Preparation and application of novel trifluoroalkyl-containing thiophenyl heterocyclic derivative

Abstract

The invention relates to preparation and application of a novel trifluoroalkyl sulfur-containing phenyl heterocyclic ring derivative. Specifically, the invention relates to a compound as shown in formula (I) containing a trifluoroalkyl thiophenyl heterocyclic derivative, an isotope labeled compound of the compound, an optical isomer, a geometric isomer, a tautomer or an isomer mixture of the compound, or a pharmaceutically acceptable salt of the compound, and application of the compound in preparation of insecticides for pest control. The compound can achieve a better pest control effect at a lower dosage, especially for pests and pest mites such as tetranychus cinnabarinus, tetranychus urticae and panonychus citri.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and specifically, to the preparation and application of novel trifluoroalkylthiophenyl heterocyclic derivatives. Background Art

[0002] In recent years, due to the long-term and extensive use of insecticides and acaricides, there have been numerous reports on insecticide- and acaricide-resistant populations. The use of existing insecticides and acaricides can no longer effectively control pests and mites as well as insects. Therefore, there is an urgent need to develop novel insecticidal and acaricidal active compounds that are effective against existing insecticide- and acaricide-resistant populations. With the continuous development and research by researchers, sulfur-containing compounds substituted with trifluoroethyl groups have gradually come into the view of researchers, and are studied in WO1999055668A, CN103664811A, JP2011042611A, JP2011219419A, JP2015036377A, WO 2012 / 012086848, WO2013 / 018928 and WO 2019 / 131575, CN 118344315 A. However, the above research results are still not very satisfactory in terms of efficacy, persistence, toxicity, etc.

[0003] When the active compounds recorded in the above-mentioned documents are used to control pests, mites and insects, they still have low killing activity. Especially at low application rates, their insecticidal and acaricidal activities are often not satisfactory, and the control effect on resistant pests and mites is even worse. Therefore, there is still an urgent need in agricultural production for new drugs that are highly efficient, low-toxic, and have excellent killing effects on resistant pests. Summary of the Invention

[0004] The object of the present invention is to provide a new type of trifluoroalkylthiophenyl heterocyclic derivative. Such compounds can achieve better pest control effects at lower doses, can efficiently kill pests, mites and insects, and are used to control animal pests (including arthropods and especially representatives of insects or Acarina). Moreover, the synthesis process of the compounds provided by the present invention is simple, the production cost is low, and there is great development potential in the future.

[0005] In a first aspect, the present invention provides a compound of formula (I) as a novel trifluoroalkylthiophenyl heterocyclic derivative, or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or mixture of isomers, or its agrochemically acceptable salt,

[0006]

[0007] Wherein,

[0008] R1 is selected from C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano-substituted C1-C6 alkyl, C3-C6 cycloalkyl C1-C3 alkyl, C3-C6 epoxyalkyl C1-C3 alkyl;

[0009] R2 and R4 are each independently selected from halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl;

[0010] R3 and R5 are selected from hydrogen;

[0011] Q is selected from ,

[0012] and may be mono- or poly-substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, trifluoroethyl, hydroxy, nitro, amino, cyano, aldehyde, carboxyl, amide, ester, methylthio, methylsulfonyl, methylsulfinyl, alkenyl, alkynyl, cyclopropyl;

[0013] n is selected from 0, 1 or 2;

[0014] Excluded: R1 is selected from CH2CH2CH3, CH(CH3)2, cyclopropylmethyl, and Q is selected from monosubstituted trifluoromethylpyridine;

[0015] And the following compounds are excluded:

[0016] 。

[0017] In one embodiment of the present invention, wherein

[0018] R1 is selected from C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, cyano-substituted C1-C3 alkyl, C3-C6 cycloalkyl C1-C3 alkyl;

[0019] R2 and R4 are each independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl;

[0020] R3 and R5 are selected from hydrogen;

[0021] Q is selected from ,

[0022] and may be mono - substituted or multi - substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, trifluoroethyl, hydroxyl, nitro, amino, cyano, aldehyde, carboxyl, amide, ester, methylthio, methylsulfonyl, methylsulfinyl, vinyl, ethynyl, cyclopropyl;

[0023] n is selected from 0, 1 or 2.

[0024] In one embodiment of the present invention, wherein,

[0025] R1 is selected from methyl, ethyl, propyl, tert - butyl, isobutyl, dichloroethyl, trichloroethyl, trichloropropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, trifluoropropyl, heptafluoropropyl, trifluorobutenyl, CH2CN, cyclopropylmethyl, glycidylmethyl;

[0026] R2 and R4 are independently selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, fluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl, trifluoropropyl, heptafluoropropyl, cyano, cyclopropyl;

[0027] R3 and R5 are selected from hydrogen;

[0028] Q is selected from ,

[0029] and may be mono - substituted or multi - substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, trifluoroethyl, hydroxyl, nitro, amino, cyano, aldehyde, carboxyl, amide, ester, methylthio, methylsulfonyl, cyclopropyl;

[0030] n is selected from 0, 1 or 2.

[0031] In one embodiment of the present invention, wherein,

[0032] R1 is selected from methyl, ethyl, trifluoromethyl, CH2CHCl2, CH2CCl3, CH2CH2CCl3, CH2CHF2, CH2CF3, CH2CH2CF3, CH2CN, cyclopropylmethyl, glycidylmethyl;

[0033] R2 and R4 are independently selected from fluorine, chlorine, bromine, methyl, trifluoromethyl, heptafluoropropyl, cyclopropyl;

[0034] R3 and R5 are selected from hydrogen;

[0035] Q is selected from ,

[0036] and may be mono - or poly - substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, trifluoroethyl, hydroxyl, nitro, amino, cyano, aldehyde, carboxyl, amide, ester, methylthio, methylsulfonyl, cyclopropyl;

[0037] n is selected from 0, 1 or 2.

[0038] In another embodiment of the present invention, wherein,

[0039] R1 is selected from CH3, CF3, CH2CH3, CH2CHF2, CH2CF3, CH2CH2CF3, CH2CN, cyclopropylmethyl;

[0040] R2 and R4 are independently selected from fluorine, chlorine, bromine, methyl, trifluoromethyl;

[0041] R3 and R5 are selected from hydrogen;

[0042] Q is selected from ,

[0043] and may be mono - or poly - substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, methyl, trifluoromethyl, nitro, cyano, carboxyl, methylthio;

[0044] n is selected from 0, 1 or 2.

