H),5.17–5.07(m,2H),2.09(t,J=8.7Hz,1H),1.94(d,J=8.5Hz,1H),1.28(s,3H ),1.28(s,3H).13CNMR(126MHz,Chloroform-d)δ170.24,157.24,147.51,145.48,142.54,140.52,138.31,13 4.10,130.04,124.80,123.42,120.83,115.24,115.10,102.10,65.52,32.75,31.76,28.26,27.74,14.84.19F NMR(471MHz,Chloroform-d)δ-138.48(dt,J=20.8,10.0Hz,2F),-153.90(ddd,J=21.8,9.8,6.7Hz,2F).HRMS(ESI)calcd for C21H16Cl2F4O3([M+H]+)463.0485; found,463.0478.

[0105]

[0106] 3-(perfluorophenoxy)benzyl(1S,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate (TFA-3-2, C21H15Cl2F5O3) is a colorless, transparent, oily liquid; yield: 69%. 1H NMR (500 MHz, Chloroform-d) δ7.36 (t, J = 7.9 Hz, 1H), 7.16 (d, J = 7.6 Hz, 1H), 7.01 (t, J = 2.1 Hz, 1H), 6.92 (dd, J = 8.3, 2.6 Hz, 1H), 6.29 (d, J = 9.0 Hz, 1H), 5.11 (q, J = 12.7 Hz, 2H), 2.09 (t, J = 8.7 Hz, 1H), 1.93 (d, J = 8.5 Hz, 1H), 1.28(s,6H).13CNMR(126MHz,Chloroform-d)δ170.26,157.22,145.11,143.15,141.09,139.27,138.32,137 .30,130.12,124.70,123.58,120.89,115.15,114.97,111.93,65.51,32.77,31.75,28.35,27.78,14.89.19F NMR(471MHz,Chloroform-d)δ-153.21–-154.47(m,2F),-159.64(t,J=21.7Hz,1F),-161.30–-162.32(m,2F).HRMS(ESI)calcd for C21H15Cl2F5O3([M+H]+)480.0318; found,480.0326.

[0107]

[0108] 3-(4-chloro-2,3,5,6-tetrafluorophenoxy)benzyl(1S,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate (TFA-3-3, C21H15Cl3F4O3) is a colorless, transparent, oily liquid; yield: 40%. 1H NMR(500MHz,Chloroform-d)δ7.36(t,J=7.9Hz,1H),7.16(d,J=7.7Hz,1H),7.04(s,1H),6.95(dd,J=8.3,2 .6Hz,1H),6.30(d,J=9.0Hz,1H),5.12(q,J=12.4Hz,2H),2.10(t,J=8.7Hz,1H),1.94(d,J=8.5Hz,1H),1.29 (s,6H).13CNMR(126MHz,Chloroform-d)δ170.20,157.12,145.62,143.73,142.95,140.94,138.44,132.7 1,130.10,124.77,123.63,120.86,115.22,115.10,108.81,65.45,32.76,31.74,28.25,27.74,14.82.19F NMR(471MHz,Chloroform-d)δ-140.27–-140.79(m,2F),-152.55–-153.09(m,2F).HRMS(ESI)calcd for C21H15Cl3F4O3([M+H]+)496.0023; found,496.0031.

[0109]

[0110] 3-(4-bromo-2,3,5,6-tetrafluorophenoxy)benzyl(1S,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate (TFA-3-4, C21H15BrCl2F4O3) is a colorless, transparent, oily liquid; yield: 74%. 1H NMR(500MHz,Chloroform-d)δ7.36(td,J=7.9,2.5Hz,1H),7.15(t,J=7.0Hz,1H),7.02(s,1H),6.94(d,J=8.2Hz,1H) ,6.28(dd,J=9.0,2.3Hz,1H),5.16–5.05(m,2H),2.08(td,J=8.7,1.4Hz,1H),1.92(d,J=8.5Hz,1H),1.27(s,6H).13C NMR(126MHz,Chloroform-d)δ170.26,157.23,146.44,145.51,144.43,141.77,138.35,133.59,130 .12,124.73,123.54,120.87,115.27,115.14,102.12,65.52,32.77,31.76,28.34,27.77,14.89.19F NMR(471MHz,Chloroform-d)δ-132.56–-132.67(m,1F),-138.42–-138.54(m,1F),-152.06–-152.26(m,1F),-153.81–-153.92(m,1F).HRMS(ESI)calcd for C21H15BrCl2F4O3([M+H]+)539.9518; found,539.9529.

