M-diacyl compound and application thereof

Abstract

The invention discloses a compound # imgabs0 # as shown in a formula I, or a stereoisomer, a nitrogen oxide, an isotope and a pharmaceutically acceptable salt thereof, Q, W1, W2, R6, R7, R8, R9, R10, R11, R12 and R13 are defined in the specification, the compound shows an excellent insecticidal effect at a low dosage, and the compound has a good application prospect. Particularly, the insecticidal composition has an outstanding effect in the aspects of fast-acting property and prevention and treatment of pests which generate resistance to the existing insecticide, and has a wide application prospect.

Description

Technical Field

[0001] The invention belongs to the field of pesticides, and specifically relates to a meta-diamide compound and application thereof. Background Art

[0002] Diamide insecticide products have attracted much attention in the global insecticide field. They are the fastest growing and most promising insecticide products in recent years. With their unique mechanism of action and excellent product performance, they have established a strong market dominance, especially in the field of lepidopteran pest control, and have now become one of the four major product types in the insecticide market. Compared with traditional insecticides, diamide insecticides have unique mechanisms of action and activity characteristics. This type of product acts on the nicotinic acid receptors in insects, causing pests to excessively release calcium ions in their body cells. The continuous increase in the concentration of released calcium ions will trigger the "muscle" contraction in the pest's body, thereby weakening and paralyzing the pest's receptors until the pest is paralyzed and dies. Diamide insecticides have three outstanding characteristics: low toxicity, broad insecticide spectrum, and no egg-killing effect.

[0003] Currently, the representative varieties of diamide insecticides that have been registered and listed, are relatively mature in commercialization, and have the highest market popularity include flubendiamide, chlorantraniliprole, cyantraniliprole, tetrachlorantraniliprole, bromofenac, and Bayer's tetrazolyl fenamide, as well as bromofenac jointly developed by BASF and Mitsui Chemicals. In 2007, the launch of flubendiamide opened the curtain of the diamide insecticide market. In 2008, the launch of chlorantraniliprole brought this type of product into the ranks of leading gains and continued to surpass traditional insecticide product types. According to S&P Global Commodity Insights data, in 2019, global diamide insecticide sales reached US$2.283 billion, with an average annual growth of 1.0% from 2014 to 2019, most of which was contributed by the sales of chlorantraniliprole.

[0004] Broflatiilide, a diamide insecticide jointly developed by Mitsui Chemicals of Japan and BASF, has now been commercialized. Its Chinese name is brofenac, and it is mainly used for fruits and vegetables, beans, cotton, corn, grains, flowers and non-crop purposes to control pests such as Lepidoptera, Coleoptera, termites, ants, cockroaches, flies, etc., with very good results.

[0005] (Bromofenac).

[0006] Broflanilide is a representative of the diamide compounds, specifically the structure of meta-carboxamidobenzamide, whose active metabolites are allosteric modulators of γ-aminobutyric acid (GABA)-gated chloride ion channels, which are more selective for GABA and have the characteristics of broad spectrum and high efficiency. Guided by the novel mechanism of action of diamide insecticides, more pesticide chemical companies are committed to developing more types of new diamide insecticides with fast-acting high insecticidal activity at low doses. For example, Chinese patent CN109497062B discloses a diamide compound, its preparation method and application, and a representative structure, cyproflumizone:

[0007] (Ciprofenamide)

[0008] The inventors of the present application discovered a series of novel diamide insecticides with higher activity, lower usage and better environmental friendliness during the research process, and completed the present invention. Summary of the invention

[0009] The present invention provides a new type of isophthalic acid amide insecticide with higher activity, lower dosage and better environmental friendliness. The compound of the present invention adopts a specific difluorocyclopropylmethyl group to replace the hydrogen atom on the amine at a specific position of isophthalic acid amide, thereby achieving a relatively excellent insecticidal effect, especially in terms of rapid effect and excellent effect on the prevention and control of existing resistant pests.

[0010] The technical solution provided by the present invention is: a compound represented by formula I:

[0011]

[0012] , or its stereoisomers, nitrogen oxides, isotopes and pesticide-acceptable salts,

[0013] Wherein, Q is selected from the following groups:

[0014]

[0015] ,in, Indicates the connection end;

[0016] W1 and W2 are independently selected from oxygen (O) or sulfur (S);

[0017] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13Each of the following is independently selected from one or more of hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl and optionally substituted alkynyl.

[0018] The present invention also discloses a compound of formula II as an intermediate for synthesizing a compound of formula I.

[0019]

[0020] Among them, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each of the following is independently selected from one or more of hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl and optionally substituted alkynyl.

[0021] The present invention also provides a compound of formula III as an intermediate for preparing the compound of formula I.

[0022]

[0023] Wherein, Q is selected from the following groups:

[0024]

[0025] ,in, Indicates the connection end;

[0026] W1 and W2 are independently selected from O or S;

[0027] R1, R2, R3, R4, R5, R6, R7, R8, R9 are independently selected from one or more of hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl and optionally substituted alkynyl;

[0028] L is a leaving group, preferably a halogen.

[0029] The present invention also provides an insecticidal composition, which contains the compound represented by formula I of the present invention, its stereoisomer, its nitrogen oxide compound, isotope or pesticide acceptable salt as an active ingredient.

