Preparation and application of substituted benzimino thiazolidone derivative

Abstract

The invention relates to a preparation method and an application of a substituted benzimino thiazolidone derivative. Specifically, the invention relates to a compound 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 pharmaceutically acceptable salt thereof, 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 such as tetranychidae, microcosaridae, acaridae, tarsonidae, aleuridae and root-knot nematode, and can be used for controlling pests such as tetranychidae, microcosaridae, gall mite, tarsonidae, aleuridae and the like. # imgabs0 #

Description

Technical Field

[0001] The 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 large-scale use of acaricides, there have been a large number of reports on acaricide-resistant populations. The use of existing acaricides has been unable to achieve effective control of harmful mites. Therefore, there is an urgent need to develop new acaricidal active compounds that are effective against existing acaricide-resistant populations. With the continuous development and research of researchers, trifluoroethyl-substituted sulfur-containing compounds have gradually entered the researchers' field of vision. WO1999055668A, CN103664811B, JP5280972B, JP2011219419A, JP2015036377A, WO 2012 / 012086848, WO 2013 / 018928 and WO 2019 / 131575 have all studied trifluoroethyl-substituted sulfur-containing compounds. However, the above research results are still not satisfactory in terms of efficacy, durability, toxicity, etc.

[0003] It is known that the active compounds recorded in the above-mentioned literature still have low killing activity when controlling pests, especially mites. In particular, their miticide 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. Summary of the invention

[0004] The object of the present invention is to provide a new class of substituted phenyliminothiazolidinone derivatives, which can achieve better pest control effects at lower dosages, especially for mites such as Tetranychus, Acaridae, Tarsonematidae, Acaridae, etc.

[0005] In the 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 a pesticidally acceptable salt thereof as a substituted phenyliminothiazolidinone derivative,

[0006]

[0007] in,

[0008] R 1 Selected from C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 1-C 6 Haloalkyl, C 1 -C 6 Alkoxy or C 1 -C 6 Haloalkoxy;

[0009] R 2 , R 3 , R 4 , R 7 are independently selected from hydrogen, halogen, C 1 -C 6 Alkyl or C 1 -C 6 Haloalkyl;

[0010] R 5 Selected from hydrogen, halogen, C 1 -C 6 Alkyl, C 1 -C 6 Haloalkyl, C 1 -C 6 Alkoxy or C 1 -C 6 Haloalkoxy;

[0011] R 6 Selected from C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 1 -C 6 Alkylamide, (C 1 -C 6 Alkylamino)-C 1 -C 6 Alkyl, C 3 -C 6 Cycloalkyl ketone, (C 1 -C 6 Alkoxy)-C 1 -C 6 Alkyl, (C 1 -C 6 (alkylthio)-C 1 -C 6 Alkyl, C 3 -C 12 Cycloalkyl, C 3 -C 6 Heterocyclic group, C 6 -C 10 Aryl, C 5 -C 12 Heteroaryl, (C 3 -C 12Cycloalkyl)-C 1 -C 6 Alkyl, (C 3 -C 6 Heterocyclyl)-C 1 -C 6 Alkyl, (C 6 -C 10 Aryl)-C 1 -C 6 Alkyl, (C 5 -C 12 Heteroaryl)-C 1 -C 6 alkyl;

[0012] and may be substituted or polysubstituted by one or more identical or different substituents selected from: halogen, hydroxyl, cyano, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, C 1 -C 6 Haloalkyl, C 1 -C 6 Haloalkoxy, C 6 -C 10 Aryl, C 1 -C 6 Alkyl esters;

[0013] n is selected from the numbers 0, 1 or 2.

[0014] In one embodiment of the present invention,

[0015] R 1 Selected from C 1 -C 4 Alkyl, C 2 -C 4 Alkenyl, C 2 -C 4 Alkynyl, C 1 -C 4 Haloalkyl, C 1 -C 4 Alkoxy or C 1 -C 4 Haloalkoxy;

[0016] R 2 , R 3 , R 4 , R 7 are independently selected from hydrogen, halogen, C 1 -C 4 Alkyl or C 1 -C 4 Haloalkyl;

[0017] R 5 Selected from hydrogen, halogen, C 1 -C 4 Alkyl, C 1 -C 4 Haloalkyl, C 1 -C 4 Alkoxy or C 1 -C 4 Haloalkoxy;

