Pyrazole amide compound and use thereof

Abstract

The present invention relates to the technical field of pesticides, and in particular to a pyrazole amide compound and a use thereof. The compound is as shown in general formula I, wherein Q represents O or S, W represents CH or N, X represents hydrogen, halogen, alkyl, etc., Y represents halogen or alkyl, Z represents alkyl, alkenyl, alkynyl, cycloalkyl, etc., and M represents hydrogen or alkyl. The compound has good prevention and treatment activity on pests such as green peach aphids, peanut aphids, and bird cherry-oat aphids.

Description

A pyrazole amide compound and its application Technical Field

[0001] The present invention belongs to the technical field of pesticides, and in particular relates to a pyrazole amide compound and application thereof. Background Art

[0002] In recent years, due to the long-term use of pesticides, pests and diseases have developed resistance, making them difficult to control with existing pesticides. Furthermore, some known pesticides are highly toxic, or some damage ecosystems through their long-term residual effects. Despite the numerous known pesticides, such as WO2012143317A1, which discloses a pyrazole compound and its use as a pesticide, there remains a need to develop new pesticides with low toxicity and low residual effects. Summary of the Invention

[0003] In order to solve the above problems existing in the prior art, the present invention provides a pyrazole amide compound and its application. The compound has good control activity against pests such as green peach aphid and cereal aphid.

[0004] The technical solution adopted in the present invention is as follows:

[0005] A pyrazole amide compound represented by general formula I and its stereoisomers, salts, tautomers and N-oxides:

[0006] Among them, Q represents O or S;

[0007] W represents CH or N;

[0008] X represents hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, aryl or heterocyclic group;

[0009] Y represents halogen or alkyl;

[0010] Z represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, The "alkyl", "alkenyl" or "alkynyl" is optionally substituted by at least one group selected from cyano, halogen, cycloalkyl, -OR1, -SR1, -(CO)OR1, -C(O)N(R1)2, -(SO)R1, -(SO2)R1, aryl or heterocyclic group;

[0011] M represents hydrogen or an alkyl group;

[0012] R1 each independently represents hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, aryl or heterocyclic group;

[0013] The aforementioned "cycloalkyl", "cycloalkenyl", "heterocyclic", "aryl", is optionally selected from oxo, halogen, cyano, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, -OR 10 , -SR 10 ,-(CO)R 10 、-(CO)OR 10 ,-(SO)R 10 or -(SO2)R 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2O-, -CH2CH2CH2O- or -CH=CHCH=CH-; or a saturated carbon atom on the ring is connected to both ends of unsubstituted or halogen-substituted -OCH2CH2O- to form a ring structure;

[0014] R 10 Each of them is independently hydrogen, alkyl, haloalkyl, aryl or heterocyclic group which is unsubstituted or substituted by at least one group selected from halogen and alkyl.

[0015] In one embodiment, X represents hydrogen, halogen, C1-C8 alkyl, halo-C1-C8 alkyl, C2-C8 alkenyl, halo-C2-C8 alkenyl, C2-C8 alkynyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl, aryl or heterocyclyl;

[0016] Y represents halogen or C1-C8 alkyl;

[0017] Z represents C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, The "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally substituted by at least one group selected from cyano, halogen, C3-C8 cycloalkyl, -OR1, -SR1, -(CO)OR1, -C(O)N(R1)2, -(SO)R1, -(SO2)R1, aryl or heterocyclic group;

[0018] M represents H or C1-C8 alkyl;

[0019] R1 each independently represents hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, halogenated C2-C8 alkenyl, C2-C8 alkynyl, halogenated C2-C8 alkynyl, aryl or heterocyclic group;

[0020] The aforementioned "C3-C8 cycloalkyl", "C3-C8 cycloalkenyl", "heterocyclic group", "aryl", is optionally selected from oxo, halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, -OR 10 , -SR 10 ,-(CO)R 10 、-(CO)OR 10 ,-(SO)R 10 or -(SO2)R 10 or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2O-, -CH2CH2CH2O- or -CH=CHCH=CH-, or a saturated carbon atom on the ring is connected to both ends of unsubstituted or halogen-substituted -OCH2CH2O- to form a ring structure;

[0021] R 10 Each is independently hydrogen, C1-C8 alkyl, C1-C8 haloalkyl, aryl or heterocyclic group which is unsubstituted or substituted with at least one group selected from halogen and C1-C8 alkyl.

[0022] In another embodiment, X represents hydrogen, halogen, C1-C6 alkyl, halo-C1-C6 alkyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C2-C6 alkynyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl, aryl or heterocyclyl;

[0023] Y represents halogen or C1-C6 alkyl;

[0024] Z represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, The "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally substituted by at least one group selected from cyano, halogen, C3-C6 cycloalkyl, -OR1, -SR1, -(CO)OR1, -C(O)N(R1)2, -(SO)R1, -(SO2)R1, aryl or heterocyclic group;

[0025] M represents H or C1-C6 alkyl;

[0026] R1 each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, halogenated C2-C6 alkynyl, aryl or heterocyclic group;

[0027] The aforementioned "C3-C6 cycloalkyl", "C3-C6 cycloalkenyl", "heterocyclic", "aryl", is optionally selected from oxo, halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, -OR 10 , -SR 10 ,-(CO)R 10 、-(CO)OR 10 ,-(SO)R 10 or -(SO2)R 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2O-, -CH2CH2CH2O- or -CH=CHCH=CH-, or a saturated carbon atom on the ring is connected to both ends of unsubstituted or halogen-substituted -OCH2CH2O- to form a ring structure.

[0028] R 10 Each is independently hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, aryl or heterocyclic group which is unsubstituted or substituted with at least one group selected from halogen and C1-C8 alkyl.

[0029] In another embodiment, Q represents O; W represents CH; and X represents hydrogen.

[0030] In another embodiment, M represents hydrogen.

[0031] In the definitions of compounds represented by the above general formula and in all the following structural formulae, the technical terms used, whether used alone or in compound terms, represent the following substituents: Alkyl groups having more than two carbon atoms may be straight-chain or branched. Examples of alkyl groups include C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl, such as n-propyl or isopropyl; C4 alkyl-butyl, such as n-butyl, isobutyl, tert-butyl, or 2-butyl; C5 alkyl-pentyl, such as n-pentyl; and C6 alkyl-hexyl, such as n-hexyl, isohexyl, and 1,3-dimethylbutyl. Similarly, examples of alkenyl groups include vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl. Alkynyl is for example ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.Multiple bonds can be in any position of each unsaturated group.Cycloalkyl is a carbocyclic saturated ring system with for example three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.Similarly, cycloalkenyl is a monocyclic alkenyl with for example three to six carbocyclic ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, wherein double bonds can be in any position.Halogen is fluorine, chlorine, bromine or iodine.

[0032] Unless otherwise specified, the "aryl" mentioned in the present invention includes but is not limited to phenyl, naphthyl, The "heterocyclic group" includes but is not limited to saturated or unsaturated non-aromatic cyclic groups etc., and also include but are not limited to heteroaryl, i.e. an aromatic cyclic group containing, for example, 3 to 6 ring atoms and optionally fused to a benzo ring, wherein 1 to 4 (e.g. 1, 2, 3 or 4) heteroatoms of the ring atoms are selected from oxygen, nitrogen and sulfur, for example

[0033] If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different groups selected from the groups mentioned. Furthermore, identical or different substituent characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed from different atoms and units. At the same time, compounds known to those skilled in the art to be chemically unstable under standard conditions are excluded from the scope of the claims.

[0034] In addition, unless otherwise specified, the term "substituted by at least one group" as used herein means substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without a specific connection position can be connected at any position, including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position as long as it complies with the chemical bond connection rules. For example, a heteroaryl group substituted by 1 methyl group Can represent wait.

[0035] The term "compound of the present invention" or "compound of formula I" encompasses compounds as defined herein as well as stereoisomers, salts, tautomers or N-oxides thereof. The term "compound of the present invention" is to be understood as equivalent to the term "compound according to the invention" and therefore also encompasses stereoisomers, salts, tautomers or N-oxides thereof.

[0036] The term "N-oxide" includes any compound of formula I having at least one tertiary nitrogen atom oxidized to an N-oxide moiety.

