Imidazole compound and application thereof

Abstract

The invention provides a compound shown as a formula I. In the formula I, X1, X2 and R1-R5 are defined in the specification. The compound disclosed by the invention has a relatively good insecticidal effect, shows a relatively excellent effect in the aspects of fast-acting property and persistent effect, and has a relatively good application prospect.

Description

Technical Field

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

[0002] In crop production, particularly in agriculture and horticulture, losses caused by pests remain significant, making the development of insecticides a crucial research area. Some fused heterocyclic compounds exhibit good insecticidal effects, as disclosed in patents such as CN103717598A, CN109843864A, and WO2020 / 03207A1. Summary of the Invention

[0003] This invention provides an imidazole compound with excellent insecticidal activity against pests. Compared with existing insecticides, the compound of this invention has better insecticidal effect, and its rapid and sustained effects are better than those of existing insecticides.

[0004] Specifically, this invention discloses a compound of formula I, its nitrogen oxide, its stereoisomer, and its salt.

[0005]

[0006] in,

[0007] X1 is independently selected as N or CR6;

[0008] X2 is independently selected from N;

[0009] R1, R2, R3, R4, and R6 are each independently selected from H, halogens, CN, NO2, and Cl-C. 10 Alkyl, halogenated C1-C 10 Alkyl, optionally substituted C3-C 10 cycloalkyl, optionally substituted C3-C 10 Cycloalkylalkyl, optionally substituted C1-C 10 Alkyl sulfinyl, optionally substituted C1-C 10 Alkyl sulfinyl, optionally substituted C1-C 10 Alkyl sulfonyl, halogenated C1-C 10 alkylsulfonyl, optionally substituted C1-C 10 Alkoxy, optional substituted C1-C 10 Alkylthio, optionally substituted C1-C 10 alkyl carbonyl or optionally substituted C1-C 10 alkoxycarbonyl;

[0010] R5 is independently selected from H, halogens, CN, NO2, or optionally substituted C1-C. 10 Alkyl, optionally substituted C1-C 10 Alkoxy, optional substituted C1-C 10 Alkylthio, optionally substituted C2-C6 alkenyl, optionally substituted C2-C6 ynyl, optionally substituted C3-C8 cycloalkyl C2-C6 ynylynyl, optionally substituted C2-C6 ynyloxy, optionally substituted C3-C8 cycloalkyl, optionally substituted heterocyclic, optionally substituted C1-C 10 alkylsulfonyl, optionally substituted C1-C 10 Alkylsulfonylimide group.

[0011] The present invention also provides a composition comprising the compound of formula I described herein.

[0012] Preferably, the above composition comprises the compound described in this invention and at least one adjuvant selected from surfactants, solid diluents, and liquid diluents.

[0013] Preferably, the application of the compound of Formula I or the composition of the present invention in the control of plant pests.

[0014] On the other hand, the present invention provides a method for therapeutic or preventative control of plant or crop pests by contacting the compound of Formula I or the composition of the present invention with plant propagation material. Detailed Implementation

[0015] 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.

[0016] Furthermore, to better illustrate the present invention, numerous specific details are provided in the following detailed embodiments.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] When the compounds of the present invention can exist in tautomer form, the compounds described above and below should be understood, where applicable, to also include the corresponding tautomer forms, even if such tautomer forms are not explicitly mentioned in each case.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] This invention C n -C m The subscripts n and m in the formula all indicate the number of carbon atoms in the group. For example, C1-C 10 This indicates the presence of 1 to 10 carbon atoms, preferably C1-C6 alkyl. 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. The alkoxy group is derived from the mentioned alkyl group.

[0025] In this invention, the halogen is typically fluorine, chlorine, bromine, or iodine, preferably fluorine, bromine, or chlorine. Accordingly, this also applies to halogens combined with other structures, such as haloalkyl groups. Haloalkyl groups preferably have a chain length of 1 to 6 carbon atoms, more preferably a chain length of 1 to 4 carbon atoms.

[0026] Halogenated alkyl groups, preferably halogenated C1-C 10Alkyl groups, more preferably halogenated C1-C6 alkyl groups, examples such as 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, etc., but not limited thereto.

[0027] C3-C 10 Cycloalkyl refers to cycloalkyl groups containing 3 to 10 carbon atoms, preferably C3-C8 cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, etc.

