Diphenylamine compounds and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and specifically relates to diphenylamine compounds and the use thereof. The compounds are as shown in general formula I, wherein R1, R3, X2, X3 and X5 each independently represent hydrogen, halogen, nitro, cyano, etc.; R2 represents haloalkyl; R4 represents nitro or haloalkyl; X1 represents halogen; and X4 represents haloalkyl. The compounds have excellent control effect on pests such as mites.

Description

Diphenylamine compounds and their applications Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to a diphenylamine compound and its applications. Background Technology

[0002] In recent years, due to the long-term use of pest control agents, such as insecticides or fungicides, pests have acquired resistance, becoming difficult to control with existing pesticides or fungicides. Furthermore, some known pest control agents are highly toxic, or some damage ecosystems through their long-term residues. In this context, despite the large number of known insecticides and fungicides, such as JP1983113151A which discloses diphenylamine compounds and their applications as pest control agents, there is still a need to develop new pest control agents with low toxicity and low residue. Summary of the Invention

[0003] To address the aforementioned problems in the prior art, this invention provides a diphenylamine compound and its applications. The compound exhibits excellent control effects against harmful organisms such as mites.

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

[0005] A diphenylamine compound as shown in Formula I:

[0006] Wherein, R1, R3, X2, X3, and X5 independently represent hydrogen, halogen, nitro, cyano, unsubstituted or selected from halogen, -OR 11 -S(O) n R 11 or-(CO)OR 11 At least one substituent of the alkyl, alkenyl, ynyl, cycloalkyl or cycloalkylalkyl, trialkylsilyl, aryl, heterocyclic, -OR 11 , -(CO)R 11 , -(CS)R 11 -(CO)OR 11 , -(CO)N(R 11 )2,-(CS)N(R 11 )2, -N(R 11 )2,-S(O) n R 11 or -SO2N(R) 11 )2;

[0007] R2 represents a haloalkyl group;

[0008] R4 represents nitro or haloalkyl;

[0009] X1 represents halogen;

[0010] X4 represents a haloalkyl group;

[0011] R 11 Each group independently represents hydrogen, aryl, heterocyclic, or unsubstituted or selected from halogens, -OR 12 -S(O) n R 12 or-(CO)OR 12 The alkyl, alkenyl, ynyl, cycloalkyl, or cycloalkylalkyl groups substituted by at least one substituent are included.

[0012] R 12 Each can independently represent hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, cycloalkenyl, aryl, or heterocyclic groups;

[0013] The aforementioned "heterocyclic" or "aryl" group is independently unsubstituted or substituted with a group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl substituted with alkyl or halogen, phenyl, and phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy. 21 -SR 21 -(CO)OR 21 , -S(O) n R 21 , -N(R 21 )2 or -O-alkylene-(CO)OR 21 The ring is substituted by at least one group, or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-.

[0014] n is 0, 1, or 2;

[0015] R 21 Each is independently hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy.

[0016] In one specific embodiment, R1, R3, X2, X3, and X5 independently represent hydrogen, halogen, nitro, cyano, unsubstituted or selected from halogen, -OR 11 -S(O) n R 11 or-(CO)OR 11At least one substituent of which is a C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C8 alkyl, triC1-C8 alkylsilyl, aryl, heterocyclic, -OR 11 , -(CO)R 11 , -(CS)R 11 -(CO)OR 11 , -(CO)N(R 11 )2,-(CS)N(R 11 )2, -N(R 11 )2,-S(O) n R 11 or -SO2N(R) 11 )2;

[0017] R2 represents a halogenated C1-C8 alkyl group;

[0018] R4 represents nitro or halo-C1-C8 alkyl;

[0019] X4 represents a halogenated C1-C8 alkyl group;

[0020] R 11 Each group independently represents hydrogen, aryl, heterocyclic, or unsubstituted or selected from halogens, -OR 12 -S(O) n R 12 or-(CO)OR 12 The C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C8 alkyl groups are substituted by at least one substituent.

[0021] R 12 Each of these groups independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, or heterocyclic groups.

[0022] The aforementioned "heterocyclic" or "aryl" is independently unsubstituted or substituted with a group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl or halogen, phenyl, and phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halo-C1-C8 alkoxy, -OR 21 -SR21 -(CO)OR 21 , -S(O) n R 21 , -N(R 21 )2 or -O-(C1-C8 alkylene)-(CO)OR 21 The ring is substituted by at least one group, or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-.

[0023] R 21 Each is independently hydrogen, C1-C8 alkyl, halo-C1-C8 alkyl, phenyl, or a phenyl group substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy, or halo-C1-C8 alkoxy.

[0024] In one specific embodiment, R1, R3, X2, X3, and X5 independently represent hydrogen, halogen, nitro, cyano, unsubstituted or selected from halogen, -OR 11 -S(O) n R 11 or-(CO)OR 11 At least one substituent may be a C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl-C1-C6 alkyl, triC1-C6 alkylsilyl, aryl, heterocyclic, or -OR 11 , -(CO)R 11 , -(CS)R 11 -(CO)OR 11 , -(CO)N(R 11 )2,-(CS)N(R 11 )2,-N(R 11 )2,-S(O) n R 11 or -SO2N(R) 11 )2;

[0025] R2 represents a halo-C1-C6 alkyl group;

[0026] R4 represents nitro or halo-C1-C6 alkyl;

[0027] X4 represents a halogenated C1-C6 alkyl group;

[0028] R 11 Each group independently represents hydrogen, aryl, heterocyclic, or unsubstituted or selected from halogens, -OR 12 -S(O) n R12 or-(CO)OR 12 The C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl-C1-C6 alkyl groups are substituted by at least one substituent.

[0029] R 12 Each of these groups independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, or heterocyclic groups.

[0030] The aforementioned "heterocyclic group" or "aryl group" is independently unsubstituted or substituted with a group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl or halogen, phenyl, and phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo-C1-C6 alkoxy, -OR 21 -SR 21 -(CO)OR 21 , -S(O) n R 21 , -N(R 21 )2 or -O-(C1-C6 alkylene)-(CO)OR 21 The ring is substituted by at least one group, or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-.

[0031] R 21 Each is independently hydrogen, C1-C6 alkyl, halo-C1-C6 alkyl, phenyl, or a phenyl group substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy, or halo-C1-C6 alkoxy.

