Meta-diamide compound containing aromatic ring or heteroaromatic ring substituent, preparation method therefor, composition, and use thereof

Abstract

The present invention relates to the field of pesticide insecticides, and in particular, to a meta-diamide compound containing an aromatic ring or heteroaromatic ring substituent as represented by formula (I), a stereoisomer thereof, an agriculturally acceptable salt thereof, a preparation method therefor, an insecticidal composition, and use thereof in the field of pest prevention and control. R1, R2, Het, and Q are as defined herein.

Description

A meta-diamide compound containing aromatic ring or aromatic heterocyclic substituted compounds, its preparation method, composition and application Technical Field

[0001] This invention relates to the field of insecticides, and more specifically to a m-diamide compound containing an aromatic ring or aromatic heterocyclic substituted compound as shown in formula (I), its stereoisomers, its agriculturally acceptable salts, its preparation method, insecticidal compositions, and their use in controlling pests. Background Technology

[0002] WO2010018714A1 discloses a class of amide derivatives as shown in the figure below, pest control agents containing these amide derivatives, and their application methods:

[0003] Compound 7-1621 is specifically disclosed in Table 55 of the specification, and compounds 7-1630 and 7-1651 are specifically disclosed in Table 56.

[0004] WO2009080203A2 discloses an aminobenzamide derivative, as shown in the figure below, which is a useful agent for controlling animal parasites.

[0005] Specifically, Table 1 of the specification discloses compounds I-1-288 to I-1-314, for example:

[0006] These known compounds in the prior art exhibit narrow applicability or lack satisfactory insecticidal or acaricidal activity. In particular, their insecticidal or acaricidal activity at low application rates and / or their safety to non-target organisms still require improvement. Summary of the Invention

[0007] Therefore, the object of the present invention is to provide a compound that has strong insecticidal activity, particularly at low application rates, sufficiently low toxicity to humans and non-target organisms, and / or high compatibility with crops, and also exhibits a broad activity spectrum against a wide range of harmful organisms.

[0008] The compounds of formula (I), their stereoisomers, and their agriculturally acceptable salts provided by this invention offer advantages over the prior art, examples of which include better biological or environmental properties, wider application methods, better insecticidal or acaricidal effects, and good compatibility with beneficial plants. The compounds of formula (I), their stereoisomers, and their agriculturally acceptable salts can be used in combination with other compositions to improve efficacy, particularly against resistant insects.

[0009] In all formulas specified below, unless otherwise defined, substituents and symbols have the same meaning as described in formula (I). The wavy lines of chemical groups indicate sites attached to the rest of the molecule.

[0010] This invention provides a meta-diamide compound containing aromatic ring or aromatic heterocyclic substitution as shown in formula (I), its stereoisomers, and agriculturally acceptable salts thereof:

[0011] in,

[0012] Het is selected from any of the following groups:

[0013] R a Selected from halogen atoms, C1-C4 alkyl groups, halo-C1-C4 alkyl groups, C1-C4 alkoxy groups, halo-C1-C4 alkoxy groups, C1-C4 alkylthio groups, or phenyl groups.

[0014] n is 0, 1, 2, 3, 4, or 5, and when n is selected from 2, 3, 4, or 5, R a Same or different;

[0015] R1 is selected from H, -CN, -NO2, halogen atom, C1-C3 alkyl, halo-C1-C3 alkyl or halo-C1-C3 alkoxy;

[0016] R2 is selected from H, halogen atom, halogenated C1-C3 alkyl or halogenated C1-C3 alkoxy;

[0017] Q is selected from phenyl, phenyl with a substituent, pyridyl, pyridyl with a substituent, thienyl, thienyl with a substituent, 1-methylpyrazolyl, 1-methylpyrazolyl with a substituent or benzo[d][1,3]dioxolane with a substituent;

[0018] The substituent in Q is selected from at least one of the following groups: -CN, -NO2, halogen atom, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C3 alkyl-S(O). p -or halogenated C1-C3 alkyl-S(O) p -; When there are more than two substituents, each substituent may be the same or different, and p is selected from 0, 1 or 2.

[0019] Preferably,

[0020] in,

[0021] Het is selected from any of the following groups:

[0022] R a Selected from F, Cl, Br, I, C1-C3 alkyl, halo-C1-C3 alkyl, C1-C3 alkoxy, halo-C1-C4 alkoxy, or C1-C3 alkylthio.

[0023] n is 0, 1, 2, or 3, and when n is selected from 2 or 3, R a Same or different;

[0024] R1 is selected from F, Cl, Br, I, -CH3, -CHF2, -CH2CHF2, -CF3, -OCH3, -CH2CF3, -OCHF2, -OCH2CHF2, -OCF3, -OCH2CF3, -CN or -NO2;

[0025] R2 is selected from H, F, Cl, Br, I, -CHF2, -CH2CHF2, -CF3, -CH2CF3, -OCHF2, -OCH2CHF2, -OCF3 or -OCH2CF3;

[0026] Q is selected from any of the following groups:

[0027] X is selected from -CN, -NO2, halogen atom, C1-C3 alkyl, halo-C1-C3 alkyl, C1-C3 alkoxy, halo-C1-C3 alkoxy, C1-C2 alkyl-S(O). p -or C1-C2 haloalkyl-S(O) p -, p is selected from 1 or 2;

[0028] m is selected from 0, 1, 2, 3, 4 or 5; and when m is selected from 2, 3, 4 or 5, X is the same or different;

[0029] k is selected from 0, 1, 2, 3 or 4; and when n is selected from 2, 3 or 4, X is the same or different;

[0030] o is selected from 0, 1, 2, or 3; and when o is selected from 2 or 3, X is the same or different;

[0031] r is selected from 0, 1, or 2; and when r is selected from 2, X is either the same or different.

[0032] More preferably,

[0033] in,

[0034] Het is selected from any of the following groups:

[0035] R aSelected from F, Cl, Br, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2F, -CF2H, -CF3, -OCH3, -OCH2CH3, -OCH(CH3)2, -OCF2H, -OCF3, -SCH3, -SCH2CH3, -SCH2CH2CH3 or -SCH(CH3)2;

[0036] R1 is selected from Cl, Br, I, -CHF2, -CF3, -OCH3, -OCF3, -OCHF2, -CN, or -NO2;

[0037] R2 is selected from -CHF2, -CF3, -OCHF2, or -OCF3;

[0038] Q is selected from any of the following groups:

[0039] The F2, -OCF3, -OCH2CF3, -SOCH3, -SOCH2CH3, -SO2CH3, -SO2CH2CH3, -SOCF3, -SOCH2CF3, -SO2CF3 or -SO2CH2CF3.

[0040] More preferably,

[0041] in,

[0042] Het is selected from any of the following groups:

[0043] R1 is selected from Br or I;

[0044] R2 is selected from -CF3 or -OCHF2;

[0045] Q is selected from any of the following groups:

[0046] More preferably,

[0047] in,

[0048] Het is selected from any of the following groups:

[0049] R1 is selected from Br or I;

[0050] R2 is selected from -CF3;

[0051] Q is selected from any of the following groups:

[0052] The compounds of formula (I) of the present invention can be described by the specific compounds listed in Table 1, but the present invention is not limited to these compounds.

[0053] Table 1 shows the compounds of formula (I).

[0054] The compound of formula (I) of the present invention may exist in the form of one or more stereoisomers. Stereoisomers are isomers with the same composition but different atomic spatial arrangements, including enantiomers, diastereomers, cis-trans isomers (also called geometric isomers), and trans-isomers. Trans-isomers arise from restricted rotation around a single bond, where the rotational energy barrier is high enough to allow the separation of isomeric substances. Those skilled in the art will understand that when a stereoisomer is enriched relative to other stereoisomers, or when it is separated from other stereoisomers, it may be more active and / or may exhibit beneficial effects. Furthermore, those skilled in the art know how to separate, enrich, and / or selectively prepare said stereoisomers.

[0055] "Stereoisomer" or "stereoisomeric form" refers to a stereoisomer of a compound that is substantially free of other stereoisomers of the compound. For example, a stereoisomerically pure compound having one chiral center will substantially be free of its opposite enantiomers. A stereoisomerically pure compound having two chiral centers will substantially be free of its other diastereomers. A typical stereoisomerically pure compound contains more than about 60% by weight of one stereoisomer and less than about 40% by weight of other stereoisomers of the compound, more than about 80% by weight of one stereoisomer and less than about 20% by weight of other stereoisomers of the compound, more than about 90% by weight of one stereoisomer and less than about 10% by weight of other stereoisomers of the compound, more than about 95% by weight of one stereoisomer and less than about 5% by weight of other stereoisomers of the compound, or more than about 97% by weight of one stereoisomer and less than about 3% by weight of other stereoisomers of the compound. The compounds may have a chiral center and may exist as racemic, enantiomers alone, or diastereomers and mixtures thereof. All such isomeric forms (including mixtures thereof) are included in the examples disclosed herein. The use of the stereoisomeric pure forms of such compounds and the use of mixtures of those forms are included in the examples disclosed herein. For example, mixtures comprising equal or unequal amounts of enantiomers of a particular compound may be used in the methods and compositions disclosed herein. These isomers may be asymmetrically synthesized or resolved using standard techniques such as chiral columns or chiral resolving agents.

[0056] The compounds of formula (I) of the present invention generally exist in more than one form, and therefore all crystalline and amorphous forms of the compounds of formula (I). Amorphous forms include embodiments as solids, such as waxes and gums, and embodiments as liquids, such as solutions and melts. Crystalline forms include embodiments that substantially represent a single crystal type and embodiments that represent mixtures of polymorphs (i.e., different crystal types). The term "polymorph" refers to a specific crystalline form of a compound that can crystallize in different crystalline forms, having different arrangements and / or conformations of molecules in the crystal lattice. Although polymorphs may have the same chemical composition, their compositions may also differ due to the presence or absence of co-crystallization water or other molecules that can be weakly or strongly bound in the crystal lattice. The chemical, physical, and biological properties of polymorphs may differ, such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension, dissolution rate, and bioavailability. Those skilled in the art will understand that, relative to another polymorph or mixture of polymorphs of the same compound represented by formula (I), a polymorph of the compound represented by formula (I) may exhibit beneficial effects (e.g., suitability for preparing useful formulations, improved biological properties). The preparation and isolation of specific polymorphs of the compound represented by formula (I) can be achieved by methods known to those skilled in the art, including, for example, crystallization using selected solvents and temperatures. The compounds of the present invention can exist as one or more crystalline polymorphs. The present invention includes individual polymorphs and mixtures of polymorphs, including mixtures enriched in one polymorph relative to other polymorphs.

[0057] The present invention also provides a method for preparing the compound of formula (I) described above, its stereoisomers, and agriculturally acceptable salts thereof, characterized in that:

[0058] Compound (II) is reacted with compound (VIII) in an organic solvent in the presence of a base to prepare compound (I), wherein the organic solvent is selected from pentane, n-hexane, cyclohexane, heptane, octane, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, petroleum ether, diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, ethyl acetate, butyl acetate, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, acetone, and butanone. At least one of 4-methyl-2-pentanone, cyclohexanone, N-methylpyrrolidone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide; the base is selected from at least one of 4-dimethylaminopyridine (DMAP), trimethylamine, triethylamine, diisopropylethylamine, pyridine, 2-methylpyridine, 3-methylpyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or 2,6-dimethylpyridine; R1, R2, Het, and Q are as defined above.