[0037] The groups attached to the backbone of formula I may contain one or more chiral centers. In this case, formula I exists in different enantiomeric or diastereomeric forms, depending on the substituents. The present invention relates to every possible stereoisomer of formula I, i.e. to single enantiomers or diastereomers and mixtures thereof.

[0038] Compounds of formula I may be amorphous or may exist in one or more different crystalline states (polymorphs), which may have different macroscopic properties (e.g., stability) or exhibit different biological properties (e.g., activity). The present invention relates to amorphous and crystalline compounds of formula I, mixtures of different crystalline states of the corresponding compound I, and amorphous or crystalline salts thereof.

[0039] The salts of the compounds of the formula I are preferably agriculturally acceptable salts. These can be formed in a customary manner, for example, if the compound of the formula I has a basic function, by reacting the compound with an acid of the anion in question.

[0040] Agriculturally usable salts of the compounds of the formula I encompass in particular the acid addition salts of those acids whose cations and anions, respectively, do not adversely affect the insecticidal action of the compounds of the formula I.

[0041] The anions of usable acid addition salts are mainly chloride, bromide, fluoride, bisulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and anions of C1-C4 alkanoic acid (preferably formate, acetate, propionate and butyrate). They can be formed by reacting a compound of formula I with an acid of the corresponding anion (preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid).

[0042] Another embodiment of the present application is a method for preparing the pyrazole amide compound, comprising the following steps:

[0043] (1) The compound represented by the general formula II is reacted with the compound represented by the general formula III to obtain the compound represented by the general formula I. The reaction equation is as follows:

[0044] Alternatively, (2) the compound represented by the general formula IV is reacted with the compound represented by the general formula V to obtain the compound represented by the general formula I, wherein the reaction equation is as follows:

[0045] Wherein, Hal represents a halogen, and the substituents M, Q, W, X, Y and Z are as defined above.

[0046] In one embodiment, the reactions of steps (1) and (2) are both carried out in the presence of a base and a solvent.

[0047] In a specific embodiment, the base is selected from at least one of an inorganic base (such as NaH, KH, NaOH, KOH, K2CO3, Na2CO3, Cs2CO3, KF, CsF, etc.) or an organic base (such as pyrazole, triethylamine, DIEA, potassium trimethylsilanolate, AcOK, AcONa, MeONa, EtONa, t-BuONa, t-BuOK, etc.).

[0048] In one embodiment, the solvent is selected from at least one of DMF, dimethyl sulfoxide, thionyl chloride, ethyl acetate, tetrahydrofuran, methyltetrahydrofuran, dimethylformamide or dioxane.

[0049] The preparation method of the compound of the present invention can be prepared by referring to WO2012143317A1, etc. N-oxides of the compound of formula I can be prepared by oxidizing compound I according to standard methods for preparing heteroaromatic N-oxides, for example, by the method described in Journal of Organometallic Chemistry 1989, 370, 17-31.

[0050] If individual compounds cannot be prepared via the routes described above, they can be prepared by derivatization of other compounds I or by known modifications of the synthetic routes described. For example, in individual cases, certain compounds I can advantageously be prepared from other compounds I by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation, etc.

[0051] The reaction mixture can be worked up in a known manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude product by chromatography (e.g., on aluminum oxide or silica gel). Some intermediates and end products can be obtained in the form of colorless or light brown viscous oils, which are removed from volatile components or purified from volatile components under reduced pressure and moderately elevated temperature. If the intermediates and end products are obtained in solid form, they can be purified by recrystallization or grinding.

[0052] The present invention also provides an intermediate compound, as shown in the above formula II, III, IV or V.

[0053] In addition, another embodiment of the present application is an insecticidal composition comprising a biologically effective amount of at least one pyrazoleamide compound.

[0054] In one embodiment, the insecticidal composition comprises a biologically effective amount of at least one of the pyrazole amide compounds (component A), and at least one other active ingredient (component B) selected from the following compounds:

[0055] (1) Acetylcholinesterase (AChE) inhibitor: chlorpyrifos (CAS No.: 2921-88-2);

[0056] (2) GABA-gated chloride channel antagonist: fipronil (CAS No.: 120068-37-3);

[0057] (3) Nicotinic acetylcholine receptor (nAChR) allosteric modulator: spinosad (CAS No.: 168316-95-8);

[0058] (4) Nicotinic acetylcholine receptor (nAChR) competitive modulator: Imidacloprid (CAS No.: 138261-41-3);

[0059] (5) Sodium channel modulator: Lambda-cyhalothrin (CAS No. 91465-08-6);

[0060] (6) Allosteric modulator of glutamate-gated ammonium ion channel (GluCl): avermectin (CAS No.: 71751-41-2);

[0061] (7) Acetyl-CoA carboxylase inhibitor: spirotetramat (CAS No.: 203313-25-1);

[0062] (8) Ryanodine receptor modulator: cyantraniliprole (CAS No.: 736994-63-1);

[0063] (9) String modulator-unknown target site: flonicamid (CAS No.: 158062-67-0);

[0064] (10) GABA-gated chloride channel allosteric modulator: oxazolidinone (CAS No.: 2892524-05

[0065] 7);

[0066] (11) String organ TRPV channel modulators: (CN202411096509.0);

[0067] (12) The mechanism of action is unknown: (CN202410765633.5).

[0068] In another specific embodiment, the weight ratio of active ingredients A and B in the composition is 1:500-100:1, 1:200-80:1, 1:150-50:1, 1:100-20:1, 1:80-10:1, 1:50-5:1, 1:30-1:1, 1:20-1:3 or 1:10-1:5.

[0069] In one embodiment, the composition further comprises a formulation adjuvant.

[0070] In another embodiment, the composition further comprises other active ingredients.

[0071] The present application also provides a use of a pyrazole amide compound or a composition thereof for controlling pests.

[0072] The present invention also provides a method for controlling pests, which comprises contacting the pests or their environment with a biologically effective amount of the above-mentioned pyrazole amide derivatives or their composition, such as treating the pests, their food supply, their habitat or their breeding grounds with an insecticidally effective amount of the compound or composition of the present invention as defined above; or cultivated plants, plant propagation materials (such as seeds), soil, areas, materials or environments in which the pests grow or may grow; or materials, cultivated plants, plant propagation materials (such as seeds), soil, surfaces or spaces to be protected from attack or infection by pests.

[0073] The present invention also relates to a method for protecting growing plants from invertebrate pests, preferably insect populations, from attack or infestation, which method comprises contacting the plants, or the soil or water in which the plants are growing or may grow, with a pesticidally effective amount of at least one compound of the present invention (including stereoisomers, salts, tautomers or N-oxides thereof) or a composition of the present invention.

[0074] Preferably, the method of the invention is used to protect plant propagation materials (e.g. seeds) and plants grown therefrom from attack or infestation by invertebrate pests and comprises treating the plant propagation materials (e.g. seeds) with an insecticidally effective amount of a compound of the invention as defined above or with an insecticidally effective amount of an agricultural composition as defined above and hereinafter. The method of the invention is not limited to the protection of "substrates" (plants, plant propagation materials, soil materials, etc.) that have been treated according to the invention and thereby also has a preventive effect (e.g. protection) on plants grown from treated plant propagation materials (e.g. seeds), wherein the plants themselves have not been treated.

[0075] For the purposes of the present invention, "invertebrate pests" are preferably selected from arthropods and nematodes, more preferably from harmful insects, spiders and nematodes, even more preferably from insects, mites and nematodes. In the meaning of the present invention, "invertebrate pests" are most preferably insects.

[0076] The compounds of the present invention (including their salts, stereoisomers and tautomers) are particularly useful for controlling insects, preferably sucking or piercing insects, for example from the orders Thysanoptera, Diptera and Hemiptera, especially the following genera:

[0077] Hemiptera (especially aphids): Acyrthosiphon onobrychis, larch aphid, Aphidula nasturtii, beet aphid, strawberry root aphid, apple aphid, cotton aphid, North American tea aphid, Cinnamon aphid, leaf roller aphid, elderberry aphid, pea aphid, eggplant aphid, euphorbia aphid, plum aphid, peach aphid, Brachycaudus prunicola, cabbage aphid, Capitophorus horni, Cerosipha gossypii, strawberry aphid, tea aphid, Caucasian fir aphid, spruce aphid, root aphid, Dysaulacorthum pseudosolani, plant aphid, pear aphid, broad bean leafhopper, peach aphid, Hyperomyzus lactucae, wheat aphid, euphorbia aphid, rose aphid, nest aphid, Melanaphis pyrarius, wheat aphid, Myzodes persicae, onion gall aphid, Myzus cerasi, plum gall aphid, black tea aphid, rice planthopper, stalk gall aphid, sugarcane planthopper, hops aphid, apple psyllid, pear psyllid, onion gall aphid, corn aphid, cereal aphid, apple grass aphid, Sappaphis mala, Sappaphis mali, wheat aphid, Schizoneura lanuginosa, wheat aphid, whitefly, citrus aphid and grape phylloxera.