[0018] R 6 Selected from C 1 -C 6 Alkyl, C 2 -C 4 Alkenyl, C 2 -C 4 Alkynyl, C 1 -C 4 Alkylamide, (C 1 -C 4 Alkylamino)-C 1 -C 4 Alkyl, C 3 -C 6 Cycloalkyl ketone, (C 1 -C 4 Alkoxy)-C 1 -C 4 Alkyl, (C 1 -C 4 (alkylthio)-C 1 -C 4 Alkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Heterocyclic group, C 6 -C 10 Aryl, C 5 -C 10 Heteroaryl, (C 3 -C 6 Cycloalkyl)-C 1 -C 4 Alkyl, (C 3 -C 6 Heterocyclyl)-C 1 -C 4 Alkyl, (C 6 -C 10 Aryl)-C 1 -C 4 Alkyl, (C 5 -C 10 Heteroaryl)-C 1 -C 4 alkyl;

[0019] and may be substituted or polysubstituted by one or more identical or different substituents selected from: halogen, hydroxyl, cyano, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 1 -C 4 Haloalkyl, C 1 -C 4 Haloalkoxy, C 6 -C 10 Aryl, C 1 -C 4 Alkyl esters;

[0020] n is selected from 0, 1, 2.

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

[0022] R 1 Selected from -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-CH 2 Cl, -CHF 2 、-CH 2 F, -CF 3 、-CH 2 CF 3 、-CH 2 CHF 2 , -CF 2 CH 3 , -CF 2 CHF 2 、-CH 2 CCl 3 、-CH 2 CHCl 2 、-CH 2 CF 2 Cl, -CH 2 CH 2 CF 3 , -CF 2 CHF 3 、-CH 2 CF 2 CF 3 、-CH 2 CF 2 CF2 CF 3 、-CH 2 CH 2 CH 2 CF 3 、-CH(CF 3 ) 2 、-CF(CH 3 ) 2 ,-CF(CF 3 ) 2 ,-C(CF 3 ) 3 、-OCH 3 、-OCH 2 CH 3 、-OCH 2 CH 2 CH 3 、-CH 2 OCH 3 ;

[0023] R 2 , R 3 , R 4 , R 7 independently selected from hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-CH 2 Cl, -CHF 2 、-CH 2 F, -CF 3 、-CH 2 CF 3 , -CF 2 CH 3 、-CH 2 CH 2 CF 3 、-CH(CF 3 ) 2 、-CF(CH 3 ) 2 ,-CF(CF 3 ) 2 ,-C(CF 3 ) 3 ;

[0024] R 5 Selected from hydrogen, fluorine, chlorine, bromine, iodine, -CH3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-CH 2 Cl, -CHF 2 、-CH 2 F, -CF 3 、-CH 2 CF 3 , -CF 2 CH 3 、-CH 2 CH 2 CF 3 、-CH(CF 3 ) 2 、-CF(CH 3 ) 2 ,-CF(CF 3 ) 2 ,-C(CF 3 ) 3 、-OCH 3 、-OCH 2 CH 3 、-OCH 2 CH 2 CH 3 、-CH 2 OCH 3 ;

[0025] R 6 Selected from C 1 -C 6 Alkyl, C 2 -C 4 Alkenyl, C 2 -C 4 Alkynyl, C 1 -C 4 Alkylamide, (C 1 -C 4 Alkylamino)-C 1 -C 4 Alkyl, C 3 -C 6 Cycloalkyl ketone, (C 1 -C 4 Alkoxy)-C 1 -C 4 Alkyl, (C 1 -C 4 (alkylthio)-C 1 -C4 Alkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Heterocyclic group, C 6 -C 10 Aryl, C 5 -C 10 Heteroaryl, (C 3 -C 6 Cycloalkyl)-C 1 -C 4 Alkyl, (C 3 -C 6 Heterocyclyl)-C 1 -C 4 Alkyl, (C 6 -C 10 Aryl)-C 1 -C 4 Alkyl, (C 5 -C 10 Heteroaryl)-C 1 -C 4 alkyl;

[0026] and may be substituted or polysubstituted by one or more identical or different substituents selected from: halogen, hydroxyl, cyano, C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 1 -C 4 Haloalkyl, C 1 -C 4 Haloalkoxy, C 6 -C 10 Aryl, C 1 -C 4 Alkyl esters;

[0027] n is selected from 0, 1, 2.

