Pyrimidinium salt compounds and uses thereof

Abstract

The application discloses a compound of formula I, wherein R 1 -R 5 , X, Y and Z are defined in the description. The compound has good insecticidal effect and wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of agricultural insecticides, in particular to a novel structure of pyrimidinyl salt compound insecticide. The present application also relates to intermediates for preparing these compounds, compositions comprising these compounds and to their use in the control or prevention of plant pests in agriculture or horticulture. TECHNICAL BACKGROUND

[0002] Mesionic compounds are a special and important class of molecules. The first mesionic compound, sydnone, was synthesized by Mackney and Earl in 1935. In 1949, Baker and Ollis first proposed the concept of mesionic compounds, which are a class of five or six-membered dipolar heterocyclic compounds with delocalized π electrons in the ring, with partial positive charge on the ring, and atoms or substituents covalently bonded to the ring with a negative charge in equilibrium with it. Such compounds cannot be accurately represented by any covalent structure or polar structure, so they are called mesionic compounds. These compounds have very wide applications in the fields of anti-inflammatory, anti-depression, anti-tumor, etc. At the same time, mesionic compounds have become a new research hotspot in the field of insecticides in the past decade. DuPont Company first disclosed mesionic compounds with insecticidal activity in 2008. Since then, domestic and foreign plant protection companies have joined the research and development of mesionic insecticides.

[0003] Patent CN 103459387 B (2015-08-26) discloses a new mesionic insecticide with a specific substitution form, which has the following structure:

[0004]

[0005] Among them, the compound trifluorophenylpyrimidine is disclosed, which has the following structure The compound has good insecticidal effect. Since then, a large number of pyrimidinyl salt compounds have been disclosed in patents such as CN102574815A, CN103582639A, CN104311554A, CN110317200B, etc. However, the effect in some aspects is still not satisfactory.

[0006] Therefore, there is a continuous need for new compounds that are more effective, more economical, less toxic, more environmentally safe, or have different action sites.

[0007] The present application provides a novel structure of pyrimidinyl salt compound with a specific substitution mode, which has excellent activity. SUMMARY

[0008] The present application provides a pyrimidinyl salt compound, its nitroxide, salt and composition thereof, which has excellent insecticidal activity and can be used as an insecticide for crops.

[0009] In particular, the present application discloses a compound of formula I,

[0010]

[0011] wherein,

[0012] R 1 is H, C1-C6 alkyl;

[0013] R 2 is H, halogen or C1-C6 alkyl;

[0014] R 3 is H, C1-C6 alkyl;

[0015] R 4 is H, C1-C6 alkyl;

[0016] R 5 is C1-C6 alkyl, C1-C6 haloalkyl, substituted C3-C6 cycloalkyl, preferably methyl, trifluoromethyl, cyclopropyl, C1-C6 haloalkyl substituted cyclopropyl, halogen substituted cyclopropyl;

[0017] X, Y and Z are each independently O or N or C.

[0018] The present application also provides a composition comprising the compound according to the present application.

[0019] Preferably, the above composition comprises the compound according to the present application and at least one auxiliary selected from the group consisting of surfactants, solid diluents and liquid diluents.

[0020] Preferably, the compound according to the present application or the composition according to the present application is used for controlling plant pests.

[0021] In another aspect, the present application provides a method for the therapeutic or prophylactic control of pests of plants or crops, by applying the compound according to the present application or the composition according to the present application to seeds, plants or plant fruits or to the soil in which plants are growing or are to grow. DETAILED DESCRIPTION

[0022] For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application. Unless otherwise explicitly indicated, in the entire specification and claims, the term "comprise" or its variants such as "contain" or "include" etc. should be understood as including the stated components or steps, and not excluding other components or steps.

[0023] In addition, in order to better illustrate the present application, numerous specific details are given in the following specific embodiments.