[0030] The present invention also provides a method for controlling pests, comprising applying an effective dose of the compound represented by formula I of the present invention, its stereoisomers, its nitrogen oxides, deuterated substances or pesticide-acceptable salts or the insecticide composition of the present invention to the harmful organisms to be controlled or the medium in which they grow.

[0031] The present invention has the following beneficial effects:

[0032] The compound of the present invention adopts a specific difluoro-substituted cyclopropyl group to replace the hydrogen atom on one terminal amine of the diamide to achieve relatively excellent insecticidal activity, especially in terms of rapid effect and control of resistant pests, which is more excellent than the existing diamide compounds. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. 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. Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "including" will be understood to include the stated components or steps, without excluding other material components or steps.

[0034] In addition, in order to better illustrate the present invention, numerous specific details are given in the following detailed description.

[0035] Those skilled in the art will appreciate that the present invention can be implemented without certain specific details. In some embodiments, raw materials, methods, means, etc. that are well known to those skilled in the art are not described in detail in order to highlight the main purpose of the present invention.

[0036] If the compounds of formula I described herein are capable of forming geometrical isomers, such as E / Z isomers, endo / exo isomers, etc., both the pure isomers and mixtures thereof can be used in the compositions of the present invention.

[0037] If the compounds of the formula I described herein have one or more chiral centers and therefore exist as enantiomers or diastereomers, the pure enantiomers, racemates or diastereomers can be used in the compositions of the invention.

[0038] Unless otherwise specified, all technical terms used in the present disclosure have the same meaning as commonly understood by those skilled in the art to which the present disclosure belongs. All patents and publications related to the present disclosure are incorporated herein by reference in their entirety.

[0039] Unless otherwise indicated, the following definitions used herein shall apply. For the purposes of this disclosure, chemical elements are consistent with the Periodic Table of the Elements, CAS version, and Handbook of Chemistry and Physics, 75th edition, 1994. In addition, general principles of organic chemistry can be found in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausalito: 1999, and "March's Advanced Organic Chemistry" by Michael B. Smith and Jerry March, John Wiley & Sons, New York: 2007, the entire contents of which are incorporated herein by reference.

[0040] The term "optionally" or "optionally substituted" means that the event or situation described subsequently may but need not occur. That is, the description includes the case where the event or situation described occurs as well as the case where it does not occur. For example, "optionally substituted by 1, 2, 3 or 4..." includes the case where the group is substituted by 1, or 2, or 3, or 4 of the substituents described, and the case where the group is not substituted by the substituents described. Furthermore, when the group is substituted by more than one of the substituents described, the substituents are independent of each other, that is, the more than one substituents described may be different from each other or the same.

[0041] As described in the present disclosure, the compounds of the present disclosure may be optionally substituted with one or more substituents, such as the above formula compounds, or as the specific examples in the embodiments, subclasses, and a class of compounds included in the present disclosure. In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced by a specific substituent. Unless otherwise indicated, an optional substituent group can be substituted at each substitutable position of the group. When more than one position in the given structural formula can be substituted by one or more substituents selected from a specific group, the substituents can be substituted at each position in the same or different manner. Wherein, the "one or more substituents" means one or more substituents, and the number of specific substituents is determined by the number of positions at which the substituted group can be substituted. The substituents may include, but are not limited to, hydrogen, oxo (=O), halogen, cyano, nitro, hydroxyl, thiol, carboxyl, amino, alkyl, alkyloxy, alkylthio, alkenyl, alkynyl, hydroxyalkyl, haloalkyl, etc., wherein the substituents have the meanings described in the present disclosure, and can be further substituted by the substituents described in the present disclosure or substituted by the same or different substituents.

[0042] In addition, it should be noted that, unless explicitly stated otherwise, the description methods used in the present disclosure "each... is independently" and "... are each independently" and "... are independently" can be interchanged and should be understood in a broad sense. They can mean that in different groups, the specific options expressed by the same symbols do not affect each other, or that in the same group, the specific options expressed by the same symbols do not affect each other.

[0043] Unless otherwise specified, the numerical ranges recorded in this specification and claims are equivalent to recording at least each specific integer value therein. For example, the numerical range "1-20" is equivalent to recording each integer value in the numerical range "1-10", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and each integer value in the numerical range "11-20", namely 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. For another example, the numerical range "1-10" is equivalent to recording each integer value in the numerical range "1-10", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. In addition, when certain numerical ranges are not defined as "integers", it should be understood that the two endpoints of the range, each integer in the range, and each decimal in the range are recorded. For example, "1-99%" should be understood as not only recording each integer of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, ... 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, but also at least recording the sum of each integer therein and 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, respectively.

[0044] In the present invention, the % content refers to the mass percentage unless otherwise specified.

[0045] In the "one or more", "one or more" described herein, "multiple" or "a variety" means 2 or more, for example, an integer number greater than or equal to 2, for example 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0046] "At least one" or "at least one" described herein means "one or more" or "one or more".

[0047] In the "one, two or more", "a kind, two or more" described herein, "more" or "more types" means a number greater than 2, for example, an integer greater than or equal to 3, for example 3, 4, 5, 6, 7, 8, 9 or 10, etc.

