An isoxazoline benzoyl hydrazine compound, its preparation method and application

Abstract

This application provides an isoxazoline benzoyl hydrazine compound, its preparation method, and its application. The structural formula of the isoxazoline benzoyl hydrazine compound is shown in Formula I: -I. The isoxazoline benzoyl hydrazine compound provided in this application has good control effects on various agricultural pests. The preparation method of the isoxazoline benzoyl hydrazine compound provided in this application is simple and easy to produce.

Description

Technical Field

[0001] This application relates to the field of pesticide technology, and in particular to an isoxazoline benzoyl hydrazine compound, its preparation method and application. Background Technology

[0002] Current agricultural pest control methods still primarily rely on the use of pesticides. The widespread use of traditional pesticides has led to problems such as the development of pesticide resistance in pests and environmental pollution risks. Furthermore, the long-term use of some classic pesticides has resulted in many pests developing severe resistance. With increasing environmental requirements, the creation of green pesticides will be a new trend in the future development of plant protection.

[0003] Therefore, it is necessary to develop new and more efficient pesticide compounds. Summary of the Invention

[0004] To discover more efficient, broad-spectrum, low-toxicity, and non-cross-resistance pesticide lead and candidate compounds, the inventors designed and synthesized a series of isoxazoline benzoyl hydrazide compounds. Furthermore, the inventors conducted insecticidal and acaricidal activity tests on these isoxazoline benzoyl hydrazide compounds. The results showed that these compounds exhibited good insecticidal and acaricidal activity at low concentrations, low toxicity to non-target organisms, safety for mammals, and no negative environmental effects, meeting the development requirements of environmentally friendly green pesticides and possessing high application value.

[0005] To address at least one of the aforementioned technical problems, in a first aspect, this application provides an isoxazoline benzoyl hydrazine compound or a pesticide-acceptable salt thereof, the structural formula of which isoxazoline benzoyl hydrazine compound is shown in Formula I:

[0006] I; Among them, Het is selected from , , R1 and R2 are independently selected from hydrogen, C3-C5 cycloalkyl, and C1-C6 alkyl, respectively; R3, R4, and R5 are independently selected from hydrogen and C1-C3 alkyl, respectively; and R6 and R7 are independently selected from hydrogen, C1-C6 alkyl, phenyl, halogen, or C1-C6 alkyl-substituted phenyl and C1-C6 alkyl-S-, respectively. Ar selected R8 is selected from halogen, cyano, C1-C6 alkyl, halogen-substituted C1-C6 alkyl, and n1 is selected from integers from 0 to 5; R9 is selected from hydrogen and C1-C3 alkyl groups; R 10 Selected from fluorine-substituted C1-C3 alkyl groups.

[0007] Preferably, the structural formula of the isoxazoline benzoyl hydrazine compound is as follows: .

[0008] Preferably, R8 is independently selected from halogens and halogen-substituted C1-C3 alkyl groups.

[0009] Preferably, Ar is selected from , , .

[0010] Preferably, Het is selected from , , , , , .

[0011] Preferably, the isoxazoline benzoyl hydrazine compound is selected from the following structures: , , , , , , , , , , , , , , , , , .

[0012] Preferably, the isoxazoline benzoyl hydrazine compound is selected from the following structures: , , , , , , , , .

[0013] Secondly, the present invention provides a method for preparing the above-mentioned isoxazoline benzoyl hydrazine compound or its pesticide-acceptable salt, wherein the reaction formula for preparing the isoxazoline benzoyl hydrazine compound is shown below: ; Where X is a halogen; The preparation steps of the isoxazoline benzoyl hydrazine compound include: reacting compound A and compound B under the action of an acid-binding agent to obtain a reaction solution containing the isoxazoline benzoyl hydrazine compound, purifying the solution to obtain the isoxazoline benzoyl hydrazine compound.

[0014] Preferably, the reaction formula for preparing the isoxazoline benzoyl hydrazine compound is as follows: ; Where X is chlorine.

[0015] Thirdly, this application provides an agricultural insecticide and acaricide composition comprising the above-mentioned isoxazoline benzoyl hydrazine compounds or their pesticide-acceptable salts.