[0024] Those skilled in the art should understand that the present application can also be implemented without certain specific details. In some embodiments, the raw materials, methods, means, etc. which are well known to those skilled in the art are not described in detail, in order to highlight the main idea of the present application.

[0025] If the compounds of formula I according to the present application are capable of forming geometric isomers, for example E / Z isomers, both the pure isomers and mixtures thereof can be used in the compositions according to the present application.

[0026] If the compounds of formula I according to the present application have one or more chiral centers and thus occur as enantiomers or diastereomers, the pure enantiomers, racemates, diastereomers can be used in the compositions according to the present application.

[0027] When the compounds according to the present application can exist in the form of tautomers, the above and below mentioned compounds are, where applicable, to be understood as including the corresponding tautomeric forms, even if these tautomeric forms are not explicitly mentioned in each case.

[0028] The above and below mentioned compounds are, where applicable, to be understood as including the corresponding tautomeric forms, even if these tautomeric forms are not explicitly mentioned in each case.

[0029] Any asymmetric atom (for example, carbon, etc.) of the compounds according to the present application can exist in the form of a racemic or enantiomerically enriched form, for example in the (R)-, (S)- or (R,S)-configurational form.

[0030] If the compounds of formula I according to the present application have functional groups which can be ionized, they can also be used in the form of their agriculturally acceptable salts or mixtures thereof.

[0031] Suitable are those salts of cations which have no adverse effect on the action of the active compounds ("agriculturally acceptable"). Preferred cations are the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron.

[0032] Anions of useful acid addition salts are primarily chloride, bromide, fluoride, iodide, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate.

[0033] C n -C m The indices n and m in Cn-Cm in each case denote the number of carbon atoms in the radical. For example, C1-C6 denotes the group containing from 1 to 6 carbon atoms. The alkyl groups mentioned in the context of substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, n-butyl, sec-butyl, isobutyl or t-butyl. Alkoxy groups are derived from the mentioned alkyl groups.

[0034] Halogen in the present application is typically fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine. Correspondingly, this also applies to halogen in combination with other structures, such as haloalkyl. Haloalkyl 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 are, for example, 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-C6cycloalkyl means cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl and the like, substituted C3-C6cycloalkyl means that C3-C6cycloalkyl can be substituted with C1-C6alkyl, halogen and C1-C6haloalkyl groups and the like, but is not limited thereto.

[0035] The term "plant propagation material" is to be understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative plant material, such as cuttings or tubers, for example potatoes. There can be mentioned, for example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and plant parts. There can also be mentioned germinated plants and seedlings which are to be transplanted after germination or emergence from the soil. These seedlings can be protected by treatment of the whole or of parts with the active compound. Preferably, "plant propagation material" is to be understood as meaning seeds.

[0036] The compounds of formula I are zwitterionic inner salts. "Inner salts" which are known in the art as "zwitterions" are electrically neutral molecules, but carry a positive and a negative charge in each valence bond structure of the different atoms according to the valence bond theory. For the sake of brevity, the molecular structure of formula I is described as a single valence bond structure herein, but this particular valence bond structure is to be understood as referring to all structures of the compound of formula I including those arising because of electron delocalization, e.g. in case of the compound described in CN 103459387 A which has six valence bond structures. Thus, unless otherwise indicated, a reference herein to formula (I) refers to all valence bond structures of this compound as well as other (e.g. molecular orbital theory) structures.

[0037] The present application provides a compound of formula I,

[0038]

[0039] wherein,

[0040] R 1 is H, C1-C6 alkyl, preferably H;

[0041] R 2 is H, halogen or C1-C6 alkyl, preferably H, halogen;

[0042] R 3 is H, C1-C6 alkyl, preferably H;

[0043] R 4 is H, C1-C6 alkyl, preferably H;

[0044] R 5 is C1-C6 alkyl, C1-C6 haloalkyl, substituted C3-C6 cycloalkyl, preferably methyl, trifluoromethyl, cyclopropyl, C1-C6 haloalkyl substituted cyclopropyl, halogen substituted cyclopropyl, particularly preferred methyl, trifluoromethyl, cyclopropyl, trifluoromethyl substituted cyclopropyl, halogen substituted cyclopropyl;

[0045] X, Y and Z are each independently selected from O or N or C.