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

[0029] R 1 Selected from -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-CH 2 Cl, -CHF2 、 -CH 2 F, -CF 3 、 -CH 2 CF 3 、 -CF 2 CH 3 、 -CH 2 CH 2 CF 3 、 -CH(CF 3 ) 2 、 -CF(CH 3 ) 2 、 -CF(CF 3 ) 2 、 -C(CF 3 ) 3 、 -OCH 3 、 -OCH 2 CH 3 、 -OCH 2 CH 2 CH 3 、 -CH 2 OCH 3 ;

[0030] R 2 、 R 3 、 R 4 、 R 7 are each independently selected from hydrogen, hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 、 -CH 2 CH 3 、 -CH 2 CH 2 CH 3 、 -CH(CH 3 ) 2 、 -C(CH 3 ) 3 、 -CH 2 Cl, -CHF 2 、 -CH 2 F, -CF 3 、 -CH 2 CF 3 、 -CF 2 CH 3 、 -CH 2 CH 2 CF 3 、 -CH(CF 3 ) 2 、 -CF(CH 3 ) 2 、 -CF(CF 3 ) 2 、 -C(CF 3 )3 ;

[0031] R 5 Selected from hydrogen, hydrogen, fluorine, chlorine, bromine, iodine, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-C(CH 3 ) 3 、-CH 2 Cl, -CHF 2 、-CH 2 F, -CF 3 、-CH 2 CF 3 , -CF 2 CH 3 、-CH 2 CH 2 CF 3 、-CH(CF 3 ) 2 、-CF(CH 3 ) 2 ,-CF(CF 3 ) 2 ,-C(CF 3 ) 3 、-OCH 3 、-OCH 2 CH 3 、-OCH 2 CH 2 CH 3 、-CH 2 OCH 3 ;

[0032] R 6 Selected from C 1 -C 6 Alkyl, C 2 -C 4 Alkenyl, C 2 -C 4 Alkynyl, C 1 -C 4 Alkylamide, (C 1 -C 4 Alkylamino)-C 1 -C 4 alkyl, ( C 1 -C 4 Alkoxy)-C 1 -C 4 Alkyl, (C1 -C 4 (alkylthio)-C 1 -C 4 Alkyl or the following groups,

[0033]

[0034] and may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, amino, hydroxyl, -CH 3 、-CH 2 OH, -CH 2 CH 3 , -CHF 2 , -CF 3 、-C(CH 3 ) 3 、-OCH 3 、-OCH 2 CH 3 、-OCF 3 , -Ph;

[0035] n is selected from 0, 1, 2.

[0036] For the sake of simplicity, the "substituted phenyliminothiazolidinone derivatives", "compounds of formula (I)" or "compounds of the present invention" mentioned below may also include 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.

[0037] The term "optical isomer" means that when a compound has one or more chiral centers, each chiral center may exist in the R configuration or the S configuration, and the various isomers thus constituted are optical isomers. Optical isomers include all diastereomers, enantiomers, mesomers, racemates or mixtures thereof. For example, optical isomers can be separated by chiral chromatography or by chiral synthesis.

[0038] The term "geometric isomer" means that when a double bond exists in a compound, 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 a mixture thereof.

[0039] The term "tautomer" refers to an isomer that is produced by the rapid movement of an atom in a molecule between two positions. Those skilled in the art will understand that tautomers can transform into each other and may reach an equilibrium state and coexist under a certain state.

[0040] 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).

[0041] Unless otherwise indicated, the reference herein to "substituted phenyliminothiazolidinone derivatives", "compounds of formula (I)" or "compounds of the present invention" also encompasses isotope-labeled compounds obtained by replacing any atom in the compound with an isotope atom thereof. The present invention includes all pharmaceutically acceptable isotope-labeled compounds of the compound of formula (I), wherein one or more atoms are replaced by atoms having the same atomic number as the atoms usually found in nature but with a different atomic mass or mass number.

[0042] 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 18 O, and isotopes of sulfur such as 35 S.

[0043] 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.

[0044] The compounds of formula (I) can exist in the form of pesticide-acceptable salts, such as 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 occur in the compounds of formula (I).

[0045] The pesticide-acceptable salts of the compound of formula (I) include its acid addition salts and base addition salts. Suitable acid addition salts are formed by 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.

[0046] To avoid ambiguity, the following definitions are given for the terms used in this article. Unless otherwise specified, the meanings of the terms used in this article are as follows.