[0045] Specifically, when Q is selected from Q1, R3 = H, and R5 = H,

[0046] (I - 1)

[0047] wherein,

[0048] R1 is selected from CF3, CH2CF3, CH2CHF2, CH2CH2CF3, CH2CN, cyclopropylmethyl;

[0049] R2 is selected from fluorine, chlorine, methyl;

[0050] R4 is selected from fluorine, chlorine, methyl;

[0051] X1 is selected from H, fluorine, chlorine, bromine, methyl, trifluoromethyl, cyano, nitro, amino;

[0052] X2 is selected from H, fluorine, chlorine, bromine, methyl, difluoromethyl, trifluoromethyl, nitro, amino, carboxyl, ester, amide, cyclopropyl;

[0053] X3 is selected from H, fluorine, chlorine, bromine, methyl, difluoromethyl, trifluoromethyl, nitro, cyano, methylthio, ethylthio, methylsulfinyl, methylsulfonyl, cyclopropyl, vinyl, ethynyl;

[0054] X4 is selected from H, fluorine, chlorine, bromine, difluoromethyl, trifluoromethyl, cyano, cyclopropyl;

[0055] n is selected from 0, 1, 2.

[0056] The following compounds are excluded:

[0057] 。

[0058] More preferably,

[0059] (I-1-1)

[0060] wherein, R1, R2, R4, n are as defined above,

[0061] X1 is selected from H, fluorine, chlorine, cyano, nitro;

[0062] X2 is selected from H, fluorine, chlorine, methyl, trifluoromethyl, nitro, cyano;

[0063] X3 is selected from fluorine, chlorine, bromine, trifluoromethyl, nitro, cyano, methylthio, methylsulfinyl, methylsulfonyl, cyclopropyl.

[0064] The following compounds are excluded:

[0065] 。

[0066] More preferably,

[0067] (I-1-2)

[0068] wherein,

[0069] X1 is selected from fluorine, chlorine;

[0070] X3 is selected from fluorine, chlorine, bromine, trifluoromethyl, nitro, cyano, methylthio, cyclopropyl;

[0071] n is selected from 0, 1, 2.

[0072] More preferably,

[0073] (I-1-3)

[0074] wherein,

[0075] X2 is selected from H, fluorine, chlorine;

[0076] X3 is selected from fluorine, chlorine, bromine, nitro, cyano, methylthio;

[0077] n is selected from 0, 1, 2.

[0078] Specifically, when Q is selected from Q2, R3 = H, and R5 = H,

[0079] (I-2)

[0080] Among them,

[0081] R1 is selected from CH3, CF3, CH2CH3, CH2CHF2, CH2CF3, CH2CH2CF3, CH2CN, cyclopropylmethyl;

[0082] R2 is selected from chlorine, methyl;

[0083] R4 is selected from fluorine, chlorine, bromine, methyl;

[0084] X1 is selected from H, fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl, nitro, amino, carboxyl, hydroxyl, methoxy, COOCH;

[0085] X2 is selected from H, fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, nitro, amino, carboxyl, hydroxyl, cyano, formyl, methoxy, COOCH, COOCH3, COCH3, CONH2, CONHCH 3、 SCH3, SOCH3, SO2CH3;

[0086] X3 is selected from H, fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, nitro, amino, carboxyl, hydroxyl, cyano, methoxy, methylthio, methylsulfinyl, methylsulfonyl, methyl formate, CONHCH3, cyclopropyl, vinyl, ethynyl;

[0087] X4 is selected from H, fluorine, chlorine, methyl;

[0088] n is selected from 0, 1, 2.

[0089] The following compounds are excluded:

[0090]

[0091] More preferably,

[0092] (I-2-1)

[0093] Among them, R1, R2, R4, and n are defined as above,

[0094] X2 is selected from H, fluorine, chlorine, bromine, methyl, trifluoromethyl, cyano, nitro;

[0095] X3 is selected from fluorine, chlorine, bromine, cyano, nitro, cyclopropyl, SCH3;

[0096] n is selected from 0, 1, 2.

[0097] The following compounds are excluded:

[0098] .

[0099] More preferably,

[0100] (I-2-2)

[0101] Among them,

[0102] R1 is selected from CH2CH3, CH2CHF2, CH2CF3, CH2CH2CF3;

[0103] X2 is selected from H, fluorine, chlorine, bromine, methyl, trifluoromethyl, cyano, nitro;

[0104] X3 is selected from fluorine, chlorine, bromine, cyano, nitro, cyclopropyl, SCH3;

[0105] n is selected from 0, 1, 2.

[0106] Specifically, when Q is selected from Q3, R3 = H, and R5 = H,

[0107] (I-3)

[0108] Among them,

[0109] R1 is selected from CF3, CH2CF3, CH2CH2CF3;

[0110] R2 is selected from fluorine, methyl;

[0111] R4 is selected from fluorine, methyl;

[0112] X1 is selected from H, fluorine, chlorine;

[0113] X2 is selected from H, fluorine, chlorine, bromine, methyl;

[0114] X3 is selected from H, fluorine, chlorine, difluoromethyl, trifluoromethyl, cyano;

[0115] X4 is selected from H, fluorine, methyl, trifluoromethyl, CH2CF3;

[0116] n is selected from 0, 1, 2.

[0117] More preferably,

[0118] (I-3-1)

[0119] Wherein,

[0120] R1 is selected from CH2CH3;

[0121] X1 is selected from H, fluorine, chlorine;

[0122] X3 is selected from H, fluorine, chlorine, trifluoromethyl;

[0123] X4 is selected from H, fluorine;

[0124] n is selected from 0, 1, 2.

[0125] For the sake of simplicity, the "novel trifluoroalkylthiophenyl heterocyclic derivative", "compound of formula (I)" or "compound of the present invention" described hereinafter may also cover any isotopically labeled compound of the compound of formula (I), or its optical isomers, geometric isomers, tautomers or mixtures of isomers, or its agrochemically acceptable salts.

[0126] The term "optical isomers" means that when a compound has one or more chiral centers, each chiral center can exist in the R configuration or the S configuration, and the various isomers thus formed are optical isomers. Optical isomers include all diastereoisomers, enantiomers, meso forms, racemates or mixtures thereof. For example, optical isomers can be separated by a chiral chromatographic column or by chiral synthesis.

[0127] The term "geometric isomers" means that when there is a double bond in a compound, the compound can exist as a cis isomer, a trans isomer, an E isomer and a Z isomer. Geometric isomers include cis isomers, trans isomers, E isomers, Z isomers or mixtures thereof.

[0128] The term "tautomers" refers to isomers resulting from the rapid movement of a certain atom in a molecule between two positions. Those skilled in the art can understand that tautomers can be converted into each other and may coexist in an equilibrium state in a certain state.

[0129] The term "nematodes" includes all species of the phylum Nematoda, and in particular, species that are parasites on plants in the context (such as species of Aphelenchida, Meloidogyne, Tylenchida, and other species).

[0130] Unless otherwise specified, when referring to "novel trifluoroalkylthiophenyl heterocyclic derivatives", "compounds of formula (I)", or "compounds of the present invention" herein, it also encompasses isotopically labeled compounds obtained by replacing any atom in the compound with its isotopic atom. The present invention includes all pharmaceutically acceptable isotopically labeled compounds of formula (I), wherein one or more atoms are replaced with atoms having the same atomic number as the atoms normally found in nature but different atomic masses or mass numbers.