[0028] C3-C 10 Cycloalkylalkyl, preferably C3-C 10 cycloalkyl-C1-C 10 Alkyl groups, more preferably C3-C8 cycloalkyl-C1-C6 alkyl groups;

[0029] C1-C 10 Examples of alkyl sulfinyl groups include, but are not limited to, trifluoromethyl sulfinyl, trifluoroethyl sulfinyl, etc.

[0030] C1-C 10 Examples of alkyl sulfonyl groups are preferably trifluoromethylsulfonyl, monofluoromethylsulfonyl, difluoromethylsulfonyl, trifluoroethylsulfonyl, etc., but are not limited thereto.

[0031] In this invention, the term "heterocyclic group" refers to a saturated or partially unsaturated carbon ring containing one to four heteroatoms selected from nitrogen, oxygen, and sulfur as ring members. Such a ring does not contain adjacent oxygen atoms, adjacent sulfur atoms, or adjacent oxygen and sulfur atoms within the ring. The aforementioned "heterocyclic group" also includes aromatic ring systems containing at least one heteroatom selected from nitrogen, oxygen, and sulfur, and preferably at most three heteroatoms as ring members. Heteroaryl rings do not contain adjacent oxygen atoms, adjacent sulfur atoms, or adjacent oxygen and sulfur atoms within the ring. Preferred examples include aziridine, aziridine, pyrrolidine, piperidine, morpholine, piperazine, homopiperazine, tetrahydrofuran, dioxane, 2,5-diazabicyclo[2,2,1]heptane and 3,7-diazabicyclo[3,3,0]octane, and more preferably aziridine, aziridine, pyrrolidine, piperidine, morpholine, piperazine, homopiperazine, 2,5-diazabicyclo[2,2,1]heptane and 3,7-diazabicyclo[3,3,0]octane, pyrrolidine, piperidine, piperazine, morpholine, pyridine, pyrimidine, pyrazine, pyridazine, pyrrole, pyrazole, imidazole, triazole, isoxazole, oxazole, isothiazole, thiazole, tetraazole, furan, thienyl, and oxadiazole, but are not limited thereto.

[0032] In this invention, "optional substitution" means that the relevant group may or may not be substituted. When substituted, the substituent may be halogen, cyano, hydroxyl, haloalkyl, or C3-C. 10 cycloalkyl and halogenated C3-C 10 Substitution with cycloalkyl, heterocyclic, etc.

[0033] 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.

[0034] This invention discloses a compound of formula I.

[0035]

[0036] in,

[0037] X1 is independently selected as N or CR6;

[0038] X2 is independently selected from N;

[0039] R1, R2, R3, R4, and R6 are each independently selected from H, halogens, CN, NO2, or optionally substituted C1-C atoms. 10 Alkyl, optionally substituted C3-C 10 cycloalkyl, optionally substituted C3-C 10 cycloalkyl-C1-C 10 Alkyl, optionally substituted C1-C 10 Alkyl sulfinyl, optionally substituted C1-C 10 Alkyl sulfinyl, optionally substituted C1-C 10 alkylsulfonyl, optionally substituted C1-C 10 alkylsulfonylimide group, optionally substituted C1-C 10 Alkoxy, optional substituted C1-C 10 Alkylthio, optionally substituted C1-C 10 alkyl carbonyl or optionally substituted C1-C 10 alkoxycarbonyl;

[0040] R5 is independently selected from H, halogens, CN, NO2, or optionally substituted C1-C. 10 Alkyl, optionally substituted C1-C 10 Alkoxy, optional substituted C1-C 10Alkylthio, optionally substituted C2-C6 alkenyl, optionally substituted C2-C6 ynyl, optionally substituted C3-C8 cycloalkylynyl, optionally substituted C2-C6 ynyloxy, optionally substituted C3-C8 cycloalkyl, optionally substituted heterocyclic, optionally substituted C1-C 10 alkylsulfonyl, optionally substituted C1-C 10 Alkylsulfonylimide group.

[0041] In some preferred technical solutions, X1 is independently selected as N or C;

[0042] In some particularly preferred technical solutions, X1 is N;

[0043] In some preferred technical solutions, R1 is independently selected from H, halogens, CN, NO2, and Cl-C. 10 Alkyl, halogenated C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio group; preferably H, halogen, CN, NO2, C1-C6 alkyl, halogenated C1-C6 alkyl, or C1-C6 alkoxy.

