Benzimidazole salt compound with insecticidal activity, preparation method and application

Abstract

The invention discloses a benzimidazole salt compound with insecticidal activity as well as a preparation method and application thereof, and aims to solve the problem that an existing insecticide cannot give consideration to insecticidal activity and resistance at the same time. The salt compound containing the benzimidazole structure provided by the invention has good insecticidal activity on aedes aegypti, mythimna orientalis and plutella xylostella, has no cross resistance or obvious negative cross resistance on aedes aegypti pyrethroid-resistant strains, and has the control effect on the plutella xylostella equivalent to that of commercial insecticide permethrin sold in the market. A lead compound with application potential and an innovative research and development thought are provided for creating novel resistance treatment pesticides with negative cross resistance characteristics.

Description

Technical Field

[0001] This invention relates to the fields of medicinal chemistry and plant protection technology, specifically to a benzimidazole salt compound with insecticidal activity, its preparation method, and its application. Background Technology

[0002] With the continued rapid growth of the global population, food security has become a major challenge facing human society. Plant diseases and pests, as major threats to agricultural production, seriously affect food supply security and the balance of plant ecosystems. These harmful organisms not only cause damage such as reduced crop yields, slowed growth, and leaf drop, but may also trigger secondary diseases. Statistics show that more than 50% of annual crop yield losses are caused by diseases and pests. Pesticides, as an indispensable plant protection tool in modern agricultural production systems, play a crucial role in pest control, ensuring agricultural harvests, and maintaining food security. However, the long-term and extensive use of traditional chemical pesticides, while bringing huge economic benefits, has also brought adverse effects such as environmental pollution, resistance, resurgence, and residues. To address these problems with current pesticides, it is essential to develop new, green, efficient, and low-risk pesticides.

[0003] Benzimidazole, as a nitrogen-containing bicyclic heterocyclic compound, has become a core framework for drug design due to its broad biological activity and excellent structural modifiability. Drugs developed based on its structure cover not only anti-infective fields such as antiparasitic and antifungal agents, and anti-proliferative activities such as antitumor and antimalarial drugs, but also various active drugs for treating metabolic diseases such as hypertension and regulating the nervous system such as anticonvulsants. Imidazole salts belong to the ionic liquid category and possess environmentally friendly properties such as low volatility and high thermal stability, as well as bioactivity driven by structure design. These properties give imidazole salts enormous application potential and unique technological advantages in the field of green pesticide creation. Therefore, researching novel benzimidazole salt compounds, exploring their structure-activity relationships, and screening highly active, highly selective, and environmentally friendly lead compounds is of significant theoretical and practical value for promoting the innovative development of next-generation green pesticides. Summary of the Invention

[0004] To overcome the above-mentioned technical defects, the present invention provides a benzimidazole salt compound with insecticidal activity, its preparation method and application.

[0005] The technical solution of the present invention is as follows:

[0006] A benzimidazole salt compound with insecticidal activity, the general structural formula of which is shown in Formula I and / or Formula II: Formula I; Formula II; In formula I, R1 is at least one of H or halogen; R2 is selected from at least one of H, hydroxyl, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-C6 hydrocarbon, C1-C6 alkoxy and C1-C6 alkylamine. R3 is selected from at least one of H, hydroxyl, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-C6 hydrocarbon, C1-C6 alkoxy, C1-C6 alkylamine, C1-C12 alkyl, C1-C12 alkenyl and C1-C12 alkynyl. In Formula II, R1 is at least one of CH3 or a halogen; R2 is selected from at least one of H, hydroxyl, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-C6 hydrocarbon, C1-C6 alkoxy, C1-C6 alkylamine, C1-C12 alkyl, C1-C12 alkenyl and C1-C12 alkynyl.

[0007] Optionally, the compound in Formula I includes at least one of the following: .

[0008] Optionally, the compound in Formula II includes at least one of the following: .

[0009] The method for preparing any of the insecticidal benzimidazole salt compounds according to the present invention includes the following synthetic route: .

[0010] Optionally, the synthesis steps of the compound in Formula I include: Step 1: Add compound a and the acid-binding agent to an organic solvent, heat the mixture for a period of time, then lower the temperature. Add compound b dropwise, maintaining the temperature until the reaction is complete. After cooling to room temperature, add distilled water, filter, collect the solid, wash, and dry to obtain intermediate c. The structural formula of compound a is: The structural formula of compound b is: ; Step 2: Dissolve intermediate c and compound d in a solvent and heat the mixture until complete. After cooling, add a mixed solvent, collect the precipitated solid, wash and dry it to obtain product (I); The structural formula of compound d is: .

[0011] Optionally, the organic solvent is dimethyl sulfoxide, and the acid-binding agent is potassium hydroxide; the molar ratio of compound a to potassium hydroxide is 1:1.5, and the reaction temperature is 100°C; the molar ratio of compound a to compound b is 1:1, and the reaction temperature is 40°C; the organic solvent is anhydrous. N , N -Dimethylformamide; the molar ratio of intermediate c to compound d is 1:1, the reaction temperature is 80℃; the mixed solvent is petroleum ether and ethyl acetate. v / v =2 / 1.

[0012] Optionally, the synthesis steps of the compound in Formula II include: Step 1: Add compound e and the acid-binding agent to an organic solvent, heat the mixture for a period of time, then lower the temperature. Add compound f dropwise, maintaining the temperature until the reaction is complete. After cooling to room temperature, add distilled water, filter, collect the solid, wash, and dry to obtain intermediate g. The structural formula of compound e is: The structural formula of compound f is: ; Step 2: Dissolve intermediate g and compound h in an organic solvent, heat and react until complete; cool, add mixed solvent, collect the precipitated solid, wash and dry to obtain formula (II). The structural formula of compound h is: .

[0013] Optionally, the organic solvent is dimethyl sulfoxide, and the acid-binding agent is potassium hydroxide; the molar ratio of compound e to potassium hydroxide is 1:1.5, and the reaction temperature is 100°C; the molar ratio of compound e to compound f is 1:1, and the reaction temperature is 40°C; the organic solvent is anhydrous. N , N -Dimethylformamide; the molar ratio of intermediate g to compound h is 1:1, the reaction temperature is 80℃; the mixed solvent is petroleum ether to ethyl acetate. v / v =2 / 1.

[0014] The application of any of the benzimidazole salt compounds with insecticidal activity described in this invention in the preparation of insecticides.

[0015] Optionally, the insecticide is used to control armyworm, diamondback moth, cereal aphid and / or Aedes aegypti mosquito.

[0016] The advantages of this invention compared to the prior art are: The activity against diamondback moth is comparable to that of the commercial drug permethrin. The compound exhibits negative cross-resistance characteristics, providing a new strategy for overcoming existing bottlenecks in resistance management. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0018] The benzimidazole salt compounds with insecticidal activity provided by this invention have the following general structural formulas: Formula I or Formula II: Formula I; Formula II; In Formula I, R1 is at least one of H or halogen; R2 is selected from at least one of H, hydroxyl, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-C6 hydrocarbon, C1-C6 alkoxy, and C1-C6 alkylamine; and R3 is selected from at least one of H, hydroxyl, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-C6 hydrocarbon, C1-C6 alkoxy, C1-C6 alkylamine, C1-C12 alkyl, C1-C12 alkenyl, and C1-C12 alkynyl.