[0059] Specifically, the compounds of formula (II) of the present invention can be prepared by the various methods listed below:

[0060] Route 1:

[0061] Step i: 2-Fluoro-3-nitrobenzoyl chloride reacts with the compound of formula (III) to generate the compound of formula (IV). The reaction is carried out in the temperature range of 25°C to 120°C, preferably 100°C to 120°C. The reaction time is 0.5 to 48 hours, preferably 10 to 15 hours. The resulting compound of formula (IV) can be purified using techniques well known in the art (such as chromatography, recrystallization, etc.).

[0062] Step ii: Compound (IV) reacts in an organic solvent or water in the presence of reducing agent A to form compound (V), preferably at a reaction temperature of 40-45°C; the reaction time is 0.5-48 hours, preferably 8-10 hours. The organic solvent can be selected from alcohols such as methanol, ethanol, isopropanol, etc., and ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, etc., with methanol being preferred. Reducing agent A is selected from hydrogen, metal hydrides, half-metal hydrides and their derivatives, such as lithium aluminum hydride, diisobutyl aluminum hydride, sodium borohydride, borane, etc., with hydrogen being preferred. The pressure is 1.5-2 MPa. Hydrogen can be supplied by hydrogen storage cylinders or can be generated in situ by active metals (such as reduced iron powder, reduced zinc powder, etc.) under acidic conditions (such as hydrochloric acid, sulfuric acid) and participate in the reduction reaction. A catalytic amount of transition metal or a catalytic amount of transition metal compound is used. The transition metal can be a Group 8 subgroup compound, preferably Ni, Pd, Pt, etc. (used directly or supported by media such as activated carbon, alumina, silicon dioxide, etc.), more preferably Pt / C (10%), with a feeding ratio of 1%-5% of the mass of the compound of formula (IV).

[0063] Step iii: Compound (V) reacts with compound (VI) in an organic solvent to generate compound (VII). The organic solvent is selected from any one or a combination of at least two of alcohol solvents, ester solvents, ether solvents, halogenated hydrocarbon solvents, or benzene solvents, preferably methanol, ethanol, isopropanol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, toluene, or xylene.

[0064] Step iv: Compound (VII) reacts in an organic solvent in the presence of reducing agent B to generate compound (II). Reducing agent B is selected from NaBH4, NaBH3CN, NaBH(OAc)3, Ni, Pd, Pt, etc. (used directly or supported by media such as activated carbon, alumina, or silica), preferably NaBH3CN, Pt / C, or Pd / C. The reaction temperature is 20℃-120℃, preferably 40℃-90℃. The reaction time is 8-20 h, preferably 10-16 h.

[0065] Steps iii and iv can be carried out in separate steps, or they can be carried out simultaneously in situ or as a continuous reaction.

[0066] R1, R2, and Het are defined as above.

[0067] In the definitions of compounds of formula (I) given above, the terms used in the compilation are generally defined as follows:

[0068] Alkyl groups refer to saturated straight-chain or branched hydrocarbon groups having a specified number of carbon atoms in each case, such as C1-C6-alkyl groups, including methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, etc. 1-Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl.

[0069] Halogen-substituted alkyl groups (halogenated alkyl groups) refer to the following straight-chain or branched alkyl groups in which some or all of the hydrogen atoms can be replaced by halogen atoms, such as C1-C3 haloalkyl groups, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, and 1,1,1-trifluoropropyl-2-yl.

[0070] Alkoxy refers to a saturated straight-chain or branched alkoxy group having a specified number of carbon atoms in each case, such as C1-C6-alkoxy groups, including methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, and 1,2-dimethylpropoxy. The compounds are: 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, and 1-ethyl-2-methylpropoxy. Halogen-substituted alkoxy groups refer to the following straight-chain or branched alkoxy groups having a specified number of carbon atoms in each case: wherein in these groups, some or all of the hydrogen atoms may be replaced by halogen atoms as described above, such as C1-C3 haloalkoxy groups, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, pentafluoroethoxy, and 1,1,1-trifluoroprop-2-oxy.

[0071] The term "halogen" refers to fluorine, chlorine, bromine, or iodine. If the term is used with a group, then "halogen" or "halogen atom" refers to a fluorine, chlorine, bromine, or iodine atom.

[0072] The present invention also provides a composition, characterized in that it comprises at least one of the compound of formula (I) described above, its stereoisomer or salt thereof, wherein the compound of formula (I) is used as the active component, and the weight percentage of the active component in the composition is 0.1-99.9%.

[0073] Compositional forms include, for example, liquid irrigation, drip irrigation, and spraying. Optionally, the application form contains other pesticides and / or adjuvants that enhance action, such as penetrants, like vegetable oils (e.g., rapeseed oil, sunflower oil), mineral oils (e.g., paraffin oil), alkyl esters of vegetable fatty acids (e.g., rapeseed oil methyl ester or soybean oil methyl ester), or alkanol alkoxylates; and / or spreaders, such as alkylsiloxanes and / or salts (e.g., organic or inorganic ammonium salts or phosphonium salts, such as ammonium sulfate or diammonium hydrogen phosphate); and / or retention promoters, such as dioctyl sulfosuccinate or hydroxypropyl guar gum polymers; and / or wetting agents, such as glycerin; and / or fertilizers, such as ammonium-, potassium-, or phosphorus-containing fertilizers.

[0074] Conventional formulations include: water-soluble liquid formulations (SL), emulsion concentrates (EC), emulsions (EW), suspension concentrates (SC, SE, FS, OD), water-dispersible granules (WG), granules (GR), and capsule concentrates (CS); these formulations and other possible formulation types are documented by Crop Life International and described in the following documents: Pesticide Standards, FAO / WHO Manual on the Development and Use of Pesticide Standards, and FAO Document on Plant Production and Protection-173 (prepared by the FAO / WHO Joint Conference on Pesticide Standards, 2004, ISBN: 9251048576). In addition to one or more compounds of formula (I), the formulations may optionally contain other agrochemically active compounds.

[0075] Preferred formulations or application forms include at least one adjuvant, such as a extender, solvent, spontaneous growth promoter, carrier, emulsifier, dispersant, antifreeze, biocide, thickener; and / or other adjuvants, such as adjuvants. In the context of this invention, an adjuvant is a component that enhances the biological efficacy of the formulation, while the component itself does not possess any biological efficacy. Examples of adjuvants are agents that promote retention, spreading, adhesion to leaf surfaces, or penetration.

[0076] These formulations are prepared in a known manner, for example by mixing a compound of formula (I) with an adjuvant such as a extender, a solvent, and / or a solid carrier and / or other adjuvants such as a surfactant. The formulation is prepared in a suitable facility or before or during application.

[0077] The adjuvant used may be a substance that imparts specific properties (e.g., certain physical, technical and / or biological properties) to a formulation suitable for use with a compound of formula (I) or to an application form prepared from such formulation (e.g., ready-to-use pesticides, such as spray liquids or seed dressing products).

[0078] Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, selected from: aromatic and non-aromatic hydrocarbons (such as paraffin, alkylbenzene, alkylnaphthalene, chlorobenzene), alcohols and polyols (which may also be substituted, etherified and / or esterified if appropriate), ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidone) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).

[0079] If the extender used is water, organic solvents, for example, can also be used as co-solvents. Useful liquid solvents include: aromatic compounds such as xylene, toluene, or alkylnaphthalene; chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride, or dichloromethane; aliphatic hydrocarbons such as cyclohexane or alkanes such as petroleum fractions, mineral oils, and vegetable oils; alcohols such as butanol or ethylene glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; highly polar solvents such as dimethylformamide and dimethyl sulfoxide; and water.

[0080] In principle, all suitable solvents may be used. Examples of suitable solvents include: aromatic hydrocarbons such as xylene, toluene, or alkylnaphthalene; chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride, or dichloromethane; aliphatic hydrocarbons such as cyclohexane, alkanes, petroleum fractions, mineral oils, and vegetable oils; alcohols such as methanol, ethanol, isopropanol, butanol, or ethylene glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; strongly polar solvents such as dimethyl sulfoxide; and water.

[0081] In principle, all suitable carriers may be used. Suitable carriers include, in particular: ammonium salts and finely ground natural rocks such as kaolin, alumina, talc, chalk, quartz, palygorskite, montmorillonite, or diatomaceous earth; and finely ground synthetic rocks such as highly dispersed silica, alumina, and natural or synthetic silicates; resins; waxes; and / or solid fertilizers. Mixtures of these carriers may also be used. Useful carriers for granules include, for example, crushed and graded natural rocks such as calcite, marble, pumice, sepiolite, and dolomite; and synthetic granules of inorganic and organic powders; and granules of organic materials such as sawdust, paper, coconut husks, corn cobs, and tobacco stems.

[0082] Liquefied gaseous extenders or solvents can also be used. Particularly suitable extenders or carriers are those that are gaseous at standard temperature and atmospheric pressure, such as aerosol propellants, including halogenated hydrocarbons, as well as butane, propane, nitrogen, and carbon dioxide.

[0083] Examples of emulsifiers and / or foam formers, dispersants or wetting agents, or mixtures of these surfactants having ionic or nonionic properties include: salts of polyacrylic acid; salts of lignin sulfonic acid; salts of phenol sulfonic acid or naphthalene sulfonic acid; condensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, or with substituted phenols (preferably alkylphenols or arylphenols); salts of sulfosuccinates; taurine derivatives (preferably alkyl taurine esters); phosphate esters of polyethoxylated alcohols or phenols; fatty acid esters of polyols; and derivatives of compounds containing sulfate, sulfonate and phosphate groups, such as alkylaryl polyethylene glycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, protein hydrolysates, lignin sulfite waste, and methylcellulose. The presence of a surfactant is advantageous if one of the compounds of formula (I) and / or one of the inert carriers is insoluble in water and if the application is carried out in water.

[0084] Other adjuvants that may be present in formulations and the application forms obtained therefrom include: dyes, such as inorganic pigments like iron oxide, titanium dioxide and Prussian blue; and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes; as well as nutrients and micronutrients, such as iron salts, manganese salts, boron salts, copper salts, cobalt salts, molybdenum salts and zinc salts.

[0085] Other components that may be present include stabilizers, such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers, or other agents that improve chemical and / or physical stability. Foam generators and defoamers may also be present.

[0086] In addition, the formulation and the resulting form of application may contain the following substances as additional adjuvants: adhesives, such as carboxymethyl cellulose; and natural and synthetic polymers in powder, granule or latex form, such as gum arabic, polyvinyl alcohol and polyvinyl acetate; and natural phospholipids, such as cephalin and lecithin and synthetic phospholipids. Other adjuvants may be mineral oils and vegetable oils.

[0087] Other adjuvants may also be present in the formulation and the resulting form of use, if appropriate. Examples of such additives include fragrances, protective colloids, adhesives, glues, thickeners, thixotropic agents, penetrants, retention enhancers, stabilizers, chelating agents, complexing components, wetting agents, and spreading agents. Generally, compounds of formula (I) may be combined with any solid or liquid additive commonly used for formulation purposes.