[0131] Examples of isotopes suitable for inclusion in the compounds of the present invention include isotopes of hydrogen, such as 2 H (D) and 3 H (T), isotopes of carbon, such as 11 C, 13 C and 14 C, isotopes of chlorine, such as 37 Cl, isotopes of fluorine, such as 18 F, isotopes of iodine, such as 123 I and 125 I, isotopes of nitrogen, such as 13 N and 15 N, isotopes of oxygen, such as 15 O, 17 O and 18 O, and isotopes of sulfur, such as 35 S.

[0132] The isotopically labeled compounds of formula (I) can generally be prepared by conventional techniques known to those skilled in the art or by using appropriate isotopically labeled reagents in place of the previously used unlabeled reagents in a manner similar to the methods described in the examples and preparations attached herein.

[0133] The compounds of formula (I) can exist in the form of agrochemically acceptable salts, for example, acid addition salts and / or base addition salts of the compounds of formula (I). Unless otherwise specified, "agrochemically acceptable salts" as used herein include acid addition salts or base addition salts that can occur in the compounds of formula (I).

[0134] The agrochemically acceptable salts of the compounds of formula (I) include their acid addition salts and base addition salts. Suitable acid addition salts are formed from acids that form non-toxic salts. For a review of suitable salts, see Handbook of Pharmaceutical Salts: Properties, Selection and Use by Stahl and Wermuth (Wiley-VCH, 2002). Methods for preparing the agrochemically acceptable salts of the compounds described herein are known to those skilled in the art.

[0135] To avoid ambiguity, the terms used herein are defined below. Unless otherwise indicated, the meanings of the terms used herein are as follows.

[0136] As used herein, the term "substituted" means that one or more (preferably 1 to 5, more preferably 1 to 3) hydrogen atoms in a group are independently replaced by a corresponding number of substituents.

[0137] As used herein, the term "each independently" means that when the number of substituents is more than one, these substituents may be the same or different.

[0138] As used herein, the term "alkyl" refers to saturated aliphatic hydrocarbons, including straight-chain and branched-chain. In some embodiments, the alkyl group has 1-8, or 1-6, or 1-3 carbon atoms. For example, the term "C 1-8 alkyl" refers to a straight-chain or branched-chain group of atoms having 1-8 carbon atoms. The term "C 1-8 alkyl" includes the terms "C 1-6 alkyl", "C1-C3 alkyl", and "C1-C4 alkyl" in its definition. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, isopentyl, neopentyl, (R)-2-methylbutyl, (S)-2-methylbutyl, 3-methylbutyl, 2,3-dimethylpropyl, 2,3-dimethylbutyl, hexyl, etc. The alkyl group may optionally be substituted with one or more (e.g., 1 to 5) suitable substituents.

[0139] As used herein, the term "haloalkyl" refers to an alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). For example, the term "C 1- C6 haloalkyl" refers to a C 1- C6 alkyl group having one or more halogen substituents (up to perhaloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). As another example, the term "C 1-"C3 haloalkyl" means a C 1- C3 alkyl group (up to a perhaloalkyl group, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). Examples of haloalkyl groups include: CF3, C2F5, CHF2, CH2F, CH2CF3, CH2Cl, etc. In the case of polyhalogenation, the halogen atoms may be the same or different. In the context of the present invention, the halogen is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine.

[0140] As used herein, the term "alkoxy", whether by itself or in combination with other terms such as haloalkoxy, shall be understood in this application to mean O-alkyl, where the term "alkyl" is defined as above.

[0141] As used herein, the term "cycloalkyl" means C3-C8-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Among these groups, C3-C6-cycloalkyl is preferred. Among them, the term "cyclopropyl" is abbreviated as Cyc.

[0142] As used herein, the term "epoxyalkyl" means C3-C8-epoxyalkyl, such as epoxypropyl, epoxybutyl, epoxyamyl, epoxyhexyl, epoxyheptyl and epoxyoctyl. Among these groups, C3-C6-epoxyalkyl is preferred.

[0143] As used herein, the term "C3-C6 cycloalkyl C1-C3 alkyl" means a C1-C3 alkyl having a C3-C6 cycloalkyl substituent and shall be understood in this application as R-(C1-C3)alkyl-(C3-C6)cycloalkyl. Where the terms "cycloalkyl" and "alkyl" are defined as above.

[0144] As used herein, the term "C3-C6 epoxyalkyl C1-C3 alkyl" means a C1-C3 alkyl having a C3-C6 epoxyalkyl substituent and shall be understood in this application as R-(C1-C3)alkyl-(C3-C6)epoxyalkyl. Where the terms "epoxyalkyl" and "alkyl" are defined as above.

[0145] In this document, the number ranges related to the number of substituents, the number of carbon atoms, and the number of ring atoms represent the individual listing of all integers within that range, and the range is only used as a simplified notation. For example: "1-4 substituents" means 1, 2, 3 or 4 substituents; "3-8 ring atoms" means 3, 4, 5, 6, 7 or 8 ring atoms. Therefore, the number ranges related to the number of substituents, the number of carbon atoms, and the number of ring atoms also cover any of its sub-ranges, and each sub-range is also considered to be disclosed herein.

[0146] The compounds of the present invention can be prepared in various ways known to those skilled in the art of organic synthesis. Those skilled in the art can refer to the synthetic routes of the specific compounds in the specific embodiments of the present invention and appropriately adjust the reaction raw materials and reaction conditions to obtain the synthetic methods of other compounds.

[0147] The following synthetic schemes describe the steps for preparing the compounds disclosed in the present invention. Among them, R1, R2, R3, R4, R5 and n have the meanings described in the present invention.

[0148]

[0149] Intermediate 1 reacts with different electrophilic reagents in a basic environment to obtain Intermediate 2. Intermediate 2 first forms diazobenzene with sodium nitrite, and then the corresponding haloarene 3 is obtained through radical decomposition under the catalysis of cuprous halide or potassium iodide, where T is bromine or iodine. Intermediate 3 reacts to form Intermediate 4, where X is B(OH)2 or pinacolato boranyl. Intermediate 4 undergoes a Suzuki coupling reaction with the halide of Q to obtain the thioether product in Formula I. The thioether product in Formula I is oxidized to the oxidation target product in Formula I in the presence of an oxidant such as m-CPBA or hydrogen peroxide. Intermediate 3 can also directly undergo a Suzuki coupling reaction with the boric acid (borate ester) of Q to obtain the thioether product in Formula I.

[0150] In addition, the above intermediate compounds and their raw materials can be prepared by referring to the methods reported in WO2006043635, WO2010100189, CN102341376A, WO2013092350, WO2013157229, WO2007131680, WO2013030262, WO2018015852, WO2014202510, WO2014202505, WO2015004028, WO2021056922, WO2021005081 and Fries, Pascal H., and Daniel Imbert. "Parallel NMR based on solution magnetic-susceptibility differences. Application to isotopic effects on self-diffusion." Journal of Chemical & Engineering Data 55.5 (2010): 2048-2054., etc.