[0044] In some preferred technical solutions, R2 is independently selected from H, halogens, CN, NO2, and Cl-C. 10 Alkyl, halogenated C1-C 10 Alkyl, C1-C 10 Alkyl sulfinyl, halogenated C1-C 10 alkyl sulfinyl, C1-C 10 Alkyl sulfonyl, halogenated C1-C 10 Alkyl sulfonyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, C1-C 10 Alkyl carbonyl or C1-C 10 Alkoxycarbonyl; preferably H, halogen, CN, NO2, C1-C6 alkyl, halo-C1-C6 alkyl, halo-C1-C6 alkylsulfonyl; particularly preferably trifluoromethyl or trifluoromethanesulfonyl.

[0045] In some preferred technical solutions, R3 is independently selected from H, halogens, CN, NO2, and Cl-C. 10 Alkyl, halogenated C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio group; preferably H, halogen, CN, NO2, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio group; particularly preferably H, halogen, CN, NO2, C1-C6 alkyl, halogenated C1-C6 alkyl.

[0046] In some preferred technical solutions, R4 is independently selected from H, C1-C 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl-C1-C 10 Alkyl, C1-C 10 Alkyl sulfinyl, halogenated C1-C 10 alkyl sulfinyl, C1-C 10 Alkyl sulfonyl, halogenated C1-C 10 Alkyl sulfonyl group; preferably H, C1-C6 alkyl, C3-C 10 Cycloalkyl-C1-C6 alkyl, C3-C 10 cycloalkyl or C1-C 10 Alkyl sulfonyl; particularly preferred are H, methyl, ethyl, propyl, cyclopropyl, cyclopropylmethyl, cyclopropylethyl, methanesulfonyl or ethanesulfonyl.

[0047] In some preferred technical solutions, R5 is independently selected from H, halogens, CN, NO2, Cl-C. 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, optionally substituted C3-C8 cycloalkyl-C2-C6 ynyl, optionally substituted C2-C6 ynyloxy, optionally substituted C3-C8 cycloalkyl-C3-C8 cycloalkyl, optionally substituted heterocyclic, C1-C 10 Alkyl sulfonyl, C1-C 10 Alkylsulfonylimide group; halogenated C1-C 10 Alkyl sulfonyl, halogenated C1-C 10 Alkylsulfonylimide group; preferably H, halogen, CN, NO2, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C3-C8 cycloalkyl-C2-C6 ynyl, optionally substituted cyclopropyl-cyclopropyl, optionally substituted heterocyclic group; particularly preferred H, C3-C8 cycloalkyl-C2-C6 ynyl, cyclopropyl-cyclopropyl substituted with H, halogen or halogenated C1-C6 alkyl, heterocyclic group substituted with halogen or halogenated C1-C6 alkyl or C3-C8 cycloalkyl.

[0048] In some preferred technical solutions, R6 is independently selected from H, halogens, CN, NO2, Cl-C. 10 Alkyl or halogenated C1-C 10 Alkyl group; preferably H, halogen, CN, NO2, C1-C6 alkyl or halogenated C1-C6 alkyl.

[0049] Particularly preferred, the compound of formula I is selected from the compounds in Table 1 below.

[0050] Table 1

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] 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. The following synthetic schemes and examples are for further illustration of the invention.

[0060] 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.

[0061] This invention provides a method for preparing a compound of formula I, the synthetic route of which is as follows:

[0062]

[0063] The definitions of X1, X2, R1, R2 and R4 are as defined in Equation I.

[0064] The conventional synthetic procedure is as follows: in an organic solvent, in the presence of a basic substance and a condensing agent, compound II and compound III are reacted to obtain compound I.

[0065] 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.

[0066] The application of the compounds or compositions described in this invention in the control of plant pests.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] Agricultural and horticultural insecticides containing the compounds of the present invention or their salts or nitrogen oxides as active ingredients are suitable for controlling various agricultural, forestry, horticultural, grain storage pests, sanitary pests or nematodes that cause damage to rice, fruit trees, vegetables, other crops and flowers.