[0032] In the definitions of compounds shown in the above general formulas and in all the following structural formulas, the technical terms used, whether alone or in compound terms, represent the following substituents: alkyl groups having more than two carbon atoms can be straight-chain or branched. For example, the compound term "-O-alkylene-(CO)OR". 21"The alkylene group can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. The alkyl group is, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl, or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl, and 1,3-dimethylbutyl. Similarly, the alkenyl group is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl." -yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl. Alkynyl groups are, for example, ethynyl, propynyl, but-2-yn-1-yl, but-3-yn-1-yl, and 1-methylbut-3-yn-1-yl. Multiple bonds can be in any position in each unsaturated group. Cycloalkyl groups are carbocyclic saturated ring systems having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Similarly, cycloalkenyl groups are monocyclic alkenyl groups having, for example, three to six carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, where double bonds can be in any position. Halogens are fluorine, chlorine, bromine, or iodine.

[0033] Unless otherwise specified, the term "aryl" in this invention includes, but is not limited to, phenyl, naphthyl, and... The "heterocyclic group" includes, but is not limited to, saturated or unsaturated non-aromatic cyclic groups. And, including but not limited to, heteroaryl groups, i.e., aromatic cyclic groups containing, for example, 3 to 6 ring atoms and optionally fused with benzo[a] rings, wherein 1 to 4 (e.g., 1, 2, 3, or 4) heteroatoms are selected from oxygen, nitrogen, and sulfur, for example

[0034] The terms "optional" or "optionally" mean that the event or situation described below may or may not occur, and the description includes instances where said event or situation occurs and instances where said event or situation does not occur. For example, the term "optionally...substituted" means that the specified atom or group is unsubstituted or substituted by one or more substituents. If a group is substituted by a group, this should be understood to mean that the group is substituted by one or more groups, either the same or different, selected from those groups mentioned. Furthermore, the same or different substitution characters contained in the same or different substituents are chosen independently and may be the same or different. This also applies to ring systems formed from different atoms and units. Meanwhile, the scope of the claims excludes compounds that are chemically unstable under standard conditions, as known to those skilled in the art.

[0035] Furthermore, unless otherwise specified, the phrase "replaced by at least one group" in this invention refers to being replaced by, for example, 1, 2, 3, 4, or 5 groups; groups without specific attachment positions (including heterocyclic groups, aryl groups, etc.) can be attached at any position, including positions attached to C or N; if it is substituted, the substituent can also be substituted at any position, as long as it conforms to the rules of chemical bond attachment. For example, a heteroaryl group substituted by one methyl group. Can represent wait.

[0036] Compounds of Formula I, in their respective free or salt forms, and where appropriate, their tautomers, may exist as one of the possible isomers or as mixtures thereof, for example, as pure isomers, such as enantiomers and / or diastereomers, or as mixtures of isomers, such as mixtures of enantiomers, such as racemic mixtures, diastereomer mixtures, or racemic mixtures, depending on the number of asymmetric carbon atoms present in the molecule, their absolute and relative configurations, and / or on the configuration of the non-aromatic double bonds present in the molecule; the present invention relates to these pure isomers and also to all possible mixtures of isomers and should be understood in this sense in each of the above and below, even if stereochemical details are not specifically mentioned in each case. The present invention therefore covers all such isomers and tautomers and mixtures thereof in all proportions, together with isotopic forms, such as deuterated compounds.

[0037] In another embodiment, Formula I is also understood to include their salts or hydrates. Exemplary salts include, but are not limited to, hydrochlorides, hydrobroms, and hydroiodates.

[0038] Those skilled in the art will also understand that, unless otherwise stated, additional substitutions are permitted, provided that the rules of chemical bonding and strain energy are satisfied and the product still exhibits insecticidal activity.

[0039] Another embodiment of this application is a method for preparing the diphenylamine compound, comprising the following steps:

[0040] The substituents R1, R2, R3, R4, X1, X2, X3, X4, and X5 are defined as described above, and Hal represents halogen.

[0041] In one specific embodiment, the reaction is carried out in the presence of a solvent.

[0042] In another specific embodiment, a base is added during the reaction process.

[0043] In one specific embodiment, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, or ethyl acetate.

[0044] In one specific embodiment, the base is selected from at least one of inorganic bases (such as NaH, KH, K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KOAc, AcONa, K3PO4, t-BuONa, EtONa, NaOH, KOH, NaOMe, etc.) or organic bases (such as pyrazole, triethylamine, DIEA / DIPEA, etc.).

[0045] Preferably, the compounds of this application are applied in formulation form, said formulation comprising one or more compounds of Formula I and a botanically acceptable carrier. The concentrated formulation may be dispersed in water or other liquids for application, or the formulation may be a dust or granules that can be applied immediately without further processing. The formulation may be prepared according to methods commonly used in the field of agricultural chemistry.

[0046] This application contemplates the use of all media through which the one or more compounds can be formulated for delivery and use as fungicides / insecticides. Typically, the formulation is applied as an aqueous suspension or emulsion. The suspension or emulsion can be prepared from water-soluble, water-suspendable, or emulsifiable formulations, which are generally referred to as wettable powders when the water-soluble, water-suspendable, or emulsifiable formulation is a solid; or as emulsifiable oils, aqueous suspensions, or suspension concentrates when the water-soluble, water-suspendable, or emulsifiable formulation is a liquid. It is readily understood that any substance capable of incorporating these compounds can be used, provided that the desired use is achieved without significantly impairing the activity of these compounds as antifungals / insecticides.

[0047] Wettable powders that can be pressed into water-dispersible particles comprise a homogeneous mixture (intimate mixture) of one or more compounds of Formula I, an inert carrier, and a surfactant. The concentration of the compound in the wettable powder, by weight of the total wettable powder, can range from about 10 wt% to about 90 wt%, more preferably from about 25 wt% to about 75 wt%. In the preparation of the wettable powder formulation, the compound can be mixed with any finely pulverized solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite, diatomaceous earth, refined silicates, etc. In this operation, the finely pulverized carrier and surfactant are typically blended with and ground with the compound.

[0048] The emulsifiable concentrate of Formula I can be contained in a suitable liquid at a conventional concentration, for example, from about 1 wt% to about 50 wt%, based on the total weight of the emulsifiable concentrate. The compound can be dissolved in an inert support, which is a mixture of a water-miscible solvent or a water-immiscible organic solvent and an emulsifier. The emulsifiable concentrate can be diluted with water and oil to form a spray mixture in the form of an oil-in-water emulsion. Useful organic solvents include the aromatic fractions of petroleum, particularly the high-boiling cycloalkane and alkene fractions, such as heavy aromatic naphtha. Other organic solvents may also be used, such as terpene solvents including rosin derivatives, aliphatic ketones such as cyclohexanone, and complex alcohols such as 2-ethoxyethanol.