[0151] The present invention lists a number of synthesized exemplary compounds, and the specific group selections are shown in Tables 1 to 3 below, and the compound data is shown in Table 4. It should be understood that the scope of the present invention is not limited to the exemplary compounds listed in the following tables, and the group selections of the compounds in Table 1 below can be combined arbitrarily without any particular limitation. Some general formula I compounds of the present invention are shown below, but the present invention is by no means limited to these compounds.

[0152] (I-1)

[0153] Table 1

[0154]

[0155]

[0156] (I-2)

[0157] Table 2

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165] (I-3)

[0166] Table 3

[0167]

[0168]

[0169] Table 4 Characterization Data of Some Exemplary Compounds

[0170]

[0171]

[0172]

[0173]

[0174] In a second aspect, the present invention provides an insecticide composition comprising a compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or a pesticidally acceptable salt thereof, and a pesticidally acceptable carrier. It can be applied to animal pests and / or their habitats to control unwanted animal pests.

[0175] The formulation comprises at least one compound of the present invention and at least one agriculturally useful adjuvant, such as a carrier and / or a surfactant.

[0176] The pesticidally acceptable carrier can be an organic or inorganic inert carrier material. For example, suitable carriers include water, gelatin, gum arabic, magnesium stearate, talc, vegetable oils, polyalkylene glycols, petrolatum, mannitol, cellulose, cellulose derivatives, sodium saccharin, magnesium carbonate, brine, glycerol, ethanol, etc. In addition, the insecticide composition may also contain other additives, such as preservatives, stabilizers, emulsifiers, buffers, diluents, binders, wetting agents, lubricants, glidants, etc.

[0177] The compound of formula (I) of the present invention can also be used in the form of a mixture with one or more suitable substances as follows: fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbial agents, beneficial microorganisms, herbicides, fertilizers, bird repellents, phytotonics, sterilants, safeners, chemical pheromones and / or plant growth regulators, so as to, for example, broaden the spectrum of action, extend the duration of action, increase the rate of action, prevent rejection or prevent the development of resistance. In addition, such combinations of active ingredients can improve plant growth and / or tolerance to abiotic factors, such as tolerance to high or low temperatures, to drought or to high water content or soil salinity. It can also improve flowering and fruiting performance, optimize germination ability and root development, promote harvesting and increase yield, affect ripening, improve the quality and / or nutritional value of harvested products, extend the shelf life of harvested products and / or improve the processing performance of harvested products.

[0178] The dosage form of the insecticide composition of the present invention can be a liquid dosage form, a solid dosage form or a semi-solid dosage form, without particular limitation. In some embodiments, the dosage form of the insecticide composition is selected from powder, granule, liquid, suspension or spray, preferably wettable powder, wettable liquid, soluble powder, dispersible liquid, aqueous solution, microemulsion, emulsifiable concentrate, emulsion in water, sprayable solution, dispersible oil suspension, microcapsule suspension, water dispersible granule, water soluble granule, macrogranule, granule for broadcasting and soil application, aerosol, ultra-low volume agent and wax product.

[0179] The content of the compound of the present invention in its insecticide composition can be adjusted according to actual needs (such as dosage form, application method, application object, etc.), including but not limited to 0.001 mg / L - 10 mg / L, such as 0.001 mg / L, 0.01 mg / L, 0.1 mg / L, 0.5 mg / L, 1 mg / L, 2.5 mg / L, 5 mg / L or 10 mg / L.

[0180] The specific application frequency can be determined by those skilled in the relevant art, such as once a day, once every two days, once every three days, once every four days, once every five days, once every six days, twice a day, three times a day, etc.

[0181] In a third aspect, the present invention provides the use of a compound of formula (I) or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its agrochemically acceptable salt in the preparation of an insecticide for pest control.

[0182] The compounds of the present invention are suitable for controlling pests or mites, that is, controlling pests or mites. The pests or mites refer to harmful or unwanted insects or mites, especially harmful or unwanted insects or mites encountered in the fields of agriculture, forestry, storage protection, material protection and hygiene. When the compounds of the present invention are used at low concentrations, they also show excellent control effects on various pests or mites, and have insecticidal or acaricidal activity at each stage of the life cycle of pests or mites (such as eggs, larvae (nymphs), pupae, adults). For those pests or mites that have developed resistance to traditional insecticides or acaricides, the compounds of the present invention also show excellent control activity.

[0183] The present invention also relates to a method for controlling pests or mites, which method comprises applying a pest control effective amount of a compound of formula (I) to the location of the insects, the insect habitat, the pest habitat, the area to be protected, or directly on the insects to be controlled. The compounds of the present invention can also be used to control other invertebrate pests or organisms.

[0184] Specifically, the insect habitat, pest habitat or mite habitat refers to the environment where insects, pests or mites live or where their eggs are present, including the surrounding air, the food they consume or the objects they come into contact with. For example, by applying the active compound to the seeds of the plant (before planting), to the seedlings, or to the planted cuttings, leaves, stems, fruits, grains and / or roots, or to the soil or other growth media (before or after crop planting), insects or mites that eat, damage or come into contact with edible agricultural products, ornamental plants, turf, forage plants or other economically valuable plants can be controlled. It is also possible to protect these plants against diseases caused by viruses, fungi or bacteria by controlling sap-sucking pests such as whiteflies, planthoppers, aphids, etc. or mites such as Tetranychus urticae, Tetranychus cinnabarinus, etc.; the plants include plants obtained by conventional breeding methods, and also plants with insect or mite resistance, herbicide resistance, high yield / or other beneficial characteristics obtained by genetically modifying through modern biotechnology. It is expected that these compounds can be applied to protect articles and / or places such as fabrics, paper, stored grains, seeds and other foods, houses, buildings, etc., by applying the compounds of the present invention to these objects or near these objects, for example, by using conventional treatment methods directly or by allowing the compounds to act on their environment, habitat or storage space, such as by dipping, spraying, evaporation, atomization, spreading, smearing, injection, and in the case of propagation materials (especially seeds), also by applying one or more coatings.

[0185] In the field of animal health, namely veterinary medicine, the compounds of formula (I) of the present invention are active against animal parasites, especially ectoparasites or endoparasites. The term "endoparasite" particularly includes worms and protozoa, such as coccidia. Ectoparasites are generally and preferably arthropods, especially insects or mites.

[0186] In the field of veterinary medicine, the compounds of formula (I) with favorable warm-blooded animal toxicity are suitable for controlling parasites that occur in animal breeding and animal husbandry of domestic animals, breeding animals, zoo animals, laboratory animals, experimental animals and domestic pets. They are active against all or specific developmental stages of the parasites.