[0088] Useful retention promoters include all those substances that reduce dynamic surface tension (such as dioctyl sulfosuccinate) or increase viscoelasticity (such as hydroxypropyl guar gum polymer).

[0089] In the context of this invention, a useful penetrant is any substance commonly used to improve the penetration of agrochemically active compounds into plants. In the context of this invention, a penetrant is defined as its ability to penetrate from (usually aqueous) application liquids and / or from spray coatings into the plant epidermis, thereby increasing the mobility of the active compound within the epidermis. Methods described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used to determine this property. Examples include: alcohol alkoxylates, such as coconut fat ethoxylate (10) or isotrimethylene ethoxylate (12); fatty acid esters, such as rapeseed oil methyl ester or soybean oil methyl ester; fatty amine alkoxylates, such as tallow amine ethoxylate (15); or ammonium salts and / or phosphonium salts, such as ammonium sulfate or diammonium hydrogen phosphate.

[0090] The formulation preferably comprises 0.00000001% by weight to 98% by weight of a compound of formula (I), more preferably 0.01% by weight to 95% by weight of a compound of formula (I), and most preferably 0.5% by weight to 90% by weight of a compound of formula (I), based on the weight of the formulation.

[0091] In application forms (especially pesticides) prepared from formulations, the content of compound (I) can vary over a wide range. In application forms, the concentration of compound (I) is typically from 0.00000001% by weight to 95% by weight, preferably from 0.00001% by weight to 1% by weight, based on the weight of the application form. Application is carried out in a conventional manner suitable for the application form.

[0092] Compounds of formula (I) may also be used in combination with one or more suitable substances including: fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbial agents, beneficial organisms, herbicides, fertilizers, bird repellents, phytotonics, reproductive inhibitors, safety agents, chemical pheromones, and / or plant growth regulators, thereby, for example, broadening the spectrum of action, prolonging the duration of action, increasing the rate of action, preventing rejection, or preventing the development of resistance. Furthermore, such active compound compositions can improve plant growth and / or tolerance to abiotic factors, such as high or low temperatures, drought, or high water levels or soil salinity. They can also improve flowering and fruiting performance, optimize germination capacity and root development, promote harvesting and increase yield, influence ripening, improve the quality and / or nutritional value of harvested products, prolong storage life, and / or improve the processability of harvested products.

[0093] Furthermore, compounds of formula (I) can be mixed with other active compounds or chemical pheromones such as attractants and / or bird repellents and / or plant activators and / or growth regulators and / or fertilizers. Similarly, compounds of formula (I) can be used to improve plant performance, such as the growth, yield, and quality of harvested plants.

[0094] In a particular embodiment of the invention, the compound of formula (I) is mixed with other compounds (preferably those described below) in a formulation or in an administration form prepared from such formulation.

[0095] If one of the compounds mentioned below can exist in different tautomeric forms, those forms are also included, even if not explicitly mentioned in various cases. Depending on the circumstances, if all the mixed components mentioned are capable of forming salts based on their functional groups, they may also form salts with suitable bases or acids.

[0096] The active compounds referred to herein by their common names are known and described, for example, in *The Pesticide Manual* (16th edition, British Crop Protection Council 2012), or can be found on the Internet (e.g., http: / / www.bcpcpesticidecompendium.org / ). This classification is based on the IRAC mode of action classification scheme applicable at the time of filing of this application.

[0097] Compounds of formula (I) can also be combined with biological pesticides. Biological pesticides include, in particular, bacteria, fungi, yeasts, plant extracts, and products formed by microorganisms, including proteins and secondary metabolites.

[0098] Biological pesticides include bacteria such as spore-forming bacteria, root-colonizing bacteria, and bacteria that act as biological insecticides, fungicides, or nematicides.

[0099] As a safety agent for mixed components:

[0100] Compounds of formula (I) may be combined with a safener, such as benoxacor, cloquintocet(-mexyl)), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole(-ethyl)), fenclorim, flurazole, fluxofenim, furilazole, and bis(benoxaconic acid) ethyl ester. oxadifen(-ethyl)), mefenpyr(-diethyl)), naphthalic anhydride, oxabetrinil, 2-methoxy-N-{4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS52836-31-4).

[0101] The present invention also provides a method for controlling pests, characterized in that the compound of formula (I) described above, its stereoisomers and agriculturally acceptable salts thereof, or the composition described above are applied to the pest or its growth environment.

[0102] Harmful organisms include agricultural or non-agricultural invertebrate pests.

[0103] The growth environment of pests includes plants and plant parts, all of which can be treated according to the methods provided in this invention. In this document, "plant" should be understood to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants), such as cereals (wheat, rice, rye, barley, rye, oats), corn, soybeans, potatoes, sugar beets, sugarcane, tomatoes, bell peppers, cucumbers, melons, carrots, watermelons, onions, lettuce, spinach, leeks, legumes, cabbage (such as head cabbage) and other vegetable varieties, cotton, tobacco, rapeseed, and fruit plants (fruits include apples, pears, citrus fruits, and grapes). Crop plants can be plants that can be obtained through conventional breeding and optimization methods or through biotechnological methods and genetic engineering methods or a combination of these methods, including transgenic plants and plant cultivars that may or may not be protected by plant breeders' rights. "Plant" should be understood to mean all developmental stages, such as seeds, seedlings, and early (immature) plants up to and including mature plants. Plant parts should be understood to refer to all above-ground and underground parts and organs of a plant, such as buds, leaves, flowers, and roots. Examples given include leaves, needles, stems, branches, flowers, fruiting bodies, fruits, and seeds, as well as roots, tubers, and rhizomes. Plant parts also include harvested plants or harvested plant parts, as well as materials for asexual and sexual reproduction, such as cuttings, tubers, rhizomes, slips, and seeds.

[0104] The treatment of plants and plant parts using the compound of formula (I) of the present invention is carried out directly by conventional treatment methods or by applying the compound to its environment, habitat or storage space, for example by impregnation, spraying, evaporation, atomization, sowing, application, injection, and in the case of propagation materials, especially seeds, by applying one or more layers of coating.

[0105] As described above, all plants and their parts can be processed according to the present invention. In some preferred embodiments, wild plant species and cultivated plant species, or those obtained by conventional biological breeding methods such as hybridization or protoplast fusion, and their parts are processed. In another preferred embodiment, transgenic plants and cultivated plant species (genetically modified organisms) obtained by genetic engineering methods—if appropriate, in combination with conventional methods—and their parts are processed. The terms “part” or “plant part” or “plant component” have been explained above. According to the present invention, it is particularly preferred to process plants of commercially available conventional cultivated plant species or those currently in use. Cultivated plant species should be understood to mean plants with new characteristics (“traits”) and obtained through conventional breeding, by mutagenesis, or by recombinant DNA technology. They can be cultivated varieties, varieties, biotypes, or genotypes.

[0106] Transgenic plants, seed treatment, and integration events: Preferred transgenic plants or plant cultivars (those obtained through genetic engineering) treated according to the present invention include all plants that have received genetic material through genetic modification that confers particularly advantageous useful characteristics (“traits”) to these plants. Examples of such traits include: better plant growth, enhanced tolerance to high or low temperatures, enhanced tolerance to drought or water or soil salinity levels, improved flowering performance, easier harvesting, accelerated maturation, higher harvest yield, higher quality and / or higher nutritional value of the harvested product, and better storage capacity and / or processability of the harvested product. Other, and particularly emphasized, examples of these properties include: enhanced plant resistance to animal and microbial pests, such as insects, arachnids, nematodes, mites, slugs, and snails, attributable to, for example, toxins formed in plants, particularly those formed in plants through the genetic material of Bacillus thuringiensis (e.g., through genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb, and CryIF and combinations thereof); enhanced plant resistance to plant pathogenic fungi, bacteria, and / or viruses, such as resistance acquired through systemic absorption (SAR), systemins, phytoalexins, elicitors, and resistance genes and the corresponding expressed proteins and toxins; and enhanced plant tolerance to certain herbicidal active compounds, such as imidazolinones, sulfonylureas, glyphosate, or phosphinothricin (e.g., the "PAT" gene). Genes that confer the desired trait can also coexist in transgenic plants in combination. Examples of transgenic plants mentioned include important crop plants such as cereals (wheat, rice, rye, barley, rye, oats), corn, soybeans, potatoes, sugar beets, sugarcane, tomatoes, peas, and other vegetable varieties; cotton, tobacco, rapeseed; and fruit plants (fruits such as apples, pears, citrus fruits, and grapes), with particular emphasis on corn, soybeans, wheat, rice, potatoes, cotton, sugarcane, tobacco, and rapeseed. The particularly emphasized trait is enhanced plant resistance to insects, arachnids, nematodes, slugs, and snails.

[0107] The present invention also provides the use of a compound of formula (I) as described above, its stereoisomers, and agriculturally acceptable salts thereof, or the composition described above, in the control of pests.

[0108] Conventional treatment methods utilize the compound of formula (I) to directly treat plants and plant parts, or to treat them by acting on their environment, habitat, or storage space. These conventional treatment methods include, for example, soaking, spraying, atomizing, irrigating, evaporating, dusting, misting, sowing, foaming, smearing, spreading, injection, watering (soaking), drip irrigation, and, in the case of propagation material, especially seeds, dry seed treatment as powder, wet seed treatment as solution, slurry treatment as water-soluble powder, treatment by crusting, or coating with one or more layers. The compound of formula (I) can also be applied using ultra-low volume methods or injected into the soil in its application form or the compound of formula (I) itself.

[0109] The preferred direct treatment of the plant is foliar application, that is, applying the compound of formula (I) to the leaves. In this case, the treatment frequency and application rate should be adjusted according to the level of infestation by the pest. In the case of systemic active compounds, the compound of formula (I) also enters the plant via the root system. The plant is then treated by applying the compound of formula (I) to the plant's habitat. This can be done by, for example, saturation; or by soil application, that is, introducing the compound of formula (I) of the present invention in solid form (e.g., in granule form) to the plant's growing site; or by drip irrigation application (often also referred to as "chemical irrigation"), that is, liquid application of the compound of formula (I) of the present invention from surface or subsurface drip irrigation lines for a certain period of time, while applying different amounts of water at specific locations near the plant. In the case of rice crops, this can also be accomplished by metering the compound of formula (I) into the flooded rice paddy in solid application form (e.g., as granules).

[0110] Treatment methods also include seed treatment, but existing technologies still have a number of problems. Therefore, there is a need to develop methods for protecting seeds and germinating plants that require no or at least significantly reduce the additional application of pesticides during storage, after sowing, or after emergence. Furthermore, it is necessary to optimize the amount of active compounds used to provide optimal protection for seeds and germinating plants against animal pests, without harming the plants themselves. In particular, seed treatment methods should also take into account the inherent insecticidal or nematicidal properties of pest-resistant or pest-tolerant transgenic plants to achieve optimal protection for seeds and germinating plants with minimal pesticide use.

[0111] In particular, the present invention also relates to a method for protecting seeds and germinating plants from pests by treating seeds with one of the compounds of formula (I). The method of the present invention for protecting seeds and germinating plants from pests also includes a method of treating seeds simultaneously or sequentially with the compound of formula (I) and the mixed component in one operation. This also includes a method of treating seeds with the compound of formula (I) and the mixed component at different times.