[0048] The term "alkyl" as used in the present disclosure means a saturated straight or branched monovalent hydrocarbon group. When the number of carbon atoms is not used when describing an "alkyl", it means that the alkyl has any number of carbon atoms. When the number of carbon atoms is used when describing an "alkyl", it means that the alkyl has the stated number of carbon atoms. For example, an alkyl group can be C1-C 20 Alkyl refers to a saturated, straight-chain or branched, monovalent hydrocarbon group containing 1 to 20 carbon atoms, wherein the alkyl group may be optionally substituted with one or more substituents described in the present disclosure. Unless otherwise specified, the alkyl group contains 1 to 20 carbon atoms. In some embodiments, the alkyl group contains 1 to 12 carbon atoms, such as "C1-C 12 In some other embodiments, the alkyl group is an alkyl group containing 1-6 (1, 2, 3, 4, 5 or 6) carbon atoms, i.e., a "C1-C6 alkyl"; in some other embodiments, the alkyl group is an alkyl group containing 1-4 (1, 2, 3 or 4) carbon atoms, i.e., a "C1-C4 alkyl"; in some other embodiments, the alkyl group contains 1-3 carbon atoms, i.e., a "C1-C3 alkyl".

[0049] Examples of alkyl groups include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), n-propyl (n-Pr, -CH2CH2CH3), isopropyl (i-Pr, -CH(CH3)2), n-butyl (n-Bu, -CH2CH2CH2CH3), isobutyl (i-Bu, -CH2CH(CH3)2), sec-butyl (s-Bu, -CH(CH3)CH2CH3), tert-butyl (t-Bu, -CH(CH3)CH2CH3), u, -C(CH3)3), n-pentyl (-CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1 -butyl (-CH2CH(CH3)CH2CH3), n-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH2CH3 ), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3), n-heptyl, n-octyl, and the like.

[0050] The term "alkenyl" refers to a straight or branched monovalent hydrocarbon group having at least one carbon-carbon sp2 double bond. When the number of carbon atoms is not used in describing an "alkenyl", it means that the alkenyl has any number of carbon atoms selected from 2 or more. When the number of carbon atoms is used in describing an "alkenyl", it means that the alkenyl has the stated number of carbon atoms. For example, the alkenyl is "C2-C 12"Alkenyl", which means a straight or branched monovalent hydrocarbon group containing 2-12 carbon atoms, wherein there is at least one carbon-carbon sp2 double bond. Wherein, the alkenyl group may be optionally substituted with one or more substituents described in the present disclosure, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". In some embodiments of the alkyl group, the alkenyl group contains 2-8 (2, 3, 4, 5, 6, 7 or 8) carbon atoms; in other embodiments, the alkenyl group contains 2-6 (2, 3, 4, 5 or 6) carbon atoms; in yet other embodiments, the alkenyl group contains 2-4 (2, 3 or 4) carbon atoms, or contains 3-6 (3, 4, 5 or 6) carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH=CH2), allyl (-CH2CH=CH2), allyl (-CH=CHCH3) and the like.

[0051] The term "alkynyl" refers to a straight or branched monovalent hydrocarbon group having at least one carbon-carbon sp triple bond. When the number of carbon atoms is not used in describing an "alkynyl", it means that the alkynyl has any number of carbon atoms selected from 2 or more. When the number of carbon atoms is used in describing an "alkynyl", it means that the alkynyl has the stated number of carbon atoms. For example, the alkynyl is "C2-C 12 "Alkynyl" refers to a straight or branched monovalent hydrocarbon group containing 2-12 carbon atoms, wherein at least one carbon-carbon sp triple bond is present. The alkynyl group may be optionally substituted with one or more substituents described in the present disclosure. In some embodiments, the alkynyl group contains 2-8 (2, 3, 4, 5, 6, 7 or 8) carbon atoms; in other embodiments, the alkynyl group contains 2-6 (2, 3, 4, 5 or 6) carbon atoms; in yet other embodiments, the alkynyl group contains 2-4 (2, 3 or 4) carbon atoms, or 3-6 (3, 4, 5 or 6) carbon atoms. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, and the like.

[0052] The term "oxo" refers to a substituent in which a carbon atom, a nitrogen atom or a sulfur atom is oxidized to form an oxy group (=O).

[0053] The term "alkoxy" means that an alkyl group is connected to the rest of the molecule through an oxygen atom, i.e., "alkoxy", wherein the alkyl group has the meaning as described in the present disclosure. In some embodiments, the alkyloxy group contains 1-6 carbon atoms; in other embodiments, the alkyloxy group contains 1-4 carbon atoms; in yet other embodiments, the alkyloxy group contains 1-3 carbon atoms. The alkyloxy group may be optionally substituted with one or more substituents described in the present disclosure. Examples of alkyloxy groups include, but are not limited to, methoxy (MeO, -OCH3), ethoxy (EtO, -OCH2CH3), 1-propoxy (n-PrO, n-propoxy, -OCH2CH2CH3), and the like.

[0054] The term "alkylthio" means that an alkyl group is connected to the rest of the molecule through a sulfur atom, i.e., "alkylthio", wherein the alkyl group has the meaning as described in the present disclosure. In some embodiments, the alkylthio group contains 1-6 carbon atoms; in other embodiments, contains 1-4 carbon atoms; in yet other embodiments, contains 1-3 carbon atoms. The alkylthio group can be optionally substituted with one or more substituents described in the present disclosure, illustratively, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, or tert-butylthio.