[0187] Agricultural livestock include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffaloes, rabbits, reindeer, fallow deer, and especially cattle and pigs; or poultry such as turkeys, ducks, geese, and especially chickens; or fish or crustaceans in aquaculture, for example; or - depending on the situation - insects such as bees.

[0188] Domestic pets include, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets, and especially dogs, cats, caged birds; reptiles, amphibians or ornamental fish.

[0189] In the field of animal health, the term "control" or "controlling" as used herein means that the compound of formula (I) can effectively reduce the incidence of a particular parasite in an animal infected with such a parasite to a harmless level. More specifically, "control" as used herein means that the compound of formula (I) kills each parasite, inhibits its growth or inhibits its reproduction.

[0190] In the context of this patent application, the term "hygiene" should be understood to mean any and all measures, preventive measures and methods aimed at preventing diseases - especially infectious diseases - and for protecting the health of humans and animals and / or protecting the environment and / or maintaining cleanliness. According to the invention, this particularly includes measures for cleaning, disinfecting and sterilizing, for example, textiles or hard surfaces (especially surfaces made of glass, wood, cement, porcelain, ceramics, plastics or metals) to ensure that they are free from hygienic pests and / or their secretions. In this regard, the scope of protection of the present invention preferably excludes methods of surgical or therapeutic treatment applied to the human or animal body and diagnostic methods carried out on the human or animal body.

[0191] Thus, the term "hygiene field" encompasses all areas, technical fields and industrial applications in which these hygiene measures, preventive measures and methods are important, such as hygiene in kitchens, bakeries, airports, bathrooms, swimming pools, department stores, hotels, hospitals, cattle pens, animal husbandry, etc.

[0192] The inventors of the present invention have found that even when administered at a low dose, the compounds of the present invention are also capable of controlling animal pests encountered in agriculture, horticulture, livestock farming, aquaculture, forestry, gardens and leisure facilities, protection of stored products and materials, and the hygiene field, especially insects, arachnids, worms, nematodes and molluscs. These compounds are preferably used as insecticides. They are effective against both normally sensitive and resistant species and against all or some of the developmental stages. The above pests include animal pests and include insects, mites or nematodes, specifically including:

[0193] Pests from the phylum Arthropoda, especially from the class Arachnida, such as those from the order Acarina, such as the family Tetranychidae (e.g., Tetranychus spp. such as Amphitetranychus viennensis, Eotetranychus spp., Panonychus spp., or Oligonychus spp.), such as Acarus spp. (e.g., Acarus siro, Aceria kuko, Aceria sheldoni), Aculops spp., Aculus spp. (e.g., Aculus fockeui, Aculus schlechtendali), Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp. (e.g., Brevipalpus phoenicis), Bryobia spp. (e.g., Bryobia graminum, Bryobia praetiosa), Centruroides spp., Chorioptes spp., Dermatophagoides spp. (e.g., Dermatophagoides pteronyssinus, Dermatophagoides farinae), Dermacentor spp., Dermanyssus gallinae;

[0194] Pests from the order Coleoptera, such as Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp. (such as Agriotes linneatus, Agriotes mancus), Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp. (such as Anthonomus grandis), Anthrenus spp., Apion spp., Apogonia spp., Atomaria spp. (such as Atomaria linearis), Attagenus spp., Baris caerulescens, Bruchidius obtectus, Bruchus spp. (such as Bruchus pisorum, Bruchus rufimanus), Cassida spp., Cerotoma trifurcata, Ceuthorhynchus spp. (such as Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae), Chaetocnema spp. (such as Chaetocnema confinis, Chaetocnema denticulata, Chaetocnema ectypa), Cleonus mendicus, Conoderus spp., Cosmopolites spp. (such as Cosmopolites sordidus);

[0195] Pests / arthropods from the order Diptera, e.g., Aedes spp. (e.g., Aedes aegypti, Aedes albopictus, Aedes sticticus, Aedes vexans), Agromyza spp. (e.g., Agromyza frontella, Agromyza parvicornis), Anastrepha spp., Anopheles spp. (e.g., Anopheles quadrimaculatus, Anopheles gambiae), Asphondylia spp., Bactrocera spp. (e.g., Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera oleae), Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus spp., Chrysomyia spp., Chrysops spp., Chrysozona pluvialis, Cochliomyia spp., Contarinia spp. (e.g., Contarinia johnsoni, Contarinia nasturtii, Contarinia pyrivora);

[0196] Pests from the order Heteroptera, for example, Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp. (such as Cimex adjunctus, Cimex hemipterus, Cimex lectularius, Cimex pilosellus), Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp.;

[0197] Pests from the order Homoptera, such as Acizzia acaciaebaileyanae, Acizziadodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp. (such as Acyrthosiphon pisum), Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp. (such as Amrasca bigutulla, Amrasca devastans), Anuraphis cardui, Aonidiella spp. (such as Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata), Aphanostigma piri, Aphis spp (such as Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis hederae, Aphis illinoisensis, Aphis middletoni, Aphis nasturtii, Aphis nerii);

[0198] Pests from the order Hymenoptera, such as Acromyrmex spp., Athalia spp. (e.g., Athalia rosae), Atta spp., Diprion spp. (e.g., Diprion similis), Hoplocampa spp. (e.g., Hoplocampa cookei, Hoplocampa testudinea), Lasius spp.;

[0199] Pests from the order Isoptera, such as Coptotermes spp., Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Microtermes obesi, Odontotermes spp., Reticulitermes spp. (e.g., Reticulitermes flavipes, Reticulitermes hesperus);

[0200] Pests from the order Lepidoptera, such as Achroia grisella, Acronicta major, Adoxophyes spp. (such as Adoxophyes orana), Aedia leucomelas, Agrotis spp. (such as Agrotis segetum, Agrotis ipsilon), Alabama spp. (such as Alabama argillacea), Amyelois transitella, Anarsia spp., Anticarsia spp. (such as Anticarsia gemmatalis), Argyroploce spp., Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp. (such as Chiloplejadellus, Chilo suppressalis), Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Conopomorpha spp.;

[0201] Pests from the order Orthoptera or Saltatoria, such as the house cricket (Acheta domesticus), Dichroplus spp., Gryllotalpa spp. (such as the European mole cricket (Gryllotalpa gryllotalpa)), Hieroglyphus spp., Locusta spp. (such as the migratory locust (Locusta migratoria)), Melanoplus spp. (such as Melanoplus devastator), the desert locust (Schistocerca gregaria);

