Preparation and application of substituted benzimino thioxazolidinone (oxazolidinone) derivative

Abstract

The invention discloses a substituted benzimino thioxazolidinone derivative as shown in a formula (I) or an isotope labeled compound thereof, or an optical isomer, a geometric isomer, a tautomer or an isomer mixture thereof, or a pesticide pharmacologically acceptable salt thereof, and application of the compound in preparation of a pesticide for pest prevention and control, and particularly discloses a substituted benzimino thioxazolidinone derivative or an isotope labeled compound thereof, or an optical isomer, a geometric isomer, a tautomer or an isomer mixture thereof. The compound can achieve a better pest control effect at a lower dosage, and especially can be used for controlling pests such as tetranychidae, microcosaridae, acaridae, tarsonemidae, aleuridae and root-knot nematode and can be used for controlling pests such as tetranychidae, microcosaridae, gall mite, tarsonemidae and the like.

Description

Preparation and Application of Substituted Benzoimidothiazolidinone Derivatives Technical Field

[0001] The present invention belongs to the field of pesticides, and in particular relates to the preparation and application of substituted phenyliminothiazolidinone derivatives. Background Art

[0002] In recent years, due to the long-term and extensive use of acaricides, numerous reports of acaricide-resistant populations have emerged. Existing acaricides are no longer effective in controlling pest mites. Therefore, there is an urgent need to develop novel acaricidal compounds that are effective against populations resistant to existing acaricides. With continued research and development, trifluoroethyl-substituted sulfur-containing compounds have gradually come into the spotlight. Trifluoroethyl-substituted sulfur-containing compounds have been studied in WO1999055668A, CN103664811A, JP2011042611A, JP2011219419A, JP2015036377A, WO 2012 / 012086848, WO 2013 / 018928, and WO 2019 / 131575. However, the results of these studies remain unsatisfactory in terms of efficacy, durability, and toxicity.

[0003] It is known that the active compounds described in the literature mentioned above still have low killing activity when controlling pests, especially mites. In particular, their acaricidal activity is often unsatisfactory at low usage rates, and the control effect on resistant spider mites is even worse. Therefore, new drugs with high efficiency, low toxicity, and excellent killing effect on resistant mites are still urgently needed in agricultural production.

[0004] Summary of the Invention

[0005] The present invention aims to provide a new class of substituted phenyliminothiazolidinone derivatives, which can achieve better pest control effects at lower doses, especially against mites such as Tetranychus, Tenebrionidae, Gall Miteidae, Tarsonemidae, Acaridae, and Heterodermidae.

[0006] In a first aspect, the present invention provides a compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or an agrochemically acceptable salt thereof, which is a substituted phenyliminothiazolidinone derivative.

[0007] in,

[0008] R1 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy;

[0009] R2, R3, R4, R7 are independently selected from hydrogen, halogen, C1-C6 alkyl or C1-C6 haloalkyl;

[0010] R5 is selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy;

[0011] R6 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkylamide, (C1-C6 alkylamino)-C1-C6 alkyl, C3-C6 cycloalkylketone, (C1-C6 alkoxy)-C1-C6 alkyl, (C1-C6 alkylthio)-C1-C6 alkyl, C3-C 12 Cycloalkyl, C3-C6 heterocyclic, C6-C 10 Aryl, C5-C 12 Heteroaryl, (C3-C 12 Cycloalkyl)-C1-C6 alkyl, (C3-C6 heterocyclyl)-C1-C6 alkyl, (C6-C 10 Aryl)-C1-C6 alkyl, (C5-C 12 heteroaryl)-C1-C6 alkyl;

[0012] and may be monosubstituted or polysubstituted by one or more identical or different substituents selected from the group consisting of: halogen, hydroxyl, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C6-C 10 Aryl, C1-C6 alkyl esters;

[0013] n is selected from the numbers 0, 1 or 2, and A is selected from O or S.

[0014] In one embodiment of the present invention,

[0015] R1 is selected from C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0016] R2, R3, R4, R7 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyl;

[0017] R5 is selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy;

[0018] R6 is selected from C1-C6 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkylamide, (C1-C4 alkylamino)-C1-C4 alkyl, C3-C6 cycloalkylketone, (C1-C4 alkoxy)-C1-C4 alkyl, (C1-C4 alkylthio)-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 heterocyclyl, C6-C 10 Aryl, C5-C 10 Heteroaryl, (C3-C6 cycloalkyl)-C1-C4 alkyl, (C3-C6 heterocyclyl)-C1-C4 alkyl, (C6-C 10 Aryl)-C1-C4 alkyl, (C5-C 10 heteroaryl)-C1-C4 alkyl;

[0019] and may be monosubstituted or polysubstituted by one or more identical or different substituents selected from the group consisting of: halogen, hydroxyl, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C6-C 10 Aryl, C1-C4 alkyl esters;

[0020] n is selected from 0, 1, 2, and A is selected from O or S.

[0021] In another embodiment of the present invention, wherein,

[0022] R1 is selected from -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CH2CHF2, -CF2CH3, -CF2CHF2, -CH2CCl3, -CH2CHCl2, -CH2CF2Cl, - CH2CH2CF3, -CF2CHFCF3, -CH2CF2CF3, -CH2CF2CF2CF3, -CH2CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -CH2OCH3;

[0023] R2, R3, R4, R7 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3, -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3;

[0024] R5 is selected from hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3, -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -CH2OCH3;

[0025] R6 is selected from C1-C6 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkylamide, (C1-C4 alkylamino)-C1-C4 alkyl, C3-C6 cycloalkylketone, (C1-C4 alkoxy)-C1-C4 alkyl, (C1-C4 alkylthio)-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 heterocyclyl, C6-C 10 Aryl, C5-C 10 Heteroaryl, (C3-C6 cycloalkyl)-C1-C4 alkyl, (C3-C6 heterocyclyl)-C1-C4 alkyl, (C6-C 10 Aryl)-C1-C4 alkyl, (C5-C 10 heteroaryl)-C1-C4 alkyl;

[0026] and may be monosubstituted or polysubstituted by one or more identical or different substituents selected from the group consisting of: halogen, hydroxyl, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C6-C 10 Aryl, C1-C4 alkyl esters;

[0027] n is selected from 0, 1, 2, and A is selected from O or S.