[0016] Preferably, the formulation of the pesticide includes emulsions, water-in-oil emulsions, microemulsions, suspensions, capsule suspensions, water-soluble granules, fine granules, soluble concentrates, poison grains, block poison baits, granular poison baits, flake poison baits, concentrated poison baits, slow-release blocks, electrostatic sprays, oil-in-water emulsions, smoke cans, smoke candles, smoke tubes, smoke sticks, smoke sheets, smoke pellets, ointments, thermal fogging agents, solid / liquid mixtures, liquid / liquid mixtures, solid / solid mixtures, medicated paints, microparticles, tracking powders, oil suspensions, oil-dispersible powders, concentrated gels, spraying agents, seed coating agents, smearing agents, film-forming oils, ultra-low volume liquids, and vapor release agents.

[0017] Preferably, the mass percentage of isoxazoline benzoyl hydrazine compounds or their pesticide-acceptable salts in the agricultural insecticide and acaricide composition is 0.1%-99.9%.

[0018] Preferably, the agricultural insecticide and acaricide composition further includes adjuvants, wherein the adjuvants in the agricultural insecticide and acaricide composition have a mass percentage of 0.1%-99.9%.

[0019] Preferably, the additives include at least one of solvents, surfactants, emulsifiers, and pH adjusters.

[0020] Preferably, the additives include acetone and an emulsifier in a volume ratio of 1:(8-10).

[0021] Preferably, the emulsifier comprises 0.5-3% by mass of APG0810, 8-12% by mass of 505 emulsifier, 3-5% by mass of 700# emulsifier, 8-12% by mass of xylene, 3-8% by mass of 604# emulsifier, and 200# solvent oil.

[0022] Preferably, the concentration of the isoxazoline benzoyl hydrazine compound or its pesticide-acceptable salt in the agricultural insecticide and acaricide composition is 10-10. 5 mg / L.

[0023] Preferably, the pesticide-acceptable salt of the isoxazoline benzoyl hydrazine compound is prepared by reacting the isoxazoline benzoyl hydrazine compound with a chemically acceptable acid, wherein the chemically acceptable acid is an inorganic acid or an organic acid, wherein the inorganic acid is selected from at least one of hydrochloric acid, sulfuric acid, phosphoric acid and hydrobromic acid, and the organic acid is selected from at least one of oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid and benzoic acid.

[0024] Preferably, the pesticide also includes agricultural insecticides, such as acetamiprid, difenoconazole, chlorpyrifos, abamectin, imidacloprid, spinosad, heptamethrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, deltamethrin, cypermethrin, β-cyhalothrin, λ-cyhalothrin, dichlorvos, permethrin, allethrin, bifenthrin, permethrin, fenpyroxene, flufenoxuron, flufenoxuron, imidacloprid, acetamiprid, chlorpyrifos, thiamethoxam, thiamethoxam, dinotefuran, diflubenzuron, diflubenzuron, diflubenzuron, diflubenzuron, flufenoxuron, acetamiprid, lufenuron, diflubenzuron ... The following is a list of at least one of the following: urea, flufenoxuron, diphenylfluorourea, flufenoxuron, fenflurfen, chlorfenapyr, methoxyfenozide, cyclofenozide, dichlorvos, quinalphos, pyridaben, leafhopper powder, carbaryl, pirimicarb, fenpropathrin, isoprocarb, fenitrothion, sec-butylcarbide, leaf spray, carbaryl, fenitrothion, bromopropylate, thiamethoxam, azoxystrobin, pyridaben, tetradifon, propargite, difenoconazole, pymetrozine, spirodiclofen, spirotetramat, triazophos, thiamethoxam, chlorfenapyr, tetrachlorfenapyr, flufenoxuron, flufenoxuron, cyantraniliprole, butenylflufenoxam, azoxystrobin, bromopropylate, pyrazinone, etoxazole, pyridaben, pyridaben, pyriproxyfen, emamectin, pendimethalin.

[0025] Fourthly, this application provides the use of the above-mentioned isoxazoline benzoyl hydrazine compounds or their pesticide-acceptable salts or the above-mentioned pesticides in the preparation of insecticides and / or acaricides and / or tickicides.

