Pyridopyrimidinium salt compounds and uses thereof

Abstract

The application discloses a compound of formula I, wherein R 1 -R 6 , X, Y and Z are defined in the description. The compound has good insecticidal effect and wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of agricultural insecticides, specifically relating to a novel pyridopyrimidine onium salt compound insecticide. The invention also relates to intermediates for preparing these compounds, compositions comprising these compounds, and their use in the control or prevention of plant pests in agriculture or horticulture. Technical Background

[0002] Metonylic compounds are a special and important class of molecules. Mackney and Earl synthesized the first metonylic compound, sydnone, in 1935. In 1949, Baker and Ollis first proposed the concept of metonylic compounds, which are five- or six-membered dipolar heterocyclic compounds in which the π electrons within the ring are delocalized, the ring carries a partial positive charge, and the atoms or substituents covalently bonded to the ring carry a negative charge to balance it. These compounds cannot be accurately represented by any single covalent or polar structure, hence the name metonylic compounds. These compounds have a wide range of applications in anti-inflammatory, antidepressant, and antitumor fields. Meanwhile, metonylic compounds have become a new research hotspot in the field of insecticides in the past decade or so. DuPont first disclosed a metonylic compound with insecticidal activity in 2008, and since then, domestic and international plant protection companies have joined the research and development of metonylic insecticides. Numerous pyrimidine onium salt compounds have been disclosed in patents such as CN103459387A, CN102574815A, CN103582639A, CN104311554A, and CN 110317200B, but their effects in some aspects remain unsatisfactory. Therefore, there is a continued need for novel compounds that are more effective, more economical, less toxic, safer for the environment, or have different sites of action.

[0003] The invention provides a novel pyrimidine onium salt compound with a specific substitution mechanism and excellent activity. Summary of the Invention

[0004] This invention provides a pyridopyrimidine onium salt compound, its nitrogen oxides, salts, and combinations thereof, which have excellent insecticidal activity and can be used as an insecticide for crops.

[0005] Specifically, this invention discloses a compound of formula I.

[0006]

[0007] in,

[0008] R 1 It is H, C1-C6 alkyl;

[0009] R 2It is H, halogen, or C1-C6 alkyl;

[0010] R 3 It is H, C1-C6 alkyl;

[0011] R 4 It is H, C1-C6 alkyl;

[0012] R 5 It is a C1-C6 alkyl, C1-C6 haloalkyl, or substituted C3-C6 cycloalkyl, preferably methyl, trifluoromethyl, cyclopropyl, C1-C6 haloalkyl-substituted cyclopropyl, or halogen-substituted cyclopropyl; R 6 It is H, halogen, or C1-C6 alkyl;

[0013] X, Y, or Z can each be independently O, N, or C.

[0014] The present invention also provides a composition comprising the compound described herein.

[0015] Preferably, the above composition comprises the compound described in this invention and at least one adjuvant selected from surfactants, solid diluents, and liquid diluents.

[0016] Preferably, the application of the compound or composition of the present invention in the control of plant pests.

[0017] On the other hand, the present invention provides a method for therapeutic or preventative control of plant or crop pests by applying the compound or composition of the present invention to seeds, plants or plant fruits, or to soil in which plants are growing or need to grow. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprising of," etc., will be understood to include the stated components or steps, without excluding other substances or steps.

[0019] Furthermore, to better illustrate the present invention, numerous specific details are provided in the following detailed embodiments.

[0020] Those skilled in the art will understand that the present invention can be practiced even without certain specific details. In some embodiments, materials, methods, and means well known to those skilled in the art are not described in detail in order to highlight the spirit of the invention.

[0021] If the compound of Formula I described in this invention can form geometric isomers, such as E / Z isomers, then both the pure isomers and mixtures thereof can be used in the compositions of this invention.

[0022] If the compound of Formula I described in this invention has one or more chiral centers and is therefore present as an enantiomer or diastereomer, then the pure enantiomer, the racemic version, or the diastereomer may be used in the compositions of this invention.

[0023] When the compounds of the present invention can exist in tautomer form, the meanings stated above and below shall apply where applicable.

[0024] The term "compound" should be understood to also include the corresponding tautomers, even if these tautomers are not explicitly mentioned in each case.

[0025] Any asymmetric atom (e.g., carbon, etc.) in the compounds disclosed in this invention can exist in racemic or enantiomerically enriched forms, such as (R)-, (S)-, or (R,S)- configurations.