[0078] Non-limiting examples of pests or nematodes that control or prevent damage to useful plants according to this invention include:

[0079] Examples of lepidopteran pests include, but are not limited to, the green tussock moth, citrus swallowtail butterfly, bean leafroller, sedge armyworm, fall webworm, Asian corn borer, yellow cutworm, sugarcane yellow borer, yellow swallowtail butterfly, and rice stem borer.

[0080] Examples of hemiptera pests include, but are not limited to, rice green ailanthus, cottony cushion scale (Acyrthos iphon pisum), oak leafhopper, citrus scale insect, pyrethrum aphid, yellow round-hoofed scale, soybean aphid, tobacco whitefly, corn aphid, omnivorous leafhopper, small green leafhopper, pine leafhopper, peach aphid, apple psyllid, apple leaf mirid bug (Heterocordylusflavipes), apple gall aphid (Myzusmalisuctus), apple aphid, apple leafhopper, apple aphid, and cotton aphid.

[0081] As pests of the order Coleoptera, examples include, but are not limited to, the bean weevil, the rice weevil, the yellow-striped flea beetle, the yellow-spotted longhorn beetle, the yellow-spotted longhorn beetle, the corn weevil, the red flour beetle, the rice weevil, the potato leaf beetle, the beetle flea beetle, the large green scarab beetle, the cucumber flea beetle, and the pine needle longhorn beetle.

[0082] Examples of Diptera pests include, but are not limited to, Culex pipiens pallens, beet leafminer, serpentine leafminer, housefly, melon fly, cherry fruit fly, Anopheles sinensis, and apple fruit fly.

[0083] Examples of Hymenoptera pests include cabbage leaf bees, chestnut gall bees, black-backed white radish leaf bees, rose leaf bees, Japanese turnip leaf bees, leafcutter ants, and fire ants, but are not limited to these.

[0084] Examples of pests belonging to the order Orthoptera include, but are not limited to, the southern rice grasshopper, the small rice grasshopper, the migratory grasshopper, and the short-winged rice grasshopper.

[0085] As pests of the order Thysanoptera, examples include rice thrips, rice tube thrips, yellow thrips, citrus thrips, lily thrips, etc., but are not limited to these.

[0086] Examples of mites that are pests include, but are not limited to, hawthorn spider mite, redback spider mite, two-spotted spider mite, citrus spider mite, and apple spider mite.

[0087] Examples of isoptera pests include, but are not limited to, house termites, Japanese wood ants, black-winged subterranean termites, and northern reticulitermes speratus.

[0088] Examples of cockroaches include, but are not limited to, the black-breasted cockroach, the German cockroach, the oriental cockroach, the Japanese cockroach, and the American cockroach.

[0089] Examples of nematodes include, but are not limited to, strawberry bud nematode, rice tip nematode, northern root-knot nematode, southern root-knot nematode, and soybean cyst nematode.

[0090] Examples of mollusks include, but are not limited to, the golden apple snail, the giant African snail, the yellow slug, and other snails.

[0091] The concentration of the active ingredient in the external or internal parasite control agent of the present invention is typically 0.001 to 100% by mass, preferably 0.001 to 99% by mass, and more preferably about 0.005 to 20% by mass.

[0092] Beneficial plants for which the agricultural and horticultural insecticides of the present invention can be used are not particularly limited, but may include, for example, cereals (e.g., rice, barley, wheat, rye, oats, corn, etc.), legumes (soybeans, red beans, broad beans, peas, kidney beans, peanuts, etc.), fruit trees (apples, citrus fruits, pears, grapes, peaches, plums, cherries, walnuts, chestnuts, almonds, bananas, etc.), vegetables and fruits (cabbage, tomatoes, spinach, broccoli, lettuce, onions, scallions (scallions, winter onions, etc.), green peppers, eggplants, strawberries, peppers, okra, leeks, etc.), and root vegetables (carrots, potatoes, sweet potatoes, taro, radishes, turnips, lotus roots, burdock, etc.). Garlic, chives, etc.), processing crops (cotton, hemp, sugar radish, hops, sugarcane, beet, olive, rubber, coffee, tobacco, tea, etc.), melons (pumpkin, cucumber, watermelon, cantaloupe, honeydew melon, etc.), forage grasses (orchardgrass, sorghum, tilapia, clover, alfalfa, etc.), grasses (Korean grass, creeping bentgrass, etc.), spices and other ornamental crops (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), flowers (chrysanthemum, rose, carnation, orchid, tulip, lily, etc.), garden trees (ginkgo, cherry, coral wood, etc.), forest trees (fir, spruce, pine, cypress, fir, juniper, eucalyptus, etc.), and other plants.