[0202] Pests from the order Thysanoptera, such as the corn leaf tier (Anaphothrips obscurus), the rice thrips (Baliothrips biformis), the grapevine thrips (Drepanothris reuteri), Enneothrips flavens, Frankliniella spp. (such as the tobacco thrips (Frankliniella fusca), the western flower thrips (Frankliniella occidentalis), the soybean thrips (Frankliniella schultzei), the wheat thrips (Frankliniella tritici), the blueberry thrips (Frankliniella vaccinii), the Williams' thrips (Frankliniella williamsi)), Heliothrips spp., the greenhouse thrips (Hercinothrips femoralis), the grapevine thrips (Rhipiphorothrips cruentatus), Scirtothrips spp., the cardamom thrips (Taeniothrips cardamoni), Thrips spp. (such as the melon thrips (Thrips palmi), the onion thrips (Thrips tabaci));

[0203] Plant pests from the phylum Nematoda, namely plant-parasitic nematodes, especially those of the genus Aglenchus spp. (such as Aglenchus agricola), Anguina spp. (such as Anguina tritici), Aphelenchoides spp. (such as Aphelenchoides arachidis, Aphelenchoides fragariae), Belonolaimus spp. (such as Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni), Bursaphelenchus spp. (such as Bursaphelenchus cocophilus, Bursaphelenchus eremus, Bursaphelenchus xylophilus); species of the genus Meloidogyne)(e.g., Meloidogyne chitwoodi, Meloidogyne fallax, Meloidogyne acronea, Meloidogyne africana, Meloidogyne arenaria, Meloidogyne arenaria thamesi, Meloidogyne artiella, Meloidogyne chitwoodi, Meloidogyne coffeicola, Meloidogyne ethiopica, Meloidogyne exigua, Meloidogyne fallax, Meloidogyne graminicola, Meloidogyne graminis, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne incognita acrita, Meloidogyne javanica, Meloidogyne kikuyensis, Meloidogyne minor, Meloidogyne naasi, Meloidogyne paranaensis, Meloidogyne thamesi, and non-migratory parasitic Meloidogyne spp.; Tylenchulus spp. (e.g., Tylenchulus semipenetrans), Xiphinema spp. (e.g., Xiphinema index);.

[0204] Arthropods from the order Phthiraptera, for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix, Ptirus pubis, Trichodectes spp.;

[0205] Arthropods from the order Siphonapterida, for example, Ceratophyllus spp., Ctenocephalides spp., Pulex spp., Tunga spp., Xenopsylla spp.; and nuisance pests and hygiene pests from the order Blattodea.

[0206] Optionally, at a certain concentration or application rate, the compound of formula (I) can also be used as a herbicide, safener, growth regulator or composition for improving plant characteristics, as a microbicide or gametocide, for example as a fungicide, antimycotic agent, bactericide, virucide (including reagents against viroids) or as a reagent against MLO (mycoplasma-like organisms) and RLO (rickettsia-like organisms). Optionally, it can also be used as an intermediate or precursor for the synthesis of other active ingredients.

[0207] Those skilled in the art can understand that the definitions and preferences described in one aspect of the present invention are equally applicable to other aspects. Those skilled in the art can understand that the embodiments of various aspects of the present invention can be combined in various ways without departing from the subject and idea of the present invention, and these combinations are also included within the scope of the present invention.

[0208] The beneficial effects of the present invention are:

[0209] Through chemical modification and molecular design of aryl sulfides with an arylamine structure, replacing the benzene ring with a Q ring containing heteroatoms, a series of compounds with more excellent activities, compounds with excellent activities for insecticidal or acaricidal use in agriculture or forestry are obtained, especially showing excellent control effects against Tetranychus urticae, Tetranychus cinnabarinus, Panonychus ulmi, and Panonychus citri. At the same time, its synthesis process is simple, the production cost is relatively low, and the potential is huge. Detailed implementation manners

[0210] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0211] The compound of formula (I) of the present invention can be synthesized by a variety of methods familiar to those skilled in the art of organic synthesis. The following specific examples give some exemplary synthetic methods of the compound of formula (I), which are well-known in the field of synthetic chemistry. Obviously, referring to the exemplary schemes in this patent, those skilled in the art can easily design other synthetic routes of the compound of formula (I) by appropriately adjusting the reactants, reaction conditions and protecting groups.

[0212] Example 1 Synthesis of 3-chloro-2-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)-5-(trifluoromethyl)pyridine (Compound 2-94)

[0213] 1.1 Synthesis of 2-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0214]

[0215] Add 2.0 g (6.80 mmol) of (5-bromo-4-fluoro-2-methylphenyl)(2,2,2-trifluoroethyl)sulfane to a reaction flask, dissolve it with 20 mL of 1,4-dioxane, and successively add 2.52 g (10.40 mmol) of bis(pinacolato)diboron, 1.94 g (20.40 mmol) of potassium acetate, and 0.29 g (0.04 mmol) of palladium(II) chloride bis(diphenylphosphinoferrocene). Heat the reaction system to 110 °C and reflux for 3 h, and monitor with TLC. Stop the reaction after the raw materials are completely disappeared. Pour the reaction system into saturated brine, extract with dichloromethane, combine the organic phases, dry, filter, and rotary evaporate to remove the solvent to obtain 1.08 g of the intermediate with a yield of 50.60%. It is not necessary to purify and continue with the next step of the reaction.

[0216] 1.2 Synthesis of 3-chloro-2-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)-5-(trifluoromethyl)pyridine (Compound 2-94)

[0217]

[0218] Add 0.1 g (0.3 mmol) of the intermediate from the previous step to the reaction flask, dissolve it in a mixed solvent of 1,4-dioxane and water. Subsequently, add 0.094 g (0.36 mmol) of 2-bromo-3-chloro-5-(trifluoromethyl)pyridine, 0.28 g (0.9 mmol) of cesium carbonate, 0.011 g (0.017 mmol) of palladium(II) dichloride bis(diphenylphosphinoferrocene) (DPPF), and 0.016 g (0.029 mmol) of 1,1'-bis(diphenylphosphino)ferrocene to the reaction system. Then heat the reaction system to 100 °C and reflux for 3 h, monitoring with TLC. Stop the reaction after the raw materials have completely disappeared, pour it into saturated brine, extract with dichloromethane, combine the organic phases, dry, and separate by column chromatography to obtain 0.063 g of the target compound 2-94 with a yield of 49.40%.

[0219] Example 2. Synthesis of 2-chloro-5-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)pyridine (Compound 2-11)

[0220]

[0221] Add 0.1 g (0.30 mmol) of 2-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane to the reaction flask and dissolve it in 1.2 mL of a mixed solvent of 1,4-dioxane:water = 5:1. Subsequently, add 0.058 g (0.36 mmol) of 5-bromo-2-chloropyridine, 0.28 g (0.9 mmol) of cesium carbonate, 0.011 g (0.017 mmol) of palladium(II) dichloride bis(diphenylphosphinoferrocene) (DPPF), and 0.016 g (0.029 mmol) of 1,1'-bis(diphenylphosphino)ferrocene to the reaction system. Then heat the reaction system to 101 °C and reflux for 3 h, monitoring with TLC. Stop the reaction after the raw materials have completely disappeared, pour it into saturated brine, extract with dichloromethane, combine the organic phases, dry, and separate by column chromatography to obtain 0.026 g of the target compound 2-11 with a yield of 26.04%.