[0026] Preferably, the above-mentioned isoxazoline benzoyl hydrazine compounds or their phytochemically acceptable salts or the above-mentioned pesticides can be used to kill pests or mites on fruit trees, vegetables and ornamental plants. The above-mentioned isoxazoline benzoyl hydrazine compounds or their phytochemically acceptable salts or the above-mentioned pesticides can also be used to kill pests or mites in the growing environment of fruit trees, vegetables and ornamental plants, such as soil and nutrient solution.

[0027] Preferably, the insects include diamondback moth, cutworm, yellow cutworm, kapok worm, bean looper, forked looper, tree looper, spruce leafroller, rice stem borer, apple leafroller, pine caterpillar, southwestern corn stalk borer, Egyptian borer, South American corn seedling borer, privet leafroller, wax borer, plum fruit moth, pear fruit moth, cotton bollworm, tobacco bud borer, corn ear borer, cabbage borer, fall webworm, apple leafminer, tomato moth, beet armyworm, coffee leafminer, spiral leafminer, grape berry leafroller, beet webworm, gypsy moth, tussock moth, peach leafminer, yellow tent caterpillar, cabbage looper, fir tussock moth, corn borer, small-eyed looper, cotton pink bollworm, Xinjiang looper, round-handled boat moth, potato leafminer, citrus Leaf miner, European white butterfly, alfalfa green armyworm, diamondback moth, soybean armyworm, wheat moth, grape leafroller, grassland armyworm, sea gray-winged armyworm, beet armyworm, green oak moth, pink-striped armyworm, pear narrow jewel beetle, straight click beetle, dark click beetle, Mexican cotton boll weevil, apple flower weevil, beet gnat beetle, pit pruning beetle, broad bean weevil, pea weevil, European lentil weevil, apple leaf roller, beet beet giant beetle, golden flower beetle, cabbage seed beetle, bladder beetle, beet shank flea beetle, asparagus leaf beetle, longhorn leaf beetle, South American leaf beetle, corn root leaf beetle, Mexican bean ladybug, tobacco flea beetle, cotton gray weevil variant, European pine bark weevil, Egyptian alfalfa leaf weevil, purple alfalfa leaf weevil, spruce eight-toothed bark beetle, tobacco leaf beetle, black-horned leaf beetle Potato leaf beetle, rice water weevil, rapeseed leaf beetle, large chestnut gill beetle, May gill beetle, rice mud beetle, grape black-eared beetle, strawberry root weevil, horseradish leaf beetle, leaf-eating gill beetle, garden flea beetle, soybean pale-legged flea beetle, yellow-striped flea beetle, Japanese scarab beetle, pea leaf weevil, grain weevil; flies and mosquitoes such as Aedes aegypti, Aedes albopictus, Aedes nigra, Mexican fruit fly, Anopheles five-spotted mosquito, Anopheles white-legged mosquito, Anopheles malaria, Anopheles white-ankle, Anopheles minimus, Anopheles four-spotted mosquito, blowfly, Mediterranean fruit fly, maggot fly, deer fly, sorghum gall midge, Culex pipiens pulveratus, Aedes mosquito, Culex quinquefasciatus, Aedes mosquito, melon fly, olive fruit fly, rapeseed leaf gall midge, onion fly, wheat field seed fly, gray field seed fly, cabbage root fly Human skin fly, small toilet fly, horse fly, tsetse fly, spiky tsetse fly, peanut field gray seed fly, striped skin fly, vegetable leafminer, American leafminer, green leaf fly, silky green fly, wheat gall midge, autumn housefly, housefly, stable carrion fly, sheep mad fly, European wheat straw fly, turnip fly, cherry fruit fly, apple fruit fly, red-tailed flesh fly, flesh fly genus, stable stinging fly, horsefly red barnacle, and European giant mosquito; thrips such as orchid thrips, smoke brown thrips, alfalfa flower thrips, oriental flower thrips, bellflower thrips, rice thrips, palm thrips, tobacco thrips; termites such as yellow-legged reticulate termite, southern reticulate termite, European reticulate termite, black-breasted reticulate termite, house termite ant; cockroaches such as German cockroach, American cockroach, Japanese cockroach, brown cockroach, Australian cockroach, and oriental cockroach;And bedbugs, aphids, leafhoppers, whiteflies, scale insects, cicadas such as *Pseudomorphus spp.*, *Pseudomorphus corniculatus*, *Pseudomorphus spp. ... Aphids, corn aphids, cereal overflow aphids, wheat two-pronged aphids, wheat long-tubed aphids, whiteflies, grape root phylloxera; ants, bees, wasps, sawflies such as Xinjiang cabbage leaf wasps, leafcutter ants, *Hemiberlesia spp.*, black hairy ants, small yellow house ants, tropical fire ants, red fire ants, black fire ants, southern fire ants, red ants, big-headed ants, velvet ants, bumblebees, hornets, yellow-edged hornets, wasps, Argentine ants; crickets, grasshoppers, locusts, house crickets, mole crickets, migratory locusts, two-striped black locusts, red-legged black locusts, Mexican black locusts, migratory black locusts, rock-dwelling black locusts, striped red locusts, American desert locusts, African desert locusts, Moroccan horn-striped locusts, garden crickets, Senegalese small car locusts, stink gland locusts, Italian locusts, Australian locusts, brown migratory locusts.