[0093] 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.

[0094] The composition containing the compounds of this 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. It can be appropriately selected from a range of 0.001g-10kg per hectare, preferably 0.01g-0.5kg, as needed.

[0095] To broaden the target range or reduce the dosage, the compounds of this invention can also be mixed with other insecticides, acaricides, nematicides, fungicides, etc., or, as needed, with herbicides, plant growth regulators, fertilizers, etc.

[0096] Preparation Examples

[0097] Generally, the compounds of the present invention can be prepared by the methods described in the present invention. 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.

[0098] Example 1 3-(ethanesulfonyl)-2-(3-(ethanesulfonyl)pyridin-2-yl)-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (Compound 2)

[0099]

[0100] The specific preparation process is as follows:

[0101] (1) Add the first solvent (tetrahydrofuran, 30 mL), the condensing agent (EDCI, 15 mmol) and the first basic substance (pyridine, 20 mmol) to the reaction flask, add compound A (10.5 mmol) and chemical B (10 mmol), and react at room temperature for 2 h to carry out the first reaction. Then add water, extract with ethyl acetate, wash the organic phase with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate under reduced pressure to obtain compound C;

[0102] (2) The obtained compound C was dissolved in a second solvent (acetic acid, 30 mL) and reacted at 120 °C for 4 h to carry out the second reaction. After cooling to room temperature, the acetic acid was evaporated, and water and ethyl acetate were added for extraction. The organic phase was adjusted to pH 8 with a saturated sodium bicarbonate aqueous solution, washed with saturated brine, dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain compound D.

[0103] (3) Compound D was dissolved in a third solvent (THF, 30 mL), and a second basic substance (0.96 g of mineral oil-coated NaH, 60 wt%, NaH 24 mmol) was added. After reacting at room temperature for 10 min, a sulfonyl compound (ethyl sulfonyl chloride, 25 mmol) was added, and the reaction was carried out at room temperature for 12 h. After the reaction, saturated ammonium chloride was added to quench the reaction, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. The mixture was filtered, and the filtrate was concentrated under reduced pressure. The product was purified by column chromatography to obtain the title compound (1.8 g), with a yield of 40%. M / Z was 448.44. 1 H NMR (400MHz, DMSO-d6) δ9.05(d,J=1.5Hz,1H),8.96(d,J=1.5Hz,1H),8.74(d,J=1.5Hz,1H,),8 .54(dd,J=8.4,1.5Hz,1H),7.89(dd,J=8.4,5.1Hz,1H),3.55-3.74(m,4H),0.89-1.07(m,6H).

[0104] Example 22 -(5-(cyclopropylethynyl)-3-(ethanesulfonyl)pyridin-2-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (compound 41)

[0105]

[0106] The specific preparation process is as follows:

[0107] The first solvent (tetrahydrofuran, 30 mL) was added to the reaction flask, along with a condensing agent (EDCI, 15 mmol) and a first basic substance (pyridine, 20 mmol). Compound 1 (10 mmol) and compound 2 (10 mmol) were added, and the mixture was reacted at room temperature for 2 h for the first reaction. Water was then added, followed by extraction with ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The filtrate was then added to the second solvent (acetic acid, 30 mL), and the mixture was reacted at 120 °C for 4 h for the second reaction. After cooling to room temperature, the acetic acid was removed, and the mixture was extracted with water and ethyl acetate. The organic phase was adjusted to pH 8 with a saturated sodium bicarbonate aqueous solution, washed again with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give 2.21 g of the title compound, in 50% yield. 1 H NMR (400MHz, DMSO-d6) δ9.14(d,J=1.5Hz,1H),8.92(d,J=1.5Hz,1H),8.89(d,J=1.8Hz,1H,),8.89(t,J=1.8Hz, 1H), 4.29 (s, 3H), 3.50 (q, J = 7.0Hz, 2H), 1.80 (tt, J = 8.1, 7.5Hz, 1H), 1.41 (t, J = 7.0Hz, 3H), 0.89-1.07 (m, 4H).