[0047] 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.

[0048] As used herein, the term "each independently" means that when the number of substituents is more than one, the substituents may be the same or different.

[0049] 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 The term "alkyl" includes in its definition the term "C 1-6 Alkyl", "C 1 -C 3 Alkyl" and "C 1 -C 4 Examples of alkyl groups 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.

[0050] 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- C 6 "Haloalkyl" refers to a C 1- C 6An alkyl group (up to a perhaloalkyl group, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). 1- C 3 "Haloalkyl" refers to a C 1- C 3 Alkyl groups (up to perhaloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). Examples of haloalkyl groups include: CF 3 , C 2 F 5 , CHF 2 , CH 2 F, CH 2 CF 3 , CH 2 Cl et al.

[0051] As used herein, the term "n-membered heterocycloalkyl" refers to a heterocycloalkyl having m carbon atoms forming a ring 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, piperazine. In addition, the heterocycloalkyl may be optionally substituted with one or more suitable substituents.

[0052] Herein, the numerical ranges related to the number of substituents, the number of carbon atoms, and the number of ring atoms represent a list of all integers within the range, and the ranges are only used as a simplified representation. 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 numerical ranges related to the number of substituents, the number of carbon atoms, and the number of ring atoms also include any subranges thereof, and each subrange is also deemed to be disclosed herein.

[0053] 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.

[0054] The following synthetic schemes describe the steps for preparing the compounds disclosed in the present invention. 1 , R 2 , R 3 , R 4 , R 5 , R 6 and n have the meanings described in the present invention.

[0055]

[0056] The compound of formula IV and its raw materials can be prepared by referring to the methods reported in WO2006043635A1, WO2010100189, CN102341376A, WO2013092350, WO2013157229, WO2007131680, WO2013030262, WO2018015852, WO2014202510, WO2014202505, WO2015004028, WO2021056922A9 or WO2021005081A1.

[0057] The present invention lists a number of exemplary compounds that have been synthesized, and their specific group selections are shown in the following table, 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 following table, and the various group selections of the compounds in Table 1 below can be combined in any way without particular limitation. Some of the compounds of general formula I of the present invention are shown below, but the present invention is by no means limited to these compounds.

[0058] Table 1 Where n = 0, the specific substituents are shown in the following table

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071] Table 2 Wherein n=1, the specific substituents are the same as those in Table 1. Table 3 Wherein n=2, the specific substituents are the same as those in Table 1.

[0072] Table 4 Compound characterization data

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] In a second aspect, the present invention provides a pesticide 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.

[0080] The pesticide-acceptable carrier may be an organic or inorganic inert carrier material, for example, suitable carriers include water, gelatin, gum arabic, magnesium stearate, talc, vegetable oil, polyalkylene glycol, vaseline, 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, adhesives, wetting agents, lubricants, glidants, etc.

[0081] 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 agents, 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.

[0082] The content of the compound of the present invention in the 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.

[0083] 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.

[0084] 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 a pesticidally acceptable salt thereof in the preparation of an insecticide for pest control.

[0085] 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 the compounds of the present invention are used in 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 the pests or mites (such as eggs, larvae (nymphs), pupae, and adults). The compounds of the present invention also show excellent control activity on pests or mites that have developed resistance to traditional insecticides or miticides.

[0086] The present invention also relates to a method for controlling pests or mites, which comprises applying a control effective amount of a compound of formula (I) to the insect locus, insect habitat, pest habitat, area to be protected, or directly to the insect to be controlled. The compounds of the present invention can also be used to control other invertebrate pests or organisms.

[0087] Specifically, the insect habitat, pest habitat or mite habitat refers to the environment where insects, pests or mites live or their eggs exist, including the surrounding air, food eaten or objects contacted. For example, by applying the active compound to the seeds of the plant (before planting), to the seedlings, or planted cuttings, leaves, stems, fruits, grains and / or roots, or to the soil or other growth media (before or after crop planting), it is possible to control insects or mites that eat, destroy or contact edible agricultural products, ornamental plants, turf, pasture plants or other plants with economic value. 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, etc. or mites such as two-spotted spider mites, cinnabar spider mites, etc.; the plants include plants obtained by conventional breeding methods, and also include plants obtained by genetic modification through modern biotechnology with 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.