[0028] In another preferred embodiment of the present invention, the following compounds may be selected:

[0029] R1 is selected from -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3 , -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -CH2OCH3;

[0030] R2, R3, R4, R7 are independently selected from hydrogen, hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3, -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3;

[0031] R5 is selected from hydrogen, hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3, -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -CH2OCH3;

[0032] R6 is selected from C1-C6 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkylamide, (C1-C4 alkylamino)-C1-C4 alkyl, (C1-C4 alkoxy)-C1-C4 alkyl, (C1-C4 alkylthio)-C1-C4 alkyl or the following groups,

[0033] and may be mono- or poly-substituted by one or more identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, amino, hydroxyl, -CH3, -CH2OH, -CH2CH3, -CHF2, -CF3, -C(CH3)3, -OCH3, -OCH2CH3, -OCF3, -Ph;

[0034] n is selected from 0, 1, 2, and A is selected from O or S.

[0035] In another preferred embodiment of the present invention, the following compounds may be selected:

[0036] R1 is selected from -CHF2, -CF3, -CH2CF3, -CH2CH2CF3;

[0037] R2, R3, R4, R7 are independently selected from hydrogen, fluorine, chlorine, -CH3, -CH2CH3;

[0038] R5 is selected from hydrogen, fluorine, chlorine, -CH3, -CH2CH3;

[0039] R6 is selected from C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, (C1-C4 alkylamino)-C1-C4 alkyl, (C1-C4 alkylthio)-C1-C4 alkyl or the following groups,

[0040] and may be mono- or poly-substituted by one or more identical or different substituents selected from the group consisting of: fluorine, chlorine, -CH3, -CF3;

[0041] n is selected from 0, 1; A is selected from S.

[0042] In another preferred embodiment of the present invention, the following compounds may be selected:

[0043] R1 is selected from -CH2CF3, -CH2CH2CF3;

[0044] R2, R3, R4, R7 are independently selected from hydrogen, fluorine, chlorine, -CH3;

[0045] R5 is selected from hydrogen, fluorine, and chlorine;

[0046] R6 is selected from C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl or cyclobutyl, and may be monosubstituted or polysubstituted by one or more identical or different substituents selected from: fluorine, chlorine, -CH3;

[0047] n is selected from 0, 1; A is selected from O.

[0048] Furthermore, the present invention also relates to novel compounds of formula II-1, II-2, III-1 and their oxides,

[0049] Wherein, the substituents R2, R3, R4, R6, R7, and n are the same as above.

[0050] Furthermore, the present invention relates to a novel intermediate V'.

[0051] For the sake of simplicity, the "substituted phenyliminothiazolidinone derivatives", "compounds of formula (I)" or "compounds of the present invention" mentioned below may also cover any isotope-labeled compounds of the compound of formula (I), or their optical isomers, geometric isomers, tautomers or isomer mixtures, or their pesticide-acceptable salts.

[0052] The term "optical isomer" 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 diastereomers, enantiomers, meso-isomers, racemates, or mixtures thereof. For example, optical isomers can be separated by chiral chromatography or by chiral synthesis.

[0053] The term "geometric isomer" means that when a compound has a double bond, the compound may exist as cis-isomers, trans-isomers, E-isomers and Z-isomers. Geometric isomers include cis-isomers, trans-isomers, E-isomers, Z-isomers or mixtures thereof.

[0054] The term "tautomer" refers to isomers that result from the rapid shift of an atom between two positions in a molecule. Those skilled in the art will appreciate that tautomers can transform into each other and, under certain conditions, may reach an equilibrium state and coexist.

[0055] The term "nematode" includes all species of the phylum Nematoda, and in this context particularly species that are parasites on plants (eg species of the orders Aphelenchida, Root-knot Nematodes, Tylenchida, and others).

[0056] Unless otherwise indicated, references herein to "substituted phenyliminothiazolidinone derivatives," "compounds of formula (I)" or "compounds of the present invention" also encompass isotopically labeled compounds in which any atom in the compound is replaced by an isotope thereof. The present invention includes all pharmaceutically acceptable isotopically labeled compounds of the compound of formula (I) in which one or more atoms are replaced by an atom having the same atomic number as the atom commonly found in nature but a different atomic mass or mass number.

[0057] Examples of suitable isotopes 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 18O, and isotopes of sulfur such as 35 S.

[0058] Isotopically labeled compounds of formula (I) can generally be prepared by conventional techniques known to those skilled in the art or by using an appropriate isotopically labeled reagent in place of the non-labeled reagent previously used in an analogous manner to the methods described in the Examples and Preparations appended herein.

[0059] The compounds of formula (I) may exist in the form of pesticide-acceptable salts, for example, acid addition salts and / or base addition salts of the compounds of formula (I). Unless otherwise indicated, "pesticide-acceptable salts" as used herein include acid addition salts or base addition salts that may be present in the compounds of formula (I).

[0060] Pesticide-acceptable salts of the compound of formula (I) include acid addition salts and base addition salts thereof. 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 pesticide-acceptable salts of the compounds described herein are known to those skilled in the art.

[0061] To avoid ambiguity, the following definitions are given for the terms used in this document. Unless otherwise specified, the meanings of the terms used in this document are as follows.

[0062] As used herein, the term "substituted" means that one or more (preferably 1 to 5, more preferably 1 to 3) hydrogen atoms in the group are independently replaced by a corresponding number of substituents.

[0063] As used herein, the term "each independently" means that when there are more than one substituent, the substituents may be the same or different.

[0064] As used herein, the term "alkyl" refers to a saturated aliphatic hydrocarbon, including straight and branched chains. 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 or branched chain radical having 1 to 8 carbon atoms. 1-8 "Alkyl" includes in its definition the term "C 1-6"C1-C3 alkyl" and "C1-C4 alkyl". 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, and the like. The alkyl group may be optionally substituted with one or more (e.g., 1 to 5) suitable substituents.

[0065] As used herein, the term "haloalkyl" refers to an alkyl group having one or more halogen substituents (up to a perhaloalkyl group, 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 C6 haloalkyl group having one or more halogen substituents 1- C6 alkyl group (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" refers to a C 1- C3 alkyl group (up to perhaloalkyl, 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.

[0066] As used herein, the term "n-membered heterocycloalkyl" refers to a heterocycloalkyl having m carbon atoms and (nm) heteroatoms forming a ring, wherein the heteroatoms are selected from O, S, and N. For example, 4-6 membered heterocycloalkyls include, but are not limited to, oxetane, thietane, azetidine, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, tetrahydropyran, tetrahydrothiopyran, piperidine, morpholine, and piperazine. In addition, the heterocycloalkyl group may be optionally substituted with one or more suitable substituents.

[0067] As used herein, numerical ranges related to the number of substituents, carbon atoms, or ring atoms represent a complete enumeration of all integers within the range, and ranges are intended merely 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, numerical ranges related to the number of substituents, carbon atoms, or ring atoms also encompass any subranges thereof, and each subrange is considered disclosed herein.