[0078] The present invention provides an agricultural composition for controlling invertebrate pests, comprising a certain amount of at least one compound of the present invention and at least one inert liquid and / or solid agronomically acceptable carrier having insecticidal activity, and if necessary, at least one surfactant.

[0079] The composition may comprise a single active compound according to the invention or a mixture of several active compounds according to the invention.The composition according to the invention may comprise an individual isomer or a mixture of isomers or a salt as well as an individual tautomer or a mixture of tautomers.

[0080] The mixtures according to the invention can be used directly, in the form of their formulations or use forms prepared therefrom, by spraying, atomizing, dusting, broadcasting or pouring, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for broadcasting or granules. The use form depends entirely on the intended purpose; it is intended that it ensures the finest possible distribution of the active compound according to the invention in each case.

[0081] The formulations are prepared in a known manner, for example by admixing the active compounds with auxiliaries suitable for the formulation of agrochemicals, such as solvents and / or carriers and, if desired, emulsifiers, surfactants and dispersants, preservatives, antifoams, antifreeze agents and, in the case of seed treatment formulations, optionally also colorants and / or binders and / or gelling agents.

[0082] Suitable solvents / carriers are, for example:

[0083] Solvents such as water, aromatic solvents (e.g. Solvesso products, xylene, etc.), paraffins (e.g. mineral fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methylpyrrolidone (NMP), N-octylpyrrolidone NOP), acetates (ethylene glycol diacetate), alkyl lactates, lactones (e.g. g-butyrolactone), diols, fatty acid dimethylamides, fatty acids and fatty acid esters, triglycerides, oils of plant or animal origin and modified oils (e.g. alkylated vegetable oils). In principle, solvent mixtures can also be used.

[0084] - carriers, for example ground natural and ground synthetic minerals, such as silica gel, finely divided silicic acid, silicates, talc, kaolin, attaclay, limestone, lime, chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground synthetic materials; fertilizers, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; and products of plant origin, such as cereal flour, bark flour, wood flour and nut shell flour; cellulose powder and other solid carriers.

[0085] Suitable emulsifiers are nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).

[0086] Examples of dispersants are lignin sulfite waste liquor and methylcellulose.

[0087] Suitable surfactants are lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonic acid esters, fatty alcohol sulfates, alkali metal, alkaline earth metal and ammonium salts of fatty acids and sulfated fatty alcohol glycol ethers, and also condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polypropylene oxide, lauryl alcohol polyglycol ether acetals, sorbitol esters.

[0088] Antifreeze agents such as glycerol, ethylene glycol, propylene glycol, and bactericides may also be added to the formulation.

[0089] Suitable antifoams are, for example, antifoams based on silicon stearate or magnesium stearate.

[0090] Suitable preservatives are, for example, dichlorophen and benzyl alcohol hemiformal.

[0091] Suitable thickeners are compounds which impart pseudoplastic flow behavior to the formulation, ie high viscosity at rest and low viscosity during the stirring phase. In this context, mention may be made, for example, of commercially available thickeners based on polysaccharides, such as Xanthan Gum®. (From Kelco ), 23 (Rhone Poulenc) or (from RT Vanderbilt) or organic layered silicates, e.g. (from Engelhardt). Suitable defoamers for the dispersions according to the invention are, for example, silicone emulsions (e.g., SRE, Wacker, or ), long chain alcohols, fatty acids, organofluorine compounds and mixtures thereof. Biocides may be added to stabilize the compositions of the present invention against attack by microorganisms. Suitable biocides are, for example, based on isothiazolone, such as those marketed by Avecia (or Arch) under the trademark Or by Thor Chemie RS and Rohm & Haas Compounds sold by MK. Suitable antifreeze agents are organic polyols, such as ethylene glycol, propylene glycol or glycerol. These substances are generally used in an amount of not more than 10% by weight, based on the total amount of the active compound composition. If appropriate, the active compound composition of the present invention may contain 1% to 5% by weight of a buffer to adjust the pH, based on the total amount of the prepared formulation, the amount and type of buffer used depending on the chemical properties of the active compound. Examples of buffers are alkali metal salts of weak inorganic or organic acids (e.g., phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid).

[0092] Suitable substances for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions with a medium to high boiling point, such as kerosene or diesel; furthermore coal tar and oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, xylene, paraffin, tetralin, alkylated naphthalenes or their derivatives; methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone; strongly polar solvents, such as dimethyl sulfoxide, N-methylpyrrolidone and water.

[0093] Dusts, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

[0094] Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by combining the active compound with a solid carrier. Examples of solid carriers are mineral earths, such as silica gel, silicates, talc, kaolin, magnesia clay, limestone, lime, chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; and products of plant origin, such as cereal flour, bark meal, wood flour and nut shell flour; cellulose powder and other solid carriers.

[0095] Typically, the formulation (ie, the composition of the present invention) comprises 0.01% to 95% by weight, preferably 0.1% to 90% by weight, of the active ingredient. The purity of the active ingredient used is 90% to 100%, preferably 95% to 100% (according to NMR spectroscopy).

[0096] For seed treatment, the corresponding formulations can be diluted 2- to 10-fold so that the concentration of active compound by weight in the ready-to-use preparations is from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight.

[0097] Aqueous use forms can be prepared from emulsion concentrates, pastes, or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes, or oil dispersions, these substances, either as such or dissolved in an oil or solvent, can be homogenized in water with the aid of a wetting agent, tackifier, dispersant, or emulsifier. Alternatively, concentrates containing the active substance, wetting agent, tackifier, dispersant, or emulsifier, and, if appropriate, a solvent or oil, can be prepared, and these concentrates are suitable for dilution with water.

[0098] The concentrations of the active ingredients in the ready-to-use products can vary within relatively wide ranges. Typically, these concentrations are from 0.0001% to 10%, preferably from 0.01% to 1%.

[0099] The active ingredients can also be used successfully in the ultra-low volume process (ULV), it being possible to apply formulations comprising more than 95% by weight of active ingredient, or even to apply the active ingredient without additives.

[0100] In the methods and uses of the present invention, the compounds of this invention can be used together with other active ingredients, for example, with other pesticides, insecticides, herbicides, fertilizers (such as ammonium nitrate, urea, potash and superphosphate), plant toxins and plant growth regulators, safeners and nematicides. These additional ingredients can be used sequentially or in combination with the above-mentioned composition, and if appropriate, they can also be added just before use (tank mix). For example, plants can be sprayed with the composition of the present invention before or after treatment with other active ingredients.

[0101] Pesticides that can be used together with the compounds of the present invention and that can produce potential synergistic effects include, but are not limited to, the active substances listed in WO2012143317A1.

[0102] Invertebrate pests (also referred to as "animal pests," i.e., insects, arachnids, and nematodes), plants, soil or water in which plants are growing or may grow, may be contacted with a compound of the invention or a composition comprising the same by any application method known in the art. Thus, "contacting" includes direct contact (applying the compound / composition directly to the invertebrate pest or plant - typically to the leaves, stems, or roots of the plant) and indirect contact (applying the compound / composition to the locus of the invertebrate pest or plant).

[0103] The compounds of the present invention or pesticidal compositions comprising the same can be used to protect growing plants and crops from attack or infestation by animal pests, particularly insects, mites or spiders, by contacting the plants / crops with a pesticidally effective amount of the compounds of the present invention. The term "crops" refers to both growing crops and harvested crops.

[0104] The compounds of the invention and compositions comprising them are particularly important for controlling a large number of insects on various cultivated plants, such as cereals, root crops, oilseed crops, vegetables, spice crops, ornamentals, for example durum wheat and other wheats, barley, oats, rye, corn (fodder corn and sugar corn / sweet corn and fodder corn), soybeans, oilseed crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugar beet, fodder beet, eggplant, potatoes, grasses, lawns, turf, fodder grasses, tomatoes, leeks, pumpkins, cabbage, endive, peppers, cucumbers, melons, Brassica spp., melons, beans, peas, garlic, onions, carrots, tuber plants such as potatoes, sugarcane, tobacco, grapes, petunias, geraniums / geraniums, pansies and impatiens seeds.