[0222] Example 3. Synthesis of 2-chloro-5-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)pyridine (Compound 2-11)

[0223]

[0224] 1.0 g (6.35 mmol) of 6-chloropyridine-3-boronic acid was added to a reaction flask and dissolved in a mixed solvent of 16.5 mL of 1,4-dioxane:water = 10:1. Subsequently, 2.22 g (6.35 mmol) of (4-fluoro-5-iodo-2-methylphenyl)(2,2,2-trifluoroethyl)sulfane, 6.21 g (19.06 mmol) of cesium carbonate, and 0.046 g (63.55 μmol) of dichloride of DPPF were added to the reaction system. Then, the reaction was heated under reflux in a nitrogen atmosphere. After 5 h, the reaction was stopped. The reaction system was poured into saturated brine, extracted with dichloromethane, the organic phases were combined, dried, and separated by column chromatography to obtain 1.86 g of the target compound 2-11 with a yield of 87.18%.

[0225] Example 4: Synthesis of 2-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)-5-(trifluoromethyl)pyridine (Compound 3-11)

[0226]

[0227] 0.1 g (0.33 mmol) of (5-bromo-4-fluoro-2-methylphenyl)(2,2,2-trifluoroethyl)sulfane was added to a reaction flask and dissolved in a mixed solvent of 1.2 mL of 1,4-dioxane:water = 5:1. Subsequently, 0.088 g (0.39 mmol) of 4-bromo-2-(trifluoromethyl)pyridine, 0.13 g (0.49 mmol) of bis(pinacolato)diboron, 0.32 g (0.99 mmol) of cesium carbonate, 0.014 g (0.02 mmol) of dichloride of DPPF, and 0.018 g (0.033 mmol) of 1,1'-bis(diphenylphosphino)ferrocene were added to the reaction system. Then, the reaction system was heated to 101 °C and refluxed for 4 h, and monitored by TLC. After the raw materials completely disappeared, the reaction was stopped, poured into saturated brine, extracted with dichloromethane, the organic phases were combined, dried, and separated by column chromatography to obtain 0.016 g of the target compound 3-11 with a yield of 20.10%.

[0228] Test Example: Biological Activity Test

[0229] Test Example 1: Biological Activity Test against Adult Tetranychus cinnabarinus

[0230] Experimental method: The experiment was carried out with reference to the agricultural industry standard NYT 1154.6-2006, using the insect immersion method for determination. Vicia faba seedlings with consistent plant growth were selected, and thick and tender leaves were cut into the shape of two leaves and one stem. Then, one of the leaves was cut into the shape of one leaf and one stem and inserted into a 5 mL sample bottle filled with water. 30 adult mites were selected for each leaf. Each test chemical was accurately weighed and dissolved in a small amount of DMSO to prepare a stock solution of 10,000 mg / L. This stock solution was diluted 100 times with a 0.1% Tween 80 aqueous solution to obtain a test solution with a concentration of 100 mg / L. After the test insects were stabilized on the leaves, they were immersed in the prepared liquid medicine for 5-10 s, and the excess liquid medicine was blotted with filter paper and air-dried naturally. Each treatment was repeated 3 times, and a blank control was set. The impregnating solution used in the control group was an aqueous solution of DMSO and Tween in the same proportion. Subsequently, the experimental targets were placed in an artificial climate chamber (24-26 °C, L:D = 16:8, RH 60%) for cultivation. After 72 h, the death situation of adult mites was checked and recorded. When the body of the insect was touched with forceps, the feet not moving or having no response was regarded as a dead insect.

[0231] Calculation method:

[0232] Corrected mortality rate (%) = [(treatment mortality rate - control mortality rate) / (1 - control mortality rate)] × 100%

[0233] Among some exemplary compounds of the present invention, the following compounds have good control effects on adult Tetranychus cinnabarinus at a concentration of 100 mg / L, and the mortality rate reaches 100%: Compounds 1-2, 1-3, 1-4, 1-12, 1-19, 1-27, 1-59, 1-60, 1-61, 2-1, 2-4, 2-5, 2-7, 2-8, 2-11, 2-12, 2-14, 2-16, 2-18, 2-21, 2-22, 2-23, 2-24, 2-28, 2-29, 2-32, 2-38, 2-41, 2-43, 2-45, 2-46, 2-53, 2-58, 2-63, 2-68, 2-72, 2-74, 2-140, 2-146, 2-147, 2-268, 3-4, 3-5, 3-7, 3-11, 3-22, 3-24.

[0234] Among some exemplary compounds of the present invention, the following compounds have good control effects on adult Tetranychus cinnabarinus at a concentration of 10 mg / L, with a mortality rate reaching over 90%: Compound 1-2, 1-4, 1-27, 1-59, 2-4, 2-5, 2-7, 2-11, 2-12, 2-14, 2-18, 2-21, 2-24, 2-29, 2-32, 2-38, 2-41, 2-43, 2-45, 2-46, 2-63, 2-68, 2-146, 2-147, 2-268, 3-4, 3-5, 3-7, 3-11, 3-24.

[0235] According to the above method, exemplary Compound 2-1 and 2-11 in this patent, Compound 3 in WO2024007862A1 (denoted as CK2 in the text), Compound II-43 in WO1999055668A1 (denoted as CK3 in the text), II-51 (denoted as CK4 in the text), II-61 (denoted as CK5 in the text), and II-69 (denoted as CK6 in the text) were selected as positive control substances for the bioactivity determination of adult Tetranychus cinnabarinus, and the results are shown in Table 5.

[0236]

[0237] Table 5 Acaricidal activities of some exemplary compounds against adult Tetranychus cinnabarinus

[0238]

[0239] From the comparison between the exemplary compounds of the present invention and the control compounds CK2 - CK6, it can be seen that the compounds of the present invention have higher acaricidal activities compared with the prior art.

[0240] Through a large number of experiments, the inventors of the present invention, based on the molecular skeletons of existing compounds, through the strategy of bioisostere replacement, carried out a systematic study on the structure-activity relationship (SAR) for the skeleton of (4-fluoro-2-substituted-5-substituted)-2,2,2-trifluoroethyl sulfide (sulfoxide or sulfone) on the basis of the molecular skeletons of existing acaricides, thereby obtaining the compounds of general formula I of the present invention.

[0241] During the research process, the inventors of the present invention non-obviously found that in the structure of (4-fluoro-2-substituted-5-pyridyl)-2,2,2-trifluoroethyl sulfide (sulfoxide or sulfone), when the 5-position substituent is a pyridine ring and the substituent on the pyridine ring is an electron-withdrawing group, high-activity compounds can be obtained. The new compounds are highly effective at low doses, manifested by having high acaricidal activities at a concentration of 10 mg / L, and even showing excellent acaricidal activities at extremely low doses of 1.0 mg / L or even 0.39 mg / L, and are safe for crops.