[0049] The emulsifiers that can be advantageously used in this application can be readily determined by those skilled in the art and include a variety of nonionic emulsifiers, anionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers, or blends of two or more emulsifiers. Examples of nonionic emulsifiers used to prepare the emulsifiable concentrates include polyalkylene glycol ethers, and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines, or fatty acids with ethylene oxide or propylene oxide, such as ethoxylated alkylphenols and carboxylic acid esters dissolved in polyols or polyoxyethylenes. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include oil-soluble salts of alkyl aryl sulfonic acids (e.g., calcium salts), oil-soluble salts of sulfated polyglycol ethers, and suitable salts of phosphorylated polyglycol ethers.

[0050] Representative organic liquids that can be used in the preparation of the emulsifiable concentrates of the compounds of this application are aromatic liquids such as xylene and propylbenzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkylamides of various fatty acids, especially dimethylamides and diol derivatives of fatty glycols such as n-butyl ether, ethyl ether or methyl ether of diethylene glycol, methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oils, aromatic solvents, paraffin oils, etc.; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, etc.; esters of the above vegetable oils; etc. Mixtures of two or more organic liquids can also be used in the preparation of the emulsifiable concentrate. Organic liquids include xylene and propylbenzene fractions, with xylene being the most preferred in some cases. Surfactant dispersants are typically used in liquid formulations, and the amount of the surfactant dispersant is from 0.1 to 20 wt% based on the total weight of the dispersant and one or more compounds. The formulation may also contain other compatible additives, such as plant growth regulators and other bioactive compounds used in agriculture.

[0051] Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of formula I dispersed in an aqueous medium, with a concentration of about 1 wt% to about 50 wt% by weight of the total aqueous suspension. The suspension is prepared by finely grinding one or more of the compounds, and vigorously mixing the ground compounds into a medium composed of water and surfactants selected from the same type described above. Other components, such as inorganic salts and synthetic or natural gums, may also be added to increase the density and viscosity of the aqueous medium.

[0052] Compounds of Formula I can also be applied in granular form, particularly for application to soil. By total weight, the granular formulation typically contains about 0.5 wt% to about 10 wt% of the compound dispersed in an inert carrier, which is wholly or mostly composed of coarsely pulverized inert material, such as attapulgite, bentonite, diatomaceous earth, clay, or similar inexpensive materials. The formulation is typically prepared by dissolving the compound in a suitable solvent and applying it to a granular carrier pre-formed to a suitable particle size (ranging from about 0.5 to about 3 mm). The suitable solvent is one in which the compound is substantially or completely soluble. The formulation can also be prepared by forming the carrier, compound, and solvent into a paste or ointment, then crushing and drying to obtain the desired granular particles.

[0053] Powders containing compound I can be prepared by homogenizing one or more of the compounds in powder form with a suitable powdery agricultural carrier, such as kaolin clay, crushed volcanic rock, etc. The powder may suitably contain about 1% to about 10% of the compounds by weight.

[0054] The formulation may additionally contain co-active surfactants to enhance the deposition, wetting, and penetration of the compound onto target crops and microorganisms. These co-active surfactants may optionally be used as a component of the formulation or as a tank mixture. The amount of the co-active surfactant is typically from 0.01 to 1.0 vol% by water spray volume, preferably 0.05 to 0.5 vol%. Suitable co-active surfactants include, but are not limited to, ethoxylated nonylphenol, ethoxylated synthetic alcohols or ethoxylated natural alcohols, sulfosuccinates or sulfosuccinates, ethoxylated organosiloxanes, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrates (mineral oil (85%) + emulsifier (15%)); nonylphenol ethoxylates; benzyl cocoyl dimethyl quaternary ammonium salts; blends of petroleum hydrocarbons, alkyl esters, organic acids, and anionic surfactants; C9-C 11 Alkyl polyglycosides; phosphorylated alcohol ethoxylates; natural primary alcohols (C 12 -C 16Ethoxylated compounds; di-sec-butylphenol EO-PO block copolymers; polysiloxane-methyl-terminated compounds; nonylphenol ethoxylated compounds + urea ammonium nitrate; emulsified methylated seed oils; tridecyl alcohol (synthetic) ethoxylated compounds (8EO); tallow amine ethoxylated compounds (15EO); PEG (400) dioleate-99. The formulations may also comprise oil-in-water emulsions, such as those disclosed in U.S. Patent Application Serial No. 11 / 495,228, the contents of which are incorporated herein by reference.

[0055] The formulation may optionally include a combination containing other pesticide compounds. These additional pesticide compounds may be fungicides, insecticides, herbicides, nematicides, acaricides, arthropodicides, fungicides, or combinations thereof, which are compatible with the compound of this application in the chosen application medium and do not antagonize the activity of the compound of this application. Therefore, in the described embodiments, the other pesticide compounds are used as supplementary toxins for the same or different pesticide uses. The Formula I compound and the pesticide compound may typically be present in combination in a weight ratio of 1:100 to 100:1.

[0056] In addition, another embodiment of this application is an insecticidal composition comprising a biologically effective amount of a compound of formula I; preferably, in one embodiment, it further comprises a formulation adjuvant; in another embodiment, it further comprises other active ingredients.

[0057] Another embodiment of this application is the use of the compound of formula I or the above-described insecticidal composition in the control of pests.

[0058] Another embodiment of this application is a method for controlling pests, comprising exposing the pest or its environment to a biologically effective amount of a compound of formula I or the above-described insecticidal composition.

[0059] In one specific embodiment, a biologically effective amount of the compound of the present invention or the composition as defined above is used to treat a pest, its food source, its habitat or breeding ground, or cultivated plants in which the pest grows or may grow, plant propagation material (such as seeds), soil, area, material or environment, or material, cultivated plants, plant propagation material (such as seeds), soil, surface or space to be protected against pest infestation or contamination.

[0060] The term “pest control” refers to the suppression of pest development (including death, reduced food intake, and / or mating disruption), and related expressions can be defined similarly.