[0111]

[0112] 3-(2,3,5,6-tetrafluoro-4-iodophenoxy)benzyl(1S,3R)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate (TFA-3-5, C21H15Cl2F4IO3) is a colorless, transparent, oily liquid; yield: 65%. 1H NMR(500MHz,Chloroform-d)δ7.36(t,J=7.9Hz,1H),7.15(dt,J=7.6,1.2Hz,1H),7.02(d,J=2.5Hz,1H),6.94(dd,J=8.3, 2.6Hz,1H),6.29(d,J=8.9Hz,1H),5.11(q,J=12.6Hz,2H),2.08(t,J=8.7Hz,1H),1.92(d,J=8.4Hz,1H),1.27(s,6H).13C NMR(126MHz,Chloroform-d)δ170.27,157.23,147.54,145.56,142.54,140.57,138.24,134.10,130 .05,124.75,123.43,120.85,115.26,115.12,102.12,65.55,32.75,31.76,28.33,27.76,14.88.19F NMR(471MHz,Chloroform-d)δ-138.39–-138.54(m,2F),-153.82–-153.94(m,2F).HRMS(ESI)calcd for C21H15Cl2F4IO3([M+Na]+)610.9274; found,610.9274.

[0113] 1. The Wheaton bottle test (CDC Bottle Assay) was used to test the anti-mosquito activity against adult mosquitoes. The specific experimental protocol is as follows:

[0114] (1) Determination of the resistance level of adult female Aedes albopictus mosquitoes

[0115] 1) Sample Solution Preparation: Accurately weigh 10.0 mg of deltamethrin and bifenthrin sample and place in a clean glass vial. Use a pipette to add 10.0 mL of acetone to the vial. Cover and shake to completely dissolve the sample. If the sample remains insoluble, ultrasound can be used to assist dissolution. Prepare a 1.00 mg / mL stock solution. For each sample, dilute one set of low-concentration and one set of high-concentration sample solutions. Prepare 5-6 concentration series for each solution. The low-concentration solution is used for activity testing in sensitive adult mosquitoes, while the high-concentration solution is used for activity testing in resistant adult mosquitoes. Use acetone as a control.

[0116] 2) Test method for the insecticide resistance level of adult Aedes albopictus mosquitoes: Use a pipette to accurately transfer 1.0 mL of the diluted sample solution to be tested and slowly add it to a clean, dry Wheaton bottle. After closing the lid, slowly rotate the bottle to allow the sample to be evenly adhered to the inside of the bottle. After multiple rotations, when the sample solution in the bottle flows slowly, open the bottle cap and place the bottle upside down in a fume hood to evaporate for 1 hour to allow the acetone to evaporate to dryness.

[0117] Using a mosquito aspirator, 3-7-day-old female mosquitoes (female mosquitoes) were removed from the mosquito cage in advance and placed in temporary storage tubes, with 25-30 female mosquitoes per tube. After the acetone in the Wheaton jar evaporated quickly, the female mosquitoes were transferred to the Wheaton jar. The jar was capped and placed upside down on the laboratory table, allowing the female mosquitoes and the sample to interact with each other for 2 hours at 28°C. The number of knockdown female mosquitoes in the Wheaton jar was observed every 15 minutes after the start of the test (knockdown was defined as a female mosquito lying down in the jar or failing to fly after being gently tapped). After the 2-hour test period, the female mosquitoes were removed from the jar using a low-pressure vacuum pump and transferred to a disposable culture cup. A cotton ball soaked in 5% glucose solution was placed on the cup to provide food for the female mosquitoes in the culture cup. The culture cup was placed in a constant temperature and humidity incubator set at 28±2°C, 75±10% relative humidity, and a 14-hour light:dark cycle. After 24 hours of culture, the number of dead female mosquitoes in each culture cup (female mosquitoes that were motionless or unable to fly were considered dead by tapping the body and bottom of the culture cup) and the total number were recorded. Three parallel groups were set up for each experiment, and each sample was measured three times.

[0118] If the mortality rate of the blank group is less than 3%, the experimental results do not need to be corrected; if the mortality rate of the blank group is between 3-10%, the experimental results should be corrected using the Abbott formula; if the mortality rate is higher than 10%, the experimental results are invalid and the experiment should be repeated.

[0119] Among them, A is the total number of adult mosquitoes in the culture cup, and B is the number of adult mosquitoes that died in the culture cup;

[0120] Abbott's formula is:

[0121]

[0122] 3) Statistical analysis:

[0123] Excel, Origin 2020, and SPSS 25.0 software were used for data processing and analysis to obtain the median lethal concentration (LC50), 95% confidence interval (95% CI), and resistance multiple (RR) of each insecticide. The resistance multiple (RR) calculation formula is as follows:

[0124]

[0125] 4) Evaluation of insecticide resistance in adult Aedes albopictus strains: Resistance levels were determined by the resistance multiple (RR). Generally, RR ≤ 3 indicates sensitivity; 3 < RR ≤ 10 indicates low resistance; 10 < RR ≤ 20 indicates moderate resistance; and RR > 20 indicates high resistance. The results are shown in Table 1.

[0126] Table 1 Test results of resistance level of adult Aedes albopictus mosquitoes

[0127]

[0128] Note: RR≤3 indicates sensitive; 3<RR≤10 indicates low resistance; 10<RR≤20 indicates moderate resistance; RR>20 indicates high resistance.