[0088] The inventors of the present invention have found that even if the compounds of the present invention are applied at lower doses, they are also able to control animal pests encountered in agriculture, horticulture, livestock breeding, aquaculture, forestry, gardening and leisure facilities, protection of stored products and materials, and hygiene, in particular insects, arachnids, worms, nematodes and molluscs. 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:

[0089] Pests from the phylum Arthropoda, in particular from the class Arachnida, for example 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., Boophilus spp., Brevipalpus spp. (for example Brevipalpus phoenicis), Bryobia graminum, Bryobia praetiosa), Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp.;

[0090] Pests from the order of the Coleoptera, for example, Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelasta 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., sweet potato flea beetle (Chaetocnema confinis), Chaetocnemadenticulata, corn flea beetle (Chaetocnema ectypa)), Cleonus mendicus, broad-breasted click beetle (Conoderus spp.), root neck weevil (Cosmopolites spp.) (e.g., banana black weevil (Cosmopolites sordidus));

[0091] 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);

[0092] 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 spp. hewetti), Dysdercus spp., Euschistus spp.;

[0093] 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, Aphismiddletoni, Aphis nasturtii, Aphis nerii);

[0094] 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.;

[0095] Pests from the order of the Isoptera, for example, Coptotermes spp. (e.g. Coptotermes formosanus), Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Microtermes obesi, Odontotermes spp., Reticulitermes spp. (e.g. Reticulitermes flavipes, Reticulitermes hesperus);

[0096] 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, Carposinaniponensis, Cheimatobia brumata, Chilo spp. (e.g. Chiloplejadellus, Chilo suppressalis), Choristoneura spp., Clysiaambiguella, Cnaphalocerus spp., Cnaphalocrocismedinalis, Cnephasia spp.), Conopomorpha spp.;

[0097] Pests from the order of Orthoptera or the order of Saltatoria, for example, Acheta domesticus, Dichroplus spp., Gryllotalpa spp. (e.g. Gryllotalpa gryllotalpa), Hieroglyphus spp., Locusta spp. (e.g. Locusta migratoria), Melanoplus spp. (e.g. Melanoplus devastator), Schistocerca gregaria;

[0098] Pests from the order of the Phthiraptera, for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix, Ptirus pubis, Trichodectes spp.;

[0099] 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);

[0100] 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, 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. marking Xiphinema index). .

[0101] 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.

[0102] The beneficial effects of the present invention are:

[0103] By chemically modifying and molecularly designing aromatic sulfides of 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, especially showing excellent control effects against two-spotted spider mites, cinnabarinus spider mites, apple mites, and citrus mites. DETAILED DESCRIPTION

[0104] The technical solutions in the embodiments of the present invention will be described clearly and completely below in combination with 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 creative work are within the scope of protection of the present invention.

[0105] The compounds of formula (I) of the present invention can be synthesized by various 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, referring to the exemplary schemes in this patent, those skilled in the art can easily design other synthetic routes of compounds of formula (I) by appropriately adjusting the reactants, reaction conditions and protecting groups.

[0106] Synthesis of Intermediate 1-Fluoro-2-isothiocyanato-5-methyl-4-[hydro(3,3,3-trifluoropropyl)thio]benzene (Intermediate III)

[0107]

[0108] To 3.90 g (15.40 mmol) of the raw material 2-fluoro-4-methyl-5-(3,3,3-trifluoropropyl)thio)aniline was added a mixed solution of 20 mL of water and 10 mL of DMF, and K 2 CO 3 4.26 g (30.80 mmol), stirred evenly. Slowly add CS dropwise at room temperature 2 5.86g (77.00mmol), after the addition was completed, the mixture was stirred for 3h, monitored by TLC until 2-fluoro-4-methyl-5-(3,3,3-trifluoropropyl)thio)aniline was completely converted. The reaction solution was then cooled to 0°C, and a solution of cyanuric chloride (1.42g, 7.70mmol) dissolved in 15mL DCM was added dropwise. After the addition was completed, stirring was continued at 0°C for 0.5h. The reaction mixture was then basified to pH>11 with 6N aqueous NaOH to obtain a clear solution. The organic layer was separated and extracted with DCM (3×20mL). The organic layers were combined and washed with anhydrous Na 2 SO 4The mixture was dried, filtered and the solvent was removed by rotary evaporation. The mixture was purified by silica gel column chromatography using petroleum ether as eluent to obtain 2.29 g of 1-fluoro-2-isothiocyanato-5-methyl-4-[hydrogen (3,3,3-trifluoropropyl)thio]benzene with a yield of 50.36%.