[0112] The present invention also relates to the use of the compound of formula (I) for treating seeds to protect the seeds and the resulting plants from animal pests.

[0113] Typically, compounds of formula (I) are applied to seeds in a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art.

[0114] Compounds of formula (I) can be converted into conventional seed coating formulations, such as solutions, emulsions, suspensions, powders, foams, slurries, or other seed coating compositions, as well as ULV formulations.

[0115] These formulations are prepared in a known manner by mixing the compound of formula (I) with conventional additives (e.g., conventional extenders, solvents or diluents, colorants, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins, and water).

[0116] Seed dressing formulations applicable according to the present invention can be used directly or after prior dilution with water to treat various types of seeds. For example, concentrates or formulations thereof that can be obtained by dilution with water can be used to treat the seeds of the following plants: cereals (e.g., wheat, barley, rye, oats, and triticale), as well as corn, rice, rapeseed, peas, beans, cotton, sunflower, soybeans, and sugar beets, or various different vegetables. Seed dressing formulations applicable according to the present invention, or their diluted forms, can also be used to treat the seeds of genetically modified plants.

[0117] The application rate of the seed dressing formulation that can be used according to the present invention can vary over a wide range. This is determined by the specific content of the compound of formula (I) in the formulation and the seed. The application rate of the compound of formula (I) is typically from 0.001 to 50 g / kg of seed, preferably from 0.01 to 15 g / kg of seed.

[0118] The compound of formula (I) provided by this invention can also be applied to the field of animal health.

[0119] In the field of animal health, specifically veterinary medicine, compounds of formula (I) are active against animal parasites, particularly ectoparasites or endoparasites. The term "endoparasites" specifically includes worms and protozoa, such as coccidia. Ectoparasites are generally and preferably arthropods, especially insects or mites.

[0120] In the field of veterinary medicine, compounds of formula (I) with favorable warm-blooded animal toxicity are suitable for the prevention and control of parasites in animal breeding and reproduction of livestock, breeding animals, zoo animals, laboratory animals, experimental animals, and domestic animals. They are active against all or specific developmental stages of parasites.

[0121] Agricultural livestock include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffalo, rabbits, reindeer, deer, and especially cattle and pigs; or poultry such as turkeys, ducks, geese, and especially chickens; or fish or crustaceans in aquaculture; or, depending on the circumstances, insects such as bees.

[0122] Domestic animals include, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets, especially dogs, cats, caged birds; reptiles, amphibians, or ornamental fish.

[0123] According to one specific embodiment, the compound of formula (I) is applied to a mammal.

[0124] According to another specific embodiment, the compound of formula (I) is applied to poultry, i.e., caged birds or, in particular, domestic poultry.

[0125] By using compounds of formula (I) to control animal parasites, the aim is to reduce or prevent disease, mortality, and performance decline (in the case of meat, milk, wool, hides, eggs, honey, etc.), thereby making animal husbandry more economical and simpler, and achieving better animal health.

[0126] In the field of animal health, the term "control" or "controlling" as used herein refers to compound (I) effectively reducing the incidence of various parasites in animals infected with parasites to a harmless level. More specifically, "control" as used herein refers to compound (I) effectively killing various parasites, inhibiting their growth, or suppressing their proliferation.

[0127] In veterinary medicine and animal husbandry, compounds of formula (I) are administered in suitable formulations via methods commonly known in the art, such as intravenous, parenteral, dermal, or nasal routes. Administration may be prophylactic, metaphylactically, or therapeutically.

[0128] Therefore, one embodiment of the present invention relates to a compound of formula (I) used as a medicament.

[0129] Another aspect involves compounds of formula (I) used as endoparasitic agents for antibodies.

[0130] Another specific aspect involves compounds of formula (I) used as worm control agents, and more particularly as nematicides, flatworm culprits, acanthocephalans, or lingulat culprits.

[0131] Another specific aspect involves compounds of formula (I) used as antigenic agents for animals.

[0132] On the other hand, it relates to compounds of formula (I) used as antiparasitic agents, especially arthropod scavengers, and even more particularly insecticides or acaricides.

[0133] Other aspects of the invention are veterinary formulations comprising an effective amount of at least one compound of formula (I) and at least one of the following substances: pharmaceutically acceptable excipients (e.g., solid or liquid diluents), pharmaceutically acceptable adjuvants (e.g., surfactants), particularly pharmaceutically acceptable excipients and / or pharmaceutically acceptable adjuvants commonly used in veterinary formulations.

[0134] A related aspect of the present invention is a method for preparing a veterinary formulation as described herein, comprising the steps of: mixing at least one compound of formula (I) with a pharmaceutically acceptable excipient and / or adjuvant, particularly with a pharmaceutically acceptable excipient and / or adjuvant commonly used in veterinary formulations.

[0135] Another specific aspect of the present invention is a veterinary preparation and its preparation method, wherein the veterinary preparation is selected from preparations that kill ectoparasites and preparations that kill endoparasites, and more particularly from the above-mentioned anthelmintic, antiprotozoan, and arthropod preparations, and even more particularly from preparations that kill nematodes, flatworms, acanthocephalans, lingula, insects, and mites.

[0136] On the other hand, it relates to a method for treating parasitic infections, particularly those caused by parasites selected from the ectoparasites and endoparasites mentioned herein, by administering an effective amount of a compound of formula (I) to animals in need of treatment, especially non-human animals.

[0137] On the other hand, it relates to a method of treating parasitic infections, particularly those caused by parasites selected from ectoparasites and endoparasites mentioned herein, by administering veterinary preparations as defined herein to animals in need of treatment, especially non-human animals.

[0138] On the other hand, the use of compounds of formula (I) in the treatment of parasitic infections in animals, especially non-human animals, particularly infections caused by parasites selected from the ectoparasites and endoparasites mentioned herein.

[0139] In the context of the animal health or veterinary field of this invention, the term "treatment" includes preventative, remedial, or therapeutic treatment.

[0140] In one specific embodiment, at least one compound of formula (I) for use in the veterinary field is provided in combination with other active ingredients, particularly with mixtures of endoparasite-killing agents and ectoparasite-killing agents.

[0141] In the field of animal health, a "mixture" refers not only to a product containing two (or more) different active ingredients formulated as a combined preparation and administered together, but also to a product containing individual formulations of each active compound. Therefore, when administering two or more active compounds, all active compounds may be formulated as a combined preparation or as individual formulations; alternatively, they may be in a mixture form, where some active compounds are formulated together and others are formulated individually. Individual formulations may be administered individually or sequentially with respect to the active compounds.

[0142] The compound of formula (I) provided by this invention can also be applied to the field of vector control.

[0143] The vectors are arthropods, especially insects or arachnids, which can transmit pathogens such as viruses, worms, single-celled organisms, and bacteria from a host (plant, animal, human, etc.) to a host. Pathogens can be transmitted to the host mechanically (e.g., trachoma transmitted by non-stinging flies) or by injection (e.g., malaria parasites transmitted by mosquitoes).

[0144] Compound (I) is suitable for the prevention of vector-borne diseases and / or pathogens. Therefore, another aspect of the invention is the use of compound (I) for vector control in, for example, agricultural, horticultural, gardening, and recreational equipment, as well as in the protection of materials and stored products.

[0145] The compound of formula (I) provided by this invention can also be applied to the protection of industrial materials.

[0146] Compounds of formula (I) are suitable for protecting industrial materials from insects that may infest or damage them, such as those from the orders Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psittacosae, and Zygentoma.

[0147] In the context of this invention, industrial materials are to be understood as inanimate materials, such as, preferably, plastics, adhesives, pastes, paper and cards, leather, wood, processed wood products, and coating compositions. The use of this invention for the protection of wood is particularly preferred.

[0148] Compound of formula (I) can be used with at least one other insecticide and / or at least one fungicide.

[0149] Compounds of formula (I) exist as ready-to-use pesticides, meaning they can be applied to the material without further modification. Other suitable insecticides or fungicides are particularly those mentioned above.

[0150] Compounds of formula (I) can be used to protect objects in contact with saltwater or brackish water from contamination, particularly ship hulls, bulkheads, nets, structures, mooring equipment, and signaling systems. Similarly, compounds of formula (I) can be used alone or in combination with other active compounds as antifouling agents.

[0151] The compound of formula (I) provided by this invention can also be used in the field of hygiene for the prevention and control of animal pests.

[0152] Compounds of Formula (I) are suitable for controlling animal pests in the sanitation field. In particular, the present invention can be used for the protection of indoor, sanitation, and stored products, especially for controlling insects, arachnids, ticks, and mites encountered in enclosed spaces such as dwellings, factory lobbies, offices, vehicle cabins, and livestock farms. For controlling animal pests, compounds of Formula (I) can be used alone or in combination with other active compounds and / or adjuvants. They are preferably used in indoor insecticide products. Compounds of Formula (I) are effective against susceptible and resistant species, as well as their entire developmental stages.

[0153] These pests include, for example, the following: Arachnida, Scorpiones, Araneae, and Opiliones; Chilopoda and Diplopoda; Insecta, Blattodea, Coleoptera, Dermaptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Psittacoidea, Saltatoria, Orthoptera, Siphonaptera, and Silverfish; Malacostraca, Isopoda.

[0154] They are used in, for example, aerosols, unpressurized spray products such as pump-operated sprays and atomized sprays, automatic atomization systems, sprays, foams, gels, evaporation products with evaporating tablets made of cellulose or plastic, liquid evaporators, gel and film evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth traps, moth traps and moth traps, as granules or powders, for use in spread baits or bait stations.

[0155] Based on the properties of the substituents defined above, compounds of formula (I) are acidic and can form salts, and, if suitable, can form internal salts, or form adducts with inorganic or organic bases or with metal ions. If compounds of formula (I) contain a hydroxyl group, a carboxyl group, or other groups that cause acidity, these compounds can react with bases to form salts. Suitable bases are, for example, hydroxides, carbonates, and bicarbonates of alkali metals and alkaline earth metals, particularly sodium, potassium, magnesium, and calcium; and ammonia; primary, secondary, and tertiary amines having C1-C4-alkyl groups; monoalkylolamines, dialkylolamines, and trialkylolamines of C1-C4-alkanols; choline and choline chloride; and organic amines such as trialkylamines, morpholine, piperidine, or pyridine. These salts are compounds in which the acidic hydrogen is replaced by an agriculturally suitable cation, for example, metal salts, especially alkali metal salts or alkaline earth metal salts, particularly sodium and potassium salts; or ammonium salts, organic amine salts, or quaternary ammonium salts, such as salts of cations having the formula [NRR′R″R″′]+ (where R to R″′ each independently represents an organic group, particularly alkyl, aryl, aralkyl, or alkylaryl). Also suitable are alkyl sulfonium salts and alkyl oxide sulfonium salts, such as C1-C4-trialkyl sulfonium salts and C1-C4-trialkyl oxide sulfonium salts.