[0028] Preferably, the nematode also includes control nematodes (e.g., plant parasitic nematodes such as root-knot nematodes, northern root-knot nematodes, southern root-knot nematodes, Javan root-knot nematodes), *Root-knot Nematodes*, cyst-forming nematodes, potato golden nematode, *Sacchariformis*, cereal cyst nematode, soybean cyst nematode, beet cyst nematode, clover cyst nematode, seed gall nematode, *Gracilaria*, stem and leaf nematodes, *Smilax*, stinging nematode, weed stinging nematode and other needle-stinging nematodes, pine nematode, pine wood nematode, annular nematode, *Syngonium*, *Small annular nematode*, *Rotaria*, *Medium annular nematode*, and bulb nematode. Stem nematodes, sweet potato stem nematodes, trypanosomes, trypanosomes, spiral nematodes, sheath nematodes, sheath-shaped nematodes, sheath nematodes and hemirotifers, root-burrowing nematodes, crown nematodes, spear nematodes, pseudo-root-knot nematodes, pearl nematodes, needle nematodes, transverse needle nematodes and other long needle nematodes, root rot nematodes, piercing root rot nematodes, whole short-bodied nematodes, perforating nematodes, banana perforating nematodes, kidney-shaped nematodes, spiral nematodes, residual root nematodes, primitive hairy nematodes, pseudo-hairy nematodes, growth-blocking nematodes, purslane dwarfing nematodes, compliant and compliant dwarfing nematodes, citrus nematodes, hemi-piercing nematodes, xiphoid nematodes.

[0029] The ticks and mites mentioned include: ticks (Acari order), long star tick, tropical flower tick, Persian sharp-edged tick, cattle tick, tiny cattle tick, castor hard tick, chicken skin mites, human scabies mite, apple rust mite, fine mites, and leaf mites.

[0030] Preferably, the insect includes at least one of diamondback moth and thrips; the mite is a spider mite.

[0031] In summary, this application includes at least one of the following beneficial technical effects: 1. This application provides an isoxazoline benzoyl hydrazine compound or its pesticide-acceptable salt. Based on the principles of pesticide molecular design and optimization, this application innovates the skeletal structure and selects isoxazoline benzoyl hydrazine compounds with stable structure and performance. This breaks through the limitations of traditional isoxazoline benzoyl hydrazine compounds in pesticide application and greatly expands the control range of isoxazoline benzoyl hydrazine insecticides against agricultural pests. The isoxazoline benzoyl hydrazine compounds provided in this application have good control effects on a variety of agricultural pests.

[0032] 2. This application also provides a method for preparing the above-mentioned isoxazoline benzoyl hydrazine compounds, which is simple to prepare and easy to produce.

[0033] 3. This application provides an agricultural insecticide and acaricide composition comprising the above-mentioned isoxazoline benzoyl hydrazine compounds, which has excellent insecticidal activity.