[0046] Particularly preferred, the compound of formula I is selected from:

[0047]

[0048] General synthetic procedures

[0049] In this specification, if there is any discrepancy between chemical names and chemical structures, the structure is controlling. Generally, the compounds of the present application can be prepared by the methods described herein, unless further specified. The following synthetic schemes and examples serve to further illustrate the present application.

[0050] Those skilled in the art will appreciate that the chemical reactions described in the schemes depicted herein can be used to prepare other compounds of the application by appropriate modification of the reaction conditions. Other methods for preparing compounds of the application are also deemed to be within the scope of the application. For example, the synthesis of those compounds of the application which are not exemplified herein can be successfully performed by a person skilled in the art by applying the methods described herein to the synthesis of the specific compounds or by applying other known synthetic methods.

[0051] Synthetic Scheme

[0052]

[0053] The synthetic route is to synthesize compound III by contacting compound II with oxalyl chloride, and then synthesize compound I by contacting compound III with compound IV under basic conditions. In the reaction steps, the conditions are conventional reaction conditions. The aryl-substituted malonic acid compound of formula II can be obtained by coupling the corresponding aryl iodide or aryl bromide with diethyl malonate and then hydrolysis, as described in Zhang, W. et al. Bioorganic & Medicinal Chemistry Letters, 2017, 27(4), 911-917.

[0054] The present application also provides a composition comprising a compound of formula I of the present application and at least one auxiliary selected from the group consisting of surfactants, solid diluents and liquid diluents.

[0055] The present application also provides the use of a compound or composition of the present application for controlling plant pests.

[0056] The present application also provides a method for treating plant propagation material, which comprises applying to the propagation material a composition or formulation comprising a compound of the present application.

[0057] The compounds of the present application can generally be used as the insecticidally active ingredient in a composition, i.e. a formulation, which usually also comprises a pesticidally acceptable surfactant and carrier. The carrier can be a solid carrier or a liquid carrier.

[0058] Suitable solid carriers include natural or synthetic clays and silicates, such as natural silicas and diatomaceous earth; magnesium silicates, such as talc; aluminum magnesium silicates, such as kaolin, bentonite, and mica; white carbon, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; ammonium salts, such as ammonium sulfate, hexamethylenediamine, and urea, and the like.

[0059] Liquid carriers include water and organic solvents, and when water is the solvent or diluent, organic solvents can also be used as auxiliaries or adjuvants or as antifreeze agents. Useful liquid gaseous fillers or carriers are those that are liquid at standard temperature and pressure, such as aerosol propellants, e.g., halocarbons, and butane, propane, nitrogen, and carbon dioxide, among others.

[0060] Suitable organic solvents include aromatic hydrocarbons, such as benzene, xylene, toluene, and the like; chlorinated hydrocarbons, such as chlorobenzene, vinyl chloride, trichloromethane, dichloromethane, and the like; aliphatic hydrocarbons, such as petroleum fractions, cyclohexane, light mineral oil; alcohols, such as isopropyl alcohol, butanol, ethylene glycol, glycerol, and cyclohexanol, and the like; and ethers and esters thereof; ketones, such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone, vegetable oils, such as soybean oil, rapeseed oil, and cottonseed oil, and the like.