[0061] Furthermore, the compounds described in this application can be combined with other insecticides, including insecticides, nematicides, acaricides, and arthropodicides, which are compatible with the compounds of this application in the chosen application medium and do not antagonize the activity of the compounds of this application to form an insecticidal mixture. Common insecticides include, but are not limited to: 1,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, and amiton oxalate. oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid (acid), bromofenvinfos, bromocyclen, bromo-DDT, bromophos, ethyl bromophos,Bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride Hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin I II), Cinerins, Cismethrin, Cloethocarb, Closantel, Clothianidin, Copper Acetatearsenite, Copper Arsenate, Copper Naphthenate, Copper Oleate, Coumaphos, Comithoate,Crotamiton, Crotoxyphos, Crufomate, Cryolite, Cyanofenphos, Cyanophos, Cyanthoate, Cyantraniliprole, Cycyclethrin, Cyprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Cyphenothrin, Cyromazine, Cythioate, DDT, Furadan ecarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth earth), dizinon, dichlorvos, dichlorvos, dichlorvos, diresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimethoate Fox), Dimetan, Dimethoate, Dimethrin, Dimethylvinphos, Dimetilan, Dinex, Dinex-diclexine, Dinoprop, Dinosam, Dinotefuran, Diofenolan, Dioxabenzofos, DioxacarbDioxathion, disulfoton, dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectinbenzoate, EMPC, emargine Penthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide oxide), etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, Fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuronFlucythrinate, flufenerim, flufenoxuron, flufenprox, fluvalinate, fonofos, formetanate, formetanate hydrochloride, formothion, formparanate, formparanate hydrochloride Hydrochloride, Fosmethilan, Fospirate, Fosthietan, Furathiocarb, Furethrin, Gamma-cyhalothrin, Gamma-HCH, Halfenprox, Halofenozide, HCH, HEOD, Heptachlor, Heptenophos, Heterophos, Hexaflumuron, HHDN, Hydamethylnon, Hydrocyanide cyanide), hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I Juvenile hormone I), juvenile hormone II, juvenile hormone III, kelevan, kinoprene,Lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride Chloride, mesulfenfos, metaflumizone, methicrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, emthoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methyl chloroform Chloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycinoxime, mipafox, mirex, molosultap, monocrotophos, monomehypo Monosultap, Morphothion, Moxidectin, Naftalofos, Naled, Naphthalene, Nicotine, Nifluridide, Nitenpyram, Nithiazine, Nitrilacarb, Novaluron, Noviflumuron, Omethoate, OxamylOxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate ( Phosphatate, Phosalone, Phosfolan, Phosmet, Phosnichlor, Phosphamidon, Phosphine, Phoxim, Phoxim-methyl, Pirimetaphos, Pirimicarb, Pirimiphos-ethyl, Pirimiphos-methyl, Potassium arsenite, Potassium thiocyanate, PP'-DDT, Prallethrin, Precocene I, Precocene II, Precocene III III), primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, piraclofos, pirafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II II), pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen,Pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafluorosilicate, sodium thiocyanate thiocyanate), sophamide, spintoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfurylfluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, pyrimethanil Bupirimfos, Teflubenzuron, Tefluthrin, Temephos, TEPP, Terallethrin, Terbufos, Tetrachloroethane, Tetrachlorvinphos, Tetramethrin, Tetramethylfluthrin, Theta-cypermethrin, Thiacloprid, Thiamethoxam, Thiocrofos, Thiocarboxime, Thiocyram, Thiocyram oxalateThiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazam The following pesticides are permitted: triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethocarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combination thereof.

[0062] The compounds according to the invention can act on all or individual developmental stages of normally sensitive and resistant animal pests (such as insects or representatives of mites). The insecticidal or acaricidal activity of the compounds according to the invention can be manifested directly, i.e., for example, by the destruction of pests during molting, which occurs immediately or after a period of time; or indirectly, for example, by reducing oviposition and / or hatching rates, with good activity corresponding to a destruction rate (mortality rate) of at least 50%-60%.

[0063] Examples of animal pests are:

[0064] - From mites, for example,

[0065] The genera *Acalitus* spp., *Acaricalus* spp., *Aceria* spp., *Acerola spp.* ...

[0066] - From lice, for example,

[0067] The genera *Hydrocotyle*, *Gnaphalium*, *Hydrocotyle*, *Pemphigus*, and *Psyllid*;

[0068] - From Coleoptera, for example

[0069] *Astylus atromaculatus*, *Ataenius* spp., *Atomaria linearis*, *Cerotoma* spp., *Diloboderus abderus*, *Eremnus* spp., *Lagria vilosa*, *Lagria vilosa*, *Liogenys* spp., *Maecolaspis* spp., *Megascelis* spp., *Melighetes aeneus*, *Myochrous* Armatus, genus *Otiorhynchus* spp., genus *Otiorhynchus* ...

[0070] -From the order Diptera, for example,

[0071] The genera *Aedes*, *Anopheles*, *Bactrocea oleae*, *Bradysia*, *Bradysia* spp., *Blisterella*, *Fungi*, *Culex*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Gastropoda*, *Geomyza tripunctata*, *Trichogramma*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Gallus*, *Fungi*, *Gallus*, *Fungi*, *Gallus*, *Fungi*, *Gallus*, *Fungi*, *Gallus*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, *Fungi*, and *Gallus*.

[0072] - From Hemiptera, for example,

[0073] *Acanthocoris scabrator*, *Acanthocoris*, *Amblypelta nitida*, *Bathycoelia thalassina*, *Acanthocoris*, *Clavigralla*, *Clavigralla tomentosicollis*, *Creontiades*, *Dichelops furcatus*, *Edessa*, *Euchistus*, *Eurydema pulchrum*, *Eurydema*, *Horcias nobilellus*, *Horcias*, *Murgantia*, *Murgantia* histrionic), Neomegalotomus spp., Nesidiocoris tenuis, green bug, Nysius simulans, Oebalus insularis, skin bug, wall bug, red assassin bug, cocoa mirid bug, Scaptocoris castanea, Scotinophara spp., Thyanta spp., trigger bug, cassava lace bug;