[0034] 4. The present invention also provides the application of the above-mentioned isoxazoline benzoyl hydrazine compounds in the preparation of insecticides or acaricides. Detailed Implementation

[0035] The present invention will be further described below with reference to specific embodiments. However, the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified, specific conditions in the following embodiments are performed under conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the methods used are conventional methods known in the art, and the consumables and reagents used are commercially available. Unless otherwise stated, the technical and scientific terms used herein have the same meaning as those familiar with the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be applied to the present invention.

[0036] This application provides an isoxazoline benzoyl hydrazine compound or a pesticide-acceptable salt thereof, the structural formula of which isoxazoline benzoyl hydrazine compound is shown below: ;

[0037] Preferably, Ar is selected from , , Het is selected from , , , , , .

[0038] Example 1 Specifically, the structural formulas of the isoxazoline benzoyl hydrazine compounds provided in Example 1 are shown in Table 1 below: Table 1. Structures of isoxazoline benzoyl hydrazide compounds

[0039] The reaction formula for preparing the isoxazoline benzoyl hydrazine compound is shown below: ; Where X is a halogen; The preparation steps of the isoxazoline benzoyl hydrazine compound include: reacting compound A and compound B under the action of an acid-binding agent to obtain a reaction solution containing the isoxazoline benzoyl hydrazine compound, purifying the solution to obtain the isoxazoline benzoyl hydrazine compound.

[0040] The acid-binding agent is K2CO3.

[0041] The purification process includes extraction and recrystallization, with dichloromethane used as the solvent for recrystallization.

[0042] The following example, using compound 1, illustrates the preparation method of the isoxazoline benzoyl hydrazine compounds provided in this application.

[0043] The chemical structure of compound 1 is as follows:

[0044] Relevant chemical reaction equations: ; The specific experimental procedures for preparing compound 1 are as follows: K2CO3 (1.4 g, 10 mmol) was added to a 100 mL reaction flask and (4.37 g, 10 mmol) Then add dichloroethane (50 mL), and add 20 mL containing [unspecified ingredient] dropwise at room temperature with stirring. A solution of 1.41 g (10 mmol) in dichloroethane was added and stirred for 60 min at 15–35 °C. After the reaction was complete, the solvent was removed, and then 60 mL of ethyl acetate and 10 mL of water were added sequentially. After thorough stirring, the ethyl acetate phase was separated. The ethyl acetate phase was dried over sodium sulfate, the solvent was removed, and recrystallization in dichloroethane yielded 4.62 g of a white powdery solid with a melting range of 98.6–99.4 °C and a yield of 85.6%.

[0045] The preparation methods for other isoxazoline benzoyl hydrazine compounds in Table 1 are the same as for compound 1. The only difference lies in the presence of the Ar and Het groups in the reactants.

[0046] The physicochemical properties of compounds 1, 2, 3, 4, 6, 7, 8, 9, and 12 were analyzed. 1 The H-NMR data are shown in Table 2 below.

[0047] Table 2 Characterization data of isoxazoline benzoyl hydrazine compounds

[0048] Example 2 Example 2 tested the lethality of the isoxazoline benzoyl hydrazine compounds prepared in this application against diamondback moth, spider mite, and thrips. These insect species are highly representative and can represent most of the pests occurring in the field during agricultural production. The insecticidal activity of the isoxazoline benzoyl hydrazine compounds in this application was tested as follows: 1. The lethality of the isoxazoline benzoyl hydrazine compound provided in this application against diamondback moth was determined in accordance with the Agricultural Industry Standard of the People's Republic of China, "Guidelines for Indoor Bioassay of Pesticides - Insecticides Part 14: Leaf Dipping Method" NY / T 1154.14-2008.

[0049] The procedure for determining the lethality of the isoxazoline benzoyl hydrazine compounds provided in this application against diamondback moth using the leaf immersion method is as follows: (1) Preparation of test materials: Select 3rd instar larvae of diamondback moth that have been continuously reared indoors and have the same physiological state as standard test insects, and starve them for 4 hours in advance. Select rapeseed leaves with the same growth and no pesticide residue to make leaf discs with a diameter of 1.5cm. When preparing leaf discs, try to avoid selecting parts with large and thick veins.