[0061] Suitable surface-active agents (adjuvants, emulsifiers, dispersants, protective colloids, wetting agents, and spreading agents) include all common ionic and non-ionic substances, such as ethoxylated nonylphenols, 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, and fatty acid esters, alkyl sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl ether phosphates, aryl sulfates, ethoxylated arylalkylphenols, such as tristyryl-phenol-ethoxylates, and ethoxylated and propoxylated arylalkylphenols, such as sulfated and phosphated arylalkylphenol-ethoxylates and -ethoxyl- and -propoxylates. Further examples are natural and synthetic water-soluble polymers, such as lignosulfonates, gelatin, gum arabic, phospholipids, starch, hydrophobically modified starch, and cellulose derivatives, in particular cellulose esters and cellulose ethers, and polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, and copolymers of (meth)acrylic acid and (meth)acrylic esters, and copolymers of methacrylic acid and methacrylic esters neutralized with alkali metal hydroxides, and condensates of optionally substituted naphthalenesulfonic acids with formaldehyde. The presence of a surface-active agent is necessary if one of the active ingredients and / or one of the inert carriers is not water-soluble and application is in water.

[0062] The agrochemical insecticides described herein can be prepared by the usual methods. For example, the active substances are mixed with liquid solvents and / or solid carriers, while adding surface-active agents, such as emulsifiers, dispersants, stabilizers, wetting agents, and further auxiliaries, such as binders, antifoams, foam formers, antioxidants, crystallization inhibitors, viscosity regulators, suspensions, spray droplet regulators, colorants, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, dispersants, thickeners, freezing point depressants, antimicrobials, and the like.

[0063] The agrochemical insecticides according to the application can be applied in the form of their formulations or of the application forms prepared therefrom, such as aerosols, capsule suspensions, cold-fogging concentrates, hot-fogging concentrates, encapsulated granules, fine granules, flowable concentrates for the treatment of seed, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, gases (under pressure), gas-generating products, foams, pastes, suspension concentrates, suspo-emulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water-soluble and water-dispersible granules or tablets, water-soluble or water-dispersible powders for the treatment of seed, wettable granules, active-substance-impregnated natural products and synthetic substances, and also polymeric substances and seed-coating materials, and also ULV (ultra low volume) cold-fogging and hot-fogging formulations.

[0064] The formulations according to the application can also contain further components, such as further fungicides, insecticides, herbicides, plant growth regulators, attractants, acaricides, nematicides, fertilizers, safeners and the like, which can be formulated together with liquid or solid, granular fertilizer carriers, such as ammonium nitrate, urea and the like, or mixed with fine sand or soil.

[0065] The treatment of the plants and plant parts according to the application with the compositions comprising the compounds according to the application can be carried out directly or by action on their surroundings, habitat or storage space by the customary treatment methods, for example by immersing, spraying, atomizing, irrigating, evaporating, dusting, fogging, spreading, foaming, painting, coating, watering (drenching), dripping, for plant propagation material, in particular for seeds, also by dry seed treatment, wet seed treatment, slurry treatment, encrusting, coating with one or more layers, etc. It is also possible to use the active substances effectively by the ultra-low-volume process or by injecting formulations comprising the compounds according to the application or the compounds according to the application themselves into the soil.

[0066] The present application relates to the use of the compounds or compositions comprising the compounds for controlling or preventing pests which attack useful plants.

[0067] The present application relates to non-limiting examples of pests which attack useful plants include:

[0068] Eggs, larvae and adults of Lepidoptera, such as armyworms, wireworms, geometer moths and bollworms (e.g. borer, corn borer, tropical armyworm, fall armyworm, beet armyworm, cotton leafworm, yellowstriped armyworm, black cutworm, southern armyworm, green fruitworm, cabbage looper, soybean looper, cabbage webworm, tobacco budworm; Pyralid moths, such as drillos, casebearers, webworms, pine shoot termites, cabbage looper and leaf miners (e.g. European corn borer, navel orangeworm, corn root webworm, grass webworm, rice leaffolder, cabbage coreworm, rice leaffolder, white grubs, white grubs, white grubs.