[0109] 1 H NMR (400 MHz, DMSO-d 6 )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).

[0110] 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)

[0111]

[0112] 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 bottle, dissolved in 20 mL of toluene, and then 0.16 g (1.63 mmol) of 2,2,2-trifluoroethylamine and 0.37 g (2.71 mmol) of potassium carbonate were added in sequence, and the reaction was stirred at room temperature. The reaction was tracked by TLC. After 1-fluoro-2-isothiocyanato-5-methyl-4-[hydrogen (3,3,3-trifluoropropyl) thio] benzene completely disappeared, 0.41 g (2.71 mmol) of methyl bromoacetate was added to the reaction system, and then 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, and the reaction was quenched with anhydrous Na 2 SO 4 The mixture was dried, filtered and the solvent was removed by rotary evaporation. Purification by silica gel column chromatography gave 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 (I-311) with a yield of 90.08%.

[0113] 1 H NMR (400 MHz, DMSO-d 6)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] + .

[0114] 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)

[0115]

[0116] 0.57 g (1.31 mmol) of 2-({2-fluoro-4-methyl-5-[(3,3,3-trifluoropropyl)sulfanyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one was added to the reaction bottle and dissolved in dichloromethane. The reaction system was cooled to 0°C, 0.27 g (1.57 mmol) of m-chloroperbenzoic acid was added, and the reaction was stirred at this temperature. The reaction was tracked by TLC. After the raw material was completely converted, an aqueous sodium thiosulfate solution was added to the reaction system, the reaction was stirred, and a sodium bicarbonate solution was added. The reaction was continued to stir. 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).

[0117] Compound II-311: 1 H NMR (400 MHz, DMSO-d 6)δ:7.43–7.29(m,2H),4.60(q,J=9.1Hz,2H),4.26(d,J=1.5Hz,2H),3.28(ddd,J=1 3.4,10.0,5.4Hz,2H),2.97–2.64(m,2H),2.35(s,3H).LC-MS(m / z,ESI):451[M+H] + ;

[0118] Compound III-311: 1 H NMR (400 MHz, DMSO-d 6 )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] + ;

[0119] Test example: Biological activity test

[0120] In the following test examples, the insecticide compound Ib71 disclosed in patents WO2013092350A1, CN108658816A, CN108276358A, etc., with the common name sulfiflumin (hereinafter referred to as CK 1 and insecticidal compound Ia-175 (referred to herein as CK 2 indicated) as a positive control.

[0121]

[0122] 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 by using Abbott's correction formula, and the toxicity regression equation is obtained using the DPS data processing system to calculate the LC 50 Values, 95% confidence limits, and statistical analysis were performed.

[0123] Test Example 1: Biological activity test against adults of Tetranychus urticae Koch

[0124] Experimental method: The test was carried out in accordance with the agricultural industry standard NY / T1154.13-2008, and the leaf disc spray method was used to determine the test. Clean, flat, appropriately sized, and uniformly aged kidney bean leaves were selected and spread flat on a culture dish with clean filter paper placed on it, with the reverse side facing up. The filter paper was moisturized with water, and then 30-40 adult spider mites of basically uniform physiological state were inoculated on each leaf with a brush. The compound (2 mg) was dissolved in 2 mL of DMSO solvent to form a stock solution with a concentration of 1000 mg / L. The stock solution was diluted with 0.1% Tween-80 in H 2 The solution in O was diluted 10 times to obtain a test solution with a concentration of 100 mg / L, and diluted 20 times to obtain a test solution with a concentration of 50 mg / L. The same method was used to dilute more test concentrations. Leaves with two-spotted spider mites were sprayed with a sprayer until the leaf surface and the mite body surface were just covered with droplets. Each treatment was repeated 3 times, and a blank control was set up. The spray liquid used in the control group was a DMSO and Tween aqueous solution in the same proportion. The experimental targets were placed in an artificial climate chamber (24-26℃, L∶D=16∶8, RH60%) for cultivation. After 72 hours, the death of adult mites was checked and recorded. The insect body was touched with tweezers, and the feet did not move or did not respond, which was considered dead.

[0125] Calculation method:

[0126] Corrected mortality rate (%) = [(treatment mortality rate - control mortality rate) / (1 - control mortality rate)] × 100%

[0127] Among some of the tested compounds, the following compounds showed good control effects on adults of Tetranychus urticae 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-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, and I-273. 63. I-265, I-268, I-270, I-275, I-287, 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, I I-189, II-194, 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 and II-285.