[0026] If the compounds of Formula I described in this invention have functional groups that can be ionized, they can also be used as agricultural salts or mixtures thereof.

[0027] Suitable cations are typically salts of those whose cations do not adversely affect the activity of the active compound (“agriculturally usable”). Preferred cations are alkali metal ions, preferably lithium, sodium, and potassium ions; alkaline earth metal ions, preferably calcium and magnesium ions; and transition metal ions, preferably manganese, copper, zinc, and iron ions.

[0028] The main anions in useful acid addition salts are chloride, bromide, fluoride, iodide, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, and carbonate.

[0029] This invention C n -C m The subscripts n and m in all cases indicate the number of carbon atoms in the group. For example, C1-C6 indicates 1 to 6 carbon atoms. The alkyl group appearing in the definition of substituent can be straight-chain or branched, and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl. Alkoxy groups are derived from the alkyl groups mentioned.

[0030] In this invention, the halogen is typically fluorine, chlorine, bromine, or iodine, preferably fluorine, bromine, or chlorine. Correspondingly, this also applies to halogens combined with other structures, such as haloalkyl groups. The haloalkyl group preferably has a chain length of 1 to 6 carbon atoms, more preferably a chain length of 1 to 4 carbon atoms. Examples of haloalkyl groups include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl, and 2,2,2-trichloroethyl; preferably fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, difluorochloromethyl, and dichlorofluoromethyl. C3-C6 cycloalkyl groups represent cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, etc. Substituted C3-C6 cycloalkyl means that C3-C6 cycloalkyl can be replaced by C1-C6 alkyl, halogen and C1-C6 haloalkyl, etc., but is not limited to these.

[0031] The term "plant propagation material" should be understood to refer to the reproductive parts of a plant, such as seeds that can be used for plant propagation, as well as plant materials such as cuttings or tubers, for example, potatoes. It may refer to, for example, seeds (strictly speaking), roots, fruits, tubers, bulbs, rhizomes, and plant parts. It may also refer to germinated plants and seedlings awaiting transplantation after germination or emergence from the soil. These seedlings can be protected by whole or partial immersion treatment before transplanting. Preferably, "plant propagation material" should be understood to refer to seeds.

[0032] Compounds of Formula I are methanogenic inner salts. "Inner salts," known in the art as "zwitterions," are electrically neutral molecules, but according to valence bond theory, carry both positive and negative charges in each valence bond structure of different atoms. For brevity, the molecular structure of Formula I is described herein as a single valence bond structure; however, this specific valence bond structure should be understood to include all structures arising from electron delocalization, such as the case described in CN103459387A, which has six valence bond structures. Therefore, unless otherwise specified, references to Formula (I) herein refer to all valence bond structures of the compound, as well as other structures (e.g., those based on molecular orbital theory).

[0033] This invention provides a compound represented by Formula I.

[0034]

[0035] in,

[0036] R 1 It is H, C1-C6 alkyl, preferably H;

[0037] R 2 It is H, halogen, or C1-C6 alkyl, preferably H or halogen;

[0038] R 3 It is H, C1-C6 alkyl, preferably H;

[0039] R 4 It is H, C1-C6 alkyl, preferably H;

[0040] R 5 It is a C1-C6 alkyl, a C1-C6 haloalkyl, or a substituted C3-C6 cycloalkyl, preferably methyl, trifluoromethyl, cyclopropyl, a C1-C6 haloalkyl-substituted cyclopropyl, or a halogen-substituted cyclopropyl, particularly preferably methyl, trifluoromethyl, cyclopropyl, a trifluoromethyl-substituted cyclopropyl, or a halogen-substituted cyclopropyl.

[0041] R 6 It is H, halogen or C1-C6 alkyl, preferably methyl;

[0042] X, Y, and Z are each independently selected from O, N, or C.

[0043] Particularly preferred, the compound of formula I is selected from:

[0044]

[0045]

[0046] In this specification, if there are any differences between chemical names and chemical structures, the structure is preferred. Generally, the compounds of this invention can be prepared by the methods described herein, unless further specified.

[0047] The following synthesis schemes and examples are used to further illustrate the content of the present invention.