[0129] Laboratory-reared susceptible Aedes albopictus mosquitoes were introduced from Sun Yat-sen University and reared at the Jiangmen Big Health International Innovation Institute for over 100 generations, never exposed to any insecticides. A drug-resistant strain of Aedes albopictus was introduced from the Jiangmen Center for Disease Control and Prevention and reared at the institute for three generations before use in the experiment. The Wheaton jar test was used to test the median lethal concentration (LC50) of susceptible and drug-resistant strains of Aedes albopictus, and to determine the resistance levels of the drug-resistant strains to deltamethrin and bifenthrin. The results are shown in Table 1. The drug-resistant strains of Aedes albopictus in the laboratory were moderately resistant to deltamethrin, moderately resistant to bifenthrin, and minimally resistant to transfluthrin. The drug-resistant strains in the laboratory were induced with deltamethrin. Resistance levels of the drug-resistant strains were assessed every three generations. If resistance levels decreased, they were reintroduced with deltamethrin to maintain resistance.

[0130] (2) Preliminary screening of the anti-mosquito activity of new polyfluoropyrethroid compounds against adult mosquitoes The CDC Wheaton bottle test method was used, with the median lethal concentration of cypermethrin (LC50 = 0.38 mg / mL) of the sensitive strain Aedes albopictus as the reference standard, to test the anti-mosquito activity of new polyfluoropyrethroid compounds against adult mosquitoes, and determine the 24-h anti-mosquito activity of the compounds.

[0131] 1) Sample Preparation: Accurately weigh 3.0 mg of a novel polyfluoropyrethroid compound into a glass bottle, add 3.0 mL of acetone, shake well, and prepare a 1.00 mg / mL sample stock solution for later use. The sample stock solution is stored in a -20°C refrigerator. During testing, the stock solution is diluted to a 0.40 mg / mL sample solution. Deltamethrin (0.40 mg / mL) and bifenthrin (0.40 mg / mL) are used as positive controls, and acetone is used as a blank control.

[0132] 2) Testing method for adult female Aedes albopictus mosquitoes:

[0133] To test, add 1 mL of the sample solution to a clean Wheaton bottle. Rotate the bottle to evenly adhere the sample to the inner wall of the bottle and place it in a fume hood for 1 hour to evaporate the acetone. Transfer 3-7-day-old susceptible female Aedes albopictus mosquitoes to the Wheaton bottle and allow the drug to act on them for 2 hours. After the test period, remove the female mosquitoes and place them in a constant temperature and humidity incubator. After 24 hours of incubation, record the number of dead female mosquitoes and the total number of female mosquitoes in each culture cup. Each experiment was performed in three parallel groups, and each sample was measured in triplicate.

[0134] 3) The mortality rate of the compounds was calculated and compared with that of deltamethrin and bifenthrin. The compounds with better activity were selected for the median lethal concentration test on adult mosquitoes. The results are shown in Table 2.

[0135] Table 2 Preliminary screening results of the anti-mosquito activity of new polyfluoropyrethroid compounds against susceptible adult Aedes albopictus mosquitoes

[0136]

[0137] The U.S. CDC Bottle Bioassay method was used to conduct preliminary screening of the new polyfluoro pyrethroid compounds on susceptible adult Aedes albopictus mosquitoes (the concentration used was 0.4 mg / L). The results are shown in Table 2. In Examples 1-5, the new polyfluoro pyrethroid compounds synthesized using trifluoroacetic acid hydrolyzed from bifenthrin had higher anti-mosquito activities than bifenthrin, while the anti-mosquito activities of Comparative Examples 1-4 were lower than bifenthrin. In particular, BFA-3-1 of Example 1, BFA-3-2 of Example 2, and BFA-3-4 of Example 4 had higher anti-mosquito activities. The selection of chrysanthemic acid was very important. The anti-mosquito activities of BFA-3-1, BFA-3-2, and BFA-3-4 were all higher than those of the corresponding DMA-3-1, DMA-3-2, DMA-3-4, TFA-3-1, TFA-3-2, and TFA-3-4, indicating that the selection of chrysanthemic acid type and the selection of R group have a great influence on the anti-mosquito activity.

[0138] (3) Testing of the median lethal concentration (LC50) of new polyfluoropyrethroid compounds against susceptible adult mosquitoes

[0139] Based on the preliminary screening results of anti-mosquito activity against adult mosquitoes, the highly active BFA-3-1, BFA-3-2, and BFA-3-4 were selected and diluted into a series of 5-6 concentrations. The same test method was used for testing, and the number of knockdowns and 24-hour mortality was recorded. Three parallel groups were set up for each experiment, and each sample was replicated three times. Data processing and analysis were performed using Excel, Origin 2020, and SPSS 25.0 software to obtain the median lethal concentration (LC50), 95% confidence interval (95% CI), and toxicity regression equation (y = a + bx) for each insecticide.