[0019] In Formula II, R1 is at least one of CH3 or halogen; R2 is selected from at least one of H, hydroxyl, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-C6 hydrocarbon and C1-C6 alkoxy, C1-C6 alkylamine, C1-C12 alkyl, C1-C12 alkenyl and C1-C12 alkynyl.

[0020] The method for preparing benzimidazole salt compounds provided by this invention comprises the following steps: Synthesis steps of Formula I: ; Step 1: Add compound a and the acid-binding agent to an organic solvent, heat the mixture for a period of time, then lower the temperature. Add compound b dropwise, maintaining the temperature until the reaction is complete. After cooling to room temperature, add distilled water, filter, collect the solid, wash, and dry to obtain intermediate c.

[0021] The structural formula of compound a is: ; The structural formula of compound b is: ; Step 2: Dissolve intermediate c and compound d in an organic solvent and heat the mixture until complete. After cooling, add a mixed solvent, collect the precipitated solid, wash and dry it to obtain product I.

[0022] The structural formula of compound d is: ; R1, R2, and R3 in compounds a, b, and d are defined as described above.

[0023] In step one, the organic solvent is dimethyl sulfoxide, and the acid-binding agent is potassium hydroxide; the molar ratio of compound a to the acid-binding agent is 1:1.5; the temperature during the heating reaction is 100℃; the molar ratio of compound a to compound b is 1:1; the temperature during the dropwise addition of compound b is 40℃; the added distilled water is in an ice-water mixture; the drying temperature is 50℃, and the drying is carried out under vacuum. The organic solvent in step two is anhydrous. N , N -Dimethylformamide; the molar ratio of intermediate c to compound d is 1:1; the reaction temperature is 80℃; the mixed solvent is petroleum ether / ethyl acetate ( v / v =2 / 1); In step two, the washing solution used is petroleum ether / ethyl acetate ( v / v =2 / 1); drying temperature is 50℃, vacuum drying.

[0024] Synthesis steps of Formula II: ; Step 1: Add compound e and the acid-binding agent to an organic solvent, heat the mixture for a period of time, then lower the temperature. Add compound f dropwise, maintaining the temperature until the reaction is complete. After cooling to room temperature, add distilled water, filter, collect the solid, wash, and dry to obtain intermediate g.

[0025] The structural formula of compound e is: ; The structural formula of compound f is: ; Step 2: Dissolve intermediate g and compound h in an organic solvent and heat the mixture until complete. After cooling, add a mixed solvent, collect the precipitated solid, wash and dry it to obtain Formula II.

[0026] The structural formula of compound h is: ; R1 and R2 in compounds e and f are defined as described above.

[0027] In step one, the organic solvent is dimethyl sulfoxide; the acid-binding agent is potassium hydroxide; the molar ratio of compound e to the acid-binding agent is 1:1.5; the temperature during the heating reaction is 100℃; the molar ratio of compound e to compound f is 1:1; the temperature during the dropwise addition of compound f is 40℃; the added distilled water is in an ice-water mixture state; the drying temperature is 50℃, and the drying is carried out under vacuum.

[0028] The organic solvent in step two is anhydrous. N , N-Dimethylformamide; the molar ratio of intermediate g to compound h is 1:1; the reaction temperature is 80℃; the mixed solvent is petroleum ether / ethyl acetate ( v / v =2 / 1); In step two, the washing solution used is petroleum ether / ethyl acetate ( v / v =2 / 1); the drying temperature in step two is 50℃, and vacuum drying is performed.

[0029] The present invention relates to the application of benzimidazole salt compounds with insecticidal activity in insecticidal applications. Further, the test insects are Lepidoptera, Diptera, or Hemiptera. Even more specifically, the test insects are at least one of the following: third instar larvae of the Oriental armyworm, third instar larvae of the diamondback moth, wingless adult aphids of the cereal tube aphid, or third instar larvae of the Aedes aegypti mosquito.

[0030] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials, reagents, methods, and instruments used are all conventional materials, reagents, methods, and instruments in the art, and can be obtained commercially by those skilled in the art.

[0031] The structures of the compounds in the following examples were determined by nuclear magnetic resonance (NMR) and mass spectrometry (MS).

[0032] Example 1: Preparation of 1-benzyl-3-(2,4-dichlorobenzyl)-2-phenyl-1H-benzo[d]imidazol-3-onium bromide (I-1) ; Step 1: Preparation of intermediate c In a round-bottom flask, 2-phenylbenzimidazole (8.46 mmol), potassium hydroxide (12.69 mmol), and DMSO (10 mL) were added, and the mixture was stirred at 100°C for 2 hours. The temperature was lowered to 40°C, and benzyl bromide (8.46 mmol) was added dropwise while maintaining this temperature and stirring. The reaction progress was monitored by thin-layer chromatography (TLC) until complete. The mixture was cooled to room temperature, and ice water (20 mL) was added. The white solid was collected by filtration, washed with cold water, and dried under vacuum at 50°C for 24 hours to obtain intermediate c.

[0033] Step 2: Preparation of 1-benzyl-3-(2,4-dichlorobenzyl)-2-phenyl-1H-benzo[d]imidazol-3-onium bromide (I-1) Intermediate C (1 mmol) and 2,4-dichlorobenzyl bromide (1 mmol) were dissolved in anhydrous water. N , NThe mixture was stirred at 80°C for 24 hours in dimethylformamide (2 mL). After cooling to room temperature, petroleum ether / ethyl acetate (v / v = 2 / 1) was added. The precipitated solid was collected by suction filtration and washed with a mixed solvent (petroleum ether / ethyl acetate = 2 / 1). The product was dried under vacuum at 50°C for 24 hours to give 1-benzyl-3-(2,4-dichlorobenzyl)-2-phenyl-1H-benzo[d]imidazol-3-onium bromide. White solid, yield: 72%.

[0034] Product detection data are as follows: mp: 81.4-82.1 ℃; 1 H NMR (400 MHz, Chloroform- d ) δ7.91 (d, J = 7.3 Hz, 2H), 7.74 – 7.48 (m, 8H), 7.31 (dd, J = 8.1, 2.3 Hz, 4H), 7.22 (dd, J = 8.4, 2.2 Hz, 1H), 7.17 – 7.05 (m, 2H), 5.77 (s, 2H), 5.66 (s, 2H); 13 C NMR (101 MHz, Chloroform- d ) δ 151.84, 135.77, 133.62, 133.41, 133.26,131.84, 131.55, 131.54, 130.75, 130.04, 129.79, 129.52, 128.93, 128.90,128.49, 127.72, 127.69, 126.71, 120.69, 114.43, 113.96, 51.10, 48.68. MS [M-Br] + calcd for C 27 H 21 Cl2N2 + : 443.11, found:443.11. The structure of the obtained product, after characterization, is as follows: ; Example 2 Preparation of 1-benzyl-2-phenyl-3-(2-(trifluoromethyl)phenylmethyl)-1H-benzo[d]imidazol-3-onium bromide (I-2) The difference between this embodiment and Example 1 is that in step 2, 2,4-dichlorobenzyl bromide is replaced with 2-trifluoromethylbenzyl bromide. Other steps and parameters are the same as in Example 1. 1-Benzyl-2-phenyl-3-(2-(trifluoromethyl)phenylmethyl)-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a white solid with a yield of 77%.