[0105] The compounds of this invention are used directly or in a composition by treating insects with the active compound of an insecticidal effective amount or to prevent the plant, plant propagation material such as seed, soil, surface, material or space from being attacked by insects. Application can be carried out before and after plant, plant propagation material such as seed, soil, surface, material or space are infested by insects.

[0106] In addition, invertebrate pests can be controlled by contacting a pesticidally effective amount of a compound of the invention with the target pest, its food supply, habitat, breeding ground, or its locus. Thus, application can be made before or after the locus, growing crop, or harvested crop is infested by the pest.

[0107] The compounds of the invention may also be applied preventatively to locations where pests are expected to appear.

[0108] The compounds of the present invention can also be used to protect growing plants from attack or infestation by pests by contacting the plants with a pesticidally effective amount of a compound of the present invention. Thus, "contacting" includes direct contact (applying the compound / composition directly to the pest and / or plant - typically to plant leaves, stems or roots) and indirect contact (applying the compound / composition to the locus of the pest and / or plant).

[0109] "Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is or may be growing.

[0110] Generally speaking, an "insecticidally effective amount" refers to the amount of active ingredient required to achieve an observable effect on growth, including necrosis, mortality, retardation, prevention, and removal, destruction, or reduction in the presence and activity of the target organism. The insecticidally effective amount may vary for the various compounds / compositions used in the present invention. The insecticidally effective amount of a composition may also vary depending on prevailing conditions such as the desired insecticidal effect and duration, weather, target species, location, mode of application, and the like.

[0111] The compounds of the invention are effective by contact (via soil, glass, walls, bed netting, carpeting, plant parts or animal parts) and ingestion (baits or plant parts).

[0112] The compounds of the present invention can also be applied against non-crop insect pests such as ants, termites, wasps, flies, mosquitoes, crickets or cockroaches. For use against such non-crop pests, the compounds of the present invention are preferably used in bait compositions.

[0113] Bait can be liquid, solid or semi-solid formulations (e.g. gels). Solid baits can be made into various shapes and forms suitable for the respective application, such as granules, blocks, rods, sheets. Liquid baits can be filled into various devices to ensure proper application, such as open containers, spray devices, droplet supply sources or evaporation sources. Gels can be based on aqueous or oily substrates and can be formulated according to specific requirements based on viscosity, moisture retention or aging characteristics.

[0114] The bait used in the composition is a product that is sufficiently attractive to stimulate insects such as ants, termites, wasps, flies, mosquitoes, crickets, etc. or cockroaches to eat it. The attractiveness can be regulated by using feeding stimulants or sex pheromones. Feeding stimulants are, for example, not exhaustively selected from animal and / or plant proteins (meat-, fish- or blood meals, insect parts, egg yolks), fats and oils of animal and / or plant origin or mono-, oligo- or poly-organic sugars, in particular sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or rotten parts of fruits, crops, plants, animals, insects or specific parts thereof can also be used as feeding stimulants. It is known that sex pheromones are more insect-specific. Special pheromones are described in the literature and are known to those skilled in the art.

[0115] Formulations of the compounds of the invention as aerosols (eg in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user to control pests such as flies, fleas, ticks, mosquitoes or cockroaches. Aerosol formulations preferably consist of the following components: active compound; solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffins with a boiling range of about 50-250° C. (e.g. kerosene), dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water; in addition, adjuvants, for example emulsifiers such as sorbitol monooleate, oleyl ethoxylates with 3-7 mol of ethylene oxide, fatty alcohol ethoxylates, aromatic oils such as essential oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds; if appropriate, stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if necessary, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide or mixtures of these gases.

[0116] Oil spray formulations differ from aerosol formulations in that no propellant is used.

[0117] The compounds of the present invention and their corresponding compositions can also be used in mosquito coils and fumigation sheets, cigarette boxes, vaporizer plates or long-lasting vaporizers, as well as moth-catching papers, moth-catching pads or other vaporizer systems that are not related to heat.

[0118] Methods of controlling infectious diseases transmitted by insects (e.g., malaria, dengue and yellow fever, lymphatic filariasis and leishmaniasis) using the compounds of the present invention and corresponding compositions also include treating surfaces of sheds and houses, aerial spraying and impregnating curtains, tents, clothing, bedding, tsetse fly nets, etc. Insecticidal compositions applied to fibers, fabrics, knits, nonwovens, netting materials or foils and tarpaulins preferably comprise a mixture comprising an insecticide, an optional repellent and at least one binder. Suitable repellents are, for example, N,N-diethyl-m-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3-cyclohexane-1-ylcarbonyl)-2-methylpiperidine, (2-hydroxymethylcyclohexyl)acetic acid lactone, 2-ethyl-1,3-hexanediol, dimethicone, methyl neodecanoamide (MNDA), pyrethroids not used for insect control such as {(+ / -)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysanthemate (Esbiothrin), repellents derived from plant extracts or identical to plant extracts such as 1,8-terpenoids, eugenol, (+)-Eucamalol (1), (-)-1-epi-eucamalol, or from plants such as Eucalyptus maculata, Vitex rotundifolia, Cymbopogan Crude plant extracts of plants such as Cymbopogan martinii, Cymbopogan citratus (lemongrass), and Cymopogan nartdus (lemongrass). Suitable binders are, for example, selected from polymers and copolymers of vinyl esters of aliphatic acids such as vinyl acetate and vinyl esters of branched alkane carboxylates, acrylates and methacrylates of alcohols such as butyl acrylate, 2-ethylhexyl acrylate and methyl acrylate, monoethylenically and diethylenically unsaturated hydrocarbons such as styrene, and aliphatic dienes such as butadiene.

[0119] Impregnation of curtains and bedding is usually carried out by dipping the textile material into an emulsion or dispersion of the insecticide or spraying them onto the bedding.

[0120] The compounds of the present invention and compositions thereof can be used to protect wood materials such as trees, guardrails, sleepers, and buildings such as houses, outbuildings, factories, as well as building materials, furniture, leather, fibers, vinyl products, wires and cables, etc., to prevent ants and / or termites, and to prevent ants and termites from damaging crops or humans (e.g., when pests invade houses and public facilities). The compounds of the present invention are not only applied to the surrounding soil surface or the soil under the floor to protect wood materials, but can also be applied to the surfaces of piled products such as concrete under the floor, pavilion columns, beams, plywood, furniture, etc., wood products such as particleboard, half-board, etc., and vinyl products such as coated wires, vinyl sheets, thermal insulation materials such as styrene foam, etc. In the application of preventing ants from damaging crops or humans, the ant control agent of the present invention is applied to crops or surrounding soil, or directly applied to ants' nests, etc.

[0121] The compounds according to the invention are therefore suitable for treating plant propagation material, especially seeds, for protecting them from insect pests, especially soil insect pests, and for protecting the roots and shoots of the resulting plants from soil pests and foliar insects.

[0122] The compounds of the present invention are particularly useful for protecting seeds from soil pests and protecting the roots and shoots of the resulting plants from soil pests and foliar insects. Preferably, the roots and shoots of the resulting plants are protected. More preferably, the shoots of the resulting plants are protected from piercing-sucking insects, with protection from aphids being most preferred.

[0123] The present invention therefore comprises a method for protecting seeds from insects, in particular soil insects, and for protecting the roots and shoots of rice seedlings from insects, in particular soil and foliar insects, which method comprises contacting the seeds with a compound according to the invention, including a salt thereof, before sowing and / or after pre-germination. Particularly preferred is a method in which the roots and shoots of plants are protected, more preferably a method in which the shoots of plants are protected from piercing-sucking insects, and most preferably a method in which the shoots of plants are protected from aphids.

[0124] The term seed includes seeds and plant propagules of all kinds, including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruits, tubers, kernels, cuttings, cut shoots, etc., and in preferred embodiments refers to true seeds.

[0125] The term seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.

[0126] The invention also encompasses seeds coated with or containing the active compound.

[0127] The term "coated with and / or containing" generally means that the active ingredient is predominantly on the surface of the propagation product at the time of application, but a greater or lesser portion of the ingredient may penetrate into the propagation product, depending on the method of application. When the propagation product is (re)planted, it may absorb the active ingredient.