[0068] The compounds of the present invention can be prepared in a variety of 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 of the specific embodiments of the present invention and make appropriate adjustments to the reaction raw materials and reaction conditions to obtain synthetic methods for other compounds.

[0069] The following synthetic schemes describe the steps for preparing the compounds disclosed herein. R1, R2, R3, R4, R5, R6, and n have the meanings described herein. Synthetic Scheme:

[0070] The above-mentioned intermediate compounds and raw materials can be prepared by referring to the methods reported in WO2006043635A1, WO2010100189, CN102341376A, WO2013092350, WO2013157229, WO2007131680, WO2013030262, WO2018015852, WO2014202510, WO2014202505, WO2015004028, WO2021056922 or WO2021005081.

[0071] The present invention lists a number of exemplary compounds that have been synthesized. The specific group selections are shown in the table below, and the compound data are 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 table below, and the group selections of the compounds in Table 1 below can be combined in any way without particular limitation. Some of the compounds of formula I of the present invention are shown below, but the present invention is in no way limited to these compounds.

[0072] Table 1 Wherein A=S, n=0, specific substituents are shown in the table below

[0073] Table 2 Wherein A=S, n=1, and the specific substituents are the same as those in Table 1.

[0074] Table 3 Wherein A=S, n=2, and the specific substituents are the same as those in Table 1.

[0075] Table 4 Wherein A=O, n=0, and the specific substituents are the same as those in Table 1.

[0076] Table 5 Wherein A=O, n=1, and the specific substituents are the same as those in Table 1.

[0077] Table 6 Wherein A=O, n=2, and the specific substituents are the same as those in Table 1. Table 7 Characterization data of some exemplary compounds

[0078] In a second aspect, the present invention provides an insecticide composition comprising 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, and a pesticide-acceptable carrier.

[0079] The pesticidal acceptable carrier can be an organic or inorganic inert carrier material, for example, suitable carriers include water, gelatin, gum arabic, magnesium stearate, talc, vegetable oil, polyalkylene glycol, petrolatum, mannitol, cellulose, cellulose derivatives, sodium saccharin, magnesium carbonate, saline, glycerol, ethanol, etc. In addition, the pesticide composition may also contain other additives, such as preservatives, stabilizers, emulsifiers, buffers, diluents, binders, wetting agents, lubricants, glidants, etc.

[0080] The dosage form of the insecticide composition of the present invention can be a liquid dosage form, a solid dosage form or a semisolid dosage form, without particular limitation. In some embodiments, the dosage form of the insecticide composition is selected from powders, granules, liquids, suspensions or sprays, preferably wettable powders, wettable liquids, soluble powders, dispersible liquids, aqueous solutions, microemulsions, emulsifiable concentrates, aqueous emulsions, sprayable solutions, dispersible oil suspensions, microcapsule suspensions, water-dispersible granules, water-soluble granules, large granules, granules for broadcasting and soil application, aerosols, ultra-low volume formulations and wax products.

[0081] 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 target, 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.

[0082] The specific administration frequency can be determined by technicians in the relevant field, for example, 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.

[0083] In a third aspect, the present invention provides the use of a compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or an agrochemically acceptable salt thereof in the preparation of an insecticide for pest control.

[0084] The compounds of the present invention are suitable for preventing and 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 agriculture, forestry, storage product protection and material protection, and hygiene. When used at low concentrations, the compounds of the present invention also show excellent control effects on various pests or mites, and have insecticidal or acaricidal activity at each stage of the pest or mite life cycle (such as eggs, larvae (nymphs), pupae, and adults). The compounds of the present invention also show excellent control activity against pests or mites that have developed resistance to traditional insecticides or mites.

[0085] The present invention also relates to a method for controlling pests or acarids, which comprises applying a control-effective amount of a compound of formula (I) to the locus of the insects, the insect habitat, the pest habitat, the area to be protected, or directly to the insects to be controlled. The compounds of the present invention may also be used to control other invertebrate pests or organisms.

[0086] Specifically, the insect habitat, pest habitat, or mite habitat refers to the environment where insects, pests, or mites live or where their eggs exist, including the surrounding air, food, or objects they come into contact with. For example, by applying the active compound to plant seeds (before planting), seedlings, or planted cuttings, leaves, stems, fruits, grains, and / or roots, or to soil or other growth media (before or after crop planting), it is possible to control insects or mites that eat, destroy, or come into contact with edible agricultural products, ornamental plants, turf, pasture plants, or other economically valuable plants. It is also possible to protect these plants from diseases caused by viruses, fungi, or bacteria by controlling sap-feeding pests such as whiteflies, planthoppers, aphids, or mites such as spider mites and spider mites. The plants include those bred by conventional methods, as well as plants genetically modified through modern biotechnology to impart insect or mite resistance, herbicide resistance, high yield, and / or other beneficial characteristics. It is expected that the compounds will be useful for protecting fabrics, paper, stored grain, seeds and other foodstuffs, homes, buildings and the like, and / or loci, by applying the compounds of the invention to or in the vicinity of such objects.

[0087] The inventors of the present invention have discovered that even at relatively low doses, the compounds of the present invention are effective in controlling animal pests, particularly insects, arachnids, worms, nematodes and molluscs, encountered in agriculture, horticulture, livestock breeding, aquaculture, forestry, gardening and leisure facilities, the protection of stored products and materials, and hygiene. These compounds are preferably used as insecticides. They are effective against normally sensitive and resistant species and against all or some developmental stages. The above-mentioned pests include animal pests and include insects, mites or nematodes, specifically including:

[0088] Pests from the phylum Arthropoda, in particular from the class Arachnida, for example from the order Acarina, such as the family Tetranychidae (for example Tetranychus spp., Panonychus spp. or Oligonychus spp.), such as Acarus spp. (for example Acarus siro, Aceria kuko, Aceria sheldoni), Aculops spp., Aculus spp. (for example Aculus fockeui, Aculus schlechtendali), Amblyomma spp., Amphitetranychus viennensis, Argas spp. spp.), Boophilus spp., Brevipalpus spp. (e.g., Brevipalpus phoenicis), Bryobia graminum, Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp.;

[0089] Pests from the order of the Coleoptera, for example, Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp. (e.g. Agriotes linneatus, Agriotes mancus), Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp. (e.g. Anthonomus grandis), Anthrenus spp., Apion spp., Apogonia spp.), Atomaria spp. (e.g., Atomaria linearis), Attagenus spp., Baris caerulescens, Bruchidius obtectus, Bruchus spp. (e.g., Bruchus pisorum, Bruchus rufimanus), Cassida spp., Cerotoma trifurcata, Ceuthorhynchus spp. (e.g., Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae), Chaetocnema spp. (e.g., Chaetocnema confinis), Chaetocnemadenticulata, corn flea beetle (Chaetocnema ectypa), Cleonus mendicus, broad-breasted click beetles (Conoderus spp.), Cosmopolites spp. (e.g., banana black weevil (Cosmopolites sordidus));