[0035] Product detection data are as follows: mp: 106.5-108.2 ℃; 1 H NMR (400 MHz, Chloroform- d )δ 7.92 – 7.87 (m, 2H), 7.76 (d, J = 8.3 Hz, 1H), 7.68 (dt, J = 6.3, 3.6 Hz, 2H),7.60 – 7.54 (m, 5H), 7.51 (d, J = 7.3 Hz, 1H), 7.45 (s, 1H), 7.38 (d, J = 8.0 Hz,1H), 7.33 – 7.30 (m, 3H), 7.15 – 7.09 (m, 2H), 5.77 (d, J = 15.6 Hz, 4H); 13 C NMR (101 MHz, Chloroform- d ) δ 152.06, 133.84 (d, J = 1.1 Hz), 133.71, 133.54,132.17, 131.51, 130.67, 130.11, 129.49, 129.42, 129.29, 129.17, 129.02,128.94, 128.26 (d, J = 254.2 Hz), 127.96, 127.83, 126.97, 126.69 (d, J = 5.9 Hz),120.53, 114.99, 113.46, 51.56, 47.59 (d, J = 3.4 Hz). MS [M-Br] + calcd forC 28 H 22 F3N2 + : 443.17, found:443.17. The structure of the obtained product, after characterization, is as follows: ; Example 3 Preparation of 1-benzyl-2-phenyl-3-(3-(trifluoromethoxy)phenylmethyl)-1H-benzo[d]imidazol-3-onium bromide (I-3) The difference between this embodiment and Example 1 is that in step 2, 2,4-dichlorobenzyl bromide is replaced with 3-trifluoromethoxybenzyl bromide. Other steps and parameters are the same as in Example 1. 1-Benzyl-2-phenyl-3-(3-(trifluoromethoxy)phenylmethyl)-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a white solid with a yield of 81%.

[0036] Product detection data are as follows: mp: 108.1-109.5 ℃; 1 H NMR (400 MHz, Chloroform- d )δ 7.90 – 7.87 (m, 2H), 7.77 – 7.68 (m, 2H), 7.65 – 7.53 (m, 5H), 7.37 (t, J =8.0 Hz, 1H), 7.33 – 7.29 (m, 3H), 7.22 (ddd, J = 8.0, 1.8, 1.0 Hz, 1H), 7.17 –7.10 (m, 3H), 6.86 (s, 1H), 5.80 (s, 2H), 5.65 (s, 2H); 13 C NMR (101 MHz, Chloroform- d ) δ 151.64, 149.66 (d, J = 2.2 Hz), 135.64, 133.72, 133.02, 131.74,131.70, 131.27, 130.73, 130.17, 129.56, 129.05, 127.89, 127.82, 126.85,125.75, 121.24, 120.61, 120.34 (d, J = 258.2 Hz), 119.30, 114.31, 114.28,50.95, 50.42. MS [M-Br] + calcd for C 28 H 22 F3N2O + : 459.17, found:459.17. The structure of the obtained product, after characterization, is as follows: ; Example 4 Preparation of 1-benzyl-3-(3-methoxybenzyl)-2-phenyl-1H-benzo[d]imidazol-3-onium bromide (I-4) The difference between this embodiment and Example 1 is that in step 2, 2,4-dichlorobenzyl bromide is replaced with 3-methoxybenzyl bromide. Other steps and parameters are the same as in Example 1. 1-Benzyl-3-(3-methoxybenzyl)-2-phenyl-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a yellow solid with a yield of 77%.

[0037] Product detection data are as follows: mp: 72.8-73.3 ℃; 1 H NMR (400 MHz, DMSO- d 6) δ 8.09 –7.99 (m, 2H), 7.92 (d, J = 9.4 Hz, 2H), 7.80 (t, J = 7.4 Hz, 1H), 7.76 – 7.67 (m,4H), 7.31 (d, J = 3.2 Hz, 3H), 7.26 – 7.16 (m, 3H), 6.87 (d, J = 9.4 Hz, 1H), 6.76 (d, J = 7.4 Hz, 2H), 5.61 (d, J = 16.4 Hz, 4H), 3.68 (s, 3H); 13 C NMR (101MHz, DMSO- d 6) δ 159.40, 159.40, 150.98, 135.28, 133.85, 133.15, 131.27,131.26, 130.43, 129.99, 129.68, 128.78, 128.33, 127.22, 127.03, 121.00,119.23, 114.13, 114.09, 113.61, 113.28, 55.11, 49.27, 49.15. MS [M-Br] + calcdfor C 28 H 25 N2O + : 405.20, found:405.20. The structure of the obtained product, after characterization, is as follows: ; Example 5 Preparation of 1-benzyl-3-decyl-2-phenyl-1H-benzo[d]imidazol-3-onium bromide (I-5) The difference between this embodiment and Example 1 is that in step 2, 2,4-dichlorobenzyl bromide is replaced with decane bromide. Other steps and parameters are the same as in Example 1. 1-Benzyl-3-decyl-2-phenyl-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a yellow oily substance with a yield of 61%.

[0038] The product test data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.85 (dd, J = 15.9,7.7 Hz, 3H), 7.76 – 7.53 (m, 6H), 7.32 – 7.26 (m, 3H), 7.10 – 7.03 (m, 2H), 5.62 (s, 2H), 4.45 – 4.33 (m, 2H), 1.83 (p, J = 7.4 Hz, 2H), 1.13 (s, 14H), 0.84 (t, J = 7.0 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) δ 133.50, 133.22,131.64, 131.28, 130.47, 130.10, 129.35, 128.88, 127.63, 127.52, 126.89,120.81, 114.40, 113.61, 77.10, 50.65, 47.23, 34.62, 31.80, 29.35, 29.22,29.18, 28.73, 26.48, 22.62, 14.10.MS [M-Br] + calcd for C 30 H 37 N2 + : 425.30, found:425.30.. The structure of the obtained product, after characterization, is as follows: ; Example 6 Preparation of 1-benzyl-3-dodecyl-2-phenyl-1H-benzo[d]imidazol-3-onium bromide (I-6) The difference between this example and Example 1 is that in step 2, 2,4-dichlorobenzyl bromide is replaced with dodecyl bromide. Other steps and parameters are the same as in Example 1. 1-Benzyl-3-dodecyl-2-phenyl-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a yellow oil; yield 58%.