[0128] Suitable seeds are seeds of cereals, root crops, oil crops, vegetables, spice crops, ornamentals, for example durum wheat and other wheats, barley, oats, rye, corn (fodder corn and sugar corn / sweet corn and fodder corn), soybeans, oilseed crops, crucifers, cotton, sunflower, banana, rice, oilseed rape, turnip rape, sugar beet, fodder beet, eggplant, potato, grass, lawn, turf, fodder grass, tomato, leek, pumpkin, cabbage, endive, pepper, cucumber, melon, Brassica, melon, beans, peas, garlic, onion, carrot, tuber plants such as potatoes, sugarcane, tobacco, grapes, petunia, geranium / geranium, pansy and impatiens.

[0129] Furthermore, the active compounds can be used for treating the seeds of plants which have been made tolerant to the action of herbicides or fungicides or insecticides as a result of breeding, including genetic engineering methods.

[0130] For example, the active compounds can be used to treat plants that are resistant to herbicides selected from the group consisting of sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropyl ammonium and similar active substances (see, for example, EP-A 242 236, EP-A 242 246, WO 92 / 00377, EP-A 257 993, US Pat. No. 5,013,659) or seeds of transgenic crops, such as cotton, which produce Bacillus thuringiensis toxins (Bt toxins) to render the plants resistant to certain pests (EP-A 142 924, EP-A 193 259).

[0131] Furthermore, the active compounds can also be used to treat the seeds of plants which have modified properties compared to existing plants, which may have been produced, for example, by conventional breeding methods and / or mutants or by recombinant procedures. For example, numerous cases of recombinantly modifying crops to modify the starch synthesized in plants have been described (e.g. WO 92 / 11376, WO 92 / 14827, WO 91 / 19806), or transgenic plants with a modified fatty acid composition (WO 91 / 13972).

[0132] Seed treatment applications of the active compounds are carried out by spraying or dusting the seeds before sowing of the plants and before emergence of the plants.

[0133] Conventional seed treatment formulations include, for example, flowable concentrates FS, solutions LS, dry treatment powders DS, water-dispersible powders WS for slurry treatment, water-soluble powders SS, emulsions ES and EC, and gel formulations GF. These formulations can be applied to the seeds diluted or undiluted. Application to the seeds is made before sowing, either directly on the seeds or after the seeds have been pre-germinated.

[0134] Seed treatment formulations may additionally comprise a binder and optionally a colorant.

[0135] Binders may be added to improve the adhesion of the active substance to the seed after treatment. Suitable binders are homopolymers and copolymers of alkylene oxides, such as ethylene oxide or propylene oxide, polyvinyl acetate, polyvinyl alcohol, polyvinyl pyrrolidone and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homopolymers and copolymers, polyvinylamine, polyvinylamide and polyethyleneimine, polysaccharides such as cellulose, tylose and starch, polyolefin homopolymers and copolymers, such as olefin / maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homopolymers and copolymers.

[0136] Optionally, colorants may also be included in the formulation.

[0137] An example of a gelling agent is carrageenan

[0138] In principle, the method that can be used for treating seed is all suitable seed treatment techniques known in the art, especially seed dressing technology, such as seed coating (such as seed pelleting), seed dusting and seed imbibition (such as seed soaking).Herein, "seed treatment" refers to all methods of contacting seeds with the compounds of the present invention, and "seed dressing" refers to a seed treatment method in which a certain amount of the compounds of the present invention is provided to seeds, i.e., it produces seeds comprising the compounds of the present invention. In principle, seeds can be treated at any time during the sowing of seeds after the seeds are harvested. Seeds can be treated using (for example) a "sowing box" method just before planting seeds or during planting seeds. However, it is also possible to treat in the form of seed dressing several weeks or several months (for example, up to 12 months) before planting seeds, without observing a significant reduction in efficacy.

[0139] The treatment can conveniently be carried out on unplanted seeds. The term "unplanted seeds" as used herein is intended to include seeds at any stage from harvesting the seeds to sowing the seeds in the ground for plant germination and growth.

[0140] In particular, the treatment involves mixing the seeds with the desired amount of the seed treatment formulation, either untreated or previously diluted with water, in a suitable apparatus (e.g. a mixing apparatus for mixing solids or solid / liquid mixing pairs) until the composition is evenly distributed over the seeds. If appropriate, this is followed by a drying step. DETAILED DESCRIPTION

[0141] The following examples are provided to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights claimed in the present invention is described in the claims.

[0142] Given the economical efficiency and diversity of the compounds, we have selected and synthesized a number of compounds. A selection of these compounds is listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are intended to better illustrate the present invention but are not intended to limit the present invention. Those skilled in the art should not interpret this as limiting the scope of the present invention to the following compounds.

[0143] Table 1 Compound structures and their 1 H NMR

[0144] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as described in detail. It will be understood by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific starting materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar starting materials and conditions, and these modifications or variations of the preparation methods of the present invention that result in various isomerizations of the compounds are included within the scope of the present invention. In addition, the preparation methods described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups can be protected during the reaction, etc.

[0145] The following process examples are provided to facilitate a further understanding of the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthesis of the compounds shown in the table below are either commercially available or can be readily prepared by one of ordinary skill in the art.

[0146] Examples of representative compounds are shown below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0147] 1. Synthesis of compound 4

[0148] Compound 4-1 (100 mg, 1 eq) was dissolved in dimethyl sulfoxide (DMSO) and sodium hydride (27 mg, 3 eq) was slowly added at room temperature. The mixture was stirred for 10 min and propargyl bromide (44 mg, 1.2 eq) was slowly added dropwise. After the addition was completed, the mixture was reacted at room temperature for 2 h. The intermediate control reaction was completed. The reaction solution was poured into water for quenching, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated and mixed, and purified by normal phase to obtain compound 4 (66 mg, 58%).

[0149] 2. Synthesis of Compound 255

[0150] (1) Compound 255-1 (500 mg, 1.0 eq) was dissolved in 15 mL of dichloromethane. Two drops of DMF were then added dropwise, followed by the slow addition of oxalyl chloride (600 mg, 2.0 eq). After the addition, the reaction mixture was stirred at 45°C for 1 h and monitored by LCMS until the reaction was complete. The reaction mixture was concentrated to afford compound 255-2 (500 mg, 92%).

[0151] (2) 255-3 (250 mg, 1.2 eq) was dissolved in 20 mL of dichloromethane at room temperature, and triethylamine (670 mg, 3.0 eq) was added dropwise. Compound 255-2 (500 mg, 1.0 eq) was then dissolved in dichloromethane and slowly added dropwise to the reaction mixture. After the intermediate reaction, the reaction mixture was concentrated and sampled, and purified by normal phase chromatography to obtain compound 255-4 (380 mg, 61%).

[0152] (3) Compound 255-4 (200 mg, 1.0 eq) was dissolved in dimethyl sulfoxide solution at room temperature. Sodium hydride (50 mg, 3.0 eq) was slowly added to the solution. After stirring for 10 min, propargyl bromide (100 mg, 1.2 eq) was added dropwise. After the addition, the mixture was reacted at room temperature for 2 h. The intermediate control reaction was completed. The reaction solution was poured into water for quenching, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase to obtain compound 255 (150 mg, 66%).

[0153] 3. Synthesis of Compound 267

[0154] (1) Compound 267-1 (2.6 g, 1.0 eq) was dissolved in 20 ml of EtOH at -20°C under nitrogen protection. Compound 267-2 (4.2 g, 2.0 eq) was slowly added dropwise to the reaction solution. After the addition was complete, the reaction solution was naturally warmed to room temperature and reacted for 12 hours. LCMS was used to monitor the reaction until it was complete. The remaining residue was concentrated and collected, and the solvent was dried to obtain compound 267-3, which was used directly in the next step without further treatment (light yellow liquid, 2 g, 42% yield).

[0155] (2) Compound 267-3 (2 g, 1.0 eq) was dissolved in 20 ml of AcOH at 0°C, and NaBH3CN (0.78 g, 2.0 eq) was added portionwise. After addition, the mixture was stirred at 50°C for 12 hours; the reaction was monitored by LCMS until completion. The reaction was quenched by adding water (20 mL) and extracted three times with ethyl acetate (30 mL x 3). The organic phases were combined, dried, filtered, concentrated, and then purified by normal phase purification to afford compound 267-4 (white solid, 1.2 g, 63% yield).