[0156] Compounds of formula (I) can form salts by adding a suitable inorganic or organic acid to a basic group; the inorganic acid being, for example, HCl, HBr, H₂SO₄, H₃PO₄, or HNO₃, the organic acid being, for example, a carboxylic acid (e.g., formic acid, acetic acid, propionic acid, oxalic acid, lactic acid, or salicylic acid) or a sulfonic acid (e.g., p-toluenesulfonic acid), and the basic group being, for example, an amino, alkylamino, dialkylamino, piperidinyl, morpholinyl, or pyridinyl group. In this case, the salts contain the conjugate base of the acid as an anion.

[0157] Suitable substituents (e.g., sulfonic acids or carboxylic acids) in deprotonated form can form internal salts with groups that are themselves protonable (e.g., amino groups).

[0158] The inventors have discovered that some of the compounds provided by this invention exhibit superior activity against certain target pests compared to existing compounds with similar structures.

[0159] In this invention, if there is a conflict between the naming of compounds and their structural formulas, the structural formula shall prevail, unless the structural formula is obviously incorrect. Detailed Implementation

[0160] The following examples are for illustrative purposes only and should not be construed as limiting the invention in any way. The scope of protection of this invention is defined by the claims. Simple substitutions or modifications made to this invention by those skilled in the art are all within the scope of the technical solutions protected by this invention.

[0161] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The raw materials can be commercially available or prepared by methods known in the literature or as detailed in the description. Those skilled in the art will understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although specific raw materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar raw materials and conditions. Such variations or modifications to the preparation methods of the present invention, such as various isomers of the compounds, are all included within the scope of the present invention. Furthermore, the preparation methods described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, protecting appropriate groups during the reaction process, etc.

[0162] The following method examples are provided to further illustrate the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further explain the invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds described below are either commercially available or can be easily prepared by those skilled in the art.

[0163] The analytical instruments described in the examples are as follows:

[0164] I. High Performance Liquid Chromatography (hereinafter referred to as HPLC): Using an Agilent Technologies 1260 Infinity II instrument.

[0165] Pillar: Agilent Eclipse Plus C18 3.5μm, 4.6*100mm

[0166] Mobile phase: A: water + 0.1% phosphoric acid; B: acetonitrile; Temperature: 30℃

[0167] Gradient: 10%B to 95%B over 15 min; 95%B over 3 min

[0168] Flow rate: 1 mL / min

[0169] II. Ultra-high performance liquid chromatography-tandem mass spectrometry (hereinafter referred to as LC-MS): Using a Waters, ACQUITY H-Class UPLC-SQ Detector 2 instrument.

[0170] Column: ACQUITY BEH C18 1.7μm,2.1*50mm Column

[0171] Mobile phase: A: Water + 0.2% formic acid; B: Acetonitrile; Temperature: 30℃

[0172] Gradient: 10%B to 95%B over 5 minutes; 95%B over 1 minute

[0173] Flow rate: 0.5 mL / min

[0174] MS method: ESI positive and negative, mass range (m / z): 100-800

[0175] III. Gas Chromatography-Tandem Mass Spectrometry (hereinafter referred to as GC-MS): Using Agilent Technologies, 7890B GC System-5977A MSD equipment.

[0176] Column: Agilent Technologies, HP-5MS UI 0.25μm, 30m*0.250mm

[0177] Injector temperature: 250℃

[0178] Column flow rate: Helium 1 mL / min

[0179] Method: Hold at 40℃ for 2 min, increase temperature to 280℃ at 20℃ / min, hold at 280℃ for 5 min, total time 19 min.

[0180] MSD transmission line temperature: 280℃

[0181] EI ion source temperature: 230℃, MS quadrupole temperature: 150℃, scan range: 30.00-400.00

[0182] In addition, the proton nuclear magnetic resonance spectra described below (hereinafter referred to as...) 1 The chemical shift values ​​of H-NMR were measured at 400 MHz (Bruker, AVANCE III HD 400M) in deuterated chloroform (CDCl3) using Me4Si (tetramethylsilane) as the reference material. When measured in deuterated dimethyl sulfoxide, the chemical shift values ​​are shown as "(DMSO-d6)" in the data. It should be noted that... 1 The symbols in the chemical shift values ​​of H-NMR have the following meanings:

[0183] s: singlet, d: doublet, dd: doublett, dt: doublettuplet, td: triplettuplet, ddd: doublettuplet, t: triplettuplet, q: quartet, sep: septet, m: multiplet, brs: broad singlet. Furthermore, in cases where two or more stereoisomers are present, the chemical shift values ​​for the resolvable signals are marked with "and".

[0184] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0185] Preparation Example 1

[0186] Preparation of compound I-90:

[0187] Step 1: Preparation of Compound III-1

[0188] Add 2-trifluoromethylaniline (24.0 g, 149.0 mmol) and tetrabutylammonium hydrogen sulfate (CH3CH2CH2CH2)4N to a 500 mL single-necked flask. + (HSO4) - 15.0 g (44.2 mmol) of sodium dithionite (Na₂S₂O₄) (78.3 g (450.0 mmol) was added, followed by 360 mL of ethyl acetate and 360 mL of water. Sodium bicarbonate (37.8 g (450.0 mmol)) was slowly added with stirring. The mixture was cooled to 0 °C, and then heptafluoro-2-iodopropane ((CF₃)₂CFI) (132.0 g (450.0 mmol)) was slowly added dropwise. After the addition was complete, the mixture was stirred overnight at room temperature. After the reaction was complete, the organic layer was separated, and the aqueous layer was extracted with ethyl acetate (100 mL * 3). The organic layers were combined, washed with saturated brine (100 mL * 3), dried over anhydrous sodium sulfate, and the solvent was removed by vacuum evaporation. The residue was the crude product of the title compound III-1, which was used directly in the next step without further processing.

[0189] Step 2: Preparation of Compound III-2

[0190] Compound III-1 obtained in step 1 above was dissolved in 150 mL of N,N-dimethylformamide (DMF) and stirred. N-bromosuccinimide (NBS) (31.8 g, 179.0 mmol) was added in portions at room temperature. After the addition was complete, the temperature was raised to 60 °C and the reaction was carried out for 2 h. After the reaction was completed, the reaction solution was slowly added to 600 mL of water and extracted with ethyl acetate (150 mL * 3). The organic phases were combined and washed with saturated brine (100 mL * 3). The solution was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The residue was purified by column chromatography to give 24.0 g of the title compound III-2.

[0191] 1 H NMR(400MHz,Chloroform-d)δ7.80(s,1H),7.61(s,1H),5.03(s,2H).

[0192] Step 3: Preparation of compound IV-1

[0193] 2-Fluoro-3-nitrobenzoic acid (16.3 g, 88.0 mmol) was dissolved in 150 mL of dichloromethane, 2 drops of DMF were added, and oxaloyl chloride (32.0 g, 185.0 mmol) was added dropwise under ice bath conditions. The reaction was carried out at room temperature. After the reaction was completed, the solution was concentrated under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. Compound III-2 (24.0 g, 58.7 mmol) prepared in step 2 and 11 mL of 1,4-dioxane were added to the solution. The temperature was raised to 110 °C and the reaction was carried out. After the reaction was completed, the solution was cooled to room temperature and diluted with 200 mL of ethyl acetate. The organic layer was washed with saturated sodium bicarbonate aqueous solution until the pH of the aqueous layer was neutral. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain 24.1 g of the title compound IV-1.

[0194] 1 H NMR (400MHz, Chloroform-d) δ8.47-8.39(m,1H),8.27(ddd,J=19.3,12.8,7.0Hz,2H),8.16(s,1H),7.94(s,1H),7.52(t,J=8.0Hz,1H).

[0195] Step 4: Preparation of compound V-1

[0196] Compound IV-1 (24.1 g, 41.9 mmol) prepared in step 3 and stannous chloride dihydrate (SnCl2·2H2O) (37.6 g, 166.8 mmol) were added to a mixture of 200 mL ethanol and 5 mL concentrated hydrochloric acid (36%), and the mixture was heated to 70 °C. After the reaction was complete, the reaction solution was concentrated under reduced pressure. The pH of the residue was adjusted to 8-9 with a 10% sodium hydroxide aqueous solution, and then extracted with ethyl acetate (100 mL * 4). The organic phases were combined and washed with saturated brine (50 mL * 3), dried over anhydrous sodium sulfate, and the solvent was removed by evaporation under reduced pressure. The residue was purified by column chromatography to give 15.3 g of the title compound V-1.

[0197] 1 H NMR(400MHz,Chloroform-d)δ8.27(d,J=14.7Hz,1H),8.14(s,1H),7.91(s,1H),7.49(d t,J=14.6,4.4Hz,1H),7.10(t,J=7.9Hz,1H),7.01(td,J=8.4,1.7Hz,1H),3.91(s,2H).

[0198] Step 5: Preparation of Compound II-1

[0199] Compound V-1 (500.0 mg, 0.92 mmol) prepared in step 4, 6-chloronicotinaldehyde (130.2 mg, 0.92 mmol), and trifluoroacetic acid (1.3 mL) were added to 10 mL of dichloromethane. Sodium cyanoborohydride (NaBH3CN) (230.5 mg, 3.67 mmol) was added in portions. The mixture was stirred at room temperature for 3 h. After the reaction was completed, 30 mL of dichloromethane was added to dilute the reaction solution, and the mixture was washed with saturated sodium bicarbonate aqueous solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The residue was purified by column chromatography to give 400.0 mg of the title compound II-1.

[0200] 1 H NMR (400MHz, DMSO-d6) δ10.57(s,1H),8.54-8.39(m,2H),7.95-7.94(m,1H),7.84(dd,J=8.3,2.5Hz,1H),7.49(d,J=8.2Hz,1H),7.05 (t,J=7.9Hz,1H),6.86(ddd,J=7.6,5.8,1.5Hz,1H),6.81(td,J=8.2,1.6Hz,1H),6.68(td,J=6.4,2.3Hz,1H),4.44(d,J=6.3Hz,2H).

[0201] Step 6: Preparation of compound I-90

[0202] 6-Fluoronic acid (70.6 mg, 0.5 mmol) was added to 3.0 mL of dichloromethane, followed by 2 drops of DMF. Oxaloyl chloride (95.2 mg, 0.75 mmol) was added dropwise under ice bath conditions. After the addition was complete, the mixture was brought to room temperature. The reaction mixture was concentrated to obtain 2-fluoropyridine-5-carboxyl chloride. Compound II-1 (221.3 mg, 0.33 mmol) prepared in step 5, sodium iodide (NaI) (200.0 mg, 1.33 mmol), and 15 mL of toluene were then added to the mixture. The mixture was heated to 110 °C and reacted for 2 h. After the reaction was complete, the reaction solution was cooled to room temperature, diluted with 20 mL of ethyl acetate, and washed with a saturated sodium bicarbonate aqueous solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to give 150.2 mg of the title compound I-90.

[0203] 1H NMR(400MHz,DMSO-d6)δ10.63(s,1H),8.44 -8.32(m,2H),8.23(s,1H),8.07-7.92(m,2H),7.85(dd,J=8.2,2.5Hz,1H),7.78-7.70(m,1H),7.58(t,J =6.7Hz,1H),7.50(d,J=8.2Hz,1H),7.38(t,J=7.8Hz,1H),7.14(d,J=8.5Hz,1H),5.12(d,J=20.1Hz,2H).