[0039] The product test data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 7.93 – 7.54 (m,10H), 7.27 (s, 4H), 7.05 (s, 2H), 5.58 (s, 2H), 4.39 (s, 2H), 1.84 (s, 2H),1.19 (s, 16H), 0.83 (t, J = 6.8 Hz, 3H); 13 C NMR (101 MHz, Chloroform- d ) δ150.56, 133.61, 133.34, 133.10, 131.68, 131.34, 130.73, 130.23, 129.65,129.39, 128.93, 127.76, 127.68, 127.08, 120.71, 114.60, 113.89, 34.77, 31.81,29.50, 29.48, 29.44, 29.37, 29.23, 29.21, 28.75, 26.57, 22.60, 14.07.MS [M-Br] + calcd for C 32 H 41 N2 + :453.33, found:453.33. The structure of the obtained product, after characterization, is as follows: ; Example 7 Preparation of 1-(2,4-dichlorobenzyl)-3-(3-methoxybenzyl)-2-phenyl-1H-benzo[d]imidazol-3-onium bromide (I-7) The difference between this embodiment and Example 4 is that benzyl bromide is replaced with 2,4-dichlorobenzyl bromide in step 1. Other steps and parameters are the same as in Example 4. 1-(2,4-dichlorobenzyl)-3-(3-methoxybenzyl)-2-phenyl-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a grayish-white solid; yield 49%.

[0040] Product detection data are as follows: mp: 106.7-108.1 ℃; 1 H NMR (400 MHz, Chloroform- d )δ 7.93 (d, J= 7.1 Hz, 2H), 7.73 – 7.64 (m, 2H), 7.63 – 7.53 (m, 6H), 7.35 (d, J = 2.1 Hz, 1H), 7.28 (d, J = 2.0 Hz, 1H), 7.23 (d, J = 4.6 Hz, 1H), 6.90 – 6.82(m, 1H), 6.67 (d, J = 7.1 Hz, 2H), 5.78 (s, 2H), 5.66 (s, 2H), 3.75 (s, 3H); 13 CNMR (101 MHz, Chloroform- d ) δ 160.37, 151.89, 135.96, 134.99, 133.73, 132.00,131.67, 131.62, 130.75, 130.71, 130.11, 130.00, 128.99, 128.47, 127.83,127.78, 118.64, 114.71, 114.20, 114.07, 112.72, 55.58, 34.66.MS [M-Br] + calcdfor C 28 H 23 Cl2N2O + :473.12, found:473.12. The structure of the obtained product, after characterization, is as follows: ; Example 8 Preparation of 1,3-bis(2,4-dichlorophenylmethyl)-2-phenyl-1H-benzimidazole-3-onium bromide (I-8) The difference between this example and Example 7 is that in step 2, 3-methoxybenzyl bromide is replaced with 2,4-dichlorobenzyl bromide. Other steps and parameters are the same as in Example 7. 1,3-bis(2,4-dichlorophenylmethyl)-2-phenyl-1H-benzimidazole-3-onium bromide is obtained. It is a white solid; yield 41%.

[0041] Product detection data are as follows: mp: 125.6-126.8℃; 1 H NMR (400 MHz, Chloroform- d ) δ8.03 – 7.96 (m, 2H), 7.68 (t, J= 7.5 Hz, 1H), 7.61 – 7.49 (m, 6H), 7.41 – 7.35(m, 4H), 7.24 (dd, J = 8.4, 2.1 Hz, 2H), 5.78 (s, 4H); 13 C NMR (101 MHz, Chloroform- d ) δ 152.10, 135.92, 133.67, 133.55, 131.71, 131.20, 130.83,130.08, 129.96, 128.54, 127.89, 120.74, 114.13, 48.93. MS [M-Br] + calcd forC 27 H 19 C l4 N2 + :511.03, found:511.03. The structure of the obtained product, after characterization, is as follows: ; Example 9 Preparation of 1,3-dibenzyl-2-phenyl-1H-benzo[d]imidazol-3-onium bromide (I-9) Step 1: Preparation of intermediate c The difference between this embodiment and Example 1 is that in step 2, 2,4-dichlorobenzyl bromide is replaced with benzyl bromide. Other steps and parameters are the same as in Example 1. 1,3-Dibenzyl-2-phenyl-1H-benzo[d]imidazol-3-onium bromide (I-9) is obtained. It is a white solid; yield 54%.

[0042] Product detection data are as follows: mp: 70.7-71.3℃; 1 H NMR (400 MHz, DMSO- d 6) δ 8.02(dd, J = 6.0, 2.8 Hz, 2H), 7.92 – 7.86 (m, 2H), 7.82 – 7.76 (m, 1H), 7.73 –7.66 (m, 4H), 7.36 – 7.28 (m, 6H), 7.22 – 7.15 (m, 4H), 5.62 (s, 4H); 13 C NMR (101 MHz, DMSO-) d6) δ 151.08, 133.87, 133.17, 131.29, 130.41, 129.69, 128.82,128.37, 127.24, 127.07, 121.00, 114.12, 49.25. MS [M-Br] + calcd for C 27 H 23 N2 + :375.19, found:375.19. The structure of the obtained product, after characterization, is as follows: ; Example 10 Preparation of 1,3-dibenzyl-2-(2-chlorophenyl)-1H-benzo[d]imidazol-3-onium bromide (I-10) Step 1: Preparation of intermediate c The difference between this example and Example 9 is that 2-phenylbenzimidazole in step 1 is replaced with 2-(2-chlorophenyl)benzimidazole. Other steps and parameters are the same as in Example 1. 1,3-Dibenzyl-2-(2-chlorophenyl)-1H-benzo[d]imidazole-3-onium bromide (I-10) was obtained. It was a yellow solid; yield 44%.

[0043] Product test data are as follows: mp: melting point 75.5-76.9℃; 1 H NMR (400 MHz, DMSO- d 6) δ8.23 – 8.15 (m, 3H), 7.88 – 7.82 (m, 1H), 7.79 – 7.72 (m, 4H), 7.29 (dd, J =5.0, 2.0 Hz, 6H), 7.11 (dd, J = 6.5, 3.0 Hz, 4H), 5.67 (s, 4H); 13 C NMR (101 MHz, DMSO- d 6) δ 147.81, 135.44, 133.89, 133.31, 133.00, 131.29, 130.56, 128.81,128.68, 128.57, 127.71, 127.58, 120.23, 114.48, 49.49. MS [M-Br] + calcd forC 27 H 22 ClN2 + :409.15, found:409.15. The structure of the obtained product, after characterization, is as follows: ; Example 11: Preparation of 1-benzyl-3-(2,4-dichlorobenzyl)-5,6-dimethyl-1H-benzo[d]imidazol-3-onium bromide (II-1) Step 1: Preparation of intermediate g In a round-bottom flask, 5,6-dimethylbenzimidazole (8.46 mmol), potassium hydroxide (12.69 mmol), and DMSO (10 mL) were added, and the mixture was stirred at 100°C for 2 hours. The temperature was lowered to 40°C, and benzyl bromide (8.46 mmol) was added dropwise while maintaining this temperature and stirring. The reaction progress was monitored by thin-layer chromatography (TLC) until complete. The mixture was cooled to room temperature, and ice water (20 mL) was added. The white solid was collected by filtration, washed with cold water, and dried under vacuum at 50°C for 24 hours to give intermediate g.