[0048] Those skilled in the art will recognize that the chemical reactions described in this invention can be suitably used to prepare many other compounds of this invention, and that other methods for preparing the compounds of this invention are considered to be within the scope of this invention. For example, the synthesis of those non-illustrative compounds according to this invention can be successfully accomplished by those skilled in the art through modification methods, such as by appropriately protecting interfering groups, by utilizing other known reagents (in addition to those described in this invention), or by making some conventional modifications to the reaction conditions. Furthermore, the reactions disclosed in this invention or the known reaction conditions are also generally accepted to be applicable to the preparation of other compounds of this invention.

[0049] General synthesis scheme

[0050]

[0051] Compound II is reacted with oxalyl chloride to synthesize compound III, which is then reacted with compound IV under alkaline conditions to synthesize compound I. The aryl-substituted malonic acid compound shown in formula II can be obtained by hydrolysis following coupling of the corresponding aryl iodine or aryl bromine with a malonate diester, as described by Zhang, W. et al. in Bioorganic & Medicinal Chemistry Letters, 2017, 27(4), 911-917.

[0052] The present invention also provides a composition comprising a compound of formula I of the present invention and at least one adjuvant selected from surfactants, solid diluents and liquid diluents.

[0053] The application of the compounds or compositions described in this invention in the control of plant pests.

[0054] The present invention also provides a method for treating plant propagation material, wherein the method comprises applying a composition or preparation containing the compound of the present invention onto the propagation material.

[0055] The compounds of this invention are generally used as insecticidal active ingredients in compositions, i.e., formulations, and typically also include pesticide-acceptable surfactants and carriers. The carrier can be a solid carrier or a liquid carrier.

[0056] Suitable solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as kaolinite, kaolin, montmorillonite and mica; silica, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; ammonium salts, such as ammonium sulfate, hexamethylenediamine and urea, etc.

[0057] Liquid carriers include water and organic solvents. When water is used as a solvent or diluent, organic solvents can also be used as auxiliaries or antifreeze additives. Useful liquefied gaseous fillers or carriers are those liquids that are gaseous at standard temperatures and pressures, such as aerosol propellants like halogenated hydrocarbons, as well as butane, propane, nitrogen, and carbon dioxide, etc.

[0058] Suitable organic solvents include aromatic hydrocarbons, such as benzene, xylene, and toluene; chlorinated hydrocarbons, such as chlorobenzene, vinyl chloride, chloroform, and dichloromethane; aliphatic hydrocarbons, such as petroleum fractions, cyclohexane, and light mineral oils; alcohols, such as isopropanol, butanol, ethylene glycol, glycerol, and cyclohexanol; their ethers and esters; ketones, such as acetone, cyclohexanone, dimethylformamide, and N-methylpyrrolidone; vegetable oils, such as soybean oil, rapeseed oil, and cottonseed oil, etc.

[0059] Suitable surfactants (adjuvants, emulsifiers, dispersants, protective colloids, wetting agents, and binders) include all common ionic and nonionic substances, such as ethoxylated nonylphenol, polyalkylene glycol ethers of straight-chain or branched alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, reaction products of fatty acid amines with ethylene oxide and / or propylene oxide, as well as fatty acid esters, alkyl sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl ether phosphates, aryl sulfates, ethoxylated arylalkylphenols (such as tristyryl-phenol-ethoxylated compounds), and ethoxylated and propoxylated arylalkylphenols such as sulfated and phosphorylated arylalkylphenol-ethoxylated and -ethoxylated and -propoxylated compounds. Other examples are natural and synthetic water-soluble polymers, such as lignin sulfonates, gelatin, gum arabic, phospholipids, starch, hydrophobically modified starch, and cellulose derivatives, particularly cellulose esters and cellulose ethers, as well as polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, and copolymers of (meth)acrylic acid and (meth)acrylates, copolymers of methacrylic acid and methacrylates neutralized with alkali metal hydroxides, and optionally substituted naphthalene sulfonates condensates with formaldehyde. The presence of a surfactant is necessary if one of the active ingredients and / or one of the inert carriers is insoluble in water and the application is carried out in water.

[0060] The agricultural chemical insecticide of the present invention can be prepared by common methods. For example, the active substance is mixed with a liquid solvent and / or a solid carrier, and surfactants such as emulsifiers, dispersants, stabilizers, and wetting agents are added. Other adjuvants may also be added, such as binders, defoamers, foaming agents, antioxidants, crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, neutralizers and buffers, corrosion inhibitors, dyes, fragrances, spreading agents, penetration enhancers, micronutrients, dispersants, thickeners, freezing point depressants, antimicrobial agents, etc.