[0108] The compounds listed in Table 2 below were prepared according to the methods described in the above embodiments.

[0109] Table 2

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118] Bioassay

[0119] 1. Test Name

[0120] Toxicity test of the compound of this invention against beet armyworm, Experiment 2: Experiment objective

[0121] The toxicity of the compound of the present invention against the beet armyworm was tested.

[0122] 3. Experimental Materials

[0123] 3.1 Selection of test subjects

[0124] beet moth larvae

[0125] Fresh cabbage leaves

[0126] 3.2 Experimental Materials and Reagents

[0127] The present invention includes compounds 1-41, 95% chlorantraniliprole technical, acetone (AC), Tween 80, and water as described in Table 1.

[0128] 4 Experimental Design

[0129] 4.1 Pharmacology

[0130] 4.1.1 Preparation of test reagents

[0131] (1) Preparation of 1% mother liquor of compounds 1 to 41: prepared using acetone as solvent.

[0132] (2) Preparation of 0.1% chlorantraniliprole mother liquor: prepared using acetone as solvent.

[0133] (3) Preparation of 0.5% Tween 80 solution: Prepared with water as solvent, and used as an emulsifier solution.

[0134] (4) Preparation of test reagents: Compounds 1 to 41 of the present invention were prepared to the required concentrations of 300 ppm and 100 ppm using mother liquor and 0.5% Tween 80 solution.

[0135] 4.2 Test Methods

[0136] 4.2.1 Test Methods

[0137] Insect soaking method.

[0138] 4.2.2 Processing Group Settings

[0139] Four treatments were set up, with three replicates for each treatment, and a control (control) of water (CK).

[0140] 4.2.3 Preparation of test insects

[0141] Beet armyworm larvae. Beet armyworm eggs were purchased from the Keyun platform; the larvae are 5 days old after laboratory hatching.

[0142] 4.2.4 Test Treatment

[0143] Line a small bowl with a damp filter paper. Cut cabbage leaves of equal size, wash and dry them, and place them in the bowl. Dip the test insects in the pesticide solution for 10 seconds, then blot the filter paper dry and place it on the cabbage leaves in the bowl. Perform three replicates for each treatment. Inoculate each replicate with 10 insects. Seal the bowl with plastic wrap and puncture holes with a needle for ventilation.

[0144] 4.2.5 Application time and observation

[0145] The mortality rate was observed after 1 hour, 2 hours, 6 hours, 12 hours, and 24 hours of treatment.

[0146] 4.2.6 Survey Methods

[0147] Abbott's formula:

[0148]

[0149] 5. Experimental Results and Analysis

[0150] Compounds 1-41 listed in Table 1 of this invention have a corrected mortality rate of over 80% at 300 pppm, and compounds 2 and 41, which are particularly preferred, have good control effects at 100 pppm (see Table 3).

[0151] Table 3. Results of tests on compounds 2 and 41 at 100 ppm

[0152]

[0153] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A compound of formula I, wherein, X1is independently selected from N or CR6; X2is independently selected from N; R1, R2, R3, R4and R6are each independently selected from H, halogen, CN, NO2, optionally substituted C1-C 10 alkyl, optionally substituted C3-C 10 cycloalkyl, optionally substituted C3-C 10 cycloalkyl-C1-C 10 alkyl, optionally substituted C1-C 10 alkylsulfinyl, optionally substituted C1-C 10 alkylsulfonyl, optionally substituted C1-C 10 alkylsulfonimidoyl, optionally substituted C1-C 10 alkoxy, optionally substituted C1-C 10 alkylthio, optionally substituted C1-C 10 alkylcarbonyl or optionally substituted C1-C 10 alkoxycarbonyl; R5is independently selected from H, halogen, CN, NO2, optionally substituted C1-C 10 alkyl, optionally substituted C1-C 10 alkoxy, optionally substituted C1-C 10 alkylthio, optionally substituted C2-C6alkenyl, optionally substituted C2-C6alkynyl, optionally substituted C3-C8cycloalkyl-C2-C6alkynyl, optionally substituted C2-C6alkynyloxy, optionally substituted C3-C8cycloalkyl, optionally substituted heterocyclyl, C2-C6alkynyl C1-C 10 alkylsulfonyl, C2-C6alkynyl C1-C 10 alkylsulfonylimino; or a stereoisomer, salt, or nitroxide thereof.