[0044] Step 2: Preparation of 1-benzyl-3-(2,4-dichlorobenzyl)-5,6-dimethyl-1H-benzo[d]imidazol-3-onium bromide (II-1) Intermediate C (1 mmol) and 2,4-dichlorobenzyl (1 mmol) were dissolved in anhydrous water. N , N The mixture was stirred in 2 mL of dimethylformamide at 80°C for 24 hours. After cooling to room temperature, petroleum ether / ethyl acetate (v / v = 2 / 1) was added. The precipitated solid was collected by suction filtration and washed with a mixed solvent (petroleum ether / ethyl acetate = 2 / 1). The product was dried under vacuum at 50°C for 24 hours to give 1,3-dibenzyl-2-(2-chlorophenyl)-1H-benzo[d]imidazolium-3-onium bromide. White solid; yield 71%.

[0045] Product detection data are as follows: mp: 108.1-109.5℃; 1 H NMR (400 MHz, Chloroform- d ) δ11.40 (s, 1H), 7.72 (d, J = 8.3 Hz, 1H), 7.45 (d, J = 6.3 Hz, 2H), 7.40 (s, 1H), 7.34 (d, J = 8.5 Hz, 4H), 7.28 (d, J = 6.9 Hz, 2H), 5.92 (s, 2H), 5.80 (s, 2H), 2.32 (d, J = 6.0 Hz, 6H); 13C NMR (101 MHz, Chloroform- d ) δ 142.47, 137.76,137.70, 136.23, 134.34, 132.79, 132.27, 130.02, 129.85, 129.79, 129.48,129.29, 129.11, 128.55, 128.19, 113.47, 113.23, 51.57, 48.03, 20.86, 20.78.MS[M-Br] + calcd for C 23 H 21 Cl2N2 + :395.11, found:395.11. The structure of the obtained product, after characterization, is as follows: ; Example 12 Preparation of 1-benzyl-3-dodecyl-5,6-dimethyl-1H-benzo[d]imidazol-3-onium bromide (II-2) The difference between this example and Example 11 is that in step 2, 2,4-dichlorobenzyl bromide is replaced with dodecyl bromide. Other steps and parameters are the same as in Example 11. 1-Benzyl-3-dodecyl-5,6-dimethyl-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a white solid; yield 62%.

[0046] Product detection data are as follows: mp: 89.8-91.5℃; 1 H NMR (400 MHz, Chloroform- d ) δ11.44 (s, 1H), 7.47 (dd, J = 7.9, 1.7 Hz, 2H), 7.40 – 7.30 (m, 5H), 5.83 (s,2H), 4.51 (t, J = 7.5 Hz, 2H), 2.41 (s, 3H), 2.36 (s, 3H), 2.02 (p, J = 8.3, 7.9Hz, 2H), 1.22 (s, 18H), 0.88 – 0.80 (m, 3H); 13 C NMR (101 MHz, Chloroform- d) δ141.74, 137.50, 133.16, 130.02, 129.42, 129.20, 128.28, 113.46, 112.74,51.15, 47.74, 31.99, 29.68, 29.58, 29.52, 29.48, 29.42, 29.12, 26.65, 22.77,20.83, 20.81. MS [M-Br] + calcd for C 28 H 41 N2 + :405.33, found:405.33. The structure of the obtained product, after characterization, is as follows: ; Example 13 Preparation of 1-benzyl-3-decyl-5,6-dimethyl-1H-benzo[d]imidazol-3-onium bromide (II-3) The difference between this embodiment and Example 11 is that 2,4-dichlorobenzyl bromide is replaced with decane bromide in step 2. Other steps and parameters are the same as in Example 11. 1-Benzyl-3-decyl-5,6-dimethyl-1H-benzo[d]imidazol-3-onium bromide. White solid; yield 65%.

[0047] Product detection data are as follows: mp: 99.6-100.8℃; 1 H NMR (400 MHz, Chloroform- d ) δ11.43 (s, 1H), 7.46 (d, J = 7.7 Hz, 2H), 7.39 – 7.30 (m, 5H), 5.82 (s, 2H), 4.51 (t, J = 7.6 Hz, 2H), 2.40 (s, 3H), 2.36 (s, 3H), 2.02 (p, J = 7.5 Hz, 2H),1.22 (s, 14H), 0.89 – 0.80 (m, 3H); 13 C NMR (101 MHz, Chloroform- d) δ 137.50,137.44, 133.15, 130.01, 129.86, 129.41, 129.19, 128.27, 113.46, 112.73,51.13, 47.73, 31.91, 29.51, 29.49, 29.46, 29.32, 29.09, 26.63, 22.73, 20.82,20.79, 14.19. MS [M-Br] + calcd for C 26 H 37 N2 + :377.30, found:377.30. The structure of the obtained product, after characterization, is as follows: ; Example 14 Preparation of 1-benzyl-5,6-dimethyl-3-(2-(trifluoromethyl)phenyl)-1H-benzo[d]imidazol-3-onium bromide (II-4) The difference between this embodiment and Example 11 is that in step 2, 2,4-dichlorobenzyl bromide is replaced with 2-trifluoromethylbenzyl bromide. Other steps and parameters are the same as in Example 11. 1-Benzyl-5,6-dimethyl-3-(2-(trifluoromethyl)phenyl)-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a white solid; yield 32%.

[0048] Product detection data are as follows: mp: 80.9-82.1℃; 1 H NMR (400 MHz, Chloroform- d ) δ11.31 (s, 1H), 7.72 – 7.69 (m, 1H), 7.52 (t, J = 6.9 Hz, 1H), 7.49 – 7.44 (m,4H), 7.36 – 7.29 (m, 4H), 7.06 (s, 1H), 5.94 (s, 2H), 5.86 (s, 2H), 2.29 (s,3H), 2.25 (s, 3H); 13 C NMR (101 MHz, Chloroform- d ) δ 142.46, 137.72, 137.68,133.35 (q, J = 1.0 Hz), 132.91, 130.65 (q, J= 1.3 Hz), 130.00, 129.94, 129.74,129.36, 129.34, 129.13, 128.22, 127.87 (d, J = 30.6 Hz), 126.63 (q, J = 5.7 Hz), 124.10 (d, J = 274.0 Hz), 113.60, 112.92, 51.53, 47.63 (q, J = 2.7 Hz), 20.72,20.70. MS [M-Br] + calcd for C 24 H 22 F3N2 + :395.17, found:395.17. The structure of the obtained product, after characterization, is as follows: ; Example 15 Preparation of 1-benzyl-5-chloro-3-(2,4-dichlorobenzyl)-1H-benzo[d]imidazol-3-onium bromide (II-5) The difference between this example and Example 11 is that 5,6-dimethylbenzimidazole is replaced with 5-chlorobenzimidazole in step 1. Other steps and parameters are the same as in Example 11. 1-Benzyl-5-chloro-3-(2,4-dichlorobenzyl)-1H-benzo[d]imidazole-3-onium bromide is obtained. It is a pale yellow solid; yield 55%.