[0128] Among some of the tested compounds, the following compounds showed good control effects on adults of two-spotted spider mites at a concentration of 2.5 mg / L, with a mortality rate of more than 80%: I-65, I-75, I-78, I-90, I-164, I-173, I-243, II-65, II-78 and II-243.

[0129] According to the above method, compounds I-65, I-90 and known compound CK were selected. 1 (sulfiflumin), CK 2 The activity of spirodiclofen against Tetranychus cinnabarinus nymphs was tested in parallel, and the results are shown in Table 5. 2 At a dosage of 500 g / ha, it showed an efficacy of more than 90% against two-spotted spider mites.

[0130] Table 5. Activity test on adults of Tetranychus urticae (72h)

[0131]

[0132] Test Example 2: Biological activity test against nymphs of Tetranychus cinnabarinus

[0133] Experimental method: leaf disc spray method was used. Fresh broad bean potted plants were taken and several adult mites were placed on the leaves. After 1 day of egg laying, the adult mites were removed and the eggs were kept for use after hatching into nymphs. The broad bean leaves were beaten into leaf discs, cotton was kept moist, and placed in a plastic culture dish. 30-40 nymphs of Tetranychus cinnabarinus were placed. The compound (2 mg) was dissolved in 2 mL of DMSO solvent to form a stock solution with a concentration of 1000 mg / L. The stock solution was diluted with 0.1% Tween-80 in H 2 The solution in O was diluted 10 times to obtain a test solution with a concentration of 100 mg / L. After the test insects were stable on the leaves, the leaf discs were placed under a Potter spray tower and sprayed with a fixed amount (2.5 mL) for 3 times, and a blank control was set up. The control group used an equal proportion of DMSO and Tween aqueous solution as the spray. After drying naturally, the experimental targets were placed in an artificial climate chamber (24-26°C, L:D=16:8, RH60%) for cultivation, and the results were investigated after 48 hours. The insect body was touched with tweezers, and no reaction was considered dead.

[0134] Calculation method:

[0135] Corrected mortality rate (%) = [(treatment mortality rate - control mortality rate) / (1 - control mortality rate)] × 100%

[0136] Among some of the tested compounds, the following compounds showed good control effects on cinnabarinus spider mite 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.

[0137] Among some of the tested compounds, the following compounds showed good control effects on cinnabarinus spider mite nymphs 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.

[0138] According to the above method, compounds I-65, I-78, I-164, I-173 and known compound CK were selected. 1 (sulfiflumin), CK 2 The activity of cinnabarinus nymphs was tested in parallel with , ethidium bromide and spiroclofonate. The experimental results are shown in Table 6.

[0139] Table 6. Activity test on cinnabarinus spider mite nymphs (72h)

[0140]

[0141] Test Example 3: Biological activity test against adults of Tetranychus cinnabarinus

[0142] Experimental method: Use leaf disc spray method to select clean, flat, appropriately sized, and uniformly aged broad bean leaves, beat the broad bean leaves into leaf discs, moisturize with cotton, place in a plastic petri dish, and inoculate 30-40 adult mites of Tetranychus cinnabarinus. Dissolve the compound (2 mg) in 2 mL DMSO solvent to form a stock solution with a concentration of 1000 mg / L. The stock solution is diluted with 0.1% Tween-80 in H 2 The solution in O was diluted 10 times to obtain a test solution with a concentration of 100 mg / L. After the test insects were stable on the leaves, the leaf discs were placed under a Potter spray tower and sprayed with a fixed amount (2.5 mL) for 3 times, and a blank control was set up. The control group used an equal proportion of DMSO and Tween aqueous solution as the spray. After drying naturally, the experimental targets were placed in an artificial climate chamber (24-26°C, L:D=16:8, RH60%) for cultivation, and the results were investigated after 48 hours. The insect body was touched with tweezers, and no reaction was considered dead.

[0143] Calculation method:

[0144] Corrected mortality rate (%) = [(treatment mortality rate - control mortality rate) / (1 - control mortality rate)] × 100%

[0145] Among some of the tested compounds, the following compounds had good control effects on adult 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-172, I-173, I-181, I-182, I-189, I-194, I-197, I-201, I-203, I-205, I-2 09. I-217, I-220, I-238, I-243, I-251, I-258, I-261, I-263, I-268, I-273, I-27 5. I-283, II-47, II-50, II-53, II-65, II-78, II-88, II-90, II-119, II-139, II-1 43. 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.