[0074] - From the order Hemiptera, for example,

[0075] The genera *Aphididae*, *Adalges* spp., *Agalliana ensigera*, *Agonoscena targionii*, *Aleurodicus* spp., *Aleurocanthus* spp., *Aleurothrixus floccosus*, *Aleyrodes brassicae*, *Amarasca biguttula*, *Amritodus atkinson*, *Aspidiotus* spp., *Aphididae*, *Aphid*, *Bactericera cockerelli*, *Brachycaudus* spp., *Cavariella aegopodii* Scop.), wax scale, brown round scale, net-seed grass leaf round scale, Cicadella spp., large white leafhopper (Cofana spectra), cryptic aphid, Cicadulina spp., brown soft scale, corn yellow-winged leafhopper, naked whitefly, citrus psyllid, wheat double-tailed aphid, western round-tailed aphid, small green leafhopper, apple woolly aphid, grape spotted leafhopper, wax clam, red gum psyllid (Glycaspis brimblecombei), cabbage tube aphid, large tail aphid (Hyalopterus spp.), super-tumor aphid, lemon green leafhopper (Idioscopus clypealis), Jacobiasca lybica, gray planthopper, ball scale, oyster shield scale, turnip aphid (Lopaphis erysimi), Lyogenys maidis, long tube aphid, Mahanarva spp., moth waxfly family (Metcalfa *Prunus pruinosa*, *Myndus crudus*, *Aphidus*, *Aphidus*, *Nilaparvata*, *Nilaparvata* spp., *Aphidus ruthae*, *Odonaspis ruthae*, *Aphidus sugarcane*, *Aphidus rubescens*, *Aphidus koscherii*, *Aphidus ...), white-backed planthopper, triangular leafhopper (Spissistilus festinus), striped planthopper (Tarophagus Proserpina), aphids, whiteflies, Tridiscus sporoboli, sunflower mealybugs (Trionymus spp.), African psyllids, bellows scale, Zygina flammigera, Zyginidia scutellaris;

[0076] - From Hymenoptera, for example,

[0077] The genera *Gilpinia* include: *Gilpinia* spp., *Gilpinia* var. *brevicornu* ... and *Gilpinia* var. *brevicornu*.

[0078] - From the order Isoptera, for example,

[0079] *Corniternes cumulans*, *Corniternes*, *Corniternes*, *Corniternes*, *Corniternes*, *Corniternes*, *Corniternes*, *Corniternes*; Tropical fire ants

[0080] -From Lepidoptera, for example,

[0081] Genus *Longwinged Roller*, Genus *Brown-banded Roller*, Genus *Clearwing*, Genus *Noctuid*, Cotton Leafworm, *Amylois spp.*, *Lysimachia spp.*, *Yellow Roller*, *Argyresthia spp.*, *Branch Roller*, *Striped Roller*, Cotton Miner, Corn Locust, Powdered Leaf Moth, Peach Fruit Borer, *Grass Moth*, *Leaf Roller*, *Chrysoteuchia topiaria*, Grape Fruit Borer, *Leaf Roller*, *Cloud Roller*, *Striped Roller*, *Shelled Moth*, Lepidoptera (White Butterfly), *Cosmophila flava*, *Cabbage Moth*, *Apple Carpet Moth*, *Small Roller*, *Boxwood Moth*, *Boxwood Silkworm*, *Stem Grass Moth*, Sudan Cotton Bollworm, *Diamond Moth*, *African Stem Moth*, *Powdered Leaf Moth*, *Epinotia* spp.), Fine-spotted Light Moth, Etiella zinckinella, Flower Roller, Ring-striped Moth, Yellow Tussock Moth, Root-cutting Moth, Feltia jaculiferia, Grapholita spp., Green Green Moth, Root-cutting Moth, Cabbage Moth, Herpetogramma spp., Fall White Moth, Tomato Codling Moth, Lasmopalpus lignosellus, Spiral Leaf Miner, Leaf Miner, Grape Flower Roller, Loxostege bifidalis, Tussock Moth, Leaf Miner, Curtain Leaf Moth, Cabbage Noctuid Moth, Tobacco Hawk Moth, Mythimna spp., Noctuid Moth, Autumn Geyser, Orniodes indica, European Corn Borer, Small Leaf Roller, Brown Leaf Roller, Small-eyed Noctuid Moth, Stem-boring Noctuid Moth, Pectinophora gossypiela, coffee leafminer, armyworm, potato leafminer, cabbage white butterfly, cabbage white butterfly, diamondback moth, bud moth, leaf roller, mint gray moth, western bean bud moth (Richia albicosta), white rice borer (Scirpophaga spp.), stem borer, long-haired leaf roller, gray-winged leaf roller, cotton leaf roller, clearwing moth, leafroller, powdery leafminer, tomato leafminer, and nest moth;

[0082] - From the order Trichophyton, for example,

[0083] The genera *Damalinea* and *Damalinea*;

[0084] -From the order Orthoptera, for example,

[0085] Cockroaches, small cockroaches, mole crickets, Madeira cockroaches, locusts, American mole crickets (Neocurtilla hexadactyla), large cockroaches, Scapteriscus spp., and desert locusts;

[0086] - From the order Psittaciformes, for example,

[0087] Booklice genus;

[0088] - From the order Siamese, for example,

[0089] The genera *Lepidoptera*, *Ctenophora*, and *Euphorbia*;

[0090] - From the order Thysanoptera, for example

[0091] Calliothrips phaseoli, genus *Calliothrips*, genus *Calliothrips*, genus *Calliothrips*, genus *Parthenothrips* spp., genus *Scirtothrips aurantii*, genus *Sericothrips* variabilis, genus *Calliothrips*, genus *Calliothrips*;

[0092] -From the order Thysanura, for example,

[0093] Silverfish.

[0094] The content of the compound as an active ingredient can be varied as needed, and the compound as an active ingredient can be used in a proportion appropriately selected within the range of 0.01-90 parts by weight per 100 parts of the agricultural and horticultural reagent of the present invention. For example, in powder, granule, emulsion or wettable powder, a suitable content of the compound as an active ingredient is 0.01-50 parts by weight (0.01-50% by weight of the total weight of the agricultural and horticultural insecticide).

[0095] The dosage of the agricultural and horticultural insecticide of the present invention varies with various factors, such as the purpose, the pest to be controlled, the plant's growth status, the pest's emergence trend, climate, environmental conditions, formulation, application method, application site, and application time. It can be appropriately selected within the range of 0.001 g to 10 kg, preferably 0.01 g to 1 kg (for the active ingredient compound) per 10 areals, depending on the purpose.

[0096] It will be apparent to those skilled in the art that any range or desired value given herein can be extended or modified without losing the desired effect. Detailed Implementation

[0097] 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.

[0098] Given the economic efficiency and diversity of the compounds, we preferentially synthesized a number of compounds, some of which are listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustration of the present invention and do not limit the invention. Those skilled in the art should not interpret this as limiting the scope of the above-mentioned subject matter of the invention to the following compounds.