[0049] Product detection data are as follows: mp: 90.5-91.3℃; 1 H NMR (400 MHz, Chloroform- d ) δ11.70 (s, 1H), 7.87 (dd, J = 14.5, 8.4 Hz, 1H), 7.60 – 7.55 (m, 1H), 7.51 –7.46 (m, 3H), 7.43 (d, J = 2.2 Hz, 2H), 7.39 – 7.34 (m, 3H), 7.32 – 7.27 (m,1H), 6.01 (d, J = 23.0 Hz, 2H), 5.86 (d, J = 21.2 Hz, 2H); 13 C NMR (101 MHz, Chloroform- d) δ 145.10, 136.66, 134.46, 133.83, 132.80, 132.25, 132.10,130.18, 130.01, 129.70, 129.64, 128.77, 128.67, 128.40, 128.28, 115.12,113.90, 52.30, 48.45. MS [M-Br] + calcd for C 21 H 16 Cl3N2 + :401.04, found:401.04. The structure of the obtained product, after characterization, is as follows: ; Example 16 Preparation of 1-benzyl-5-chloro-3-(2-(trifluoromethyl)phenyl)-1H-benzo[d]imidazol-3-onium bromide (II-6) The difference between this example and Example 15 is that 2,4-dichlorobenzyl bromide is replaced with 2-trifluoromethoxybenzyl bromide in step 2. Other steps and parameters are the same as in Example 15. 1-Benzyl-5-chloro-3-(2-(trifluoromethyl)phenyl)-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a brown oil; yield 25%.

[0050] The product test data are as follows: 1 H NMR (400 MHz, DMSO- d 6) δ 10.10 (s, 1H), 8.16 –8.09 (m, 1H), 7.94 – 7.89 (m, 1H), 7.77 – 7.69 (m, 2H), 7.58 – 7.53 (m, 3H),7.46 – 7.38 (m, 5H), 6.02 (s, 2H), 5.87 (s, 2H); 13 C NMR (101 MHz, DMSO- d 6) δ144.49, 133.68, 133.55, 132.41, 131.73, 131.18 (q, J = 1.4 Hz), 130.12, 129.90,128.99, 128.96, 128.78, 128.41, 128.30, 127.41, 126.80 (d, J = 30.1 Hz), 124.12(d, J= 274.1 Hz), 115.95, 113.85, 50.26, 47.51. MS [M-Br] + calcd for C 22 H 17 ClF3N2 + :401.10, found:401.10. The structure of the obtained product, after characterization, is as follows:

[0051] Example 17 Preparation of 1-benzyl-6-bromo-3-(2,4-dichlorophenyl)-1H-benzo[d]imidazol-3-onium bromide (II-7) The difference between this example and Example 15 is that 5-chlorobenzimidazole is replaced with 6-bromobenzimidazole in step 1. Other steps and parameters are the same as in Example 19. 1-Benzyl-6-bromo-3-(2,4-dichlorophenyl)-1H-benzo[d]imidazole-3-onium bromide is obtained. It is a gray solid; yield 58%.

[0052] Product detection data are as follows: mp: 90.2-91.4℃; 1 H NMR (400 MHz, DMSO- d 6) δ 10.06(s, 1H), 8.45 – 8.36 (m, 1H), 7.96 (dd, J = 8.8, 3.9 Hz, 1H), 7.88 – 7.77 (m,2H), 7.62 – 7.49 (m, 4H), 7.41 (tt, J = 10.7, 6.0 Hz, 3H), 5.88 (d, J = 8.7 Hz, 2H), 5.80 (d, J = 3.4 Hz, 2H); 13 C NMR (101 MHz, DMSO- d 6) δ 144.25, 134.73,134.15, 133.77, 132.35, 132.16, 130.53, 130.09, 130.05, 129.61, 129.04,128.85, 128.32, 128.13, 119.48, 116.96, 116.07, 50.03, 48.06. MS [M-Br] + calcdfor C 21 H 16 BrCl2N2 +: 444.99, found:444.99. The structure of the obtained product, after characterization, is as follows: ; Example 18 Preparation of 1-benzyl-6-bromo-3-(2-(trifluoromethyl)phenyl)-1H-benzo[d]imidazol-3-onium bromide (II-8) The difference between this embodiment and Example 17 is that in step 2, 2,4-dichlorobenzyl is replaced with 2-trifluoromethylbenzyl bromide. Other steps and parameters are the same as in Example 19. 1-Benzyl-6-bromo-3-(2-(trifluoromethyl)phenyl)-1H-benzo[d]imidazol-3-onium bromide is obtained. It is a brown oil; yield 30%.

[0053] The product test data are as follows: 1 H NMR (400 MHz, DMSO- d 6) δ 10.08 (s, 1H), 7.87 (dd, J = 7.7, 4.4 Hz, 1H), 7.83 – 7.76 (m, 1H), 7.71 – 7.62 (m, 2H), 7.57 – 7.50 (m,3H), 7.41 – 7.32 (m, 5H), 6.00 (d, J = 4.1 Hz, 2H), 5.84 (s, 2H); 13 C NMR (101MHz, DMSO- d 6) δ 144.29, 133.73, 133.62, 132.77, 131.24, 130.20, 130.07,129.67, 129.05, 129.01, 128.84, 128.46, 128.36, 126.89, 124.16 (d, J = 274.1Hz), 119.65, 116.75, 116.26, 50.29, 47.57. MS [M-Br] + calcd for C 22 H 17 BrF3N2 + :445.05, found:445.05. The structure of the obtained product, after characterization, is as follows: .

[0054] Tests to determine the insecticidal activity of the compounds used in Examples 1-18 To investigate the control effects of the compound on pests, experiments were conducted on the following species: armyworm, diamondback moth, cereal aphid, and Aedes aegypti.

[0055] Insect rearing methods: The Aedes aegypti mosquitoes used in this study included two different strains: the Waco strain (a wild type sensitive to pyrethroids) and the Puerto Rico strain (resistant to pyrethroids), both kindly donated by Professor Dong Ke of Duke University and reared in the insect rearing room of the Pesticide Research Institute of Northwest A&F University. Aedes aegypti mosquito rearing conditions: temperature 25±3℃, relative humidity (RH) 70±2%, photoperiod 12 (L):12 (D). Larvae were reared in dechlorinated water and fed a mixed feed (pig liver powder: bread flour = 1:1) daily according to their age, with fresh dechlorinated water changed every other day. Adult mosquitoes were fed 10% sucrose water, and adult live mice (experimental animal use license number: SCXK 2018-001) were used as the blood source for female adult mosquitoes. Armyworms, millipedesmus, and diamondback moths were reared in the insect rearing room of the Pesticide Research Institute of Northwest A&F University. Rearing conditions: room temperature 25±3℃.