[0069] Furthermore, agronomic and non-agronomic pests include eggs, adults and larvae of Dermaptera, including Forficulidae earwigs (e.g. European earwig, blacklipped earwig); eggs, immature stages, adults and pupae of Hemiptera and Homoptera, such as from Pentatomidae stink bugs, Cicadidae cicadas, leafhoppers, Cimicidae bed bugs, Coreidae and Delphacidae leafhoppers, Cicadellidae leafhoppers, Psyllidae psyllids, Pseudococcidae mealybugs, Margarodidae, Diaspididae and Ortheziidae scales, Tingidae lace bugs, Pentatomidae stink bugs, Cixiidae spittlebugs, and Pyrrhocoridae red bugs and boll weevils.

[0070] Eggs, larvae, pupae and adults of Acarina (mites), such as Tetranychidae spider mites and red mites (e.g. European red spider mite, two-spotted spider mite, McDaniel spider mite; Eotetranychus spp., such as grape eriophyid mite, citrus red mite; Tenuipalpidae rust mites and bud mites and other leaf-feeding mites and mites of importance in human and animal health, i.e. Dermatophagoidae house dust mites, Pyroglyphidae dermatophagoides mites, Glyciphagus spp. grain mites; Ixodidae ticks, commonly known as hard ticks, sand flies, biting midges, earwigs;

[0071] Eggs, adults and immature stages of Diptera, including leafminers (e.g. Liriomyza spp., such as vegetable leafminer; gall midges (Gall midge family), eye gnats (e.g. blackgrass stem maggot), common houseflies (e.g. Musca domestica), summer flies, stable flies (e.g. Stomoxys calcitrans), horn flies, biting midges (e.g. Culicoides spp.), mosquitoes (e.g. Aedes spp., Anopheles spp., Culex spp.), blackflies (e.g. Simulium spp.), biting midges (e.g. Culicoides spp.), whiteflies (e.g. Bemisia tabaci), and other short horned flies, horseflies (e.g. Tabanus spp.), flesh flies (e.g. Sarcophaga spp.), botflies (e.g. Dermatobia spp.), deer flies (e.g. Chrysops spp.), sheep blowflies (e.g. Ophyomyia spp.) and other short horned flies, mosquitoes (e.g. Aedes spp., Anopheles spp., Culex spp.), gnats (e.g. Bradysia spp., Simulium spp.), biting midges, blackflies and other long horned flies;

[0072] Insect pests of Isoptera, including termites of the Termitidae, Kalotermitidae and Rhinotermitidae, Reticulitermes flavipes, Reticulitermes santonica, Coptotermes formosanus, Reticulitermes virginicus, Coptotermes gestroi, Kalotermes flavicollis, Incisitermes minor, Procapittermes spp., and other economically important termites;

[0073] Insect pests of the order Siphonaptera, including Oriental rat flea, cat flea, dog flea, chicken flea, human flea, and other fleas that infest mammals and birds.

[0074] Other arthropod pests involved include spiders of the order Araneae, such as the brown recluse spider and the black widow spider, and ants of the order Formicidae, such as the fire ant.

[0075] Examples of invertebrate pests of stored grain include larger grain borer, lesser grain borer, rice weevil, maize weevil, bean bruchid, red flour beetle, khapra beetle, Mediterranean flour moth, and long necked grain beetle or rusty grain beetle.

[0076] The compounds of the present application have particular high activity against the following Lepidoptera pests (e.g. Almond moth, Fruit tree leaf roller, European leaf roller and other species of Phyllonorycter, Rice leaffolder, Rice leaf roller, Corn root webworm, Bluegrass webworm, Codling moth), Bollworm, Tobacco budworm, Cabbageworm, Cotton Kaltworm, Diamondback moth, Diamondback moth, Beet armyworm, Beet armyworm, Cabbage looper, and Heliothis spp.