[0156] (3) Compound 267-4 (1.2 g, 1.0 eq) was dissolved in 20 ml of methanol at 25°C, cooled in an ice bath, and sodium hydroxide (0.3 g, 2.0 eq) was added. After the addition was complete, the mixture was stirred at 50°C for 12 hours. LCMS was used to monitor the reaction until it was complete. 2N aqueous hydrochloric acid was added to adjust the mixture to acidic. The mixture was extracted with ethyl acetate three times (25 mL*3), dried, filtered, and concentrated to obtain compound 267-5 (0.85 g, 77% yield).

[0157] (4) At 25°C, compound 267-5 (850 mg, 1.0 eq) was dissolved in 25 ml of dichloromethane, two drops of DMF were added dropwise, and oxalyl chloride (800 mg) was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 hours; LCMS was used to monitor the reaction until it was complete, and the mixture was directly concentrated to obtain compound 267-6 (900 mg, 100% yield).

[0158] (5) Compound 3-aminopyridine (178 mg, 1 eq) was dissolved in 25 mL of dichloromethane and stirred at room temperature. Triethylamine (580 mg, 3 eq) was added dropwise. Then, 267-6 (500 mg, 1.1 eq) was dissolved in dichloromethane and slowly added dropwise to the reaction solution. After the addition was completed and the reaction was completed, the sample was directly mixed and purified to obtain compound 267-7 (450 mg, 76%).

[0159] (6) Compound 267-7 (200 mg, 1 eq) was dissolved in N,N-dimethylformamide, and sodium hydride (38 mg, 3 eq) was slowly added at room temperature. The mixture was stirred for 10 min, and propargyl bromide (75 mg, 1.2 eq) was slowly added dropwise. After the addition, the mixture was reacted at room temperature for 2 h, and the reaction was completed. The reaction solution was poured into water for quenching, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase to obtain compound 267 (87 mg, 39%).

[0160] 4. Synthesis of Compound 268

[0161] (1) Compound 4 (190 mg, 1 eq) was dissolved in DMF and stirred. After the reaction solution temperature dropped to 0°C, KI (214 mg, 2 eq), I2 (327 mg, 2 eq), and 10% KOH aqueous solution (2 mL) were slowly added. The reaction was allowed to react for 2 h, and the reaction was terminated by mid-control. The reaction solution was washed with saturated brine and extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase purification to obtain compound 268 (218 mg, 78%).

[0162] 5. Synthesis of Compound 269

[0163] Compound 4-1 (190 mg, 1 eq) was dissolved in DMF, and sodium hydride (53 mg, 3 eq) was slowly added at room temperature. The mixture was stirred for 10 min, and 269-1 (117 mg, 1.2 eq) was slowly added dropwise. After addition, the mixture was allowed to react at room temperature for 2 h, and the reaction was completed by mid-control. The reaction solution was poured into water for quenching, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and mixed. Compound 269 (97 mg, 42%) was obtained by normal phase purification.

[0164] 6. Synthesis of Compound 271

[0165] Compound 4-1 (150 mg, 1 eq) was dissolved in DMF. Sodium hydride (40 mg, 3 eq) was slowly added at room temperature. The mixture was stirred for 10 min, and 271-1 (99 mg, 1.2 eq) was slowly added dropwise. The reaction was allowed to react at room temperature for 2 h, and the reaction was completed by mid-control. The reaction solution was poured into water for quenching, then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase purification to obtain compound 271 (50 mg, 23%).

[0166] 7. Synthesis of Compound 273

[0167] (1) The raw material 273-1 (500 mg, 1.68 mmol) was dissolved in 10 ml of anhydrous toluene. Phosphorus pentasulfide (1.86 g, 8.93 mmol) was added at room temperature and the temperature was raised to 100°C. The reaction was allowed to proceed for 2 h, and the intermediate control reaction was complete. The reaction solution was concentrated and directly mixed. Silica gel column chromatography gave compound 273-2 (200 mg, 38%) as a light yellow oil.

[0168] (3) Compound 273-2 (200 mg, 1 eq) was dissolved in DMF, and sodium hydride (3 eq) was slowly added at room temperature. The mixture was stirred for 30 min, and propargyl bromide (1.2 eq) was slowly added dropwise. After the addition, the mixture was allowed to react at room temperature for 2 h, and the reaction was completed. The reaction solution was poured into water for quenching, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase purification to obtain compound 273 (101 mg, 45%).

[0169] 8. Synthesis of Compound 284

[0170] (1) To a solution of compound 284-1 (1 g, 5.12 mmol) in 10 mL of DMF was slowly added 60% sodium hydride (0.41 g, 10.24 mmol) at 0°C. The reaction solution was stirred at 0°C for 0.5 hours, and 3-bromopropyne (0.91 g, 7.68 mmol) was added dropwise to the reaction solution. The reaction solution was warmed to room temperature and stirred overnight. LCMS showed that the reaction was complete. Ice water was added to the reaction solution to quench the reaction, and the mixture was extracted with ethyl acetate. The organic phase was washed with saturated brine, and the organic phase was concentrated. The residue was purified by silica gel column chromatography to obtain compound 284-2 (0.35 g, 29%) as a brown oil.

[0171] (2) Compound 284-2 (0.35 g, 1.50 mmol) was dissolved in 10 mL of dioxane hydrochloride (4 mol / L) at room temperature. The reaction solution was stirred at room temperature for 2 hours. LCMS indicated the reaction was complete. The solvent was removed by concentration to obtain crude compound 284-3, which was used directly in the next step.

[0172] (3) Compound 284-3 was dissolved in 25 mL of DCM and stirred at room temperature. TEA (0.15 g, 4.50 mmol) was added, and then compound 284-4 (0.36 g, 1.65 mmol) was dissolved in DCM and slowly added dropwise to the reaction solution. The reaction solution was stirred at room temperature for 1 hour. LCMS showed the reaction was complete. The organic phase was concentrated and the residue was purified by silica gel column chromatography to obtain compound 284 (55 mg, 11%) as a yellow oil.

[0173] 9. Synthesis of compound 353

[0174] (1) Compound 353-1 (260 mg, 1.0 eq) was dissolved in 15 ml of dichloromethane, and two drops of DMF were added dropwise. Oxalyl chloride (2.0 eq) was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 hours. LCMS was used to monitor the reaction until it was complete. The mixture was then concentrated to give compound 353-2 (885 mg, 99% yield) as a yellow oil.

[0175] (2) 3-Aminopyridine (0.8 eq) was dissolved in 25 mL of dichloromethane and stirred at room temperature. Triethylamine (3.0 eq) was added dropwise. Then, 353-2 (885 mg, 1.1 eq) was dissolved in dichloromethane and slowly added dropwise to the reaction solution. After the addition was completed and the reaction was completed, the sample was directly mixed and purified to obtain brown oily compound 353-3 (700 mg, yield 60%).

[0176] (3) Compound 353-3 (700 mg, 1 eq) was dissolved in DMF, and sodium hydride (3.0 eq) was slowly added at room temperature. The mixture was stirred for 30 min, and propargyl bromide (1.2 eq) was slowly added dropwise. After the addition, the mixture was allowed to react at room temperature for 2 h, and the reaction was completed. The reaction solution was poured into water for quenching, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase chromatography to obtain compound 353 (190 mg, 23% yield) as a brown oil.

[0177] 10. Synthesis of Compound 355

[0178] (1) Under ice bath, compound 355-1 (0.2 g, 1 eq) was dissolved in dichloromethane and oxalyl chloride (0.35 g, 2 eq) was added. After the reaction was completed, the dichloromethane was dried and the compound was prepared for use.

[0179] 3-Aminopyridine was added to dichloromethane, and the compound from the previous step and triethylamine were added, and the mixture was reacted at room temperature. After the reaction, the mixture was purified by normal phase column to obtain compound 355-2 (213 mg, yield 80%).

[0180] (2) Compound 355-2 (0.213 g, 1 eq) was dissolved in thionyl chloride under ice-cooling, and sodium hydroxide (0.053 g, 2 eq) was added. After half an hour of reaction, propargyl bromide was added. After the intermediate control reaction, water was added to quench the reaction. The reaction was then washed three times with water and ethyl acetate. The organic phase was collected and mixed, and the mixture was passed through a normal phase column to obtain compound 355 (89 mg, 37% yield).