[0056] Activity test of Aedes aegypti: Following the World Health Organization (WHO) 2005 recommended standard method for larval immersion, the toxic activity of the test compound against Aedes aegypti larvae of different instars was evaluated. The specific procedure was as follows: The compound was dissolved in acetone to prepare a stock solution, which was then serially diluted to five concentration gradients. Thirty healthy larvae of the same instar, uniform in size and color, were selected and placed in beakers containing 99 mL of dechlorinated water. One mL of each concentration of the drug solution was added and mixed thoroughly. All beakers were placed in a temperature-controlled light incubator consistent with rearing conditions (temperature 25±3℃, RH 70±2%, photoperiod 12L:12D). Larval mortality was checked after 24 hours. The positive control group was treated with permethrin, and the solvent control group was treated with acetone. Larval mortality criteria: The larvae were considered dead if they did not react when lightly touched with an insect needle, were paralyzed, and lost their ability to swim freely in water (i.e., the escape response disappeared). The mortality rate in the solvent control group should be less than 10%; toxicity tests for each age group should be independently repeated 3-4 times.

[0057] Activity test of *Aphidius gracilis*: Leaf immersion method. The test compound was dissolved in DMSO to prepare a stock solution, which was then diluted with an aqueous solution containing 0.1% Tween-80 to the target concentration (final concentration DMSO ≤ 0.1% v / v). Wheat leaves infested with aphids were vertically immersed in the solution for 10 s, drained, and placed in a petri dish (9 cm in diameter) lined with absorbent filter paper. An aqueous solution containing 0.1% Tween-80 (containing 0.1% DMSO) was used as a blank control. Each treatment group contained 20-30 wingless adult aphids, with three biological replicates. After treatment, the aphids were placed in a rearing room. Mortality was counted after 48 h, with mortality defined as complete lack of movement response in the aphids' legs (no response to light touch). Compounds with a corrected mortality rate ≥ 50% were subjected to LC-intervention. 50 Toxicity testing.

[0058] The corrected mortality rate (%) is calculated using the following formula: Corrected mortality rate = (treatment group mortality rate - control group mortality rate) ÷ (1 - control group mortality rate) × 100; if the control mortality rate is > 20%, the calculation needs to be repeated.

[0059] Activity test of *Armoria spp.*: Fresh wheat leaves were cut into 5 mm × 5 mm pieces and immersed in an acetone solution (1 mg / mL) containing the test compound for 5 seconds. After the acetone evaporated, the drug-loaded leaves were placed in a 24-well plate (1 leaf / well), and one third-instar larva was introduced into each well. Each treatment was repeated 3-4 times, with 24 larvae per replicate. Permethrin was used as a positive control, and acetone was used as a blank negative control. The mortality rate of the test insects was then recorded at 24 h and 48 h. For compounds with a lethality rate >40%, the median lethal concentration (LC50) was further determined. 50 To judge toxicity.

[0060] Viability test of diamondback moth: The test compound, HA, and permethrin were first dissolved in DMSO to prepare a stock solution of 20 mg / mL. This stock solution was then diluted with 0.1% Tween-80 aqueous solution to a working solution of 0.1 mg / mL, ensuring the final DMSO concentration did not exceed 0.1% (volume ratio). Fresh rapeseed leaves (approximately 3 cm in diameter) were vertically immersed in the working solution for 10 seconds and drained. The petioles were then wrapped with moistened absorbent cotton to maintain moisture and placed in petri dishes. Twelve identical third-instar larvae were placed in each petri dish, and the dish was sealed with plastic wrap to prevent escape. The dishes were placed in a rearing room, and three independent biological replicates were performed. Mortality was determined by the absence of contraction upon gentle touch of the larvae's abdominal legs with a fine needle (complete lack of motility). The number of dead larvae was recorded after 72 hours, and the mortality rate was calculated. LC-LC was performed on compounds with a mortality rate ≥50%. 50 Measurement.

[0061] Table 1. Initial screening of compound activity against susceptible strains of Aedes aegypti 3rd instar larvae (10 μg / mL, 24h)

[0062] Table 2. Toxicity of the target compound against third-instar larvae of Aedes aegypti (24h)

[0063] Table 3. Initial screening of the target compound's activity against *Aphidius gracilis* (100 μg / mL, 48 h).

[0064] Table 4. Toxicity of the target compound against the rice aphid (48h)

[0065] Table 5. Initial screening of the activity of the target compounds against 3rd instar larvae of the Eastern armyworm (1 mg / mL, 24 h and 48 h).

[0066] Table 6. Toxicity of the target compound to 3rd instar larvae of the Eastern armyworm (24h and 48h).

[0067] Table 7. Toxicity of the target compound to 3rd instar larvae of the diamondback moth (72h)

[0068] Table 1 shows the activity of the compounds against the third instar larvae of the Waco strain of Aedes aegypti at a concentration of 10 μg / mL. The initial screening results are shown in Table 1. Compounds I-1, I-2, I-3, I-4, I-5, I-6, and II-3 showed a mortality rate of over 59%. Compounds with a mortality rate of over 50% were further screened (Table 2). Compounds I-1, I-2, I-3, I-4, I-5, I-6, and II-3, and permethrin showed activity against the Waco strain LC50. 50 The values ​​were 6.192 μg / mL, 4.651 μg / mL, 1.625 μg / mL, 1.667 μg / mL, 0.626 μg / mL, 0.712 μg / mL, 7.516 μg / mL, and 0.065 μg / mL, respectively. Simultaneously, the LC50 of the compound against the permethrin-resistant PuertoRico strain of Aedes aegypti was determined. 50 (Table 3), LC50 of I-1, I-2, I-3, I-4, I-5, I-6, II-3, and permethrin 50The values ​​were 1.904 μg / mL, 0.558 μg / mL, 1.033 μg / mL, 0.552 μg / mL, 0.517 μg / mL, 0.395 μg / mL, 5.417 μg / mL, and 1.474 μg / mL, respectively, all of which showed greater sensitivity to the resistant Puerto Rico strain. Their toxicity to sensitive and resistant strains and their resistance are shown in Table 2. The LC50 values ​​of compound I-2Waco and the Puerto Rico strain are also shown. 50 The resistance values ​​were 4.651 μg / mL and 0.558 μg / mL, respectively, with a resistance ratio of (4.651 / 0.558) = 0.12. The resistance ratios of compounds I-1 and I-4 were both 0.33. In comparison, permethrin showed better resistance to Waco and Puerto Rico strains. 50 The values ​​were 0.065 μg / mL and 1.474 μg / mL, respectively, with a resistance ratio as high as 22.67 (1.474 / 0.065). Compounds I-2, I-1, and I-4 showed higher sensitivity to the resistant strain and exhibited a typical negative cross-resistance relationship with permethrin.

[0069] The aphid-killing activity of the compounds was evaluated at a concentration of 0.1 mg / mL against *Aphidius gracilis*, and the results are shown in Table 3. Among the 21 compounds, compound I-2 achieved a mortality rate of 50% at 48 h. As shown in Table 4, its LC50... 50 The value was 115.00 μg / mL, while the LC50 of permethrin was... 50 The value was 26.478 μg / mL.