[0146] Test Example 4: Biological activity test on Tetranychus cinnabarinus eggs

[0147] Experimental method: leaf dipping method was used. The broad bean seedlings with good plant growth were selected, the tops were cut off, and the broad bean seedlings were cut into the shape of two leaves and one stem. The stems were inserted into an injection bottle filled with water. 10-15 female adult mites with the same physiological state were inoculated on each broad bean leaf. The female adult mites were removed after 24 hours. The compound (2 mg) was dissolved in 2 mL DMSO solvent to form a stock solution with a concentration of 1000 mg / L. The stock solution was diluted 10 times with 0.1% Tween-80 aqueous solution to obtain a test solution with a concentration of 100 mg / L. The egg-bearing leaves of 24-28 hours were beaten into leaf discs, immersed in the drug solution for 10 seconds, and then taken out. The excess drug solution was immediately absorbed with absorbent paper and placed in a 24-well plate. Cotton was used to keep it moist. Each treatment was repeated 3 times. A blank control was set. The immersion solution used in the control group was an equal proportion of DMSO and Tween aqueous solution. The experimental targets were placed in an artificial climate chamber (24-26°C, L:D=16:8, RH60%) for cultivation. After the eggs in the blank control area were hatched, the number of unhatched eggs and the number of hatched eggs in the leaf discs treated with the drug were counted.

[0148] Calculation method:

[0149] Hatching inhibition rate = (number of unhatched eggs / total number of eggs treated) × 100%

[0150] Corrected hatching inhibition rate = [(hatching inhibition rate of treatment area - hatching inhibition rate of control area) / (1 - hatching inhibition rate of control area] × 100%

[0151] 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-204, I-205, I-206, I-207, I-208, I-209, I-301. -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.

[0152] Test Example 5: Biological activity test against southern root-knot nematode

[0153] Experimental method: The biological activity of the compound against the second-instar larvae of southern root-knot nematode was tested by direct contact killing method. The compound (2 mg) was dissolved in 2 mL DMSO solvent to form a stock solution with a concentration of 1000 mg / L. The stock solution was diluted 5 times with 0.1% Tween-80 aqueous solution to obtain a test solution with a concentration of 200 mg / L. The nematodes in the soil of the collected tomatoes were extracted by Baermann funnel method, and then the large worms were removed with a 300-mesh molecular sieve, and the small worms were removed with a 325-mesh molecular sieve to obtain larvae of the same size as the second-instar larvae. Finally, centrifuge and concentrate to 10 μL containing 40-70 nematodes, then add 90 μL of the prepared test solution (200 mg / L) and 80 μL of 0.1% Tween-80 aqueous solution to the 48-well biochemical culture plate, and finally add 10 μL (40-70 nematodes) of the nematode suspension, each treatment is repeated 3 times, set up a blank control, and the test solution used in the control group is the same ratio of DMSO and Tween aqueous solution. The 48-well biochemical culture plate is placed in an artificial climate chamber (24-26℃L∶D=16∶8, RH60%) for culture, and the death situation is investigated after 48 hours, and the mortality rate is calculated.

[0154] Calculation method:

[0155] Corrected mortality rate (%) = [(treatment mortality rate - control mortality rate) / (1 - control mortality rate)] × 100%

[0156] Among some of the tested compounds, the following compounds had a good control effect on southern root-knot nematodes at a concentration of 100 mg / L, with a mortality rate of at least 75%: compound II-104.

[0157] According to the above method, compound II-104 and known compound CK were selected. 1 (sulfiflumin) was used to conduct parallel determination of the activity of the second-instar larvae of the southern root-knot nematode. The experimental results are shown in Table 7.

[0158] Table 7. Activity assay against southern root-knot nematode (48h)

[0159]

[0160]

[0161] 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, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope 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 pesticidally 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.

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.

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, -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; 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.

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.

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. 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.

7. The insecticide composition according to claim 6, 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.

8. 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.

9. The use according to claim 8, wherein the pest is selected from the family Tetranychidae, Tenebriomyidae, Cynopodiidae, Tarsonemidae, Acaridae, and Heteroderaeidae.

10. The use according to claim 9, 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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