[0090] Pests from the order of Diptera, for example, 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 orientalis), 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);

[0091] Pests from the order of the Heteroptera, for example, Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp. (e.g., Cimex adjunctus, Cimex hemipterus, Cimex lectularius, Cimex pilosellus), Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti), Dysdercus spp., and Euschistus spp.;

[0092] Pests from the order of the Homoptera, for example, Acizzia acaciae baileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp. (e.g., Acyrthosiphon pisum), Acrogonia spp., Aeneolamia spp., Agonascena spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp. (e.g., Amrasca bigutulla, Amrasca devastans), Anuraphis cardui, Aonidiella spp. (e.g. Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata), Aphanostigma piri, Aphis spp. (e.g. Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis hederae, Aphis illinoisensis, Aphis middletoni, Aphis nasturtii, Aphis nerii);

[0093] Pests from the order of the Hymenoptera, for example, Acromyrmex spp., Athalia spp. (for example Athalia rosae), Atta spp., Diprion spp. (for example Diprion similis), Hoplocampa spp. (for example Hoplocampa cookei, Hoplocampa testudinea), Lasius spp.;

[0094] Pests from the order of the Isoptera, for example, Coptotermes spp., Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Microtermes obesi, Odontotermes spp., Reticulitermes spp. (for example, Reticulitermes flavipes, Reticulitermes hesperus);

[0095] Pests from the order of the Lepidoptera, for example, Achroia grisella, Acronicta major, Adoxophyes spp. (e.g., Adoxophyesorana), Aedia leucomelas, Agrotis spp. (e.g., Agrotissegetum, Agrotis ipsilon), Alabama spp. (e.g., Alabama argillacea), Amyelois transitella, Anarsia spp., Anticarsia spp. (e.g., Anticarsia gemmatalis), Argyroploce spp., Barathra brassicae), Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capuareticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp. (e.g., Chilo plejadellus, Chilo suppressalis), Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp.), Conopomorpha spp.;

[0096] Pests from the order of Orthoptera or Saltatoria, for example, house crickets (Acheta domesticus), Dichroplus spp., Gryllotalpa spp. (for example Gryllotalpa gryllotalpa), Hieroglyphus spp., Locusta spp. (for example Locusta migratoria), Melanoplus spp. (for example Melanoplus devastator), desert locust (Schistocerca gregaria);

[0097] Pests from the order of the Phthiraptera, for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix, Ptirus pubis, Trichodectes spp.;

[0098] Pests from the order of the Thysanoptera, for example, Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp. (e.g. Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, Frankliniella vaccinii, Frankliniella williamsi), Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp.), Taeniothrips cardamoni, Thrips spp. (e.g. Thrips palmi, Thrips tabaci);

[0099] Plant pests from the phylum Nematoda, i.e. plant-parasitic nematodes, in particular Aglenchus spp. (e.g. Aglenchus agricola), Anguinas spp. (e.g. Anguina tritici), Aphelenchoides spp. (e.g. Aphelenchoides arachidis, Aphelenchoides fragariae), Belonolaimus spp. (e.g. Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni), Bursaphelenchus spp. (e.g. Bursaphelenchus spp. cocophilus), Bursaphelenchus eremus, Bursaphelenchus xylophilus); Meloidogyne spp.) (e.g., Meloidogyne chitwoodi, Meloidogyne fallax, Meloidogyne acronea, Meloidogyne africana, Meloidogyne arenaria, Meloidogyne arenaria thamesi, Meloidogyneartiella, Meloidogyne chitwoodi, Meloidogyne coffeicola, Meloidogyne ethiopica, Meloidogyne exigua, Meloidogyne fallax, Meloidogyne graminicola ... 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 species spp.) (e.g. marking Xiphinema index).

[0100] Those skilled in the art will appreciate that the definitions and preferences described in one aspect of the present invention are equally applicable to other aspects. Those skilled in the art will appreciate that the embodiments of the various aspects of the present invention can be combined in various ways without departing from the subject matter and ideas of the present invention, and these combinations are also included within the scope of the present invention.

[0101] The beneficial effects of the present invention are:

[0102] By chemically modifying and molecularly designing aromatic sulfides with aromatic amine structures and introducing heterocyclic substituents on the nitrogen atom, a series of more efficient compounds with excellent activity for use in agricultural or forestry insecticides or mites were obtained, showing outstanding control effects especially against two-spotted spider mites, cinnabarin spider mites, apple mites, and citrus mites. DETAILED DESCRIPTION

[0103] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0104] The compounds of formula (I) of the present invention can be synthesized using a variety of methods familiar to those skilled in the art of organic synthesis. The following specific examples provide some exemplary methods for synthesizing compounds of formula (I), which are well known in the field of synthetic chemistry. Obviously, by referring to the exemplary schemes in this patent, those skilled in the art can easily design other synthetic routes for compounds of formula (I) by appropriately adjusting the reactants, reaction conditions, and protecting groups.

[0105] Synthesis of Intermediate 1-Fluoro-2-isothiocyanato-5-methyl-4-[hydro(3,3,3-trifluoropropyl)thio]benzene (Intermediate III)

[0106] To 3.90 g (15.40 mmol) of the starting material 2-fluoro-4-methyl-5-(3,3,3-trifluoropropyl)thiophenylamine, a mixture of 20 mL of water and 10 mL of DMF was added, followed by 4.26 g (30.80 mmol) of K2CO3, and the mixture was stirred until uniform. 5.86 g (77.00 mmol) of CS2 was slowly added dropwise at room temperature. After the addition was complete, the mixture was stirred for 3 h, monitored by TLC, until complete conversion of the 2-fluoro-4-methyl-5-(3,3,3-trifluoropropyl)thiophenylamine was achieved. The reaction mixture was then cooled to 0°C, and a solution of cyanuric chloride (1.42 g, 7.70 mmol) dissolved in 15 mL of DCM was added dropwise. After the addition was complete, stirring was continued at 0°C for 0.5 h. The reaction mixture was then basified with 6N aqueous NaOH to a pH > 11 to obtain a clear solution. The organic layer was separated and extracted with DCM (3 x 20 mL). The organic layers were combined and dried over anhydrous Na2SO4, filtered, and the solvent was removed by rotary evaporation. Purification by silica gel column chromatography using petroleum ether as eluent gave 2.29 g of 1-fluoro-2-isothiocyanato-5-methyl-4-[hydro(3,3,3-trifluoropropyl)thio]benzene (yield: 50.36%).