[0181] 11. Synthesis of Compound 370

[0182] (1) Compound 370-1 (3.0 g, 15.29 mmol) was dissolved in 30 mL of dichloromethane. Two drops of DMF were then added dropwise, followed by the slow addition of oxalyl chloride (3.88 g, 30.58 mmol). The reaction mixture was stirred at room temperature for 1 h and monitored by LCMS until the reaction was complete. The reaction mixture was concentrated and set aside for later use.

[0183] At room temperature, 3-aminopyridine (1.72 g, 18.35 mmol) was dissolved in 20 mL of dichloromethane, and triethylamine (5.56 g, 55.05 mmol) was added dropwise. The concentrate prepared above was then dissolved in dichloromethane and slowly added dropwise to the reaction solution with continued stirring at room temperature. After the intermediate reaction, the reaction solution was concentrated and sampled, and purified by normal phase purification (PE / EA = 2 / 1) to obtain compound 370-2 (yellow oil, 2.0 g, 48% yield).

[0184] (2) Compound 370-2 (400 mg, 1.47 mmol) was dissolved in DMF at room temperature, and sodium hydride (106 mg, 4.41 mmol) was slowly added. After stirring for 10 min, propargyl bromide (210 mg, 1.76 mmol) was added dropwise. After the addition, the mixture was reacted at room temperature for 2 h, and the intermediate control reaction was completed. The reaction solution was poured into water for quenching, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and then concentrated and mixed. The mixture was purified by normal phase purification (PE / EA = 3 / 1) to obtain compound 370 (yellow oil, 120 mg, yield 26%).

[0185] 12. Synthesis of Compound 374

[0186] (1) Compound 374-1 (5.0 g, 36.72 mmol) was dissolved in 50 mL of toluene solution, and 4,4-dimethylcyclohexanone (5.56 g, 44.07 mmol) was added. The reaction solution was stirred at 80°C for 2 h. The reaction was monitored by LCMS to be complete. The reaction solution was concentrated to obtain crude compound 374-2 (pale yellow oil, 8.5 g, 95% yield), which was used directly in the next step.

[0187] (2) Compound 374-2 (8.5 g, 34.79 mmol) was dissolved in 60 mL of methanol under ice-cooling conditions. Solid sodium borohydride (1.58 g, 41.75 mmol) was then slowly added. After stirring for 1 h, the reaction was complete as monitored by LCMS. The reaction solution was concentrated, extracted with water and ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to afford crude compound 374-3 (white oil, 7.8 g, 91% yield).

[0188] (3) Compound 374-3 (7.8 g, 31.66 mmol) was dissolved in a mixture of HCl and MeOH and stirred at 80°C overnight. After the intermediate reaction, the reaction solution was drained and ethyl acetate was added to the mixture for slurrying. The precipitated solid was compound 374-4 (white solid, 3.8 g, 84% yield).

[0189] (4) Compound 374-4 (3.8 g, 26.71 mmol) was dissolved in 40 mL of anhydrous ethanol in an ice-salt bath. Sodium acetate (3.28 g, 40.06 mmol) and compound 267-2 (6.42 g, 32.06 mmol) were then added and stirred gradually to room temperature. The intermediate control reaction was completed after 2 h. The reaction solution was spin-dried and then extracted with water and ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase purification (PE / EA = 5 / 1) to give compound 374-5 (white solid, 5.5 g, 74% yield).

[0190] (5) Compound 374-5 (5.5 g, 19.76 mmol) was dissolved in 40 mL of methanol solution, and saturated aqueous sodium hydroxide solution was added dropwise. After the addition was complete, the reaction solution was transferred to an oil bath at 45°C and reacted overnight. After the mid-control reaction was completed, the reaction solution was concentrated, and the pH of the reaction solution was adjusted to acidic by adding 10 mol / L dilute hydrochloric acid. The reaction solution was then extracted with ethyl acetate, and the organic phases were combined and concentrated under reduced pressure to obtain crude compound 374-6 (3 g yellow oil, 61% yield).

[0191] (6) Compound 374-6 (0.5 g, 2.0 mmol) was dissolved in 15 mL of dichloromethane. Two drops of DMF were then added dropwise, followed by the slow addition of oxalyl chloride (0.5 g, 4.0 mmol). The reaction mixture was stirred at room temperature for 1 h and monitored by LCMS until the reaction was complete. The reaction mixture was concentrated and set aside for later use.

[0192] At room temperature, 3-aminopyridine (225 mg, 2.4 mmol) was dissolved in 20 mL of dichloromethane, and triethylamine (727 mg, 7.2 mmol) was added dropwise. The concentrate prepared above was then dissolved in dichloromethane and slowly added dropwise to the reaction solution with continued stirring at room temperature. After the intermediate reaction, the reaction solution was concentrated and sampled, and purified by normal phase purification (PE / EA = 4 / 1) to obtain compound 374-7 (pale yellow oil, 380 mg, 58% yield).

[0193] (7) Compound 374-7 (380 mg, 1.16 mmol) was dissolved in DMF at room temperature, and sodium hydride (83 mg, 3.5 mmol) was slowly added. After stirring for 10 min, propargyl bromide (165 mg, 1.4 mmol) was added dropwise. After the addition, the mixture was reacted at room temperature for 2 h, and the reaction was completed. The reaction solution was poured into water for quenching, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and then concentrated and mixed. The mixture was purified by normal phase purification (PE / EA = 3 / 1) to obtain compound 374 (yellow oil, 160 mg, 38% yield).

[0194] 13. Synthesis of Compound 378

[0195] (1) Compound 378-1 (270 mg, 1.0 eq) was dissolved in 15 ml of dichloromethane, and two drops of DMF were added dropwise. Oxalyl chloride (2.0 eq) was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 hours. LCMS was used to monitor the reaction until it was complete. The mixture was then concentrated to give compound 378-2 (296 mg, 99% yield) as a yellow oil.

[0196] (2) 3-Aminopyridine (0.8 eq) was dissolved in 25 mL of dichloromethane and stirred at room temperature. Triethylamine (3.0 eq) was added dropwise. Then, 378-2 (296 mg, 1.1 eq) was dissolved in dichloromethane and slowly added dropwise to the reaction solution. After the addition was completed and the reaction was completed, the sample was directly mixed and purified to obtain brown oily compound 378-3 (290 mg, yield 76%).

[0197] (3) Compound 378-3 (290 mg, 1.0 eq) was dissolved in DMF. Sodium hydride (3.0 eq) was slowly added at room temperature and stirred for 30 min. Propyl bromide (1.2 eq) was slowly added dropwise. After addition, the mixture was allowed to react at room temperature for 2 h, and the reaction was completed by mid-control. The reaction solution was poured into water for quenching, and then extracted three times with ethyl acetate. The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by normal phase to obtain compound 378 (55 mg, 16% yield) as a brown solid.

[0198] Biological activity evaluation (pot spray method):

[0199] A) Compound activity test:

[0200] The compound of the present invention is dissolved in acetone and then diluted with water to form a drug solution with different concentrations (ppm).

[0201] Potted radish seedlings at the 3-4 leaf stage were inoculated with green peach aphids. After 2-3 days, the test was conducted once the aphid population reached a critical mass. Wheat plants 10 cm tall were inoculated with graminoid aphids. After 2-3 days, the test was conducted once the aphid population reached a critical mass. Treatment was performed using an electric sprayer, with 1 mL of the solution applied to each potted plant. Each dose was replicated three times, with the same acetone concentration used as a control. After treatment, the plants were transferred to aquaculture conditions. After 5 days, the number of dead insects was examined, and the mortality rate was calculated using the formula: mortality (%) = (number of dead insects / number of test insects) * 100. Representative results are shown in Table 2.

[0202] Table 2 Insecticidal test results

[0203] Note: Control compound A: Control compound B: Control compound C:

[0204] B) Activity test of composition:

[0205] 1) Test method

[0206] Component A is compound 4 in Table 1, and component B is purchased or obtained by conventional methods, dissolved in acetone, and then diluted with clean water to form a solution with different concentrations (ppm).

[0207] When the target is green peach aphid, the test method is the same as described above.