2. The compound of claim 1, wherein R1 is independently selected from H, halogens, CN, NO2, and Cl-C. 10 Alkyl, halogenated C1-C 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio group; preferably H, halogen, CN, NO2, C1-C6 alkyl, halogenated C1-C6 alkyl, or C1-C6 alkoxy.

3. The compound of claim 1, wherein R2 is independently selected from H, halogens, CN, NO2, and Cl-C. 10 Alkyl, halogenated C1-C 10 Alkyl, C1-C 10 Alkyl sulfinyl, halogenated C1-C 10 alkyl sulfinyl, C1-C 10 Alkyl sulfonyl, halogenated C1-C 10 Alkyl sulfonyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, C1-C 10 Alkyl carbonyl or C1-C 10 Alkoxycarbonyl; preferably H, halogen, CN, NO2, C1-C6 alkyl, halo-C1-C6 alkyl, halo-C1-C6 alkylsulfonyl; particularly preferably trifluoromethyl or trifluoromethanesulfonyl.

4. The compound of claim 1, wherein R3is independently selected from H, halogen, CN, N02, Ci-C6-alkyl, halo-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-alkylthio; particularly preferred H, halogen, CN, N02, Ci-C6-alkyl, halo-Ci-C6-alkyl. 10 Ci-C6-alkyl, halo-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-alkylthio; particularly preferred H, halogen, CN, N02, Ci-C6-alkyl, halo-Ci-C6-alkyl. 10 Ci-C6-alkyl, halo-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-alkylthio; particularly preferred H, halogen, CN, N02, Ci-C6-alkyl, halo-Ci-C6-alkyl. 10 Ci-C6-alkyl, halo-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-alkylthio; particularly preferred H, halogen, CN, N02, Ci-C6-alkyl, halo-Ci-C6-alkyl. 10 Ci-C6-alkyl, halo-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-alkylthio; particularly preferred H, halogen, CN, N02, 5. The compound of claim 1, wherein R4is independently selected from H, Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 10 Ci-C6alkyl, haloCi-C6alkyl, C3-C6cycloalkyl, 6. The compound of claim 1, wherein R5 is independently selected from H, halogens, CN, NO2, and Cl-C. 10 Alkyl, C1-C 10 Alkoxy, C1-C 10 Alkylthio, optionally substituted C3-C8 cycloalkyl-C2-C6 ynyl, optionally substituted C2-C6 ynyloxy, optionally substituted C3-C8 cycloalkyl-C3-C8 cycloalkyl, optionally substituted heterocyclic, C1-C 10 Alkyl sulfonyl, C1-C 10 Alkylsulfonylimide group; halogenated C1-C 10 Alkyl sulfonyl, halogenated C1-C 10 Alkylsulfonylimide group; preferably H, halogen, CN, NO2, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C3-C8 cycloalkyl-C2-C6 ynyl, optionally substituted cyclopropyl-cyclopropyl, optionally substituted heterocyclic group; particularly preferred H, C3-C8 cycloalkyl-C2-C6 ynyl, cyclopropyl-cyclopropyl substituted with H, halogen or halogenated C1-C6 alkyl, heterocyclic group substituted with halogen or halogenated C1-C6 alkyl or C3-C8 cycloalkyl.

7. The compound of claim 1, wherein In some preferred embodiments, R6is independently selected from H, halogen, CN, NO2, Ci-C6alkyl or haloCi-C6alkyl. 10 Ci-C6alkyl or haloCi-C6alkyl; preferably H, halogen, CN, NO2, Ci-C6alkyl or haloCi-C6alkyl. 10 Ci-C6alkyl or haloCi-C6alkyl; preferably H, halogen, CN, NO2, Ci-C6alkyl or haloCi-C6alkyl.

8. The compound of any one of claims 1-7, wherein, Formula I is selected from the group consisting of compounds 1 to 41 in Table 1.

9. The compound of claim 8, wherein, selected from the group consisting of:

10. An insecticide composition, characterized by, comprising a compound of any one of claims 1-9.

Images