[0140] The LC50 values ​​of novel polyfluoropyrethroid compounds with good activity against susceptible adult mosquitoes were tested using the U.S. CDC Bottle Bioassay method. The results are shown in Table 3. The LC50 values ​​of compounds FA-3-1, BFA-3-2, and BFA-3-4 were comparable to those of deltamethrin (LC50 = 0.38 ± 0.08 mg / L) and transfluthrin (LC50 = 0.51 ± 0.12 mg / L). The LC50 values ​​were 0.55 ± 0.10, 0.45 ± 0.05, and 0.53 ± 0.12 mg / L, respectively, which are 3.5-4.5 times that of bifenthrin, which uses chrysanthemic acid as its source.

[0141] Table 3 Median lethal concentration (LC50) of new polyfluoropyrethroid compounds to susceptible adult mosquitoes 50 )result

[0142]

[0143] (4) Testing of the median lethal concentration (LC50) of novel polyfluoropyrethroid compounds against drug-resistant adult mosquitoes

[0144] Due to the extensive and frequent use of pyrethroids, insecticide resistance in mosquitoes is a serious problem. Therefore, evaluating the antimicrobial activity of compounds against drug-resistant mosquitoes is of practical significance. Therefore, we obtained a sample of moderately resistant Aedes albopictus mosquitoes from the Jiangmen Center for Disease Control and Prevention. After three generations of laboratory breeding, we determined their resistance levels using the Wheaton flask method. We selected several compounds with the lowest median lethal concentration (LC50) in susceptible adult mosquitoes for antimicrobial activity evaluation against resistant adult mosquitoes, and compared these results with those against susceptible mosquitoes.

[0145] The three selected compounds, BFA-3-1, BFA-3-2, and BFA-3-4, were tested using the US CDC Bottle Bioassay method against adult drug-resistant Aedes albopictus mosquitoes to determine their median lethal concentration (LC50). The results, shown in Table 4, demonstrate that the selected compounds exhibited superior activity against drug-resistant mosquitoes compared to the positive controls, deltamethrin and bifenthrin, and comparable activity to transfluthrin. BFA-3-1, BFA-3-2, and BFA-3-4 were 5-7 times more active than deltamethrin and bifenthrin.

[0146] Table 4 Median lethal concentration (LC50) of novel polyfluoropyrethroid compounds against drug-resistant adult mosquitoes 50 )result

[0147]

[0148] The resistance levels of the compounds to drug-resistant Aedes albopictus were determined by calculating their resistance multiple ratio (RR) values, as shown in Table 5. Table 5 shows that BFA-3-1, BFA-3-2, and BFA-3-4 pyrethroid compounds are sensitive to deltamethrin-resistant Aedes albopictus, do not produce cross-resistance, and have good activity against drug-resistant Aedes albopictus.

[0149] Table 5 Results of resistance levels of novel polyfluoropyrethroid compounds to drug-resistant adult mosquitoes

[0150]

[0151] Note: RR≤3 is sensitive; 3<RR≤10 is low resistance; 10<RR≤20 is moderate resistance; RR>20 is high resistance. 2. Study on the photodegradation of new polyfluorinated pyrethroid compounds and evaluation of their toxicity to aquatic organisms (1) Photodegradation experimental method

[0152] Accurately weigh 5 mg of compounds BFA-3-1, BFA-3-2, BFA-3-4, cypermethrin and bifenthrin into a brown glass bottle, add 5 mL of chromatography-grade methanol to prepare a 1 mg / mL stock solution, seal the bottle with sealing film, and keep in a refrigerator at 4°C.

[0153] 1) UV-visible absorption spectrum

[0154] The mother solution of the compound was diluted with chromatographic grade methanol to obtain a 20.00 mg / mL working solution. About 3 mL of the methanol working solution was transferred to a clean quartz cuvette. Using chromatographic grade methanol as a blank reference, a full wavelength spectrum (190-900 nm) was scanned to provide a reference for the wavelength used in the subsequent HPLC detection of photodegradation experiments. The results are shown in FIG. Figure 1-5 shown

[0155] 2) Liquid chromatography (HPLC) test conditions

[0156] All HPLC tests used isocratic elution, the chromatographic column was a Thermo Fisher Acclaim 120C18 (4.6×150 mm, 5 μm) analytical column, the mobile phase was methanol / ultrapure water, the column temperature was set to 30°C, and the injection volume was 20 μL. The specific chromatographic conditions are shown in Table 6.