[0208] Targeting peanut aphids: Plant broad bean plants in disposable water cups, one per cup. Inoculate seedlings until they reach approximately 10 cm. After 3-4 days, wait until the aphid population reaches a critical mass before conducting the test. Use a small spray bottle for spraying, spraying each bowl 6-9 times, until both sides of the leaves are moist but not dripping. Repeat each dose three times, using the same acetone control. After application, transfer the plants to rearing conditions. After 5 days, check for dead insects and calculate mortality using the formula: Mortality (%) = (number of dead insects / number of test insects) * 100.

[0209] 2) Qualitative evaluation of efficiency

[0210] Different ratios are set within the selected ratio range for toxicity testing, and the best ratio is selected based on the synergistic effect. When the synergistic effect is > 0, it indicates a synergistic effect; when the synergistic effect is close to 0, it indicates an additive effect; when the synergistic effect is < 0, it indicates an antagonistic effect. Synergistic effect = actual mortality rate - theoretical mortality rate Theoretical mortality rate = 1-(1-P1)(1-P2)

[0211] Where, P1, P2 are the mortality rates of each single dose in the mixture.

[0212] Table 3 Results of qualitative evaluation of synergistic effect of the composition

[0213] At the same time, many tests have found that the compounds and compositions of the present invention have good control activity against different types of aphids, and have the characteristics of broad spectrum, high efficiency, strong systemic activity and certain commercial value.

Claims

1. A pyrazole amide compound represented by general formula I and its stereoisomers, salts, tautomers and N-oxides: in, Q stands for O or S; W represents CH or N; X represents hydrogen, halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, aryl or heterocyclic group; Y represents halogen or alkyl; Z represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, The "alkyl", "alkenyl" or "alkynyl" is optionally substituted by at least one group selected from cyano, halogen, cycloalkyl, -OR1, -SR1, -(CO)OR1, -C(O)N(R1)2, -(SO)R1, -(SO2)R1, aryl or heterocyclic group; M represents hydrogen or an alkyl group; R1 each independently represents hydrogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, aryl or heterocyclic group; The aforementioned "cycloalkyl", "cycloalkenyl", "heterocyclic", "aryl", is optionally selected from oxo, halogen, cyano, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, -OR 10 , -SR 10 ,-(CO)R 10 、-(CO)OR 10 ,-(SO)R 10 or -(SO2)R 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2O-, -CH2CH2CH2O- or -CH=CHCH=CH-; or a saturated carbon atom on the ring is connected to both ends of unsubstituted or halogen-substituted -OCH2CH2O- to form a ring structure; R 10 Each of them is independently hydrogen, alkyl, haloalkyl, aryl or heterocyclic group which is unsubstituted or substituted by at least one group selected from halogen and alkyl.

2. The pyrazole amide compound and its stereoisomers, salts, tautomers and N-oxides according to claim 1, characterized in that: X represents hydrogen, halogen, C1-C8 alkyl, halo-C1-C8 alkyl, C2-C8 alkenyl, halo-C2-C8 alkenyl, C2-C8 alkynyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl, aryl or heterocyclic group; Y represents halogen or C1-C8 alkyl; Z represents C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, The "C1-C8 alkyl", "C2-C8 alkenyl" or "C2-C8 alkynyl" is optionally substituted by at least one group selected from cyano, halogen, C3-C8 cycloalkyl, -OR1, -SR1, -(CO)OR1, -C(O)N(R1)2, -(SO)R1, -(SO2)R1, aryl or heterocyclic group; M represents H or C1-C8 alkyl; R1 each independently represents hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halogenated C2-C8 alkynyl, halogenated C2-C8 alkenyl, aryl or heterocyclic group; The aforementioned "C3-C8 cycloalkyl", "C3-C8 cycloalkenyl", "heterocyclyl", "aryl", is optionally selected from oxo, halogen, cyano, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, -OR 10 , -SR 10 ,-(CO)R 10 、-(CO)OR 10 ,-(SO)R 10 or -(SO2)R 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2O-, -CH2CH2CH2O- or -CH=CHCH=CH-; or a saturated carbon atom on the ring is connected to both ends of unsubstituted or halogen-substituted -OCH2CH2O- to form a ring structure; R 10 Each is independently hydrogen, C1-C8 alkyl, C1-C8 haloalkyl, aryl or heterocyclic group which is unsubstituted or substituted with at least one group selected from halogen and C1-C8 alkyl.

3. The pyrazole amide compound and its stereoisomers, salts, tautomers and N-oxides according to claim 1 or 2, characterized in that: X represents hydrogen, halogen, C1-C6 alkyl, halo-C1-C6 alkyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C2-C6 alkynyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl, aryl or heterocyclic group; Y represents halogen or C1-C6 alkyl; Z represents C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, The "C1-C6 alkyl", "C2-C6 alkenyl" or "C2-C6 alkynyl" is optionally substituted by at least one group selected from cyano, halogen, C3-C6 cycloalkyl, -OR1, -SR1, -(CO)OR1, -C(O)N(R1)2, -(SO)R1, -(SO2)R1, aryl or heterocyclic group; M represents H or C1-C6 alkyl; R1 each independently represents hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, halogenated C2-C6 alkynyl, aryl or heterocyclic group; The aforementioned "C3-C6 cycloalkyl", "C3-C6 cycloalkenyl", "heterocyclyl", "aryl", is optionally selected from oxo, halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, -OR 10 , -SR 10 ,-(CO)R 10 、-(CO)OR 10 ,-(SO)R 10 or -(SO2)R 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2O-, -CH2CH2CH2O- or -CH=CHCH=CH-; or a saturated carbon atom on the ring is connected to both ends of unsubstituted or halogen-substituted -OCH2CH2O- to form a ring structure; R 10 are independently hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, aryl or heterocyclic group which is unsubstituted or substituted by at least one group selected from halogen and C1-C8 alkyl; Preferably, the compound is selected from any one of Table 1.

4. A method for preparing the pyrazole amide compound and its stereoisomers, salts, tautomers and N-oxides according to any one of claims 1 to 3, comprising the following steps: (1) The compound represented by the general formula II is reacted with the compound represented by the general formula III to obtain the compound represented by the general formula I. The reaction equation is as follows: Alternatively, (2) the compound represented by the general formula IV is reacted with the compound represented by the general formula V to obtain the compound represented by the general formula I, wherein the reaction equation is as follows: Wherein, Hal represents halogen, and the substituents M, Q, W, X, Y and Z are defined as described in any one of claims 1 to 3; Preferably, the reactions of steps (1) and (2) are both carried out in the presence of a base and a solvent; more preferably, the base is selected from at least one of an inorganic base or an organic base, and the solvent is selected from at least one of DMF, dimethyl sulfoxide, dichlorothionyl, ethyl acetate, tetrahydrofuran, methyltetrahydrofuran, dimethylformamide or dioxane.

5. An insecticide composition comprising the pyrazole amide compound according to any one of claims 1 to 3 and its stereoisomers, salts, tautomers and N-oxides; preferably, further comprising a formulation adjuvant; more preferably, further comprising other active ingredients.

6. The composition according to claim 5, characterized in that The other active ingredients are at least one of the following compounds: (1) Acetylcholinesterase (AChE) inhibitors: chlorpyrifos; (2) GABA-gated chloride channel antagonists: fipronil; (3) Nicotinic acetylcholine receptor (nAChR) allosteric modulators: spinosad; (4) Nicotinic acetylcholine receptor (nAChR) competitive modulator: Imidacloprid; (5) Sodium channel regulator: highly effective chlorfenapyr; (6) Allosteric modulators of glutamate-gated ammonium ion channels (GluCl): avermectin; (7) Acetyl Coenzyme A carboxylase inhibitor: spirotetramat; (8) ryanodine receptor modulators: cyantraniliprole; (9) String modulators - unknown target site: flonicamid; (10) GABA-gated chloride channel allosteric modulator: oxazolidinone; (11) String organ TRPV channel modulators: (12) The mechanism of action is unknown:

7. Use of the pyrazole amide compound according to any one of claims 1 to 3, and its stereoisomers, salts, tautomers and N-oxides, or the composition according to claim 5 or 6 in controlling pests.

8. A method for controlling pests, comprising contacting the pests or their environment with a biologically effective amount of the pyrazole amide compound according to any one of claims 1 to 3, its stereoisomers, salts, tautomers and N-oxides, or the composition according to claim 5 or 6.

9. An intermediate compound as represented by formula II, III, IV or V in claim 4.

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