[0050] (2) Preparation of reagent: Weigh 0.1 g of the technical grade drug (isoxazoline benzoyl hydrazine compound and positive control provided in this application), dissolve it in 1 mL of acetone, and then use emulsifiers (including 1% APG0810 by mass, 10% 505 emulsifier by mass, 4% 700# emulsifier by mass, 10% xylene by mass, 5% 604# emulsifier by mass, and then add 200# solvent oil to 100%) to make up to 10 mL in a volumetric flask. After complete dissolution, a concentration of 10 is obtained. 4 The mother liquor of mg / L was diluted 100 times with distilled water to obtain a drug solution of 100 mg / L for later use.

[0051] (3) Chemical treatment: Immerse the leaf discs in the chemical solution, remove them after 10 seconds, and place them in a ventilated area to air dry naturally. Transfer them to 9 cm diameter petri dishes containing moistened filter paper for humidity control. Inoculate each dish with 10 3rd instar larvae of the diamondback moth that have completed starvation. A solvent control (using a solution without chemical treatment (1 mL of acetone diluted to 10 mL with the above emulsifier)) and a positive control using the compound Fluxametamide were set up. Six parallel experiments were set up in each group.

[0052] (4) Feeding and observation: The treated test insects were fed and observed under the conditions of temperature (25±1)℃, photoperiod L:D=16 h:8 h and relative humidity (65±5)%.

[0053] (5) Investigation: Check the mortality of test insects 24 h and 48 h after treatment. Touch the surface of the test insect with a brush. If the insect does not move within 5 seconds, it is considered dead. Record the total number of test insects and the number of dead insects in each group, calculate the mortality rate, and take the average value. The results are shown in Table 3.

[0054] 2. The lethality of the isoxazoline benzoyl hydrazine compound provided in this application against spider mites was determined in accordance with the Agricultural Industry Standard of the People's Republic of China, "Guidelines for Indoor Bioassay of Pesticides - Insecticides Part 12: Tetranychus Slide Immersion Method".

[0055] The procedure for determining the lethality of the isoxazoline benzoyl hydrazine compounds provided in this application against spider mites using the slide immersion method is as follows: (1) Preparation of test materials: Select female adult mites that have been continuously reared indoors and are in the same physiological state as standard test insects. Cut double-sided tape into 2cm lengths and attach them to one end of a glass slide. Then, attach the backs of healthy female adult mites to the double-sided tape, taking care not to stick the mite legs, antennae, and mouthparts. Place 20 mites per slide in a petri dish lined with moist cotton, cover the slide, and place it under the conditions of temperature (25±1)℃, photoperiod L∶D=16 h∶8 h, and relative humidity (65±5)%. After 2 hours, examine the slide under a microscope, remove dead and injured individuals, and replenish the slide to 20 mites per slide.

[0056] (2) Preparation of reagent: Weigh 0.1 g of the technical grade drug (isoxazoline benzoyl hydrazine compound and positive control provided in this application), dissolve it in 1 mL of acetone, and then use emulsifiers (including 1% APG0810 by mass, 10% 505 emulsifier by mass, 4% 700# emulsifier by mass, 10% xylene by mass, 5% 604# emulsifier by mass, and then add 200# solvent oil to 100%) to make up to 10 mL in a volumetric flask. After complete dissolution, a concentration of 10 is obtained. 4The mother liquor of mg / L was diluted 100 times with distilled water to obtain a drug solution of 100 mg / L for later use.

[0057] (3) Chemical treatment: Immerse the leaves with spider mites in the chemical solution, gently shake for 5 seconds, remove them, absorb excess solution with absorbent paper, place them in a petri dish lined with moist cotton, cover the dish, and place it under the conditions of (25±1)℃, photoperiod L:D=16h:8h, and relative humidity (65±5)%. The experiment included a solvent control (using a solution without chemical treatment (1 mL of acetone diluted to 10 mL with the above emulsifier)) and a positive control of the compound Fluxametamide. Six parallel experiments were set up for each group.