[0204] Preparation Example 2

[0205] Preparation of compound I-129:

[0206] Step 1: Preparation of Compound III-3

[0207] Compound III-1 (10.0 g, 30.4 mmol) was added to 100 mL of ethanol and stirred. Concentrated sulfuric acid (98%) (3.6 g, 36.5 mmol) and N-iodosuccinimide (NIS) (8.2 g, 36.5 mmol) were added under ice bath conditions. The mixture was heated to room temperature and stirred for 1 h, then the temperature was further increased to 40 °C. After the reaction was complete, the reaction solution was neutralized with 4 M sodium hydroxide aqueous solution, followed by extraction with ethyl acetate. The organic phases were combined and washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to give 12.0 g of the title compound III-3.

[0208] Step 2: Preparation of compound IV-2

[0209] 2-Fluoro-3-nitrobenzoic acid (5.3 g, 31.6 mmol) was dissolved in 150 mL of dichloromethane, 2 drops of DMF were added, and oxaloyl chloride (4.8 g, 37.9 mmol) was added dropwise under ice bath conditions. The reaction was carried out at room temperature. After the reaction was completed, the solution was concentrated under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. Compound III-3 (12.0 g, 26.4 mmol) prepared in step 1 and 5 mL of 1,4-dioxane were added to the solution. The temperature was raised to 110 °C and the reaction was carried out. After the reaction was completed, the solution was cooled to room temperature and diluted with 200 mL of ethyl acetate. The organic layer was washed with saturated sodium bicarbonate aqueous solution until the pH of the aqueous layer was neutral. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to give 14.2 g of the title compound IV-2.

[0210] Step 3: Preparation of compound V-2

[0211] Compound IV-2 (14.2 g, 22.8 mmol) prepared in step 2 and stannous chloride dihydrate (SnCl2·2H2O) (7.7 g, 34.2 mmol) were added to a mixture of 140 mL ethanol and 5 mL concentrated hydrochloric acid (36%), and the mixture was heated to 70 °C. After the reaction was completed, the reaction solution was cooled to room temperature, concentrated under reduced pressure, and the pH of the residue was adjusted to 8-9 with a 10% sodium hydroxide aqueous solution. The residue was then extracted with ethyl acetate (100 mL * 4), the organic phases were combined, washed with saturated brine (50 mL * 3), dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to give 13.1 g of the title compound V-2.

[0212] Step 4: Preparation of Compound II-2

[0213] Compound V-2 (200.0 mg, 0.34 mmol) prepared in step 3, 6-chloronicotinaldehyde (47.8 mg, 0.34 mmol), and trifluoroacetic acid (2.0 mL) were added to 3 mL of dichloromethane. Sodium cyanoborohydride (NaBH3CN) (42 mg, 0.67 mmol) was added in portions, and the mixture was stirred at room temperature for 3 h. After the reaction was completed, 30 mL of dichloromethane was added to dilute the reaction solution, and the mixture was washed with saturated sodium bicarbonate aqueous solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The residue was purified by column chromatography to give 194.0 mg of the title compound II-2.

[0214] 1 H NMR (400MHz, DMSO-d6) δ10.59(s,1H),8.54-8.39(m,2H),7.98-7.91(m,1H),7.85(dd,J=8.3,2.5Hz,1H),7.49(d,J=8.2Hz,1H),7.05 (t,J=7.9Hz,1H),6.86(ddd,J=7.6,5.8,1.5Hz,1H),6.81(td,J=8.2,1.6Hz,1H),6.68(td,J=6.4,2.3Hz,1H),4.44(d,J=6.3Hz,2H).

[0215] Step 5: Preparation of compound I-129

[0216] Benzoic acid (78.2 mg, 0.64 mmol) was added to 1.5 mL of dichloromethane, followed by 2 drops of DMF. Oxaloyl chloride (95.2 mg, 0.75 mmol) was added dropwise under ice bath conditions. After the addition was complete, the reaction proceeded to room temperature. The mixture was concentrated to obtain benzoyl chloride. Compound II-2 (229.7 mg, 0.32 mmol) prepared in step 4, sodium iodide (NaI) (200.0 mg, 1.33 mmol), and 15 mL of toluene were then added to the mixture. The temperature was raised to 110 °C. After the reaction was complete, the reaction solution was cooled to room temperature, diluted with 30 mL of ethyl acetate, and washed with a saturated sodium bicarbonate aqueous solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to give 200.5 mg of the title compound I-129.

[0217] 1 H NMR(400MHz,DMSO-d6)δ10.63(s,1H),8.50(d,J=2.0Hz,1H),8.35(s,1H),7.93(s,1H),7.89 -7.80(m,1H),7.53(dd,J=13.9,7.5Hz,3H),7.31(d,J=32.8Hz,6H),5.07(d,J=36.0Hz,2H).

[0218] Preparation Example 3

[0219] Preparation of compound I-324:

[0220] Step 1: Preparation of Compound III-4

[0221] Add 2-(difluoromethoxy)aniline (4.5 g, 28.0 mmol), tetrabutylammonium bisulfate (CH3CH2CH2CH2)4N(HSO4) (2.85 g, 8.4 mmol), and sodium dithionite (Na2S2O4) (14.8 g, 85.0 mmol) to a 500 mL single-necked flask. Then add 50 mL of ethyl acetate and 50 mL of water. Slowly add sodium bicarbonate (7.1 g, 84.0 mmol) while stirring. Cool to 0 °C and then slowly add heptafluoro-2-iodopropane ((CF3)2CFI) (24.9 g, 84.0 mmol) dropwise. After the addition is complete, stir at room temperature overnight. After the reaction was completed, the organic layer was separated, the aqueous layer was extracted with ethyl acetate (50 mL * 3), the organic layers were combined, washed with saturated brine (20 mL * 3), dried over anhydrous sodium sulfate, and the solvent was removed by vacuum evaporation. The residue was the title compound III-4, which was an oily substance and was used directly in the next step without further treatment.

[0222] Step 2: Preparation of Compound III-5

[0223] Compound III-4 obtained in step 1 was dissolved in 50 mL of N,N-dimethylformamide (DMF) and stirred. N-bromosuccinimide (NBS) (5.0 g, 28.2 mmol) was added in portions at room temperature. After the addition was complete, the temperature was raised to 70 °C and the reaction was carried out for 2 h. After the reaction was completed, the reaction solution was slowly added to 200 mL of water and extracted with ethyl acetate (100 mL * 3). The organic phases were combined and washed with saturated brine (50 mL * 3). The solution was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The residue was purified by column chromatography to give 7.3 g of the title compound III-5.

[0224] Step 3: Preparation of compound IV-3

[0225] 2-Fluoro-3-nitrobenzoic acid (3.24 g, 21.6 mmol) was dissolved in 50 mL of dichloromethane, 2 drops of DMF were added, and oxaloyl chloride (3.3 g, 25.9 mmol) was added dropwise under ice bath conditions. The reaction was carried out at room temperature. After the reaction was completed, the solution was concentrated under reduced pressure to obtain 2-fluoro-3-nitrobenzoyl chloride. Compound III-5 (7.3 g, 18 mmol) prepared in step 2 and 3 mL of 1,4-dioxane were added to the solution. The temperature was raised to 110 °C and the reaction was carried out. After the reaction was completed, the solution was cooled to room temperature and diluted with 200 mL of ethyl acetate. The organic layer was washed with saturated sodium bicarbonate aqueous solution until the pH of the aqueous layer was neutral. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to obtain 4.85 g of the title compound IV-3.

[0226] Step 4: Preparation of compound V-3

[0227] Compound IV-3 (4.85 g, 8.5 mmol) prepared in step 3 and stannous chloride dihydrate (SnCl2·2H2O) (5.0 g, 25 mmol) were added to a mixture of 50 mL ethanol and 5 mL concentrated hydrochloric acid (36%), and the mixture was heated to 70 °C. After the reaction was completed, the reaction solution was concentrated under reduced pressure. The pH of the residue was adjusted to 8-9 with a 10% sodium hydroxide aqueous solution, and then extracted with ethyl acetate (100 mL * 4). The organic phases were combined and washed with saturated brine (50 mL * 3), dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The residue was purified by column chromatography to give 4.0 g of the title compound V-3.

[0228] 1H NMR(400MHz,Chloroform-d)δ8.15(d,J=14.0Hz,1H),7.80(s,1H),7.51(s,1H),7.44(ddd,J=8.4,6.8,1 .7Hz,1H),7.09(t,J=7.9Hz,1H),7.00(ddd,J=9.5,8.0,1.7Hz,1H),6.60(t,J=73.2Hz,1H),3.92(m,2H).

[0229] Step 5: Preparation of compound II-3

[0230] Compound V-3 (200.0 mg, 0.37 mmol), 6-chloronicotinaldehyde (47.8 mg, 0.37 mmol), and trifluoroacetic acid (2.0 mL) prepared in step 4 were added to 3 mL of dichloromethane. Sodium cyanoborohydride (NaBH3CN) (42 mg, 0.67 mmol) was added in portions, and the mixture was stirred at room temperature for 3 h. After the reaction was completed, 30 mL of dichloromethane was added to dilute the reaction solution, and the mixture was washed with saturated sodium bicarbonate aqueous solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The residue was purified by column chromatography to give 183 mg of the title compound II-3.

[0231] Step 6: Preparation of compound I-324

[0232] 6-Fluoronic acid (90.2 mg, 0.64 mmol) was added to 1.5 mL of dichloromethane, followed by 2 drops of DMF. Oxaloyl chloride (95.2 mg, 0.75 mmol) was added dropwise under ice bath conditions. After the addition was complete, the reaction proceeded at room temperature. The solution was concentrated to obtain 6-fluoronicotinic acid chloride. Compound II-3 (214 mg, 0.32 mmol) prepared in step 5, sodium iodide (NaI) (200.0 mg, 1.33 mmol), and 15 mL of toluene were then added to the solution. The mixture was heated to 110 °C. After the reaction was complete, the reaction solution was cooled to room temperature, diluted with 30 mL of ethyl acetate, and washed with a saturated sodium bicarbonate aqueous solution. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography to give 198 mg of the title compound I-324.

[0233] 1H NMR (400MHz, DMSO-d6) δ10.38(s,1H),8.36(s,1H),8.22(s,1H),8.00(s,1H),7.90(s,1H),7.85(d,J=8.4Hz,1 H),7.64(d,J=7.9Hz,1H),7.59-7.47(m,3H),7.37-7.27(m,1H),7.14(d,J=8.6Hz,1H),5.11(d,J=14.3Hz,2H).

[0234] Referring to the synthesis methods in Examples 1, 2, and 3, using the corresponding compound of formula (VIII) as a starting material, the remaining compounds of formula (I), some compounds of formula (I), and their derivatives can be obtained. 1 The H NMR spectra are listed in Table 2.

[0235] Table 2

[0236] Using preparation examples similar to those described and mentioned above, and taking into account general details related to the preparation of substituted meta-diamide compounds, the compounds described in Table 3 can be obtained, wherein Het and Q are selected from any of the substituents listed in Tables 4 and 5.