[0055] The term "alkylsulfinyl" means an alkyl group connected to the rest of the molecule through a sulfinyl group, i.e., "alkylsulfinyl", wherein the alkyl group has the meaning as described in the present disclosure. In some embodiments, the alkylsulfinyl group contains 1-6 carbon atoms; in other embodiments, contains 1-4 carbon atoms; in still other embodiments, contains 1-3 carbon atoms. The "alkylsulfinyl" group can be optionally substituted with one or more substituents described in the present disclosure, for example, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, or tert-butylsulfinyl, etc., but is not limited thereto.

[0056] The term "alkylsulfonyl" means an alkyl group connected to the rest of the molecule through a sulfonyl group, i.e., "alkylsulfonyl", wherein the alkyl group has the meaning as described in the present disclosure. In some embodiments, the alkylsulfonyl group contains 1-6 carbon atoms; in other embodiments, contains 1-4 carbon atoms; in still other embodiments, contains 1-3 carbon atoms. The alkyloxy group can be optionally substituted with one or more substituents described in the present disclosure, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, etc.

[0057] The term "alkylcarbonyl" means an alkyl group connected to the rest of the molecule through a carbonyl group (-C(=O)-), wherein the alkyl group has the meaning described in the present disclosure. Such examples include, but are not limited to, CH3-C(=O)-, etc.

[0058] The term "halogenated alkyl" refers to, for example, a linear or branched alkoxyalkyl group substituted by one or more halogen atoms which may be the same or different from each other. For example, the halogenated C1-C6 alkyl group refers to a linear or branched alkyl group having 1 to 6 carbon atoms substituted by one or more halogen atoms which may be the same or different from each other, for example, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, 2,2-difluoroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2,2-trichloroethyl, 2,2,2-tribromoethyl, 1,3-difluoro-2-propyl, 1,3-dichloro-2-propyl, 1-chloro-3-fluoro -2-propyl, 1,1,1-trifluoro-2-propyl, 2,3,3,3-tetrafluoro-n-propyl, 1,1,1,3,3,3-hexafluoro-2-propyl, 1,1,1,3,3,3-hexafluoro-2-chloro-2-propyl, 1,1,1,3,3,3-hexafluoro-2-bromo-2-propyl, 1,1,2,3,3,3-hexafluoro-2-chloro-n-propyl, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propyl, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propyl, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propyl, 2,2,3,3,3-pentafluoro-n-propyl, 3-fluoro-n-propyl, 3-chloro-n-propyl, 3-bromo-n-propyl, nonafluoro-n-butyl, nonafluoro-isobutyl, nonafluoro-sec-butyl, or nonafluoro-tert-butyl, and the like, but are not limited thereto.

[0059] The term "halogenated alkoxy" means, for example, a straight-chain or branched alkoxy group substituted with one or more halogen atoms which may be the same or different from each other. For example, the halogenated C1-C6 alkoxy group means, for example, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms substituted with one or more halogen atoms which may be the same or different from each other. Examples include difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, heptafluoro-n-propoxy, heptafluoro-isopropoxy, 2,2-difluoroethoxy, 2,2-dichloroethoxy, 2,2,2-trifluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2,2-trichloroethoxy, 2,2,2-tribromoethoxy, 1,3-difluoro-2-propoxy, 1,3-dichloro-2-propoxy, 1-chloro-3 -fluoro-2-propoxy, 1,1,1-trifluoro-2-propoxy, 2,3,3,3-tetrafluoro-n-propoxy, 1,1,1,3,3,3-hexafluoro-2-propoxy, 1,1,1,3,3,3-hexafluoro-2-chloro-2-propoxy, 1,1,1,3,3,3-hexafluoro-2-bromo-2-propoxy, 1,1,2,3,3,3-hexafluoro-2-chloro-n-propoxy, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propoxy, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propoxy, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propoxy, 1,1,2,3,3,3-hexafluoro-1-bromo-2-propoxy, 2,2,3,3,3-pentafluoro-n-propoxy, 3-fluoro-n-propoxy, 3-chloro-n-propoxy, 3-bromo-n-propoxy, nonafluoro-n-butoxy, nonafluoro-isobutoxy, nonafluoro-sec-butoxy, or nonafluoro-tert-butoxy, and the like, but are not limited thereto.