[0099] Table 1. Compound structures and their properties 1 H NMR values

[0100] 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.

[0101] 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 shown below are either commercially available or can be easily prepared by those skilled in the art.

[0102] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0103] 1. Synthesis of Compound 1

[0104] (1) Compound 1-1 (12 g, 56.34 mmol) was weighed and dissolved in 200 mL of DMF. Then, NBS (11.0 g, 61.97 mmol) was added to the solution, and the mixture was stirred overnight at room temperature. After the reaction was monitored by LCMS until complete, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 10 / 90) to give compound 1-2 (11.56 g, 70.4%).

[0105] (2) Dissolve compound 1-2 (11.56 g, 39.5 mmol) in 120 mL of DMF, then cool the solution in an ice bath. Add 60% NaH (3.16 g, 79.0 mmol) in the ice bath. After the addition is complete, keep the solution in the ice bath and stir for 30 minutes. Then add compound 1-3 (10.68 g, 39.5 mmol) to the reaction solution. After the addition is complete, transfer the reaction solution to room temperature and continue stirring for 1 hour. Monitor the reaction to ensure it is complete using LCMS. Slowly pour the reaction solution into ice water to quench the reaction. Extract with ethyl acetate. Wash the organic phase three times with saturated brine, dry and concentrate. Purify the residue by column chromatography (EA / PE = 10 / 90) to obtain compound 1 (6.24 g, 30%).

[0106] 2. Synthesis of Compound 4

[0107] Compound 4-1 (300 mg, 0.90 mmol) was dissolved in 10 mL of DMF. NaH (72 mg, 1.8 mmol) was added under ice bath conditions, and the mixture was stirred at room temperature for 0.5 h. Compound 1-3 (267 mg, 0.99 mmol) was added under ice bath conditions, and the mixture was stirred at room temperature for 0.5 h. After the reaction was complete, ice water was added to quench the reaction, and EA was added for extraction. The mixture was purified under normal phase to give compound 4 (245 mg, 0.43 mmol, yield = 48%).

[0108] 3. Synthesis of Compound 5

[0109] (1) Compound 5-1 (500 mg, 2.5 mmol) was weighed and dissolved in 10 mL of DMF. Then, NBS (0.49 g, 2.7 mmol) was added to the solution, and the reaction was carried out overnight at 25 °C. After the reaction was complete, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried and concentrated. The residue was purified by column chromatography (EA / PE = 5 / 95) to obtain compound 5-2 (0.2 g, 28%).

[0110] (2) Dissolve compound 5-2 (100 mg, 0.36 mmol) in 5 mL of DMF, cool to 0 °C, add NaH (10 mg, 0.72 mmol, 60%), and stir in an ice bath for 30 minutes after the addition is complete. Then add compound 1-3 (97.2 mg, 0.36 mmol) to the reaction solution. After the addition is complete, transfer the reaction solution to room temperature and continue stirring for 1 hour until the reaction is complete. Slowly pour the reaction solution into ice water to quench the reaction, extract with ethyl acetate, wash the organic phase three times with saturated brine, dry and concentrate, and purify the residue by column chromatography (EA / PE = 5 / 95) to obtain compound 5 (50 mg, 27%).

[0111] 4. Synthesis of Compound 6

[0112] (1) Compound 6-1 (1 g, 5 mmol) was weighed and dissolved in 10 mL of DMF. Then, NCS (0.73 g, 5.5 mmol) was added to the solution, and the reaction was carried out overnight at room temperature. After the reaction was complete, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 5 / 95) to give compound 6-2 (1 g, 86%).

[0113] (2) Dissolve compound 6-2 (0.3 g, 1.3 mmol) in 10 mL of DMF, cool to 0 °C, add NaH (104 mg, 2.6 mmol, 60%), and stir in an ice bath for 30 minutes after the addition is complete. Then add compound 1-3 (351 mg, 1.3 mmol) to the reaction solution. After the addition is complete, transfer the reaction solution to room temperature and continue stirring for 1 hour until the reaction is complete. Slowly pour the reaction solution into ice water to quench the reaction, extract with ethyl acetate, wash the organic phase three times with saturated brine, dry and concentrate, and purify the residue by column chromatography (EA / PE = 5 / 95) to obtain compound 6 (241 mg, 40%).

[0114] 5. Synthesis of Compound 8

[0115] (1) Compound 8-1 (1.674 g, 5.5 mmol) was weighed and dissolved in 10 mL of DMF. Then NCS (1.5 g, 11.0 mmol) was added to the solution. The mixture was stirred overnight at room temperature. After the reaction was complete as monitored by LCMS, it was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried and concentrated. The residue was purified by column chromatography (EA / PE = 10 / 90) to obtain compound 8-2 (1.597 g, 86%).

[0116] (2) Compound 8-2 (340 mg, 1.0 mmol) was dissolved in 3 mL of DMF. The solution was then cooled in an ice bath. NaH (80 mg, 2.0 mmol) with a content of 60% was added in the ice bath. After the addition was complete, the mixture was stirred in the ice bath for 30 minutes. Then, compound 1-3 (270 g, 1.0 mmol) was added to the reaction solution. After the addition was complete, the reaction solution was transferred to room temperature and stirred for 1 hour. The reaction was monitored by LCMS until it was complete. The reaction solution was slowly poured into ice water to quench the reaction. The mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried and concentrated. The residue was purified by column chromatography (EA / PE = 10 / 90) to obtain compound 8 (427 mg, 75%).

[0117] 6. Synthesis of Compound 9

[0118] (1) Weigh compound 9-1 (500 mg, 1.6 mmol) and dissolve it in 20 mL of DMF. Add NBS (321 mg, 1.8 mmol) and stir at room temperature for 4 h. Monitor the reaction to ensure it is complete using LCMS. Extract with ethyl acetate / water, wash the organic phase with saturated brine, dry and concentrate. Purify the residue by column chromatography (EA / PE = 5 / 95) to obtain compound 9-2 (412 mg, 1.0 mmol, 65.6%).

[0119] (2) Compound 9-2 (412 mg, 1.1 mmol) was dissolved in 8 mL DMF, and NaH (94 mg, 2.4 mmol, 60%) was added under ice bath. The mixture was stirred under ice bath for 30 min, and then compound 1-3 (320 mg, 1.2 mmol) was added. The mixture was stirred at room temperature for 1 h. The reaction was monitored by LCMS until it was complete. The mixture was quenched with water, extracted with ethyl acetate, washed with saturated brine, dried and concentrated. The residue was purified by column chromatography (EA / PE = 5 / 95) to give compound 9 (64 mg, 0.11 mmol, 9.7%).