[0157] Table 6 HPLC analysis conditions and retention times of compounds

[0158]

[0159] 3) Determination of standard curve

[0160] The mother liquors of the five compounds were diluted with chromatography-grade methanol to 40.00, 20.00, 10.00, 5.00, 2.50, and 1.25 mg / mL, respectively. HPLC determination was performed according to the chromatographic analysis listed in Table 7. The peak areas were calculated, and the concentration-peak area standard curve of each compound was drawn using Origin 2020, and the linear regression equation was obtained. The concentrations of the prepared series of samples were tested by HPLC, and the results of the drawn standard curve are shown in the figure below. Figure 6-10 As shown, the specific regression equation and R 2 The values ​​are shown in Table 7. From the results, we can see that the mass concentrations of the five samples are in the range of 1.25-40.00 mg / L, and their respective peak area-concentration standard curves show a good linear relationship. The R 2 All of them are greater than 0.9990, which meets the requirements of quantitative detection.

[0161] Table 7 Regression equations and R values ​​of the standard curves of the compounds 2 value

[0162]

[0163] 4) Photodegradation curve determination

[0164] UV degradation experiment: The mother solution of the compound was diluted to 40.00 mg / mL with chromatographic grade methanol, and the solution was placed under UV light (500W high mercury lamp) for about 10 cm for direct irradiation. A dark control was set at the same time. 1 mL of sample was taken at 0, 1, 2, 3, 5, 7, 10, 15, and 20 min of illumination, and filtered with a 0.22 μm organic filter membrane before analysis. Three parallel groups were set for each sampling and each experiment, and each experiment was repeated 3 times.

[0165] A 40 mg / L methanol solution of deltamethrin, bifenthrin, BFA-3-1, BFA-3-2, and BFA-3-4 was photodegraded under a 500W high-pressure mercury lamp. The degradation solutions sampled at various time points were analyzed by HPLC. The retention times of the compounds are shown in Table 8.

[0166] Table 8 Retention time of each compound HPLC

[0167]

[0168] The degradation rate of the compound at each time point was calculated using the peak area measured by HPLC and the standard curve regression equation. The photodegradation curve of the compound under ultraviolet light was drawn with the degradation rate as the ordinate and the time as the abscissa, as shown in the figure below. Figure 11 As shown. Figure 11 It can be seen that the degradation rate of cypermethrin and bifenthrin under ultraviolet light is higher than that of BFA-3-1, BFA-3-2 and BFA-3-4. The degradation rate of all compounds reached more than 90% within 15 minutes and was basically completely degraded in about 20 minutes. All compounds showed no obvious degradation under dark conditions.

[0169] Simulated solar degradation experiment: The compound stock solution was diluted to 40 mg / mL with chromatographic grade methanol. The solution was placed under a long arc xenon lamp (500W) at a distance of about 10 cm for direct illumination. A dark control was also set up. 1 mL of samples were collected at 0, 30, 60, 90, 120, 150, 180, 240, 300, and 360 min of illumination, respectively. The samples were filtered through a 0.22 μm organic filter membrane and analyzed. Three parallel groups were set up for each experiment, and each experiment was repeated three times.

[0170] HPLC was used to measure compound concentrations in the degradation solution under two different light sources (a 500W high-pressure mercury lamp and a 500W long-arc xenon lamp) for different illumination times. The compound degradation rates at different times were calculated based on the peak areas and the standard curve. A time-degradation rate curve was plotted with time as the abscissa and degradation rate as the ordinate. The compound degradation rate formula is shown below:

[0171]

[0172] Where C0 is the initial concentration of the compound, C t is the residual concentration of the compound at time t.

[0173] A 40 mg / L methanol solution of deltamethrin, bifenthrin, BFA-3-1, BFA-3-2 and BFA-3-4 was placed under a 500W long arc xenon lamp for photodegradation, and the degradation solution sampled at each time point was tested by HPLC.

[0174] The degradation rate of the compound at each time point was calculated using the peak area measured by HPLC and the standard curve regression equation. The photodegradation curve of the compound under simulated sunlight was drawn with the degradation rate as the ordinate and the time as the abscissa, as shown in Figure 2. Figure 12 As shown. Figure 12 Deltamethrin and bifenthrin degraded faster under simulated sunlight than BFA-3-1, BFA-3-2, and BFA-3-4, with degradation rates exceeding 80% for all compounds within 300 minutes. None of the compounds showed significant degradation within 360 minutes in the dark, indicating that methanol solutions of pyrethroid compounds are relatively stable in the dark and that degradation primarily originates from exposure to light.

[0175] 5) Determination of the photodegradation reaction order and half-life of compounds

[0176] The reaction order reflects the relationship between the concentration of reactants and the reaction rate in a chemical reaction. Generally speaking, the larger the reaction order of a chemical reaction, the greater the influence of the reactant concentration on the reaction rate of the chemical reaction. The calculation method takes the photodegradation of cypermethrin as an example.

[0177] Assume that deltamethrin in methanol solution undergoes the following reaction under UV light:

[0178] Deltamethrin + hγ → Product 1 + Product 2......