[0060] The term "halogenated alkylthio" means, for example, a straight-chain or branched alkylthio group substituted with one or more halogen atoms which may be the same or different from each other. For example, "halogenated C1-C6 alkylthio" means, for example, a straight-chain or branched alkylthio group having 1 to 6 carbon atoms substituted with one or more halogen atoms which may be the same or different from each other, such as difluoromethylthio, trifluoromethylthio, pentafluoroethylthio, heptafluoro-n-propylthio, heptafluoroisopropylthio, 2,2-difluoroethylthio, 2,2-dichloroethylthio, 2,2,2-trifluoroethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2,2-trichloroethylthio, 2,2,2-tribromoethylthio, 1,3-difluoro-2-propylthio, 1,3-dichloro-2-propylthio, 1-chloro-3 1,1,1-trifluoro-2-propylthio, 2,3,3,3-tetrafluoro-n-propylthio, 1,1,1,3,3,3-hexafluoro-2-propylthio, 1,1,1,3,3,3-hexafluoro-2-chloro-2-propylthio, 1,1,1,3,3,3-hexafluoro-2-bromo-2-propylthio, 1,1,2,3,3,3-hexafluoro-2-chloro-n-propylthio The invention also includes, but is not limited to, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propylthio group, 1,1,2,3,3,3-hexafluoro-1-bromo-2-propylthio group, 2,2,3,3,3-pentafluoro-n-propylthio group, 3-fluoro-n-propylthio group, 3-chloro-n-propylthio group, 3-bromo-n-propylthio group, nonafluoro-n-butylthio group, nonafluoro-isobutylthio group, nonafluoro-sec-butylthio group, or nonafluoro-tert-butylthio group.

[0061] The term "halogenated alkylsulfinyl" means, for example, a linear or branched alkylsulfinyl group substituted with one or more halogen atoms which may be the same or different from each other, for example, "halogenated C1-C6 alkylsulfinyl" means, for example, a linear or branched alkylsulfinyl group having 1 to 6 carbon atoms substituted with one or more halogen atoms which may be the same or different from each other, for example, difluoromethylsulfinyl, trifluoromethylsulfinyl, pentafluoroethylsulfinyl, heptafluoro-n-propylsulfinyl acyl, heptafluoroisopropylsulfinyl, 2,2-difluoroethylsulfinyl, 2,2-dichloroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2,2-trichloroethylsulfinyl, 2,2,2-tribromoethylsulfinyl, 1,3-difluoro-2-propylsulfinyl, 1,3-dichloro-2-propylsulfinyl, -Chloro-3-fluoro-2-propylsulfinyl, 1,1,1-trifluoro-2-propylsulfinyl, 2,3,3,3-tetrafluoro-n-propylsulfinyl, 1,1,1,3,3,3-hexafluoro-2-propylsulfinyl, 1,1,1,3,3,3-hexafluoro-2-chloro-2-propylsulfinyl, 1,1,1,3,3,3-hexafluoro-2-bromo-2-propylsulfinyl, 1,1,2,3,3,3-hexafluoro-2-chloro-n-propylsulfinyl , 1,1,2,3,3,3-hexafluoro-2-bromo-n-propylsulfinyl, 1,1,2,3,3,3-hexafluoro-1-bromo-2-propylsulfinyl, 2,2,3,3,3-pentafluoro-n-propylsulfinyl, 3-fluoro-n-propylsulfinyl, 3-chloro-n-propylsulfinyl, 3-bromo-n-propylsulfinyl, nonafluoro-n-butylsulfinyl, nonafluoroisobutylsulfinyl, nonafluoro-sec-butylsulfinyl, or nonafluoro-tert-butylsulfinyl, etc., but are not limited to these.

[0062] The term "halogenated alkylsulfonyl" means, for example, a straight-chain or branched alkylsulfinyl group substituted with one or more halogen atoms which may be the same or different from each other, for example, "halogenated C1-C6 alkylsulfonyl" means, for example, a straight-chain or branched alkylsulfonyl group having 1 to 6 carbon atoms substituted with one or more halogen atoms which may be the same or different from each other, for example, difluoromethylsulfonyl, trifluoromethylsulfonyl, pentafluoroethylsulfonyl, heptafluoro-n-propylsulfonyl, 1-2-difluoro-1-methyl ... 1,3-difluoro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, ...chloro-2-propylsulfonyl, 1,3-difluoro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-difluoro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-difluoro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-difluoro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-difluoro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1,3-dichloro-2-propylsulfonyl, 1 Chloro-3-fluoro-2-propylsulfonyl, 1,1,1-trifluoro-2-propylsulfonyl, 2,3,3,3-tetrafluoro-n-propylsulfonyl, 1,1,1,3,3,3-hexafluoro-2-propylsulfonyl, 1,1,1,3,3,3-hexafluoro-2-chloro-2-propylsulfonyl, 1,1,1,3,3,3-hexafluoro-2-bromo-2-propylsulfonyl, 1,1,2,3,3,3-hexafluoro-2-chloro-n-propylsulfonyl The invention also includes, but is not limited to, 1,1,2,3,3,3-hexafluoro-2-bromo-n-propylsulfonyl, 1,1,2,3,3,3-hexafluoro-1-bromo-2-propylsulfonyl, 2,2,3,3,3-pentafluoro-n-propylsulfonyl, 3-fluoro-n-propylsulfonyl, 3-chloro-n-propylsulfonyl, 3-bromo-n-propylsulfonyl, nonafluoro-n-butylsulfonyl, nonafluoroisobutylsulfonyl, nonafluoro-sec-butylsulfonyl, or nonafluoro-tert-butylsulfonyl.