[0237] Table 3

[0238] Table 4

[0239] Table 5

[0240] The compound of formula (I) of this invention was tested for its control activity against various agricultural pests, including cotton aphids, peach aphids, diamondback moths, rice stem borers, rice leaf rollers, beet armyworms, fall armyworms, cotton bollworms, whiteflies, thrips, brown planthoppers, gray planthoppers, flea beetles, and root-knot nematodes. The tested compound of formula (I) showed superior control efficacy, achieving unexpected technical results compared to existing technologies. Control efficacy grading standards:

[0241] A indicates a mortality rate of 80% to 100% or higher;

[0242] B indicates a mortality rate of 60% or higher to less than 80%;

[0243] C indicates a mortality rate of 40% or higher to less than 60%;

[0244] D indicates a mortality rate of less than 40%.

[0245] The compounds of formula (I) of the present invention were also subjected to toxicity tests on environmental organisms such as bees, giant daphnia, zebrafish, and earthworms. The compounds of formula (I) tested showed low toxicity.

[0246] Biological Example 1

[0247] Cotton aphid (Aphis gossypii (Glover))

[0248] The activity of cotton aphids was tested using the immersion method. The test unit consisted of a 9cm plastic petri dish containing cucumber leaves that had grown for one month, and was kept moist with absorbent cotton. Healthy adult aphids were inoculated onto the cucumber leaves, and after 24 hours, the adult aphids were removed, and the total number of nymphs on each plate was recorded.

[0249] Prepare the test compound, add an appropriate amount of organic solvent (solvent content not exceeding 2%), and then dilute it to different concentrations with 0.1% Tween-80 aqueous solution. Soak cucumber leaves with 2-day-old nymphs in the solution for 5 seconds, and allow the residual solution to dry completely. Perform three parallel treatments. Place all test units at 25±1℃ and a photoperiod of 16h:8h (L:D) for rearing and observation. Record the number of dead insects 72 hours after treatment and calculate the mortality rate.

[0250] Compounds of formula (I) of the present invention I-8, I-12, I-34, I-40, I-41, I-42, I-43, I-44, I-45, I-46, I-48, I-49, I-50, I-51, I-52, I-54, I-57, I- 60. I-62, I-64, I-66, I-68, I-69, I-70, I-71, I-72, I-73, I-74, I-75, I-76, I-77, I-86, I-90, I-112, I-125, I-129, I -151, I-158, I-159, I-168, I-169, I-171, I-174, I-177, I-183, I-185, I-187, I-188, I-190, I-191, I-192, I-193, I- 194. When the concentration of I-202, I-207, I-229, I-320, I-324, I-346, I-469, I-479, I-480, I-481 and I-491 is 50ppm, the mortality rate of cotton aphids is ≥80% 3 days after treatment.

[0251] Biological Example 2

[0252] Diamondback moth (Plutella xylostella (Linnaeus))

[0253] The activity of diamondback moth was tested by leaf immersion feeding. The test unit consisted of a 9cm plastic petri dish containing three fresh cabbage leaves of equal area.

[0254] Prepare the test compound by adding an appropriate amount of organic solvent (solvent content not exceeding 2%), then dilute it to different concentrations with 0.5% Triton X-100 aqueous solution. Soak fresh cabbage leaves in the solution for 10 seconds, and after the residual solution is fully dried, place them in petri dishes. Then, pick 10 third-instar larvae of diamondback moths into each petri dish, and perform three parallel treatments. Place all test units at 25±1℃ and a photoperiod of 16h:8h (L:D) for rearing and observation. Record the number of dead insects 3–5 days after treatment and calculate the mortality rate.

[0255] Compounds of formula (I) of the present invention I-8, I-12, I-34, I-40, I-41, I-42, I-46, I-48, I-49, I-50, I-51, I-52, I-54, I-57, I-60, I-62, I-64, I-66, I-68, I-6 9. I-70, I-71, I-72, I-73, I-74, I-75, I-76, I-77, I-86, I-90, I-112, I-125, I-129, I-151, I-158, I-159, I-168, I-169, I-171, I- 174, I-177, I-181, I-183, I-185, I-187, I-188, I-190, I-191, I-192, I-193, I-194, I-202, I-207, I-229, I-320, I-324, I-346, I- 469, I-470, I-471, I-472, I-473, I-475, I-476, I-477, I-479, I-480, I-481, I-483, I-489, and I-491 have a mortality rate of ≥80% on diamondback moth 3 days after treatment at a concentration of 1 ppm.

[0256] Following the above method, a number of compounds from this invention were selected and their insecticidal activity against diamondback moth was compared in parallel with that of CK. The experimental results are shown in Table 6.

[0257] Table 6

[0258] Biological Example 3

[0259] Rice stem borer (Chilo suppressalis (Walker))

[0260] The activity test of rice stem borer was conducted by leaf-immersion feeding method. The test unit was a 9cm plastic petri dish containing 15 6cm long 1-month-old rice stems.

[0261] Prepare the test compound by adding an appropriate amount of organic solvent (solvent content not exceeding 2%), and then dilute it to different concentrations with 0.5% Triton X-100 aqueous solution. Cut rice plants that have grown for one month at the root, clean them, and let them dry. Soak them in the drug solution for 10 seconds, and let the residual drug solution dry completely. Place them in a petri dish, and place filter paper in the petri dish to keep them moist. Then pick out 10 late second instar larvae of the rice stem borer into the petri dish, cover them with two layers of black cloth, and then cover the petri dish with the petri dish lid. Place all test units under the conditions of 28±1℃ and a photoperiod of 16h:8h (L:D) for rearing and observation. Record the number of dead insects 5 days after the drug treatment and calculate the mortality rate.

[0262] Compounds of formula (I) of the present invention I-12, I-34, I-40, I-49, I-50, I-51, I-62, I-68, I-72, I-73, I-90, I-129, I-69 , I-112, I-151, I-168, I-190, I-207, I-229, I-469, and I-480, when the concentration is 2ppm, the mortality of stem borer 5 days after treatment is ≥80%.

[0263] Biological Example 4

[0264] Rice leaf roller (Cnaphalocrocis medinalis Guenee)

[0265] The activity of rice leaf roller was tested using the leaf immersion method. The test unit consisted of a 7cm glass petri dish containing 10 wheat leaves about 5cm in length, with qualitative filter paper placed at the bottom of the glass petri dish and kept moist by adding water.

[0266] Prepare the test compound by adding an appropriate amount of organic solvent (solvent content not exceeding 2%), then dilute it to different concentrations with 0.1% Tween-80 aqueous solution. Cut wheat leaves to a length of about 5 cm and set aside. Immerse the wheat leaves in the prepared solutions of different concentrations for 20 seconds, then remove them and allow them to dry thoroughly on tissue paper. Transfer the wheat leaves to corresponding petri dishes, and inoculate 10 rice leaf roller larvae into each dish. Perform three parallel treatments. Place all test units in an incubator at 28±1℃ with a photoperiod of 16h:8h (L:D) for observation. Record the number of dead insects 48 hours after treatment and calculate the mortality rate.

[0267] The compound of formula (I) of this invention has excellent control efficacy against rice leaf roller.

[0268] Biological Example 5

[0269] Zebrafish (Barchydanio rerio)

[0270] Use healthy, disease-free zebrafish of uniform size. Before the experiment, they should be pre-reared under the same environmental conditions as the experimental one for 7-14 days. During the pre-rearing period, feed them 1-2 times a day, provide 12-16 hours of light per day, and clean up feces and food scraps promptly. Stop feeding 24 hours before the experiment.

[0271] The test unit was a 3L beaker, and a static test method was used. Test compounds were prepared by using organic solvents (DMSO, DMF, etc.) to create stock solutions, with a solvent content not exceeding 2%. Five to seven concentration gradients were prepared using tap water aerated for at least 24 hours. Five zebrafish were placed in each test unit, with a minimum capacity of 500mL. The poisoning symptoms and mortality rate of the fish were observed and recorded continuously for the first 6 hours of the experiment. Subsequently, the poisoning symptoms and mortality rate were observed and recorded at 24h, 48h, 72h, and 96h. The mortality rate was calculated and determined according to LC-125. 50 To determine toxicity level, the ratio of (96h) / (mg ai / L) is used. The toxicity classification standard is as follows: Extremely toxic: LC 50 ≤0.1; Highly toxic: 0.1 < LC 50 ≤1; Poisoning: 1 < LC 50 ≤10; Low toxicity: LC 50 >10.

[0272] The compound of formula (I) of the present invention exhibits low toxicity to fish.

[0273] Biological Example 6

[0274] Large Daphnia magna

[0275] Non-primate Dachshunds were cultured for at least three generations under laboratory conditions in a parthenogenetic state and were less than 24 hours old. The Dachshunds used in the experiment were healthy Dachshunds from the same maternal lineage, i.e., those that did not show any signs of stress (such as high mortality, presence of male Dachshunds and hibernating eggs, delayed primiparity, abnormal body color, etc.).

[0276] The test unit was a 50mL plastic cup. Test compounds were prepared using organic solvents (DMSO, DMF, etc.) to create a stock solution, with a solvent concentration not exceeding 0.1g / L. Five to seven concentration groups were set up. Ten juvenile Daphnia were placed in each test unit. All test units were cultured under conditions of a water temperature of 18℃~22℃ and a photoperiod of 16h:8h (L:D). The mortality rate of the large Daphnia was observed and statistically analyzed after 48 hours, based on EC... 50 To determine toxicity level, the ratio of (48h) / (mg ai / L) is as follows: Extremely toxic: EC 50 ≤0.1; Highly toxic: 0.1 < EC 50 ≤1; Poisoning: 1 < EC 50 ≤10; Low toxicity: EC 50 >10.

[0277] The compound of formula (I) of the present invention exhibits low toxicity to daphnia.

[0278] Biological Example 7

[0279] Italian worker bee (Apis mellifera L.)

[0280] Using adult Italian worker bees (Apis mellifera L.), test bees should be collected in the early morning; avoid conducting bee tests in early spring and late autumn; bees should not be used for testing within four weeks of receiving antibiotics or anti-mite drugs. Test bees should be healthy individuals of uniform size. Bees used for acute oral toxicity tests should be starved for 2 hours before the test.

[0281] 1. Acute oral toxicity

[0282] Prepare the test compound by using an organic solvent (acetone, etc.) to create a stock solution. Prepare 5-7 gradient concentrations of 50% sucrose solution, with 10 bees per concentration. Then, add 200 μL of the 50% sucrose solution containing different concentrations of the compound to the feeder. Set up a blank control group and a solvent control group. Measure the consumption of the drug solution. After the drug solution is consumed, feed the bees with the sucrose solution without the compound. Observe and record the poisoning symptoms and the number of deaths after 48 hours, calculate the mortality rate, and determine the 48-hour LD50. 50 Value and 95% confidence limit.

[0283] 2. Acute contact toxicity of bees

[0284] Prepare the test compound by using an organic solvent (acetone, etc.) to create a stock solution. Prepare 5-7 concentration gradients using a 50% sucrose solution, with 10 bees per concentration. Include a blank control group and a solvent control group. After anesthetizing the bees, apply 2 μL of the different concentrations of the test compound to the mesothorax of the bees. After the solvent evaporates, transfer the bees to test cages and feed them cotton wool soaked in sucrose water. Observe and record the poisoning symptoms and mortality rate of the bees after 48 hours, calculate the mortality rate, and determine the 48-hour LD50. 50 Value and 95% confidence limit.