[0242] Specifically, for the compounds of the present invention, in the structure of (4-fluoro-2-substituted-5-pyridyl)-2,2,2-trifluoroethyl sulfide (sulfoxide or sulfone), when the 5-position substituent is a pyridine ring, it is embodied as the pyridine substituents of Q1, Q2, and Q3. Among them, the compound obtained by substituting Q2 pyridyl shows the most remarkable broad-spectrum and high-efficiency. In Q2 pyridyl, when the substituents X1, X2, and X4 are H and the substituent X3 is an electron-withdrawing substituent such as fluorine, chlorine, cyano, nitro, etc., it shows excellent acaricidal activity; when the substituents X1 and X4 are H, X3 is an electron-withdrawing substituent such as fluorine or chlorine, and X2 is an electron-withdrawing substituent such as fluorine, chlorine, or methyl, it all shows excellent acaricidal activity. When X2 is a methyl electron-donating group, the activity is slightly weaker, but its activity is comparable to that when the substituent X3 is an electron-withdrawing substituent such as fluorine or chlorine alone; when X2 and X4 are H and both X1 and X3 are electron-withdrawing substituents, the compound also shows excellent activity, but the activity is weaker than that when X3 is substituted alone or when X2 and X3 are disubstituted. Generally speaking, the substituent of X3 has the greatest influence on the activity, and the activity is the best when it is a substituent such as fluorine, chlorine, nitro, or cyano.

[0243] The present invention successfully constructs a new system of trifluoroalkyl sulfide acaricides with high efficiency, low toxicity, and broad-spectrum characteristics by precisely regulating the spatial orientation (Q2 type) and electronic properties (strong electron-withdrawing group at the X3 position) of the pyridine ring substituents. Its core innovation lies in discovering the non-additive influence rule of substituent position on the activity of nitrogen-containing heterocyclic compounds. The established structure-activity relationship model provides a quantifiable structural optimization path for the subsequent design of heterocyclic pesticide molecules. Moreover, the synthesis cost of the compounds of the present invention is much lower than that of the prior art, having significant scientific value and industrial application prospects.

[0244] In organic molecules, due to the differences in the electronegativity, volume size, or spatial configuration of substituents, the conduction performance of the whole molecule in organisms such as insects, mites, and plants or the difference in binding to receptors will be very large, and the difference in biological activity shown will also be very large. Moreover, the conduction performance of the molecule and the suitability of binding to receptors are unpredictable and require a large amount of creative labor to obtain. Therefore, the present invention has substantial features and remarkable progress.

[0245] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or a pesticide-acceptable salt thereof, as a novel trifluoroalkylthiophenyl heterocyclic derivative. in, R1 is selected from C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, cyano-substituted C1-C6 alkyl, C3-C6 cycloalkyl C1-C3 alkyl, C3-C6 epoxyalkyl C1-C3 alkyl; R2 and R4 are independently selected from halogen, cyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl; R3 and R5 are selected from hydrogen; Q is selected from , and may be mono- or poly-substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, trifluoroethyl, hydroxyl, nitro, amino, cyano, aldehyde, carboxyl, amide, ester, methylthio, methylsulfone, methylsulfoxide, alkenyl, alkynyl, and cyclopropyl; n is selected from 0, 1 or 2; Excluded: R1 is selected from CH2CH2CH3, CH(CH3)2, cyclopropylmethyl, and Q is selected from monosubstituted trifluoromethylpyridine; And exclude the above compounds.

2. The compound of formula (I) according to claim 1, characterized in that in, R1 is selected from C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, cyano-substituted C1-C3 alkyl, C3-C6 cycloalkyl C1-C3 alkyl; R2 and R4 are independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl; R3 and R5 are selected from hydrogen; Q is selected from , and may be mono- or poly-substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, trifluoroethyl, hydroxyl, nitro, amino, cyano, aldehyde, carboxyl, amide, ester, methylthio, methylsulfone, methylsulfoxide, vinyl, ethynyl, and cyclopropyl; n is selected from 0, 1 or 2.

3. The compound of formula (I) according to claim 1, characterized in that in, R1 is selected from methyl, ethyl, propyl, tert-butyl, isobutyl, dichloroethyl, trichloroethyl, trichloropropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, trifluoropropyl, heptafluoropropyl, trifluorobutenyl, CH2CN, cyclopropylmethyl, glycidylmethyl; R2 and R4 are independently selected from fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, fluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, pentafluoroethyl, trifluoropropyl, heptafluoropropyl, cyano, and cyclopropyl; R3 and R5 are selected from hydrogen; Q is selected from , and may be mono- or poly-substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, trifluoroethyl, hydroxyl, nitro, amino, cyano, aldehyde, carboxyl, amide, ester, methylthio, methylsulfone, and cyclopropyl; n is selected from 0, 1 or 2.

4. The compound of formula (I) according to claim 1, characterized in that in, R1 is selected from methyl, ethyl, trifluoromethyl, CH2CHCl2, CH2CCl3, CH2CH2CCl3, CH2CHF2, CH2CF3, CH2CH2CF3, CH2CN, cyclopropylmethyl, glycidylmethyl; R2 and R4 are independently selected from fluorine, chlorine, bromine, methyl, trifluoromethyl, heptafluoropropyl, and cyclopropyl; R3 and R5 are selected from hydrogen; Q is selected from , and may be mono- or poly-substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, iodine, methyl, difluoromethyl, trifluoromethyl, trifluoroethyl, hydroxyl, nitro, amino, cyano, aldehyde, carboxyl, amide, ester, methylthio, methylsulfone, and cyclopropyl; n is selected from 0, 1 or 2.

5. The compound of formula (I) according to claim 1, characterized in that in, R1 is selected from CH3, CF3, CH2CH3, CH2CHF2, CH2CF3, CH2CH2CF3, CH2CN, cyclopropylmethyl; R2 and R4 are independently selected from fluorine, chlorine, bromine, methyl, trifluoromethyl; R3 and R5 are selected from hydrogen; Q is selected from , and may be mono- or poly-substituted by one or more identical or different substituents selected from fluorine, chlorine, bromine, methyl, trifluoromethyl, nitro, cyano, carboxyl, methylthio; n is selected from 0, 1 or 2.

6. An agricultural chemical preparation, characterized in that: The invention comprises the compound of formula (I) as claimed in claim 1 and an extender and / or a surfactant.

7. The agricultural chemical preparation according to claim 6, characterized in that Also contains other agrochemical active ingredients.

8. A method for controlling animal pests, characterized in that: The compound of formula (I) according to claim 1 or the agricultural chemical preparation according to claim 6 is allowed to act on animal pests and / or their habitat.

9. Use of the compound of formula (I) according to claim 1 or the agricultural chemical preparation according to claim 6 for controlling animal pests.

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