[0063] The term "haloalkenyl" means that the alkenyl group is substituted with one or more halogen groups, for example, 2-chloroprop-2-en-1-yl, 3-chloroprop-2-en-1-yl, 2,3-dichloroprop-2-en-1-yl, 3,3-dichloroprop-2-en-1-yl, 2,2,3-trichloroprop-2-en-1-yl, 2,3-dichlorobut-2-en-1-yl, 2-bromoprop-2-en-1-yl, 3-bromoprop-2-en-1-yl, 2,3-dibromoprop-2-en-1-yl, 3,3-dibromoprop-2-en-1-yl, 2,3,3-tribromoprop-2-en-1-yl or 2,3-dibromobut-2-en-1-yl, etc., but is not limited thereto.

[0064] The term "haloalkynyl" means that the alkynyl group is substituted by one or more halogen groups, for example, 1,1-fluoroprop-2-yn-1-yl, 3-chloroprop-2-yn-1-yl, 3-bromoprop-2-yn-1-yl, 3-iodoprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl, 4-iodobut-3-yn-1-yl, 5-fluoropent-3-yn-1-yl, 5-iodopent-4-yn-1-yl, 6-fluorohex-4-yn-1-yl or 6-iodohex-5-yn-1-yl, etc., but is not limited thereto.

[0065] The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0066] The "acceptable salts" of the present disclosure include acid addition salts and base addition salts, and suitable bases are hydroxides, carbonates, bicarbonates of alkali metals and alkaline earth metals, in particular sodium, potassium, magnesium, and calcium salts, as well as ammonium, primary, secondary and tertiary amines with (C1-C4)-alkyl groups, mono-, di- and trialkanolamines of (C1-C4)-alkanols, choline and choline chloride. The salt may be a salt added with an inorganic acid, which may be hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid or phosphoric acid, or a salt added with an organic acid, which may be formic acid, carbonic acid, and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated or mono- or di-unsaturated C6-C4 20 Fatty acids, alkyl sulfate monoesters, alkyl sulfonic acids (sulfonic acids with linear or branched alkyl groups having 1 to 20 carbon atoms), aryl sulfonic acids or aryl disulfonic acids (aromatic groups with one or two sulfonic acid groups, such as phenyl and naphthyl), alkyl phosphonic acids (phosphonic acids with linear or branched alkyl groups having 1 to 20 carbon atoms), aryl phosphonic acids or aryl diphosphonic acids (aromatic groups with one or two phosphonic acid groups, such as phenyl and naphthyl), wherein the alkyl and aryl groups may have other substituents, such as p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

[0067] The leaving group of the present invention is usually a group that is easy to leave, such as halogen (such as fluorine, chlorine, bromine or iodine), p-toluenesulfonyl, methylsulfonyl, etc., but is not limited thereto.

[0068] Those skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides, since nitrogen requires a lone pair of electrons to oxidize to an oxide, and those skilled in the art will also know which nitrogen-containing heterocycles can form N-oxides. Those skilled in the art will also know that tertiary amines can form N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art, and include oxidation of heterocycles and tertiary amines with peroxyacids such as peracetic acid and meta-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for preparing N-oxides have been extensively described and reviewed in the literature.

[0069] According to its molecular structure, the compounds of the present invention may be chiral, and therefore various enantiomeric forms may exist. Thus, these compounds may exist in racemic form or optically active form. The compounds of the present invention encompass isomers or mixtures, racemates in which each chiral carbon is in R or S configuration. The compounds of the present invention or their intermediates can be separated into enantiomeric compounds by chemical or physical methods known to those skilled in the art, or used in this form for synthesis. In the case of racemic amines, diastereomers are prepared from the mixture by reaction with an optically active resolution agent. Examples of suitable resolution agents are optically active acids, such as R and S forms of tartaric acid, diacetyltartaric acid, dibenzoyltartaric acid, mandelic acid, malic acid, lactic acid, suitable N-protected amino acids (e.g., N-benzoylproline or N-phenylsulfonylproline) or various optically active camphorsulfonic acids. Chromatographic enantiomer resolution can also be advantageously carried out with the aid of optically active resolving agents such as dinitrobenzoylphenylglycine, cellulose triacetate or other carbohydrate derivatives or chiral derivatized methacrylate polymers immobilized on silica gel. Suitable eluents for this purpose are aqueous or alcoholic solvent mixtures, for example, hexane / isopropanol / acetonitrile.

[0070] The corresponding stable isomers can be separated according to known methods, for example by extraction, filtration or column chromatography.

[0071] Provided herein are compounds of Formula I that contain one or more isotopically enriched atoms. Compounds of Formula I may contain unnatural proportions of atomic isotopes at one or more atoms that make up the compound of Formula I. In some embodiments, the compound is isotopically labeled, such as an isotopically labeled compound of Formula I or a pesticide pharmaceutically acceptable salt, stereoisomer, nitrogen oxide thereof, wherein a portion of one or more atoms is replaced by an isotope of the same element. Exemplary isotopes include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, and chlorine, such as 2 H. 3 H. 11 C. 13 C.14 C. 13 N. 15 O. 17 O. 35 S. 18 F and 36 Cl. Certain isotopically labeled compounds (e.g. 2 H. 3 H. 11 C. 13 C. 14 C) can be used for the study of compounds. In some embodiments, such as deuterium ( 2 Incorporation of heavier isotopes such as H) may provide certain advantages in insecticidal effects resulting from greater metabolic stability (e.g., increased in vivo half-life or reduced dosage requirements).