[0061] The agricultural chemical insecticides described in this invention can be applied in their formulation form or in the form prepared therefrom. Such forms include, for example, aerosols, capsule suspensions, cold-fogging concentrates, hot-fogging concentrates, encapsulated granules, fine granules, flowable concentrates for seed treatment, ready-to-use solutions, powders that can be dusted, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, large granules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, gaseous agents (under pressure), gas-producing products, foaming agents, pastes, suspension concentrates, emulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, powders and granules, water-soluble and water-dispersible granules or tablets, water-soluble or water-dispersible powders for seed treatment, wettable powders, natural and synthetic substances impregnated with active substances, microcapsules in polymers and seed coating materials, and ULV (ultra-low volatile organic compounds). (volume) cold fog and hot fog preparations.

[0062] The formulations described in this invention may also contain other components, such as other fungicides, insecticides, herbicides, plant growth regulators, attractants, acaricides, nematicides, fertilizers, and safeners, which can be formulated together with liquid fertilizers or solid or granular fertilizer carriers such as ammonium nitrate and urea, or mixed with fine sand or soil.

[0063] The treatment of plants and plant parts using compositions containing the compounds of this invention can be carried out directly or through conventional treatment methods applied to their surrounding environment, habitat, or storage space. These conventional treatment methods include, for example, impregnation, spraying, misting, irrigation, evaporation, dusting, fogging, sowing, foaming, smearing, coating, watering, and drip irrigation. For plant propagation materials, especially seeds, treatments can also include dry seed treatment, wet seed treatment, slurry treatment, hulling, and coating with one or more layers. The active substances can also be effectively utilized through ultra-low volume methods or by injecting formulations containing the compounds of this invention or the compounds themselves into the soil.

[0064] This invention relates to the use of the compound or a composition containing the compound as an insecticide in agriculture or horticulture for controlling or preventing pest infestation of beneficial plants.

[0065] Non-limiting examples of pests that control or prevent damage to useful plants according to the present invention include:

[0066] Hemiptera: Planthoppers, such as the small gray planthopper, brown rice planthopper, or white-backed rice planthopper, etc.;

[0067] Leafhoppers (Fragariaceae), such as the green rice leafhopper and the green rice leafhopper; aphids, such as the cotton aphid, green peach aphid, cabbage aphid, potato aphid, foxtail aphid, cereal tube aphid, and brown orange aphid; stink bugs, such as the flower-horned green stink bug, bean bee-margined stink bug, medium rice-margined stink bug, pointed-horned two-spotted stink bug, mixed tea-winged stink bug, etc.

[0068] Whiteflies, such as greenhouse whiteflies;

[0069] Scale insects, such as the California red scale insect, the citrus pointed scale insect, and the red tortoise wax scale insect;

[0070] Lepidoptera: stem borers, such as rice stem borer, rice leaf roller, cotton leaf roller, Indian millet borer, Asian corn borer, and orchid moth, etc.

[0071] Noctuid moths include the fall armyworm, the common armyworm, the cabbage cutworm, cutworms, and moths of the genera *Cynodon* and *Bulbus*, etc.

[0072] White butterflies, such as the cabbage white butterfly; leafrollers, such as the brown-banded leafroller, pear fruit moth, soybean fruit moth, cotton brown-banded leafroller, tea leafroller, apple yellow leafroller, and apple peel leafroller, etc.

[0073] Thysanoptera: Western flower thrips, palm thrips, yellow hard thrips, tobacco thrips, beautiful flower thrips, and potato thrips, etc.;

[0074] Diptera: Housefly, Culex pipiens pallens, three-knee fly, onion fly, gray ground fly, Anopheles sinensis, rice leafminer, rice leafminer and clover leafminer, etc.;

[0075] Coleoptera: Ladybug, Cucumber beetle, Yellow striped vegetable flea beetle, Rice mud beetle, Rice weevil, Rice water weevil, Cotton boll weevil, Green bean weevil, Parasitic grain weevil, Root leaf beetle, Potato leaf beetle, Red flour beetle, Brown powdery beetle, and White-spotted longhorn beetle, etc.

[0076] Orthoptera: Oriental migratory locust, African mole cricket, Hokkaido rice locust, and Japanese rice locust, etc.;

[0077] Hymenoptera: Xinjiang cabbage leaf bee, leafcutter ant, and fire ant, etc.;

[0078] Nematodes: rice tip nematode, strawberry bud nematode, soybean cyst nematode, southern root-knot nematode, short-bodied nematode, and abnormal pearl nematode, etc.