[0285] According to LD 50 The toxicity level is determined by (48h) / (μg ai / bee). The toxicity levels are classified as follows: Extremely Toxic: LD 50 ≤0.001; Highly toxic: 0.001 < LD50 50 ≤2; Poisoning: 2 < LD 50 ≤11; Low toxicity: LD 50 >11.

[0286] The compound of formula (I) of the present invention exhibits low toxicity to bees.

[0287] Biological Example 8

[0288] A child loves earthworms (Eisenia foetida)

[0289] Adult Eisenia foetida earthworms, weighing between 0.3 and 0.6 g, were used in the experiment. The experimental temperature was 20℃ ± 2℃, the relative humidity was 70%–90%, and the light intensity was 400 lx–800 lx.

[0290] Prepare the test compound by using an organic solvent (acetone, etc.) to create a stock solution. Set up 5-7 concentration gradients, with the organic solvent volume generally not exceeding 0.1 mL / L. Include a blank control group and a solvent control group. Weigh 500 g of artificial soil into a specimen bottle and add the different concentrations of the drug solution, mixing thoroughly. Place 10 earthworms in each treatment, seal the bottle opening with gauze, and incubate for two weeks. Observe and record the poisoning symptoms and mortality of the earthworms on days 7 and 14, and calculate the median lethal concentration (LC50) of the drug solution for the earthworms. 50 Value and 95% confidence limit.

[0291] According to LC 50 To determine toxicity level using (14d) / (mg ai / kg dry soil), the toxicity levels are classified as follows: Extremely toxic: LD50 50 ≤0.1; Highly toxic: 0.1 < LC 50 ≤1; Poisoning: 1 < LC 50 ≤10; Low toxicity: LC 50 >10.

[0292] The compound of formula (I) of the present invention exhibits low toxicity to earthworms.

[0293] Biological Example 9

[0294] Chlorella vulgaris

[0295] The experiment used common Chlorella vulgaris, which was cultured under sterile conditions to achieve synchronous growth. The experimental environment temperature was 21℃~24℃ (the temperature of a single experiment was controlled within ±2℃); continuous and uniform light was provided, with the light intensity difference maintained within ±15%, and the light intensity was 4440lx~8880lx.

[0296] Prepare the test compound by using an organic solvent (acetone, etc.) to create a stock solution, setting up 5-7 concentration gradients. The amount of organic solvent used should generally not exceed 0.1 mL / L. Include a blank control group and a solvent control group. Add different concentrations of the drug solution to the Chlorella solution. The experimental observation period is 72 hours, with samples taken every 24 hours. The absorbance of the algae is directly measured using a spectrophotometer. Calculate the algal growth inhibition rate according to EC. 50 To determine toxicity level using (72h) / (mg ai / L), the toxicity levels are classified as follows: Highly toxic: EC 50 ≤0.3; Poisoning: 0.3<EC50 ≤3; Low toxicity: EC 50 >3.

[0297] The compound of formula (I) of the present invention exhibits low toxicity to Chlorella.

[0298] Biological Example 10

[0299] North American quail (Colinus virginianus)

[0300] The test species is the North American quail (Colinus virginianus). The test birds should be in good health and without obvious deformities. A mortality rate of less than 5% within the first 7 days after introduction into the laboratory, and growth patterns consistent with the species' growth characteristics, are considered to indicate good health. The test birds should pass animal quarantine to ensure they are free of disease. The test birds should come from the same maternal parent and hatch on the same day.

[0301] 1. Acute oral toxicity

[0302] Prepare the test compound by using an organic solvent (acetone, etc.) to form a stock solution. Set up 5-7 concentration gradients, with 10 birds (half male and half female) for each concentration. Include a blank control group and a solvent control group. Administer different doses of the test compound (I) orally at a single dose of 1 mL / 100g body weight. Observe the poisoning and mortality of the test birds for 7 consecutive days, and determine the 7-day LD50. 50 Values ​​and 95% confidence limits. Based on LD... 50 To determine toxicity level using / (mg(ai) / kg body weight), the toxicity levels are classified as follows: Extremely Toxic: LD50 50 ≤10; Highly toxic: 10 < LD50 50 ≤50; Poisoning: 50<LD 50 ≤500; Low toxicity: LD 50 >500.

[0303] 2. Acute feeding toxicity

[0304] Prepare the test compound by using an organic solvent (acetone, etc.) to create a stock solution. Establish 5-7 concentration gradients, with 10 birds per concentration (half male, half female), and include a blank control group and a solvent control group. Use a sprayer to apply the different concentrations of the solution to the food, stirring constantly until evenly mixed. Feed the test birds with feed containing different concentrations of the test compound (I) for 5 days. Starting from day 6, feed them with feed without the test compound for 3 days. Record the birds' poisoning and mortality daily, and calculate the LC50 over 8 days. 50 Values ​​and 95% confidence limits. According to LC... 50 To determine toxicity level using / (mg(ai) / kg feed), the toxicity levels are classified as follows: Extremely toxic: LC 50≤50; Highly toxic: 50 < LC 50 ≤500; Poisoning: 500 < LC 50 ≤1000; Low toxicity: LC 50 >1000.

[0305] The compound of formula (I) of the present invention exhibits low toxicity to quail.

[0306] As shown in the results above, the compounds of the present invention generally exhibit good insecticidal effects, producing excellent insecticidal efficacy even at low application doses. Furthermore, they demonstrate good safety for environmental organisms.

[0307] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several changes and improvements without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A meta-diamide compound containing an aromatic ring or aromatic heterocyclic substituted compound as shown in formula (I), its stereoisomers, and agriculturally acceptable salts thereof: in, Het is selected from any one of the following: R a selected from a halogen atom, a C1-C4alkyl group, a halogenated C1-C4alkyl group, a C1-C4alkoxy group, a halogenated C1-C4alkoxy group, a C1-C4alkylthio group or a phenyl group, n is 0, 1, 2, 3, 4, or 5, and when n is selected from 2, 3, 4, or 5, R a are the same or different; R1 is selected from H, -CN, -NO2, halogen atom, C1-C3 alkyl, halo-C1-C3 alkyl or halo-C1-C3 alkoxy; R2 is selected from H, halogen atom, halogenated C1-C3 alkyl or halogenated C1-C3 alkoxy; Q is selected from phenyl, phenyl with a substituent, pyridyl, pyridyl with a substituent, thienyl, thienyl with a substituent, 1-methylpyrazolyl, 1-methylpyrazolyl with a substituent or benzo[d][1,3]dioxolane with a substituent; The substituent in Q is selected from at least one of the following groups: -CN, -NO2, halogen atom, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C3 alkyl-S(O). p -or halogenated C1-C3 alkyl-S(O) p -; When there are more than two substituents, each substituent may be the same or different, and p is selected from 0, 1 or 2.

2. The compound of formula (I) according to claim 1, its stereoisomers, and agriculturally acceptable salts thereof: in, Het is selected from any one of the following: R a selected from F, CI, Br, I, Ci-C3-alkyl, halo-Ci-C3-alkyl, Ci-C3-alkoxy, halo-Ci-C4-alkoxy or Ci-C3-alkylthio, n is 0, 1, 2, or 3, and when n is selected from 2 or 3, R a the same or different; R1 is selected from F, Cl, Br, I, -CH3, -CHF2, -CH2CHF2, -CF3, -OCH3, -CH2CF3, -OCHF2, -OCH2CHF2, -OCF3, -OCH2CF3, -CN or -NO2; R2 is selected from H, F, Cl, Br, I, -CHF2, -CH2CHF2, -CF3, -CH2CF3, -OCHF2, -OCH2CHF2, -OCF3 or -OCH2CF3; Q is selected from any one of the following groups: X is selected from -CN, -NO2, halogen atom, C1-C3 alkyl, halo-C1-C3 alkyl, C1-C3 alkoxy, halo-C1-C3 alkoxy, C1-C2 alkyl-S(O). p -or C1-C2 haloalkyl-S(O) p -, p is selected from 1 or 2; m is selected from 0, 1, 2, 3, 4 or 5; and when m is selected from 2, 3, 4 or 5, X is the same or different; k is selected from 0, 1, 2, 3 or 4; and when n is selected from 2, 3 or 4, X is the same or different; o is selected from 0, 1, 2, or 3; and when o is selected from 2 or 3, X is the same or different; r is selected from 0, 1, or 2; and when r is selected from 2, X is either the same or different.

3. The compound of formula (I) according to claim 2, its stereoisomers, and its agriculturally acceptable salts: in, Het is selected from any one of the following groups: R a selected from F, Cl, Br, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2F, -CF2H, -CF3, -OCH3, -OCH2CH3, -OCH(CH3)2, -OCF2H, -OCF3, -SCH3, -SCH2CH3, -SCH2CH2CH3 or -SCH(CH3)2; R1 is selected from Cl, Br, I, -CHF2, -CF3, -OCH3, -OCF3, -OCHF2, -CN, or -NO2; R2 is selected from -CHF2, -CF3, -OCHF2, or -OCF3; Q is selected from any one of the following groups: The F2, -OCF3, -OCH2CF3, -SOCH3, -SOCH2CH3, -SO2CH3, -SO2CH2CH3, -SOCF3, -SOCH2CF3, -SO2CF3 or -SO2CH2CF3.

4. The compound of formula (I) according to claim 3, its stereoisomers, and its agriculturally acceptable salts: in, Het is selected from any one of the following: R1 is selected from Br or I; R2 is selected from -CF3 or -OCHF2; Q is selected from any one of the following groups:

5. The compound of formula (I) according to claim 4, its stereoisomers, and its agriculturally acceptable salts: in, Het is selected from any one of the following: R1 is selected from Br or I; R2 is selected from -CF3; Q is selected from any one of the following groups:

6. A process for the preparation of the compounds of formula (I), their stereoisomers and their agriculturally acceptable salts according to any one of claims 1 to 5, characterized in that: Compound (II) is prepared by reacting a compound of formula (VIII) in an organic solvent in the presence of a base, wherein R1, R2, Het and Q are as defined in any one of claims 1-5.

7. The method of claim 6, wherein, The organic solvent is selected from at least one of pentane, n-hexane, cyclohexane, heptane, octane, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, petroleum ether, diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, ethyl acetate, butyl acetate, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, acetone, butanone, 4-methyl-2-pentanone, cyclohexanone, N-methylpyrrolidone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

8. The method of claim 6, wherein, The base is selected from at least one of 4-dimethylaminopyridine, trimethylamine, triethylamine, diisopropylethylamine, pyridine, 2-methylpyridine, 3-methylpyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene or 2,6-dimethylpyridine.

9. A composition characterized in that, It includes at least one of the compounds of formula (I) as described in any one of claims 1-5, their stereoisomers or salts thereof, wherein the active component is a compound of formula (I), and the composition contains an active component in a weight percentage of 0.1-99.9%.

10. A method of controlling pests, characterized by, The compound of formula (I) as described in any one of claims 1-5, its stereoisomers and agriculturally acceptable salts thereof, or the composition of claim 7, is applied to the pest or its growth environment.

11. The use of a compound of formula (I) as claimed in any one of claims 1-5, its stereoisomers, its agriculturally acceptable salts, or the composition of claim 7 in the control of pests.

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