[0107] 1 H NMR(400MHz, DMSO-d6)δ:7.47(d,J=7.4Hz,1H),7.40–7.31(m,1H),3.15(dd,J=8.3,6.9Hz,2H),2.72–2.52(m,2H),2.30(s,3H).

[0108] Example 1 Synthesis of 2-({2-fluoro-4-methyl-5-[(3,3,3-trifluoropropyl)sulfanyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (Compound I-311)

[0109] 0.40 g (1.35 mmol) of 1-fluoro-2-isothiocyanato-5-methyl-4-[hydrogen(3,3,3-trifluoropropyl)thio]benzene was added to the reaction flask and dissolved in 20 mL of toluene. 0.16 g (1.63 mmol) of 2,2,2-trifluoroethylamine and 0.37 g (2.71 mmol) of potassium carbonate were then added in sequence. The reaction was stirred at room temperature and monitored by TLC. After the complete disappearance of 1-fluoro-2-isothiocyanato-5-methyl-4-[hydrogen(3,3,3-trifluoropropyl)thio]benzene, 0.41 g (2.71 mmol) of methyl bromoacetate was added to the reaction system. The mixture was heated to 40°C for reaction. After the reaction was complete, the reaction system was poured into 100 mL of saturated saline solution. The organic phase was collected, dried over anhydrous Na2SO4, filtered, and the solvent was removed by rotary evaporation. The product was purified by silica gel column chromatography to obtain 0.53 g of 2-({2-fluoro-4-methyl-5-[(3,3,3-trifluoropropyl)sulfanyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one in a yield of 90.08%.

[0110] 1 H NMR (400MHz, DMSO-d6) δ: 7.25 (d, J = 11.3Hz, 1H), 7.01 (d, J = 8.0Hz, 1H), 4.59 (q, J = 9.1Hz, 2H), 4.23(s,2H),3.07(dd,J=8.4,6.8Hz,2H),2.52(s,2H),2.32(s,3H).LC-MS(m / z,ESI):435[M+H] + .

[0111] Example 2 Synthesis of 2-({2-fluoro-4-methyl-5-[(3,3,3-trifluoropropyl)sulfinyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (Compound II-311) and 2-({2-fluoro-4-methyl-5-[(3,3,3-trifluoropropyl)sulfonyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (Compound III-311)

[0112] 2-({2-fluoro-4-methyl-5-[(3,3,3-trifluoropropyl)sulfanyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one 0.57 g (1.31 mmol) was added to the reaction flask and dissolved with dichloromethane. The reaction system was cooled to 0°C and 0.27 g (1.57 mmol) of m-chloroperbenzoic acid was added. The reaction was stirred at this temperature and monitored by TLC. After the raw material was completely converted, an aqueous sodium thiosulfate solution was added to the reaction system and the reaction was stirred. Sodium bicarbonate solution was added and the stirring was continued. The reaction was stirred for 30 minutes, the reaction was stopped, and the mixture was extracted with dichloromethane (25 mL×3). The organic phase was collected and purified to obtain 2-({2-fluoro-4-methyl-5-[(3,3,3-trifluoropropyl)sulfinyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (II-311) and 2-({2-fluoro-4-methyl-5-[(3,3,3-trifluoropropyl)sulfonyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (Compound III-311).

[0113] Compound II-311: 1 H NMR(400MHz, DMSO-d6)δ:7.43–7.29(m,2H),4.60(q,J=9.1Hz,2H),4.26(d,J=1.5Hz,2H),3.2 8(ddd,J=13.4,10.0,5.4Hz,2H),2.97–2.64(m,2H),2.35(s,3H).LC-MS(m / z,ESI):451[M+H] + ;

[0114] Compound III-311: 1H NMR (400MHz, DMSO-d6) δ: 7.55 (dd, J=19.3, 9.7Hz, 2H), 4.59 (q, J=9.1Hz, 2H), 4.26 (s ,2H),3.66–3.55(m,2H),2.71–2.63(m,2H),2.62(s,3H).LC-MS(m / z,ESI):467[M+H] + ;

[0115] Test example: biological activity test

[0116] In the following test examples, the insecticidal compound Ib71 disclosed in patents WO2013092350A1, CN108658816A, CN108276358A, etc., with the common name sulfiflumin (represented as CK1 in the text); and the insecticidal compound Ia-175 (represented as CK2 in the text) were used as positive controls.

[0117] In the following test example, if the control mortality rate is greater than 10%, the test is repeated. If the control mortality rate is less than 10%, the acaricidal activity is measured using Abbott's correction formula, and the toxicity regression equation is obtained using the DPS data processing system to calculate the LC 50 The values, 95% confidence limits and statistical analysis were performed.

[0118] Test Example 1: Biological activity test against adults of Tetranychus urticae Koch

[0119] Experimental Method: This test was conducted in accordance with the agricultural industry standard NY / T1154.13-2008, using a leaf-disc spray method. Clean, flat, appropriately sized, and uniformly aged kidney bean leaves were placed flat on a Petri dish lined with clean filter paper, facing up. The filter paper was moistened with water. Thirty-four adult Tetranychus urticae mites of similar physiological condition were then seeded onto each leaf using a brush. The compound (2 mg) was dissolved in 2 mL of DMSO to create a 1000 mg / L stock solution. This stock solution was diluted 10-fold with 0.1% Tween-80 in HO to obtain a 100 mg / L test solution, then 20-fold to obtain a 50 mg / L test solution. The same dilution method was repeated to obtain further test concentrations. Leaves infested with adult Tetranychus urticae were sprayed using a sprayer until the leaf surface and the mites were just covered with spray droplets. Each treatment was replicated three times, with a blank control spray containing an equal ratio of DMSO and Tween solution. The experimental targets were cultured in an artificial climate chamber (24-26°C, L:D = 16:8, RH 60%). After 72 hours, adult mite mortality was recorded. Mites were considered dead if their legs remained motionless or unresponsive when touched with tweezers.

[0120] Calculation method:

[0121] Corrected mortality (%) = [(treatment mortality - control mortality) / (1 - control mortality)] × 100%

[0122] Among the partially donated compounds, the lower level compounds were present at a concentration of 100mg / L per hour, and the efficacy of controlling adult insects was good, the mortality rate reached 100%: Compounds I-47, I-50, I-65, I-72, I-7 5, I-78, I-90, I-115, I-117, I-122, I-127, I-129, I-139, I-143, I-146, I-152, I-160, I-162, I-164, I-172, I-173, I-179, I-181, I-182, I-189, I-194, I-197, I-220, I-226, I-238, I-243, I-258, I-261, I-263, I-265, I-268, I-270, I-275, I-287, I-332, I-334, I-335, I-336, I-337, I-338, I-339, I-341, I-344, I-345, I-346, I-347, I-348, I-349, II-44, II-47, II-50, II-53, II-65, II-78, II-88, II-90, II-127, II-146, II-148, II-160, II-164, II-172, II-189, II-19 4, II-201, II-203, II-217, II-220, II-230, II-238, II-240, II-243, II-251, II-258, II-265 , II-268, II-273, II-275, II-283, II-285, II-332, II-334, II-335, II-339, II-341, II-347.