[0058] (4) Feeding and observation: The treated spider mites were fed and observed under the conditions of temperature (25±1)℃, photoperiod L:D=16 h:8 h and relative humidity (65±5)%.

[0059] (5) Investigation: Check the mortality of spider mites 24 h and 48 h after treatment. Gently touch the legs or mouthparts of the mites with a brush. If there is no reaction, the mites are considered dead. Record the total number of tested mites and the number of dead mites in each group, calculate the mortality rate, and take the average value. The results are shown in Table 3.

[0060] 3. Based on the People's Republic of China Agricultural Industry Standard NY / T 3680-2020: Technical Specification for Monitoring Herbicide Resistance of Western Flower Thrips - Leaf Tube Film Method for Determining the Lethality of the Isoxazoline Benzoylhydrazine Compounds Provided in this Application to Western Flower Thrips.

[0061] The procedure for determining the lethality of isoxazoline benzoyl hydrazine compounds provided in this application against thrips using the leaf tube film method is as follows: (1) Preparation of test materials: Select adult western flower thrips that have been continuously reared indoors and are in the same physiological state as standard test insects. Select cowpea pods with uniform growth and no pesticide residues and make them into segments of about 2 cm, making sure that no beans are left at both ends of the pods. Cut off the bottom of a 10 ml centrifuge tube, then attach 200 mesh mesh, and tighten the cap for subsequent experiments.

[0062] (2) Preparation of reagent: Weigh 0.1 g of the technical grade drug (isoxazoline benzoyl hydrazine compound and positive control provided in this application), dissolve it in 1 mL of acetone, and then use emulsifiers (including 1% APG0810 by mass, 10% 505 emulsifier by mass, 4% 700# emulsifier by mass, 10% xylene by mass, 5% 604# emulsifier by mass, and then add 200# solvent oil to 100%) to make up to 10 mL in a volumetric flask. After complete dissolution, a concentration of 10 is obtained. 4The mother liquor of mg / L was diluted 100 times with distilled water to obtain a drug solution of 100 mg / L for later use.

[0063] (3) Drug treatment: Use a pipette to fill 10 mL centrifuge tubes with the drug solution through a mesh screen, let stand for 4 hours, then discard the drug solution and air dry. Each tube constitutes a replicate. Immerse the pre-cut cowpea segments in the drug solution, remove them after 10 seconds, and let them air dry naturally at room temperature. Use tweezers to pack the dried cowpea segments into centrifuge tubes treated with the corresponding concentration of drug solution, one segment per tube. Set up a solvent control (using a solution without the drug solution (1 mL of acetone diluted to 10 mL with the above emulsifier)) and a positive control drug, the compound Fluxametamide. Set up 5 parallel experiments for each group.

[0064] (4) Inoculation: Use a pipette to transfer thrips into centrifuge tubes, about 15 to 20 test thrips per tube, and then cover the tubes.

[0065] (5) Feeding and observation: The treated test insects were fed and observed under the conditions of temperature (25±1)℃, photoperiod L:D=16 h:8 h and relative humidity (65±5)%.

[0066] (6) Investigation: The mortality of test insects was checked 24 h and 48 h after treatment. The insects that could not crawl when touched with the tip of a brush were considered dead. The total number of test insects and the number of dead insects in each group were recorded. The mortality rate was calculated and the average value was taken. The results are shown in Table 3.

[0067] In the three groups of experiments, the mortality rate of diamondback moth, spider mite, and thrips in the solvent control group was close to 0, indicating that the solvent control group had no killing effect on diamondback moth, spider mite, and thrips.

[0068] The isoxazoline benzoyl hydrazine compounds (compounds 1, 2, 3, 4, 6, 7, 8, 9, 12, and the positive control compound Fluxametamide (CK)) provided by this invention showed effective insecticidal effects against diamondback moth, spider mite, and thrips in an indoor bioassay at a concentration of 100 mg / L for 48 hours. The structure of the positive control compound Fluxametamide (CK) is as follows: .