[0072] The present invention first provides a compound shown in formula I:

[0073]

[0074] , or its stereoisomers, nitrogen oxides, isotopes and pesticide-acceptable salts,

[0075] Wherein, Q is selected from the following groups:

[0076]

[0077] ,in, Indicates the connection end;

[0078] W1 and W2 are independently selected from O or S;

[0079] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each of the following is independently selected from one or more of hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl and optionally substituted alkynyl.

[0080] Preferably, W1 and W2 are both O.

[0081] Preferably, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54, R55 10 , R 11 , R 12 and R 13 are independently selected from one of hydrogen, halogen, cyano, nitro, C1-C6 alkyl and halogenated C1-C6 alkyl, and particularly preferably, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each is independently selected from one of hydrogen, F, Cl, Br, methyl and trifluoromethyl.

[0082] The following compounds are preferred according to formula I of the present invention:

[0083]

[0084]

[0085]

[0086] The compounds of formula I of the present invention are particularly preferably the following compounds:

[0087]

[0088] The present invention also provides an insecticidal composition, which contains a compound represented by formula I:

[0089]

[0090] , or its stereoisomers, nitrogen oxides, isotopes and pesticide-acceptable salts,

[0091] Wherein, Q is selected from the following groups:

[0092]

[0093] ,in, Indicates the connection end;

[0094] W1 and W2 are independently selected from O or S;

[0095] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each of the following is independently selected from one or more of hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl and optionally substituted alkynyl.

[0096] Preferably, in the above insecticidal composition, W1 and W2 in the compound of formula I are both O.

[0097] Preferably, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54, R55 10 , R 11 , R 12 and R 13 are independently selected from one of hydrogen, halogen, cyano, nitro, C1-C6 alkyl and halogenated C1-C6 alkyl, and particularly preferably, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each is independently selected from one of hydrogen, F, Cl, Br, methyl and trifluoromethyl.

[0098] Preferably, the compound of formula I in the above insecticide composition is selected from the following compounds:

[0099]

[0100]

[0101]

[0102] Preferably, in the above insecticidal composition, Formula I is selected from the following compounds:

[0103]

[0104] Preferably, the above insecticidal composition further contains another active ingredient B, and the other active ingredient B is a neonicotinoid insecticide such as thiamethoxam, imidacloprid, clothianidin, thiacloprid, acetamiprid, nitenpyram, dinotefuran, cycloheximide, or is selected from flupyfuranone, sulfoxaflor, flonicamid, pymetrozine, buprofezin, triflubenzuron, dichlorothiazide, afidopyropen, pyrifluquinazon, benzpyrimoxan, cyproconazole, tebuconazole, prothioconazole, cyproconazole, azoxystrobin, trifloxystrobin, pyraclostrobin, picoxystrobin, metalaxyl-M, metalaxyl, fludioxonil, prochloraz, cyanamide, one or more of cyanostrobin. Preferably, the mass ratio of the compound of formula I to B is 1:100 to 100:1, more preferably 1:10 to 10:1.

[0105] The present invention also provides a compound of formula II, characterized in that the compound of formula II has the following structure:

[0106]

[0107] Among them, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each of the following is independently selected from one or more of hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl and optionally substituted alkynyl.

[0108] Preferably, in the above formula II, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13are independently selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, optionally substituted alkynyl; preferably one or more of hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl and halogenated C1-C6 alkylsulfonyl, preferably, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 are independently selected from one or more of hydrogen, halogen, cyano, nitro, C1-C6 alkyl and halogenated C1-C6 alkyl. Preferably, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 They are independently selected from one or more of hydrogen, F, Cl, Br, methyl and trifluoromethyl.

[0109] The present invention also provides a compound of formula III:

[0110]

[0111] Wherein, Q is selected from the following groups:

[0112]

[0113] ,in, Indicates the connection end;

[0114] W1 and W2 are independently selected from O or S;

[0115] R1, R2, R3, R4, R5, R6, R7, R8, R9 are independently selected from one or more of hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl and optionally substituted alkynyl;

[0116] L is a leaving group, preferably a halogen.

[0117] Preferably, in the above-mentioned compound of formula III, W1 and W2 are both O, and R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from one or more of hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, and optionally substituted alkynyl; preferably hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated One or more of C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl and halogenated C1-C6 alkylsulfonyl, preferably, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from one of hydrogen, halogen, cyano, nitro, C1-C6 alkyl and halogenated C1-C6 alkyl, particularly preferably, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from one of hydrogen, F, Cl, Br, methyl and trifluoromethyl.

[0118] The preparation method of the compound of formula I of the present invention can be carried out by the following scheme:

[0119] Solution 1:

[0120]

[0121] Among them, Q, L, W1, W2, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 The definition of is consistent with that in the above formula I.

[0122] The general synthesis step is to react the compound of formula II with the intermediate M in the presence of a base in a solvent to prepare the compound of formula I.

[0123] Option 2:

[0124]

[0125] Among them, Q, L, W1, W2, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 The definition of is consistent with that in the above formula I.

[0126] The general synthesis step is to react the compound of formula III with the intermediate N in the presence of a base in a solvent to prepare the compound of formula I.