[0123] Among the partially tested compounds, the lower level compounds have a concentration of 2.5mg / L per hour and two-spot leaf insect control efficacy, mortality rate of 80% or more: I-65, I-75, I-78, I-90, I-164, I-173, I-243, II-65, II-78, II-243 , I-332, I-334, I-335, I-338, I-339, I-341, I-344, I-347, I-349, II-65, II-78, II-243, II-332, II-335, II-339, II-341, II-347.

[0124] According to the above method, compounds I-65 and I-90 were selected and tested in parallel with the known compounds CK1 (sulfiflumin), CK2, and spirodiclofen for their activity against Tetranychus cinnabarinus nymphs. The experimental results are shown in Table 8. CK2 is known to exhibit an efficacy of over 90% against Tetranychus urticae at a dose of 500 g / ha.

[0125] Table 8. Activity assay against adult Tetranychus urticae (72 h)

[0126] Test Example 2: Biological activity test against Tetranychus cinnabarinus nymphs

[0127] Experimental Method: Using a leaf disc spray method, fresh broad bean plants were seeded with adult insects. One day after egg laying, the adult mites were removed and the eggs were ready for use after hatching into nymphs. The broad bean leaves were then broken into leaf discs, moistened with cotton, and placed in a plastic Petri dish. 30-40 nymphs of Tetranychus cinnabarinus were seeded. The compound (2 mg) was dissolved in 2 mL of DMSO to form a stock solution at a concentration of 1000 mg / L. This stock solution was diluted 10-fold with 0.1% Tween-80 in H2O to produce a test solution at a concentration of 100 mg / L. After the test insects were stabilized on the leaves, the leaf discs were sprayed with a fixed amount (2.5 mL) in a Potter spray tower. Three replicates were used, with a blank control and a control group sprayed with an equal ratio of DMSO and Tween water. After air drying, the test specimens were incubated in a climatic chamber (24-26°C, L:D = 16:8, RH 60%). Results were evaluated after 48 hours. Use tweezers to touch the insect body; if there is no reaction, it is considered dead.

[0128] Calculation method:

[0129] Corrected mortality (%) = [(treatment mortality - control mortality) / (1 - control mortality)] × 100%

[0130] Among some of the tested compounds, the following compounds showed good control effects on Tetranychus cinnabarinus nymphs at a concentration of 100 mg / L, with a mortality rate of 100%: compounds I-47, I-50, I-53, I-65, I-72, I-75, I-78, I-90, I-98, I-111, I-115, I-117, I-119, I-122, I -125, I-129, I-139, I-140, I-143, I-146, I-152, I-158, I-160, I-162, I-164, I-172, I-173, I-181, I-182, I-189, I-194, I-197, I-201, I-203, I-209, I-220, I-238, I-240, I-243, I-258, I-261, I-263, I-273, I-275, I-283, II-47, II-50 ,II-53,II-56,II-65,II-78,II-85,II-88,II-90,II-119,II-139,II-143,II -146, II-148, II-162, II-164, II-172, II-189, II-194, II-201, II-203, II-220, II-230, II-238, II-243, II-265, II-268, II-270, II-275, II-283 and II-285.

[0131] Among some of the tested compounds, the following compounds had a good control effect on the nymphs of Tetranychus cinnabarinus at a concentration of 2 mg / L, with a mortality rate of more than 80%: I-65, I-78, I-85, I-90, I-146, I-164, I-173, II-65, II-78, II-85, II-90, and II-164.

[0132] According to the above method, compounds I-65, I-78, I-164, and I-173 were selected and tested in parallel with the known compounds CK1 (sulfiflumin), CK2, ethoxaclonil, and spiroclofen for their activity against Tetranychus cinnabarinus nymphs. The experimental results are shown in Table 9.

[0133] Table 9. Activity assay against Tetranychus cinnabarinus nymphs (72 h)

[0134] Test Example 3: Biological activity test against adults of Tetranychus cinnabarinus

[0135] Experimental Method: Using the leaf disc spray method, clean, flat, appropriately sized, and uniformly aged broad bean leaves were selected. The leaves were then broken into leaf discs, moistened with cotton, and placed in a plastic Petri dish. 30-40 adult Tetranychus cinnabarinus mites were then inoculated. The compound (2 mg) was dissolved in 2 mL of DMSO to form a stock solution of 1000 mg / L. This stock solution was diluted 10-fold with 0.1% Tween-80 in H2O to produce a test solution of 100 mg / L. After the test insects were stabilized on the leaves, the leaf discs were sprayed with a fixed amount (2.5 mL) in a Potter spray tower. This was repeated three times, with a blank control treated with an equal ratio of DMSO and Tween-80 aqueous solution. After air drying, the test specimens were incubated in an artificial climate chamber (24-26°C, L:D = 16:8, RH 60%). Results were assessed after 48 hours. Insects were considered dead if no reaction was detected by prodding with tweezers.

[0136] Calculation method:

[0137] Corrected mortality (%) = [(treatment mortality - control mortality) / (1 - control mortality)] × 100%

[0138] Among some of the tested compounds, the following compounds showed good control effects on adults of Tetranychus cinnabarinus at a concentration of 100 mg / L, with a mortality rate of 100%: compounds I-47, I-50, I-53, I-65, I-72, I-75, I-78, I-88, I-90, I-98, I-111, I-115, I-117, I-119, I-122, I-125, I-129, I-139, I-140, I-143, I-146, I-148, I-152, I-158, I-160, I-162, I-164, I-

[0139] 172, I-173, I-181, I-182, I-189, I-194, I-197, I-201, I-203, I-205, I-209, I-217, I-220, I-238, I-

[0140] 243, I-251, I-258, I-261, I-263, I-268, I-273, I-275, I-283, II-47, II-50, II-53, II-65, II-78, II-88, II-90, II-119, II-139, II-143, II-146, II -148, II-162, II-164, II-172, II-189, II-194, II-201, II-203, II-220, II-230, II-238, II-243, II-265, II-268, II-270, II-275, II-283, II-285.