[0070] The activity of the compounds against *Armoria spp.* was evaluated at a concentration of 1 mg / mL, using permethrin as a control. The results are shown in Table 5. Compounds with a mortality rate of 50% or higher were further screened. The results are shown in Table 6: LC50 of compounds I-1, I-2, I-3, I-4, I-7, II-1, and permethrin against *Armoria spp.* at 24 h. 50 The values ​​were: 657 μg / mL, 544 μg / mL, 605 μg / mL, 733 μg / mL, 614 μg / mL, and 1.176 μg / mL. The LC50 values ​​of compounds I-1, I-2, I-3, I-4, I-7, II-1, and permethrin against armyworms after 48 hours were also determined. 50 The values ​​are: 209μg / mL, 117μg / mL, 164μg / mL, 515μg / mL, 755μg / mL, 350μg / mL, 0.718μg / mL.

[0071] To evaluate the insecticidal activity of the compounds against diamondback moth, we used the rapeseed leaf infusion method to assess the insecticidal activity of the compounds at a concentration of 100 μg / mL, with permethrin as a control. The results are shown in Table 7. The LC50 values ​​of compounds I-1, I-2, I-3, and permethrin at 24 h against diamondback moth were... 50 The values ​​were: 47.47 μg / mL, 57.81 μg / mL, 23.38 μg / mL, and 32.495 μg / mL. Compounds I-1, I-2, and I-3 showed activity against diamondback moth comparable to permethrin.

[0072] Systematic activity evaluation revealed that the compound (benzimidazole substituted at positions 2 / 5 / 6) exhibited cross-species insecticidal activity, showing significant toxicity against Aedes aegypti, cereal aphid, oriental armyworm, and diamondback moth. Compound I-2 showed particularly strong LC50 against pyrethroid-resistant and susceptible Aedes aegypti strains. 50 The values ​​were 0.558 μg / mL and 4.651 μg / mL (resistance ratio 0.20), respectively, showing significant negative cross-resistance; LC50 against wingless adult *Aphidius gracilis*... 50 The value was 115.00 μg / mL; in addition, I-1, I-2, and I-3 also showed good insecticidal activity against armyworms and diamondback moths, and had certain stomach poison activity against armyworms, with a 48h LC50 value of 115.00 μg / mL. 50 The values ​​ranged from 117 to 209 μg / mL; the LC50 values ​​of compounds I-1, I-2, and I-3 against diamondback moth were... 50 The values ​​were 47.47 μg / mL, 57.81 μg / mL, and 23.38 μg / mL, respectively, and were related to permethrin (LC50). 50 The value is equivalent to 32.495 μg / mL.

[0073] In summary, target compounds I-1, I-2, and I-3 exhibit insecticidal activity against the Oriental armyworm, diamondback moth, and Aedes aegypti. Of particular note is their negative cross-resistance against pyrethroid-resistant strains. This demonstrates the potential application value of these compounds in controlling resistant lepidopteran pests and mosquitoes, and also reveals their mechanism of action, which may differ from existing agents.

[0074] The above description is merely a preferred embodiment of the present invention. These specific embodiments are different implementations based on the overall concept of the present invention, and the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A benzimidazole salt compound with insecticidal activity, characterized in that, The general structural formula of the compound is shown in Formula I and / or Formula II: Formula I; Formula II; In formula I, R1 is at least one of H or halogen; R2 is selected from at least one of H, hydroxyl, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-C6 hydrocarbon, C1-C6 alkoxy and C1-C6 alkylamine. R3 is selected from at least one of H, hydroxyl, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-C6 hydrocarbon, C1-C6 alkoxy, C1-C6 alkylamine, C1-C12 alkyl, C1-C12 alkenyl and C1-C12 alkynyl. In Formula II, R1 is at least one of CH3 or a halogen; R2 is selected from at least one of H, hydroxyl, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, C1-C6 hydrocarbon, C1-C6 alkoxy, C1-C6 alkylamine, C1-C12 alkyl, C1-C12 alkenyl and C1-C12 alkynyl.

2. The benzimidazole salt compound with insecticidal activity according to claim 1, characterized in that, The compound in Formula I includes at least one of the following: 。 3. The benzimidazole salt compound with insecticidal activity according to claim 1, characterized in that, The compound in Formula II includes at least one of the following: 。 4. A method for preparing the benzimidazole salt compound with insecticidal activity as described in any one of claims 1-3, characterized in that, The synthetic route includes: 。 5. The method for preparing the insecticidal benzimidazole salt compound according to claim 4, characterized in that, The synthesis steps of the compound in Formula I include: Step 1: Add compound a and the acid-binding agent to an organic solvent, heat the mixture for a period of time, then lower the temperature. Add compound b dropwise, maintaining the temperature until the reaction is complete. After cooling to room temperature, add distilled water, filter, collect the solid, wash, and dry to obtain intermediate c. The structural formula of compound a is: The structural formula of compound b is: ; Step 2: Dissolve intermediate c and compound d in a solvent and heat the mixture until complete. After cooling, add a mixed solvent, collect the precipitated solid, wash and dry it to obtain product (I); The structural formula of compound d is: .

6. The method for preparing the insecticidal benzimidazole salt compound according to claim 5, characterized in that, The organic solvent is dimethyl sulfoxide, and the acid-binding agent is potassium hydroxide; the molar ratio of compound a to potassium hydroxide is 1:1.5, and the reaction temperature is 100℃; the molar ratio of compound a to compound b is 1:1, and the reaction temperature is 40℃; the organic solvent is anhydrous. N , N -Dimethylformamide; the molar ratio of intermediate c to compound d is 1:1, the reaction temperature is 80℃; the mixed solvent is petroleum ether and ethyl acetate. v / v =2 / 1.

7. The method for preparing the insecticidal benzimidazole salt compound according to claim 4, characterized in that, The synthesis steps of the compound in Formula II include: Step 1: Add compound e and the acid-binding agent to an organic solvent, heat the mixture for a period of time, then lower the temperature. Add compound f dropwise, maintaining the temperature until the reaction is complete. After cooling to room temperature, add distilled water, filter, collect the solid, wash, and dry to obtain intermediate g. The structural formula of compound e is: The structural formula of compound f is: ; Step 2: Dissolve intermediate g and compound h in an organic solvent, heat and react until complete; cool, add mixed solvent, collect the precipitated solid, wash and dry to obtain formula (II). The structural formula of compound h is: .

8. The method for preparing the insecticidal benzimidazole salt compound according to claim 7, characterized in that, The organic solvent is dimethyl sulfoxide, and the acid-binding agent is potassium hydroxide; the molar ratio of compound e to potassium hydroxide is 1:1.5, and the reaction temperature is 100℃; the molar ratio of compound e to compound f is 1:1, and the reaction temperature is 40℃; the organic solvent is anhydrous. N , N -Dimethylformamide; the molar ratio of intermediate g to compound h is 1:1, the reaction temperature is 80℃; the mixed solvent is petroleum ether to ethyl acetate. v / v =2 / 1.

9. The use of the benzimidazole salt compound with insecticidal activity as described in any one of claims 1-3 in the preparation of insecticides.

10. The application according to claim 9, characterized in that, The insecticide is used to control the Eastern armyworm, diamondback moth, cereal aphid and / or Aedes aegypti mosquito.

Images