[0120] 7. Synthesis of Compound 10

[0121] (1) Dissolve 10⁻¹ (1.12 g, 1.0 eq) in 20.0 mL of DMF, add NBS (0.96 g, 1.1 eq) in portions, and react at room temperature for 3 h. Take the reaction solution, dilute with acetonitrile, and monitor by LC-MS. The starting material disappears, and the product becomes the main peak. Pour the reaction solution into water and extract three times with ethyl acetate. Combine the organic phases, wash the organic phase once with saturated brine, and concentrate. Purify by column chromatography (EA:PE = 1:10) to obtain a brown oily substance 10⁻² (1.5 g, yield = 90%).

[0122] (2) Dissolve 10⁻² (0.14 g, 1.0 eq) in DMF (5.0 mL), add NaH (36 mg, 2.0 eq) under ice bath conditions, stir for 10 min, and then add 1⁻³ (0.135 g, 1.1 eq). React at room temperature for 3 h. Take the reaction solution, dilute with acetonitrile, and monitor by LC-MS. The starting material disappears, and the product becomes the main peak. Pour the reaction solution into water and extract three times with ethyl acetate. Combine the organic phases, wash the organic phase once with saturated brine, and concentrate. Purify by column chromatography (pure PE) to obtain a yellow solid 10 (113 mg, yield = 45.2%).

[0123] 8. Synthesis of Compound 11

[0124] Dissolve 11-1 (0.14 g, 1.0 eq) in 5.0 mL DMF, add NaH (36 mg, 2.0 eq) under ice bath conditions, stir for 10 min, then add 1-3 (0.135 g, 1.1 eq). React at room temperature for 3 h. Take the reaction solution, dilute with acetonitrile, and monitor by LC-MS. The starting material disappears, and the product becomes the main peak. Pour the reaction solution into water and extract three times with ethyl acetate. Combine the organic phases, wash once with saturated brine, and concentrate. Purify by column chromatography (pure PE) to obtain a yellow solid 11 (116 mg, yield = 47.1%).

[0125] 9. Synthesis of Compound 14

[0126] (1) Compound 14-1 (0.7 g, 3.5 mmol) was weighed and dissolved in 10 mL of DMF. Then, NCS (1.16 g, 8.75 mmol) was added to the solution, and the reaction was carried out overnight at 25 °C. After the reaction was complete, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 5 / 95) to obtain compound 14-2 (350 mg, 37%).

[0127] (2) Dissolve compound 14-2 (0.35 g, 1.3 mmol) in 10 mL of DMF, cool to 0 °C, add NaH (104 mg, 2.6 mmol, 60%), and stir in an ice bath for 30 minutes after the addition is complete. Then add compound 1-3 (351 mg, 1.3 mmol) to the reaction solution. After the addition is complete, transfer the reaction solution to room temperature and continue stirring for 1 hour until the reaction is complete. Slowly pour the reaction solution into ice water to quench the reaction, extract with ethyl acetate, wash the organic phase three times with saturated brine, dry and concentrate, and purify the residue by column chromatography (EA / PE = 5 / 95) to obtain compound 14 (92 mg, 13%).

[0128] 10. Synthesis of Compound 60

[0129] (1) Compound 60-1 (15.87 g, 61.5 mmol) was weighed and dissolved in 200 mL of DMF. Then, NCS (9.17 g, 67.65 mmol) was added to the solution, and the mixture was stirred overnight at room temperature. After the reaction was monitored by LCMS until complete, the mixture was extracted with ethyl acetate. The organic phase was washed three times with saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 10 / 90) to give compound 60-2 (16.93 g, 94%).

[0130] (2) Dissolve compound 60-2 (600 mg, 2.05 mmol) in 5 mL of DMF, then cool the solution in an ice bath. Add 60% NaH (164 mg, 4.10 mmol) in the ice bath. After the addition is complete, keep the solution in the ice bath and stir for 30 minutes. Then add compound 60-3 (625 mg, 2.05 mmol) to the reaction solution. After the addition is complete, transfer the reaction solution to room temperature and continue stirring for 1 hour. Monitor the reaction to ensure it is complete using LCMS. Slowly pour the reaction solution into ice water to quench the reaction. Extract with ethyl acetate. Wash the organic phase three times with saturated brine, dry and concentrate. Purify the residue by column chromatography (EA / PE = 10 / 90) to obtain compound 60 (870 mg, 75%).

[0131] Bioactivity evaluation:

[0132] After dissolving the active ingredient in acetone, the solution was diluted with distilled water to a gradient dosage. Pre-prepared peanut leaf discs were placed in petri dishes, and then sprayed using a spray tower. After spraying, the petri dishes were opened and allowed to air dry completely at room temperature. Test mites of the species *Tetranychus truncatula*, *Tetranychus two-spotted*, and *Tetranychus carmineus*, all with consistent physiological states and kept indoors, were inoculated into the center of the leaf discs. Fifteen test mites of uniform growth were inoculated into each leaf disc, and this was repeated three times. The highest dose of acetone solution served as a control. After inoculation, the mites were placed in a treatment room. The treated mites were then placed in the treatment room under normal rearing conditions. Results were assessed after 48 hours, and mortality rates for each treatment were recorded. Representative data are shown in Table 2. Mortality rate = (Number of dead mites / Number of test mites) × 100%.

[0133] Table 2 Insecticidal activity test results

[0134] Note: N represents no data; reference compound A:

[0135] Meanwhile, numerous tests have revealed that the compounds and their compositions described in this invention exhibit good control activity against various types of pests, such as mites. They are characterized by broad spectrum, high efficiency, and strong systemic activity, and can effectively control harmful organisms, thus possessing certain commercial value.