[0141] Test Example 4: Biological activity test against Tetranychus cinnabarinus eggs

[0142] Experimental Method: Using the leaf dip method, select healthy broad bean seedlings, trim the tops, and cut each seedling into two leaves and one stem. The stems were placed in a water-filled injection bottle. Each leaf was inoculated with 10-15 female adult mites of consistent physiological status. After 24 hours, the female mites were removed. The compound (2 mg) was dissolved in 2 mL of DMSO to create a stock solution at a concentration of 1000 mg / L. This stock solution was diluted 10-fold with 0.1% Tween-80 aqueous solution to create a test solution at a concentration of 100 mg / L. Leaf discs were punched from 24-28 hour-old ovulated leaves and dipped in the solution for 10 seconds. The discs were then removed and immediately blotted with absorbent paper to remove excess solution. The discs were then placed in 24-well plates and moistened with cotton. Each treatment was replicated three times. A blank control was used. The dip solution used for the control group was an equal ratio of DMSO and Tween-80 aqueous solution. The experimental targets were placed in an artificial climate chamber (24-26°C, L:D=16:8, RH 60%) for cultivation. After the eggs in the blank control area hatched, the number of unhatched eggs and hatched eggs in the drug-treated leaf discs were counted.

[0143] Calculation method:

[0144] Hatching inhibition rate = (number of unhatched eggs / total number of eggs treated) × 100%

[0145] Corrected hatching inhibition rate = [(hatching inhibition rate of treatment area - hatching inhibition rate of control area) / (1 - hatching inhibition rate of control area] × 100%

[0146] Among some of the tested compounds, the following compounds had a good control effect on Tetranychus cinnabarinus eggs at a concentration of 100 mg / L, with a mortality rate of 100%: compounds I-47, I-50, I-65, I-72, I-75, I-78, I-90, I-98, I-109, I-117, I-122, I-125, I-127, I-129, I-139, I-140, I-143 , I-146, I-152, I-158, I-160, I-162, I-164, I-172, I-173, I-181, I-182, I-189, I-194, I-197, I-201, I-203, I-205, I-209, I-217, I-220, I-238, I-243, I-258, I-261, I-263, I- 275, I-283, II-44, II-47, II-50, II-53, II-65, II-78, II-88, II-90, II-139, II-143, II-146, II-148, II-164 , II-172, II-189, II-194, II-201, II-203, II-220, II-230, II-243, II-265, II-268, II-275, II-283, II-285.

[0147] Test Example 5: Biological activity test against southern root-knot nematode

[0148] Experimental Methods: The bioactivity of the compounds against second-instar larvae of the southern root-knot nematode was tested using a direct contact toxicity assay. The compound (2 mg) was dissolved in 2 mL of DMSO to form a stock solution at a concentration of 1000 mg / L. This stock solution was diluted five-fold with 0.1% Tween-80 aqueous solution to obtain a test solution at a concentration of 200 mg / L. Nematodes were extracted from harvested tomato soil using a Baermann funnel method. Large larvae were removed using a 300-mesh molecular sieve, followed by small larvae removed using a 325-mesh molecular sieve. Larvae of comparable size to second-instar larvae were obtained. Finally, the solution was concentrated by centrifugation to 10 μL containing 40-70 nematodes. Then, 90 μL of the prepared test solution (200 mg / L) and 80 μL of 0.1% Tween-80 aqueous solution were added to a 48-well biochemical culture plate. Finally, 10 μL of the nematode suspension (40-70 nematodes) was added. Each treatment was replicated three times, with a blank control containing an equal ratio of DMSO and Tween-80 aqueous solution. The 48-well biochemical culture plate was incubated in a climatic chamber (24-26°C, L:D = 16:8, RH 60%). After 48 hours, mortality was observed and the mortality rate was calculated.

[0149] Calculation method:

[0150] Corrected mortality (%) = [(treatment mortality - control mortality) / (1 - control mortality)] × 100%

[0151] Among some of the tested compounds, the following compound had a good control effect on southern root-knot nematode at a concentration of 100 mg / L, with a mortality rate of at least 75%: compound II-104.

[0152] According to the above method, compound II-104 and the known compound CK1 (sulfiflumin) were selected for parallel determination of activity against second-instar larvae of the southern root-knot nematode. The experimental results are shown in Table 10.

[0153] Table 10. Activity assay against southern root-knot nematode (48h)

[0154] Test Example 6: Potted bioactivity assay against Tetranychus cinnabarinus nymphs

[0155] Experimental Method: Using the whole-plant spray method, green beans were planted in pots approximately 7 cm in diameter, with one plant per pot. A single leaf was retained from green bean seedlings approximately 8 cm tall and 30-70 spider mite nymphs were inoculated. After the infestation stabilized, the number of spider mite nymphs on the leaves was recorded. A certain amount of the original drug was weighed using a 0.0001 g scale and prepared into a 1% stock solution in DMF. This solution was then diluted to the test concentration in distilled water containing 0.1% Tween-80. Leaves were sprayed from both sides using a throat sprayer, 2.5 mL per pot, three times. A blank control was established, and a control group was sprayed with an equal ratio of DMSO and Tween-80 water. After air drying, the test specimens were incubated in an artificial climate chamber (24-26°C, L:D = 16:8, RH 60%). Results were assessed after 72 hours. Insects were touched with tweezers; no reaction was considered dead.

[0156] Calculation method:

[0157] Corrected mortality (%) = [(treatment mortality - control mortality) / (1 - control mortality)] × 100%

[0158] According to the above method, compounds I-173 and I-335 were selected and tested in parallel with known compounds CK1 (sulfiflumin), CK2, and ethidium bromide for their activity against Tetranychus cinnabarinus nymphs. The experimental results are shown in Table 11.

[0159] Table 11. Potted activity assay against Tetranychus cinnabarinus nymphs (72 h)

[0160] Test Example 7: Potted plant bioactivity assay against Tetranychus cinnabarinus eggs

[0161] Experimental Method: Using the whole-plant spray method, green beans were planted in pots approximately 7 cm in diameter, with one plant per pot. A single leaf was retained from green bean seedlings approximately 8 cm tall. 15-30 adult red spider mites were inoculated. After 24 hours, the adults were removed and the number of eggs on the leaves was examined. Plants with fewer eggs were removed, and those with 30-100 eggs were retained. A certain amount of the original drug was weighed using a balance (0.0001 g), prepared into a 1% stock solution in DMF, and then diluted to the test concentration in distilled water containing 0.1% Tween-80 for later use. A throat sprayer was used to spray the leaves from both sides, 2.5 mL per pot, three times in duplicate. A blank control was set up, and the control group was sprayed with an equal proportion of DMSO and Tween-80 aqueous solution. After natural drying, the experimental targets were placed in an artificial climate chamber (24-26°C, L:D=16:8, RH60%) for cultivation. The results were investigated after 7 days, and the number of live insects, dead insects and unhatched eggs on the leaves were recorded.