[0179] Assuming that the order of the photodegradation reaction of deltamethrin methanol solution is n, the rate equation of its photodegradation reaction can be expressed as:

[0180] d[A] / dt=k n [A] n

[0181] Where [A] is the concentration of deltamethrin corresponding to time t, k n is the reaction rate constant. Integrating the formula yields:

[0182] Assuming the reaction is a zero-order reaction (n=0),

[0183] [A]0-[A]=k0t

[0184] Assuming the reaction is first-order (n=1),

[0185] ln[A] / [A]0=-k1t

[0186] Assuming the reaction is a second-order reaction (n=2),

[0187] 1 / ([A])-1 / [A]0=k2t

[0188] Assuming the reaction is a tertiary reaction (n=3),

[0189]

[0190] Calculate the rate constant k based on the compound concentration at different times and each integral formula n If the k value required by an integral is n The value is a constant, then the k n The n value corresponding to the value is the reaction order of the reaction.

[0191] Table 9 k of photodegradation reaction of deltamethrin methanol solution under ultraviolet light n Value fitting results

[0192]

[0193] Table 10 k of photodegradation reaction of deltamethrin methanol solution under simulated sunlight n Value fitting results

[0194]

[0195] k of deltamethrin methanol solution under UV light and simulated sunlight n The fitting results are shown in Tables 9 and 10. From the results, we can see that when n = 1, the reaction rate k n The values ​​are relatively constant, indicating that the degradation reaction of cypermethrin methanol solution under ultraviolet light and simulated sunlight is a first-order reaction. According to the first-order reaction rate equation, -ln([A] / [A]0) is used as the vertical coordinate and time t is used as the horizontal coordinate to draw a linear regression equation. The slope is the reaction rate constant k. The half-life of the compound (t 1 / 2 ) is usually calculated using the following formula:

[0196] t 1 / 2 =0.693 / k

[0197] The k value in the formula is the rate constant.

[0198] The above method was used to calculate the k of each compound methanol solution under different light sources. n The linear function change of -ln([A] / [A]0) of the compound methanol solution under ultraviolet light and simulated sunlight with time is shown in the figure below. Figure 13-14 As shown, the regression equation, reaction rate constant (k) and half-life (t 1 / 2 ) as shown in Tables 11 and 12.

[0199] Table 11 Photodegradation reaction rate constant k and half-life t of compounds under UV light in methanol 1 / 2

[0200]

[0201]

[0202] Table 12 Photodegradation reaction rate constant k and half-life t of compounds in methanol under simulated sunlight 1 / 2

[0203]

[0204] Photodegradation experiments revealed that the photodegradation of pyrethroids in methanol is a first-order reaction, with degradation rates significantly higher under UV light than under simulated sunlight. Emission wavelength is related to energy distribution. High-pressure mercury lamps emit wavelengths concentrated in the ultraviolet region, resulting in shorter wavelengths and higher energy. In photodegradation experiments, UV light provides more energy to pyrethroids, exciting them more rapidly and facilitating further charge separation, thereby promoting photocatalytic activity and accelerating the degradation of pyrethroids.

[0205] Photostability plays a great limiting role in the application of pyrethroid compounds. The half-life of the compound is too long, making it difficult to degrade in the environment, which can easily lead to residues and enrichment, causing serious and persistent harm to the environment. If the half-life is too short or it is extremely unstable to light, it will limit the scope of use of the pesticide, causing the compound to be decomposed before it reaches its efficacy during use, and it will not be able to achieve an effective insecticide and pest control effect. Through photodegradation experiments, the photodegradation reaction rate and half-life of the new multi-fluoro pyrethroid compounds (BFA-3-1, BFA-3-2 and BFA-3-4) are similar to those of the positive controls cypermethrin and bifenthrin, indicating that the scope of use should also be similar to that of these two pyrethroid compounds, and can be widely used for mosquito control and agricultural pest control.

[0206] (2) Aquatic toxicity test methods

[0207] 1) Acute toxicity prediction

[0208] Toxicity prediction software uses modern computer technology, combined with chemistry, toxicology, and existing data, to predict the toxicity of new compounds, providing a theoretical basis for toxicity research of new compounds. This project used EeosarApplication 2.2 and TEST5.1.2 software to predict the toxicity of compounds with good activity.

[0209] Table 13 Results of acute toxicity prediction (Eeosar Application 2.2) of new polyfluoropyrethroid compounds

[0210]

[0211]

[0212] Table 14 Results of acute toxicity prediction (TEST5.1.2) of new polyfluoropyrethroid compounds

[0213]

[0214] The toxicity of the novel polyfluoropyrethroid compounds BFA-3-1, BFA-3-2, BFA-3-4, deltamethrin, and bifenthrin was predicted using the software Eeosar Application 2.2 and TEST5.1.2. The results are shown in Figures 13 and 14. Eeosar Application 2.2 predicted the toxicity to aquatic organisms (fish, water fleas, and green algae). The results showed that the acute aquatic toxicity of BFA-3-1, BFA-3-2, and BFA-3-4 was comparable to that of deltamethrin and less toxic than bifenthrin. TEST5.12 predicted the acute toxicity to aquatic organisms (fathead minnow and large Daphnia magna) and mammals (oral rats). The results showed that the aquatic toxicity of BFA-3-1, BFA-3-2, and BFA-3-4 was comparable to that of the positive controls (deltamethrin and bifenthrin), but their toxicity to mammals was 2-5 times lower than that of the positive controls.