[0079] Blattodea: German cockroach, black-breasted cockroach, American cockroach, brown-spotted cockroach, and Oriental cockroach, etc.;

[0080] Order Acari: Family Tetranychidae (e.g., Tetranychus bicornuate, Tetranychus citrus, and Tetranychus spp., etc.).

[0081] Within the scope of this invention, useful plants include the following plant species: cereals (wheat, barley, rye, oats, rice, corn, sorghum, and related species); sugar beets (sugar beets and forage sugar beets); pome fruits, stone fruits, and soft fruits (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, and blackberries); legumes (lentils, beans, peas, soybeans); oil crops (rapeseed, mustard, olives, sunflowers, coconuts, castor oil plants, cocoa beans, peanuts, or soybeans); and cucurbits (pumpkins, cucumbers, melons). ; fiber plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruits, tangerines); vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, red peppers); laurel plants (avocados, camphor, camphor) or plants such as tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, bananas, and natural rubber plants, along with turf, ornamental and forest plants such as flowers, shrubs, broad-leaved trees or evergreen trees such as conifers, and plant propagation materials.

[0082] The composition containing the compounds of the present invention is simple to use; it is applied to the pest or its growth medium. The dosage of the composition varies depending on weather conditions, formulation, timing of application, method of application, area covered, target pest, and target crop.

[0083] Preparation Examples

[0084] Generally, the compounds of the present invention can be prepared by the methods described herein, unless otherwise specified. The raw materials, reagents, etc., used to prepare the compounds of the present invention are commercially available or can be prepared by conventional methods in the art.

[0085] Implementation 1

[0086]

[0087] 1.1 Synthesis of 1,1-(3-methyl-2-pyridyl)carboxamide

[0088] In a 250 mL reaction flask equipped with a stirrer and thermometer, 120 mL of toluene, 11.96 g (0.26 mol) of formic acid, and 26.5 g (0.26 mol) of acetic anhydride were added. At room temperature, 21.6 g (0.2 mol) of 2-amino-3-methylpyridine was added dropwise, and the reaction was maintained at 25–30 °C for 8 h. After the reaction was complete, the mixture was cooled to room temperature, and white needle-like crystals precipitated. 100 mL of water was added for extraction, followed by extraction with 2 × 50 mL of toluene. The organic phases were combined and washed with 100 mL of 10% (mass fraction) NaHCO3 until neutral. The solution was concentrated to obtain 27.0 g of white needle-like crystals, with a yield of 99% and a melting point of 136–138 °C.

[0089] Synthesis of 1,2N-[(2-chloro-5-thiazolyl)methyl]-3-methyl-2-pyridineamine

[0090] In a 250 mL reaction flask equipped with a stirrer and thermometer, 110 mL of methanol, 18.5 g (0.11 mol) of 2-chloro-5-chloromethylthiazole, 13.6 g (0.1 mol) of N-(3-methyl-2-pyridyl)carboxamide, and 15.2 g (0.11 mol) of K₂CO₃ were added. The mixture was heated to 50 °C and reacted for 3 h. After the reaction was complete, the mixture was cooled, and 80 mL of water was added. The mixture was stirred at 10 °C for 1 h. The mixture was filtered and dried to give 17 g of a yellow solid, with a yield of 71% and a melting point of 127–128 °C.

[0091] Synthesis of diethyl 1,32-(3-chloro-5-cyanophenyl)malonate

[0092] In a 250 mL reaction flask equipped with a stirrer, reflux condenser, and thermometer, N2 was introduced, followed by the addition of 100 mL tetrahydrofuran, 0.1 mol 3,5-dichlorobenzonitrile, 0.11 mol diethyl malonate, and 0.12 mol Cs₂CO₃. The mixture was heated to 70 °C and reacted for 8 h. The reaction was then stopped, filtered, concentrated, extracted with 200 mL ethyl acetate, washed with 100 mL saturated ammonium chloride solution, and dissolved to obtain an orange concentrate, which was directly used for hydrolysis.