[0069] Table 3. Insecticidal activity test results of isoxazoline benzoyl hydrazine compounds

[0070] Table 3 shows that the isoxazoline benzoyl hydrazine compounds provided in this invention all exhibit good insecticidal and acaricidal activity, achieving unexpected results. Compound 12, in particular, showed significantly better lethality against diamondback moth, spider mites, and thrips than the positive control compound Fluxametamide. Furthermore, the isoxazoline benzoyl hydrazine compounds provided in this invention demonstrated remarkable specificity, exhibiting ideal control effects against agricultural pests. They are suitable for further development and utilization as commercial agricultural insecticides, something that would be unexpected and inconceivable to those skilled in the art without inventive effort. Moreover, the isoxazoline benzoyl hydrazine compounds provided in this invention possess stable photochemical properties. In controlling agricultural pests, they overcome the limitations of traditional isoxazoline benzoyl hydrazine insecticides, greatly expanding the control range of agricultural pests by isoxazoline benzoyl hydrazine pesticides, far exceeding the expectations of those skilled in the art.

[0071] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. An isoxazoline benzoyl hydrazine compound or a pesticide-acceptable salt thereof, characterized in that, The structural formula of the isoxazoline benzoyl hydrazine compound is shown in Formula I: I； Among them, Het is selected from , , R1 and R2 are independently selected from hydrogen, C3-C5 cycloalkyl, and C1-C6 alkyl, respectively; R3, R4, and R5 are independently selected from hydrogen and C1-C3 alkyl, respectively; and R6 and R7 are independently selected from hydrogen, C1-C6 alkyl, phenyl, halogen, or C1-C6 alkyl-substituted phenyl and C1-C6 alkyl-S-, respectively. Ar selected R8 is selected from halogen, cyano, C1-C6 alkyl, halogen-substituted C1-C6 alkyl, and n1 is selected from integers from 0 to 5; R9 is selected from hydrogen and C1-C3 alkyl groups; R 10 Selected from fluorine-substituted C1-C3 alkyl groups.

2. The isoxazoline benzoyl hydrazine compound or its pesticide-acceptable salt according to claim 1, characterized in that, The structural formula of the isoxazoline benzoyl hydrazine compound is shown below: R8 is selected from halogens and halogen-substituted C1-C3 alkyl groups.

3. The isoxazoline benzoyl hydrazine compound or its pesticide-acceptable salt according to claim 1, characterized in that, Ar selected , , Het is selected from , , , , , .

4. The isoxazoline benzoyl hydrazine compound or its pesticide-acceptable salt according to claim 1, characterized in that, The isoxazoline benzoyl hydrazine compounds are selected from the following structures: 、 、 、 、 、 、 、 、 。 5. A method for preparing an isoxazoline benzoyl hydrazine compound or a pesticide-acceptable salt thereof according to any one of claims 1-4, characterized in that, The reaction formula for preparing the isoxazoline benzoyl hydrazine compound is shown below: ； Where X is a halogen; The preparation steps of the isoxazoline benzoyl hydrazine compound include: reacting compound A and compound B under the action of an acid-binding agent to obtain a reaction solution containing the isoxazoline benzoyl hydrazine compound, purifying the solution to obtain the isoxazoline benzoyl hydrazine compound.

6. An agricultural insecticide and acaricide composition, characterized in that, Includes isoxazoline benzoyl hydrazide compounds as described in any one of claims 1-4, or their pesticide-acceptable salts.

7. The agricultural insecticide and acaricide composition according to claim 6, characterized in that, In the agricultural insecticide and acaricide composition, the mass percentage of isoxazoline benzoyl hydrazine compound or its pesticide-acceptable salt is 0.1%-99.9%.

8. The agricultural insecticide and acaricide composition according to claim 6, characterized in that, It also includes adjuvants, wherein the adjuvants in the agricultural insecticide and acaricide composition are present in a mass percentage of 0.1%-99.9%.

9. The use of an isoxazoline benzoyl hydrazine compound according to any one of claims 1-4 or a pesticide-acceptable salt thereof, or an agricultural insecticide and acaricide composition according to any one of claims 6-8, in the preparation of insecticides and / or acaricides.

10. The application according to claim 9, characterized in that, The insect includes at least one of diamondback moth and thrips; the mite is a spider mite.

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