[0215] 2) Zebrafish acute toxicity test

[0216] 2.1) Test organisms

[0217] Adult zebrafish (Danio rerio) were purchased from Nanjing EzeRinka Biotechnology Co., Ltd., approximately 3 months old, 3-5 cm long, and weighing approximately 300 mg. Upon receipt, the fish were placed in a constant temperature (28 ± 1°C) incubator for 1 hour. One-third of the packaging was filled with purified water. After 2 hours of stagnation, the fish were transferred to a plastic culture basin filled with purified water and cultured for 1 day under a 14:10 light-dark cycle. During this time, a small amount of fish feed (consumed within 3 minutes) was fed. After 2-3 days of acclimatization, the fish were ready for acute aquatic toxicity testing.

[0218] 2.2) Preparation of test sample solutions: Compounds (BFA-3-1, BFA-3-2, BFA-3-4, deltamethrin, and bifenthrin) were accurately prepared as 1 mg / mL methanol (analytical grade) solutions (stock solutions) and diluted with purified water to produce a series of test solutions at different concentrations. The test solution concentrations for deltamethrin were 0, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, and 0.06 mg / L; the test solution concentrations for bifenthrin were 0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, and 1.0 mg / L; and the test solution concentrations for compounds BFA-3-1, BFA-3-2, and BFA-3-4 were 0, 0.05, 0.1, 0.2, 0.4, 0.8, 1.6, and 3.2 mg / L.

[0219] The stock solutions (1 mg / L) of the compounds (BFA-3-1, BFA-3-2, BFA-3-4, deltamethrin, and bifenthrin) were irradiated under ultraviolet light and simulated natural light to completely degrade them (HPLC detection). The degradation solutions were diluted with pure water to obtain test solutions of 0.05, 0.50, and 2.50 mg / L.

[0220] 2.3) Adult zebrafish exposure experiment

[0221] 2L of test solution at different concentrations was added to plastic culture basins, and 10 adult zebrafish were added to each basin. The blank control was a pure water solution containing 4% methanol, and three parallel groups were set up for each concentration. The culture basins were placed in a laboratory at 28±1°C with a light-dark cycle of 14h:10h. The test lasted for 96h, and the exposure solution was changed every 24h. The mortality rate was recorded at 24, 48, and 96h (the zebrafish's tail was gently touched with a clean disposable pipette. If there was no physiological activity, it was considered dead). No food was fed during the exposure period, and dead fish and debris were picked out promptly.

[0222] 2.4) Data statistics and processing: Excel, Origin 2020, and SPSS 25.0 were used for data processing to obtain the concentration-mortality fitting curve and the 24-, 48-, and 96-h LC50 values. 50 .

[0223] Acute toxicity tests on zebrafish were conducted on BFA-3-1, BFA-3-2, BFA-3-4, deltamethrin, and bifenthrin. The results are shown in Table 15. It was found that the acute toxicity of BFA-3-1, BFA-3-2, and BFA-3-4 to zebrafish was lower than that of deltamethrin and bifenthrin, about 10 times lower than that of deltamethrin and about 3 times lower than that of bifenthrin, indicating that the toxicity to aquatic organisms was greatly improved.

[0224] Table 15 Acute toxicity median lethal concentration (LC50) of novel polyfluoropyrethroid compounds to zebrafish50 )result

[0225]

[0226] Table 16 Results of acute toxicity of novel polyfluoropyrethroid compound photodegradation products to zebrafish

[0227]

[0228] Solutions of the photodegradation products of the compounds (BFA-3-1, BFA-3-2, BFA-3-4, deltamethrin, and bifenthrin) were tested for acute toxicity in zebrafish, and the results are shown in Table 16. The results showed that after exposure to UV light and simulated natural light, the zebrafish mortality rates of the photodegradation products of all compounds were essentially the same. Among them, the photodegradation products of deltamethrin were the most toxic, approximately 10 times that of the other compounds, due to the high toxicity of the α-cyano group and the reported degradation product dibenzofuran. The photodegradation products of the novel pyrethroid compounds BFA-3-1, BFA-3-2, BFA-3-4, and bifenthrin were similar in toxicity, consistent with the acute toxicity results for the compounds in zebrafish. Based on a comprehensive evaluation of the anti-mosquito activity, photostability and aquatic toxicity of the compounds, compounds BFA-3-1, BFA-3-2 and BFA-3-4 can be considered as new pyrethroid insecticides to alleviate the problem of mosquito resistance to cypermethrin and bifenthrin.