[0077] The compounds of the present application can be mixed with one or more other biologically active compounds or agents to form a multi-component insecticide, conferring even broader spectrum of agronomic and non-agronomic uses, including insecticides, fungicides, nematicides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and root growth stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, viruses or fungi. Accordingly, the present application also relates to a composition consisting of a biologically effective amount of a compound of formula I, an N-oxide thereof, or a salt thereof, at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and at least one additional biologically active compound or agent. In the case of mixtures of the present application, the other biologically active compound or agent can be formulated together with the compounds of the present application (including compounds of formula I) to form a pre-mix, or the other biologically active compound or agent can be formulated separately from the compounds of the present application (including compounds of formula I), and the two formulations are mixed together prior to application (e.g. in a spray tank), or the two formulations are applied sequentially, one after the other, in succession.

[0078] Within the scope of the present application, useful plants include the following plant species: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pome and stone fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (lentils, peas, beans, soybeans); oil crops (rape, mustard, olives, sunflowers, coconut palms, castor oil plants, cocoa beans, groundnuts or soybeans); gourd plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruits, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, bell peppers); lauraceae (avocados, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, grapevines, hops, bananas and natural rubber plants, together with turf, ornamental and forest plants, for example flowers, shrubs, broad-leaved trees or evergreens, such as conifers, and plant propagation material.

[0079] The composition comprising the compound of the present application is applied to the pests or their growth medium using a simple method. The application dose of the composition of the present application varies depending on weather conditions, dosage form, application timing, application method, application area, target pests, target crops, and the like.

[0080] Preparation Example

[0081] Generally, the compound of the present application can be prepared by the method described in the present application, unless otherwise specified. The raw materials, reagents, and the like used in the preparation of the compound of the present application are commercially available or can be prepared by a conventional method in the art.

[0082] Example 1

[0083]

[0084] 1. Synthesis of diethyl 12-(3-cyanophenyl)propanedioate

[0085] In a 500 mL reaction flask equipped with a stirrer, a reflux condenser and a thermometer, N2was introduced, 100 mL of tetrahydrofuran was added, 0.1 mol of 3-chlorobenzonitrile, 0.11 mol of diethyl malonate, 0.12 mol of Cs2CO3, and the temperature was raised to 70°C for 8 h. The reaction was stopped, filtered, concentrated, extracted with 200 mL of ethyl acetate, washed with 100 mL of saturated ammonium chloride solution, and desolventized to obtain an orange concentrated solution, which was directly used for hydrolysis.

[0086] 1. Synthesis of diethyl 2-(3-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)propanedioate

[0087] In a 500 mL reaction flask equipped with a stirrer, reflux condenser and thermometer, N2was bubbled in, 100 mL of methanol was added, 0.1 mol of diethyl 2-(3-cyanophenyl)malonate, 0.5 mol of triethylamine, 0.2 mol of hydroxylamine hydrochloride were added, and the reaction was heated to reflux for 10 h. After the reaction was confirmed to be complete, methanol was removed, 0.2 mol of pyridine was added, 100 mL of tetrahydrofuran was added, 0.2 mol of trifluoroacetic anhydride was added dropwise at 0°C, and the reaction was allowed to proceed for 2 h. After the dropwise addition was completed, the reaction was slowly warmed to room temperature and allowed to proceed for 10 h. After the reaction was confirmed to be complete by liquid chromatography, 200 mL of ethyl acetate was added, 100 mL of water was added, and the mixture was stirred for 20 min. After the mixture was allowed to stand, the organic layer was separated, and the crude product was directly hydrolyzed.

[0088] In a 500 mL reaction flask equipped with a thermometer, 9.2 g (0.23 mol) of NaOH was dissolved in 100 mL of water, and the resulting solution was slowly added dropwise to 2-(3-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)malonate obtained in the previous step. The reaction was allowed to proceed at 25°C for 12 h. After the reaction was stopped, the reaction solution was transferred to a beaker containing a small amount of ice, and the reaction was neutralized by slowly adding concentrated hydrochloric acid. The mixture was stirred at 0°C for 4 h, and the solid was filtered and dried to obtain 9.8 g. The total yield of the two steps was 31%.