[0093] Synthesis of diethyl 1,42-(3-chloro-5-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)malonate

[0094] In a 500 mL reaction flask equipped with a stirrer, reflux condenser, and thermometer, N2 was introduced, followed by the addition of 100 mL methanol, 0.1 mol diethyl 2-(3-chloro-5-cyanophenyl)malonate, 0.5 mol triethylamine, and 0.2 mol hydroxylamine hydrochloride. The mixture was heated under reflux for 10 h. After the reaction was confirmed to be complete, 0.2 mol pyridine was added, followed by 100 mL tetrahydrofuran. 0.2 mol trifluoroacetic anhydride was then added dropwise at 0°C over 2 h. The mixture was then slowly heated to room temperature and reacted for 10 h. After the reaction was confirmed to be complete by liquid chromatography, 200 mL ethyl acetate and 100 mL water were added. The mixture was stirred for 20 min, allowed to stand for separation, and the organic phase was desoluble. The crude product was then directly hydrolyzed.

[0095] In a 500 mL reaction flask equipped with a thermometer, diethyl 2-(3-chloro-5-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)malonate obtained in the previous step was slowly added in portions to 20 mL of water. A 100 mL aqueous solution of 9.2 g (0.23 mol) NaOH was then added in portions. The reaction was carried out at 25 °C for 12 hours. The reaction was then stopped, and the reaction solution was transferred to a beaker containing a small amount of ice. Concentrated hydrochloric acid was added very carefully and slowly for neutralization. The mixture was stirred at 0 °C for 4 hours, filtered, and dried to obtain 10.5 g of solid. The combined yield of the two steps was 30%.

[0096] Synthesis of 1,52-(3-chloro-5-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)malonyl chloride

[0097] In a 250 mL reaction flask equipped with a thermometer, N2 was introduced. Six drops of N,N-dimethylformamide were added dropwise to 0.1 mol oxalyl chloride and 120 mL toluene. Then, 0.03 mol 2-(3-chloro-5-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)malonic acid was added in portions. After the addition was complete, the reaction was carried out at 25 °C for 2 h. The reaction was then stopped, and the solvent and excess oxalyl chloride were evaporated. The remaining liquid was used directly in the next step.

[0098] Synthesis of 1,61-[(2-chloro-5-thiazolyl)methyl]-3-(3-chloro-5-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)-2-hydroxy-9-methyl-4-oxo-4H-pyrido[1,2-a]pyrimidine onium inner salt

[0099] In a 250 mL reaction flask equipped with a thermometer, 0.03 mol of 2-(3-chloro-5-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)malonyl chloride and 100 mL of toluene were added. The mixture was cooled to 0 °C, and 0.03 mol of N-[(2-chloro-5-thiazolyl)methyl]-3-methyl-2-pyridinium chloride was added in portions. After the addition was complete, the mixture was allowed to stand at room temperature for 2 h. The mixture was then cooled to 0 °C, and a mixture of 0.06 mol of triethylamine and 20 mL of toluene was added dropwise. After the addition was complete, the mixture was allowed to stand at room temperature for another 2 h. The reaction was stopped, and the mixture was filtered to obtain a yellow solid. The solid was separated by chromatography using ethyl acetate and petroleum ether, with a yield of 40%.

[0100] The following compounds were synthesized using a method similar to that described above.

[0101]

[0102]

[0103]

[0104] Biological example: Insecticide activity assay

[0105] To evaluate the control efficacy against peach aphids (Myzus persicae) via contact and / or systemic methods, experimental units consisted of small open containers containing 12-16 day old radish plants. The plants were pre-infested by placing 50-60 aphids from a leaf cut from a cultivated plant onto a single leaf of the experimental plant. As the leaf dehydrated, the aphids moved across the experimental plant. After pre-infestation, the soil in the experimental unit was covered with a layer of sand.

[0106] The test compound was prepared using a solution containing 10% acetone, 85% water, and a nonionic surfactant, wherein the nonionic surfactant was alkylaryl polyethylene oxide. The prepared compound was applied by spraying. The test compound was sprayed at a concentration of 250 ppm, and the test was performed in triplicate. After spraying the prepared test compound, each test unit was allowed to dry for 1 hour, and then a black net cover was placed on top. The test units were kept in a growth chamber at 19–22°C and 50–70% relative humidity for 6 days. Plant feeding damage was then visually assessed based on the observed amount of phytophagy.

[0107] Compounds 1-10, tested at 250 ppm, provided excellent to superior control efficacy, achieving 100% mortality.

Claims

1. A compound characterized by, selected from the group consisting of:

2. A composition characterized in that, comprising a compound of claim 1 and at least one auxiliary agent selected from the group consisting of surfactants, solid diluents and liquid diluents.

3. Use of a compound of claim 1 or a composition of claim 2 for controlling plant pests.

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