[0229] The above is a specific implementation of the present invention, and its description is relatively specific and detailed, but it should not be understood as limiting the scope of the present invention. For those skilled in the art, various modifications and improvements can be made without departing from the concept of the present invention, and these obvious alternative forms are all within the scope of protection of the present invention.

Claims

1. A polyfluoropyrethroid compound, characterized in that: The structural formula of the polyfluoropyrethroid compound is: wherein R is one of H, F and Br.

2. The method for synthesizing polyfluoropyrethroid compounds according to claim 1, wherein: The following steps are involved: S1. Weigh trifluoroacetic acid BFA, 4-dimethylaminopyridine DMAP, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDCI and the intermediate into a round-bottom flask. The molar ratio of trifluoroacetic acid BFA, 4-dimethylaminopyridine DMAP, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride EDCI and the intermediate is 1:2:2:1.

5. The structural formula of the intermediate is R is one of H, F and Br; S2. Add appropriate amount of dichloromethane to the round-bottom flask, stir, and react at room temperature for 6 hours. obtaining a reaction product; S3. Add saturated salt water and dichloromethane to extract the reaction product, shake well and let stand to separate the layers, and collect the dichloromethane layer after separation; S4. After removing part of the organic solvent in the dichloromethane layer by evaporation, an appropriate amount of crude silica gel is added, stirred, and purified by silica gel chromatography to obtain a novel polyfluoropyrethroid compound.

3. The method for synthesizing polyfluoropyrethroid compounds according to claim 2, characterized in that: The synthesis method of the intermediate is as follows: weighing a secondary reactant into a corresponding round-bottom flask, placing the flask in an ice-water bath and cooling it to 0°C, slowly adding an appropriate amount of anhydrous methanol, stirring until completely dissolved, then adding sodium borohydride, continuing to stir for 10 minutes, removing the ice-water bath, and reacting at room temperature for 2 hours, wherein the molar ratio of the secondary reactant to the sodium borohydride is 1:1.5; after the reaction is completed, placing the round-bottom flask in an ice-water bath, slowly adding a 2 mol / L hydrochloric acid solution to quench the sodium borohydride until no bubbles are generated, thereby obtaining a secondary reaction liquid; adding saturated salt water and ethyl acetate to the secondary reaction liquid for extraction, and collecting the ethyl acetate layer; evaporating and removing part of the organic solvent in the ethyl acetate layer, adding an appropriate amount of crude silica gel, stirring, and purifying by a silica gel chromatography column to obtain the intermediate; wherein the structural formula of the secondary reactant is R is one of H, F and Br.

4. The method for synthesizing the polyfluoropyrethroid compound according to claim 3, wherein: The synthesis method of the secondary reactant is as follows: 3-hydroxybenzaldehyde and cesium carbonate are weighed in a dry two-necked round-bottom flask; under nitrogen protection, an appropriate amount of anhydrous dimethyl sulfoxide is added to the two-necked round-bottom flask; the primary reactant is slowly added with stirring, and the reaction is stirred at 25° C. for 6 hours to obtain a primary reaction solution; pure water, saturated salt water and dichloromethane are added to the primary reaction solution, and the pH of the primary reaction solution is adjusted to 3-4 with a 2 mol / L hydrochloric acid solution, and the dichloromethane layer is collected after shaking and layering, and part of the organic solvent in the dichloromethane layer is evaporated to remove, and an appropriate amount of coarse silica gel is added and stirred, and then purified by silica gel chromatography to obtain a secondary reactant; the molar ratio of 3-hydroxybenzaldehyde, cesium carbonate and primary reactant is 2:3:3; the structural formula of the primary reactant is R is one of H, F and Br.

5. The method for synthesizing the polyfluoropyrethroid compound according to claim 4, wherein: The trifluoroacetic acid BFA is obtained by adding sodium hydroxide to a 50% ethanol solution of bifenthrin, hydrolyzing the solution at 95° C., and then extracting the solution. The molar ratio of bifenthrin to sodium hydroxide is 1:

3.

6. The method for synthesizing the polyfluoropyrethroid compound according to claim 5, characterized in that: The reaction endpoints of trifluoroacetic acid, secondary reactants, intermediates and novel polyfluoropyrethroid compounds were detected by thin layer chromatography.

7. The method for synthesizing the polyfluoropyrethroid compound according to claim 5, characterized in that: The aqueous phase extracted during the reaction of trifluoroacetic acid, secondary reactants, intermediates and novel polyfluoropyrethroid compounds is extracted with a corresponding organic phase solvent and then transferred to a corresponding organic phase layer.

8. The method for synthesizing polyfluoropyrethroid compounds according to claim 3, characterized in that: During the reaction of trifluoroacetic acid, secondary reactants, intermediates and novel polyfluoropyrethroid compounds, anhydrous magnesium sulfate is added to the organic phase layer after extraction several times in small amounts to remove residual water.

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