Claims

1. A diphenylamine compound as shown in Formula I: in, R1, R3, X2, X3, and X5 independently represent hydrogen, halogen, nitro, cyano, unsubstituted or selected from halogen, -OR 11 -S(O) n R 11 or-(CO)OR 11 At least one substituent of the alkyl, alkenyl, ynyl, cycloalkyl or cycloalkylalkyl, trialkylsilyl, aryl, heterocyclic, -OR 11 , -(CO)R 11 , -(CS)R 11 -(CO)OR 11 , -(CO)N(R 11 )2,-(CS)N(R 11 )2, -N(R 11 )2,-S(O) n R 11 or -SO2N(R) 11 )2; R2 represents a haloalkyl group; R4 represents nitro or haloalkyl; X1 represents halogen; X4 represents a haloalkyl group; R 11 Each group independently represents hydrogen, aryl, heterocyclic, or unsubstituted or selected from halogens, -OR 12 -S(O) n R 12 or-(CO)OR 12 The alkyl, alkenyl, ynyl, cycloalkyl, or cycloalkylalkyl groups substituted by at least one substituent are included. R 12 Each can independently represent hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl, cycloalkenyl, aryl, or heterocyclic groups; The aforementioned "heterocyclic" or "aryl" group is independently unsubstituted or substituted with a group selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, cycloalkyl substituted with alkyl or halogen, phenyl, and phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy. 21 -SR 21 -(CO)OR 21 , -S(O) n R 21 , -N(R 21 )2 or -O-alkylene-(CO)OR 21 The ring is substituted by at least one group, or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-. n is 0, 1, or 2; R 21 Each is independently hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy, or haloalkoxy.

2. The diphenylamine compound according to claim 1, characterized in that, R1, R3, X2, X3, and X5 independently represent hydrogen, halogen, nitro, cyano, unsubstituted or selected from halogen, -OR 11 -S(O) n R 11 or-(CO)OR 11 At least one substituent of which is a C1-C8 alkyl, C2-C8 alkenyl, C2-C8 ynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C8 alkyl, triC1-C8 alkylsilyl, aryl, heterocyclic, -OR 11 , -(CO)R 11 , -(CS)R 11 -(CO)OR 11 , -(CO)N(R 11 )2,-(CS)N(R 11 )2, -N(R 11 )2,-S(O) n R 11 or -SO2N(R) 11 )2; R2 represents a halogenated C1-C8 alkyl group; R4 represents nitro or halo-C1-C8 alkyl; X4 represents a halogenated C1-C8 alkyl group; R 11 Each group independently represents hydrogen, aryl, heterocyclic, or unsubstituted or selected from halogens, -OR 12 -S(O) n R 12 or-(CO)OR 12 The C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl-C1-C8 alkyl groups are substituted by at least one substituent. R 12 Each of these groups independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl, or heterocyclic groups. The aforementioned "heterocyclic" or "aryl" is independently unsubstituted or substituted with a group selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halo-C1-C8 alkyl, halo-C2-C8 alkenyl, halo-C2-C8 alkynyl, C3-C8 cycloalkyl substituted with C1-C8 alkyl or halogen, phenyl, and phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halo-C1-C8 alkoxy, -OR 21 -SR 21 -(CO)OR 21 , -S(O) n R 21 , -N(R 21 )2 or -O-(C1-C8 alkylene)-(CO)OR 21 The ring is substituted by at least one group, or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-. R 21 Each is independently hydrogen, C1-C8 alkyl, halo-C1-C8 alkyl, phenyl, or a phenyl group substituted with at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy, or halo-C1-C8 alkoxy.

3. The diphenylamine compound according to claim 1 or 2, characterized in that, R1, R3, X2, X3, and X5 independently represent hydrogen, halogen, nitro, cyano, unsubstituted or selected from halogen, -OR 11 -S(O) n R 11 or-(CO)OR 11 At least one substituent may be a C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl-C1-C6 alkyl, triC1-C6 alkylsilyl, aryl, heterocyclic, or -OR 11 , -(CO)R 11 , -(CS)R 11 -(CO)OR 11 , -(CO)N(R 11 )2,-(CS)N(R 11 )2, -N(R 11 )2,-S(O) n R 11 or -SO2N(R) 11 )2; R2 represents a halo-C1-C6 alkyl group; R4 represents nitro or halo-C1-C6 alkyl; X4 represents a halogenated C1-C6 alkyl group; R 11 Each group independently represents hydrogen, aryl, heterocyclic, or unsubstituted or selected from halogens, -OR 12 -S(O) n R 12 or-(CO)OR 12 The C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl-C1-C6 alkyl groups are substituted by at least one substituent. R 12 Each of these groups independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl, or heterocyclic groups. The aforementioned "heterocyclic" or "aryl" is independently unsubstituted or substituted with a group selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halo-C1-C6 alkyl, halo-C2-C6 alkenyl, halo-C2-C6 alkynyl, C3-C6 cycloalkyl substituted with C1-C6 alkyl or halogen, phenyl, and phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo-C1-C6 alkoxy, -OR 21 -SR 21 -(CO)OR 21 , -S(O) n R 21 , -N(R 21 )2 or -O-(C1-C6 alkylene)-(CO)OR 21 The ring is substituted by at least one group, or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-. R 21 Each is independently hydrogen, C1-C6 alkyl, halo-C1-C6 alkyl, phenyl, or phenyl substituted with at least one group selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy carbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo-C1-C6 alkoxy; Preferably, the compound is selected from any one of the compounds in Table 1 of the specification.

4. A method for preparing a diphenylamine compound as described in any one of claims 1-3, comprising the following steps: The compound shown in general formula II is condensed with the compound shown in general formula III to prepare the compound shown in formula I, and the reaction equation is as follows: Wherein, the substituents R1, R2, R3, R4, X1, X2, X3, X4, and X5 are defined as described in any one of claims 1-3, and Hal represents a halogen; preferably, the reaction is carried out in the presence of a solvent; more preferably, a base is added during the reaction; even more preferably, the solvent is selected from at least one of DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, dioxane, dichloromethane, or ethyl acetate, and / or the base is selected from at least one of inorganic bases (such as NaH, KH, K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, KOAc, AcONa, K3PO4, t-BuONa, EtONa, NaOH, KOH, NaOMe, etc.) or organic bases (such as pyrazole, triethylamine, DIEA / DIPEA, etc.).

5. A composition for killing pests, characterized in that, It contains at least one of the diphenylamine compounds according to any one of claims 1-3 in a biologically effective amount; preferably, it further includes a formulation adjuvant; more preferably, it further includes other active ingredients.

6. A method for controlling pests, characterized in that, The composition includes at least one of the diphenylamine compounds of any one of claims 1-3 or the composition of claim 5, which brings the harmful organisms and / or fungi or their environment into biologically effective contact.

7. Use of at least one of the diphenylamine compounds as described in any one of claims 1-3 or the composition as described in claim 5 in the control of pests.

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