[0162] Calculation method:

[0163] Corrected inhibition rate (%) = [(number of unhatched eggs - number of unhatched eggs in control) / (1 - number of unhatched eggs in control)] × 100%

[0164] According to the above method, compound I-334 and known compounds CK1 (sulfiflumin), CK2, ethoxaclonil and bifenazate were selected for parallel activity determination against Tetranychus cinnabarinus eggs. The experimental results are shown in Table 12.

[0165] Table 12. Potted activity test on Tetranychus cinnabarinus eggs (7 days)

[0166] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within 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, which is a substituted phenyliminothiazolidinone derivative. in, R1 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy; R2, R3, R4, R7 are independently selected from hydrogen, halogen, C1-C6 alkyl or C1-C6 haloalkyl; R5 is selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy; R6 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkylamide, (C1-C6 alkylamino)-C1-C6 alkyl, C3-C6 cycloalkylketone, (C1-C6 alkoxy)-C1-C6 alkyl, (C1-C6 alkylthio)-C1-C6 alkyl, C3-C 12 Cycloalkyl, C3-C6 heterocyclic, C6-C 10 Aryl, C5-C 12 Heteroaryl, (C3-C 12 (cycloalkyl)-C1-C6 alkyl, (C3-C6 heterocyclyl)-C1-C6 alkyl, (C6-C 10 Aryl)-C1-C6 alkyl, (C5-C 12 Heteroaryl)-C1-C6 alkyl; and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of halogen, hydroxyl, cyano, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, C6-C 10 Aryl, C1-C6 alkyl esters; n is selected from the numbers 0, 1 or 2, and A is selected from O or S.

2. The compound of formula (I) according to claim 1 or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its pesticide-acceptable salt, wherein: R1 is selected from C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; R2, R3, R4, R7 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 haloalkyl; R5 is selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; R6 is selected from C1-C6 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkylamide, (C1-C4 alkylamino)-C1-C4 alkyl, C3-C6 cycloalkylketone, (C1-C4 alkoxy)-C1-C4 alkyl, (C1-C4 alkylthio)-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 heterocyclyl, C6-C 10 Aryl, C5-C 10 Heteroaryl, (C3-C6 cycloalkyl)-C1-C4 alkyl, (C3-C6 heterocyclyl)-C1-C4 alkyl, (C6-C 10 Aryl)-C1-C4 alkyl, (C5-C 10 Heteroaryl)-C1-C4 alkyl; and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of halogen, hydroxyl, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C6-C 10 Aryl, C1-C4 alkyl esters; n is selected from 0, 1, 2, and A is selected from O or S.

3. The compound of formula (I) according to claim 1 or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its pesticide-acceptable salt, wherein: R1 is selected from -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CH2CHF 2、 -CF2CH3, -CF2CHF2, -CH2CCl3, -CH2CHCl2, -CH2CF2Cl, -CH2CH2CF3, -CF2CHFCF3, -CH2CF2CF 3、 -CH2CF2CF2CF3, -CH2CH2CH2CF 3、 -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -CH2OCH3; R2, R3, R4, R7 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3, -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3; R5 is selected from hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3, -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -CH2OCH3; R6 is selected from C1-C6 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkylamide, (C1-C4 alkylamino)-C1-C4 alkyl, C3-C6 cycloalkylketone, (C1-C4 alkoxy)-C1-C4 alkyl, (C1-C4 alkylthio)-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 heterocyclyl, C6-C 10 Aryl, C5-C 10 Heteroaryl, (C3-C6 cycloalkyl)-C1-C4 alkyl, (C3-C6 heterocyclyl)-C1-C4 alkyl, (C6-C 10 Aryl)-C1-C4 alkyl, (C5-C 10 Heteroaryl)-C1-C4 alkyl; and may be substituted or polysubstituted by one or more identical or different substituents, the substituents being selected from the group consisting of halogen, hydroxyl, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C6-C 10 Aryl, C1-C4 alkyl esters; n is selected from 0, 1, 2, and A is selected from O or S.

4. The compound of formula (I) according to claim 1 or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its pesticide-acceptable salt, wherein: R1 is selected from -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3 , -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -CH2OCH3; R2, R3, R4, R7 are independently selected from hydrogen, hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3, -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3; R5 is selected from hydrogen, hydrogen, fluorine, chlorine, bromine, iodine, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -CH2Cl, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CH3, -CH2CH2CF3, -CH(CF3)2, -CF(CH3)2, -CF(CF3)2, -C(CF3)3, -OCH3, -OCH2CH3, -OCH2CH2CH3, -CH2OCH3; R6 is selected from C1-C6 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkylamide, (C1-C4 alkylamino)-C1-C4 alkyl, (C1-C4 alkoxy)-C1-C4 alkyl, (C1-C4 alkylthio)-C1-C4 alkyl or the following groups, and may be mono- or poly-substituted by one or more identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, amino, hydroxyl, -CH3, -CH2OH, -CH2CH3, -CHF2, -CF3, -C(CH3)3, -OCH3, -OCH2CH3, -OCF3, -Ph; n is selected from 0, 1, 2, and A is selected from O or S.

5. The compound of formula (I) according to claim 1 or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or its pesticide-acceptable salt, which has the following structure:

6. Compounds of formula II-1, II-2, III-1 and oxides thereof, in, R2, R3, R4, R6, R7, and n have the meanings defined in claim 1, or the meanings defined in claim 2, or the meanings defined in claim 3, or the meanings defined in claim 4, or the meanings defined in claim 5.

7. An insecticide composition comprising a compound of formula (I) according to any one of claims 1 to 5 or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or a pesticidally acceptable salt thereof, and a pesticidally acceptable carrier.

8. The insecticide composition according to claim 7, wherein the dosage form is selected from powders, granules, liquids, suspensions or sprays, preferably wettable powders, wettable liquids, soluble powders, dispersible liquids, aqueous solutions, microemulsions, emulsifiable concentrates, aqueous emulsions, sprayable solutions, dispersible oil suspensions, microcapsule suspensions, water-dispersible granules, water-soluble granules, large granules, granules for broadcasting and soil application, aerosols, ultra-low volume agents and wax products.

9. Use of a compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or an acceptable salt thereof in pesticides for the preparation of an insecticide for pest control according to any one of claims 1 to 5.

10. The use according to claim 9, wherein the pest is selected from the family Tetranychidae, Leptospiridae, Mylostomidae, Tarsonematidae, Acaridae, and Heteroderaeidae.

11. The use according to claim 10, wherein the pest is selected from the group consisting of Tetranychus urticae, Tetranychus cinnabarinus, Panonychus ulmi, Panonychus citri, and Meloidogyne incognita.

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