[0089] 1.32-(3-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)malonate chloride

[0090] In a 250 mL reaction flask equipped with a thermometer, N2was bubbled in, 6 drops of N,N-dimethylformamide were added dropwise to 0.1 mol of oxalyl chloride and 120 mL of toluene, and 0.03 mol of 2-(3-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)malonate was added in portions. After the addition was completed, the reaction was allowed to proceed at 25°C for 2 h. After the reaction was stopped, the solvent and excess oxalyl chloride were evaporated, and the residue was directly used in the next step.

[0091] 1.43,4-dihydro-2,4-dioxo-1-(pyrimidin-5-ylmethyl)-3-(3-(5-trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)-2H-pyrido[1,2-a]pyrimidin-1-ium-3-olate

[0092] In a 250 mL reaction flask equipped with a thermometer, 0.03 mol of 2-(3-(5- trifluoromethyl-1,2,4-oxadiazol-3-yl)phenyl)malonyl chloride was added, 100 mL of toluene was added, and the mixture was cooled to 0°C. 0.03 mol of N-pyrimidin-5-ylmethyl]2- pyridinamine was added portionwise, and after the addition was completed, the mixture was allowed to warm to room temperature and was stirred for 2 h. The mixture was 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 completed, the mixture was allowed to warm to room temperature and was stirred for 2 h. The reaction was stopped, and a yellow solid was filtered off. The solid was purified by column chromatography using ethyl acetate and petroleum ether to obtain 4.5 g of the product, with a yield of 32%.

[0093] The following compounds were synthesized by referring to the above-described similar methods

[0094]

[0095]

[0096]

[0097] Biological Example: Insecticide Activity Assay

[0098] To evaluate the control effect on Myzus persicae by contact and / or systemic means, the test unit was composed of a small open container having 12-16 day-old radish plants inside. The test plants were pre-infested by placing 50-60 aphids on one leaf of the test plant, which was cut from the cultivated plant. As the leaf dehydrated, the aphids moved to the test plant. After pre-infestation, the soil of the test unit was covered with a layer of sand.

[0099] The test compound was prepared using a solution containing 10% acetone, 85% water, and a non-ionic surfactant, which is an alkyl aryl polyethylene oxide. The prepared compound formulation was applied by a spray method. The test compound was sprayed at a concentration of 250 ppm, and the test was performed in triplicate. After the prepared test compound was sprayed, each test unit was dried for 1 h, and then a black mesh cover was placed on top. The test unit was maintained in a growth chamber at 19-22°C and 50-70% relative humidity for 6 days. Then, the plant feeding damage was visually evaluated according to the fed leaves.

[0100] The compounds 1-10 tested at 250 ppm provided excellent control effects, with a mortality of 100%.

Claims

1. A compound of formula I, in, R 1 It is H, C1-C6 alkyl; R 2 It is H, halogen, or C1-C6 alkyl; R 3 It is H, C1-C6 alkyl; R 4 It is H, C1-C6 alkyl; R 5 It is C1-C6 alkyl, C1-C6 haloalkyl, cyclopropyl, halogen-substituted C3-C6 cycloalkyl, and C1-C6 haloalkyl-substituted cyclopropyl; X and Z are each independently represented by N, and Y is represented by O.

2. The compound according to claim 1, characterized in that, R 1 It is H; R 2 It is H, halogen; R 3 It is H; R 4 It is H; R 5 It is a cyclopropyl group substituted with methyl, trifluoromethyl, or halogen.

3. The compound according to claim 1 or 2, characterized in that, Selected from the following compounds:

4. A composition, characterized in that, It comprises the compound according to any one of claims 1-3 and at least one adjuvant, said adjuvant being selected from surfactants, solid diluents and liquid diluents.

5. The use of the compound according to any one of claims 1-3 or the composition according to claim 4 in the control of plant pests.

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