[0127] In the above schemes 1 and 2, the intermediates of formula II and formula III can be synthesized by referring to conventional synthesis methods in the art (for example, referring to the method disclosed in CN109497062A), and the intermediates M and N can be purchased or obtained by conventional synthesis methods. The above intermediates II, formula III, intermediates M and N can also be synthesized by referring to the synthesis methods of the intermediate preparation examples below.

[0128] In the above preparation method, the solvent is an organic solvent, and the organic solvent is an aromatic hydrocarbon solvent, a nitrile solvent, a halogenated hydrocarbon, a ketone solvent and other suitable solvents, such as benzene, chlorobenzene, toluene, o-xylene, m-xylene, p-xylene, acetonitrile, propionitrile, acetone, methyl ethyl ketone, diethyl ketone, tert-butyl methyl ketone, dichloromethane, 1,2-dichloroethane, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and dioxane, etc., but not limited thereto.

[0129] In the above reaction, the base is an inorganic base or an organic base, and the inorganic base can be alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal and alkaline earth metal carbonates and bicarbonates and their hydroxides, etc. Preferably, lithium oxide, sodium oxide, calcium oxide, magnesium oxide, lithium hydride, sodium hydride, potassium hydride, calcium hydride, lithium carbonate, potassium carbonate, sodium carbonate, calcium carbonate, cesium carbonate, sodium bicarbonate, potassium acetate, sodium acetate, potassium tert-butoxide, sodium tert-butoxide, sodium ethoxide, sodium methoxide, sodium hydroxide or potassium hydroxide, etc., but not limited thereto, and the organic base is preferably trimethylamine, triethylamine, N,N-diisopropylethylamine, N-methylpiperidine, pyridine, N-methylmorpholine and 4-dimethylaminopyridine, etc., but not limited thereto.

[0130] The present invention also provides an insecticidal composition, which contains the compound represented by formula I of the present invention, its stereoisomer, its nitrogen oxide compound or pesticide acceptable salt as an active ingredient.

[0131] The present invention also provides a method for controlling pests, which comprises applying an effective dose of the compound represented by formula I, its stereoisomers, its nitrogen oxides or pesticide-acceptable salts or the insecticide composition of the present invention to the harmful organisms to be controlled or the medium in which they grow.

[0132] The present invention also provides an insecticidal composition, which contains the compound represented by formula I of the present invention, its stereoisomer, its nitrogen oxide compound or pesticide acceptable salt as an active ingredient.

[0133] The present invention also provides a method for controlling pests, which comprises applying an effective dose of the compound represented by formula I, its stereoisomers, its nitrogen oxides or pesticide-acceptable salts or the insecticide composition of the present invention to the harmful organisms to be controlled or the medium in which they grow.

[0134] The compounds disclosed herein can be used alone or in admixture with other known insecticides, fungicides, plant growth regulators or fertilizers.

[0135] The compounds of formula I of the present invention as active ingredients can be used to prevent various pests or sanitary pests that damage rice, fruit trees, vegetables, other crops, flowers and ornamental plants in agriculture, horticulture or stored grain products. Examples of organisms that can be prevented by the compounds represented by formula I also include pests such as nematodes. In addition, the compounds represented by Formula I have strong insecticidal effects on the following pests, such as Diaphania indica, Homona magnanima, Hellulla undalis, Adoxophyes orana fasciata, Adoxophyes honmai, Archips fuscocupreanus, Carposina niponensis, Graphholita inopinata, Grapholitamolesta, Leguminivora glycinivorella, Olethreutesmori, Phyllocnistis citrella, Tuta absoluta, Stathmopoda mas inissa, Calopterygium wilfordii, and others. thevivora,Caloptilia zachrysa), Phyllonorycter ringoniella, Spulerrina astaurota, Papilio xuthus, Pieris rapae curcivora, Heliothis virescens, Helicoverpa armigera, Cydia pomonella, Plutellaxylostella, Argyresthia conjugella, Carposina niponensis, Chilo suppressalis, Cnaphalocrocis medinalis, Ephestia elutella, Glyphodes pyloalis, Scirpophagaincertulas, Parnara guttata), Pseudaletia separata, Sesamia inferens, Mamestra brassicae, Spodoptera litura, Spodoptera exigua, Agroti sipsilon, Agrotis segetum, Autographa nigri signa, Trichoplusia ni; Hemiptera pests,Such as Macrosteles fascifrons, Nephotettix cincticeps, Arboridia apicalis, Empoasca onukii, Nilaparvata lugens, Laodelphax striatellus, Sogatella furcifera, Diaphorina citri, Aleurolobus taonabae, Bernis iaargentifolii, Bemisia tabaci, Trialeurodes vaporariorum, Lipaphis erysimi, Aphis gossypii, Aphis citricola, Myzus persicae, Ceroplastes ceriferus), Pseudococcus Comstocki, Planococcus kraunhiae, Pulvina riaaurantii, Pseudaonid ia duplex, Comstockaspis perniciosa, Unaspis yanonensis, Plautia Stali, Halyomorpha mista, Stenotus rubrovittatus, Trigonotylus caelestialium; Coleoptera pests,Such as Anomala rufocuprea, Popillia japonica, Lasioderma serricorne, Lyctus brunneus, Epilachna vigintiotopunctata, Callosobruchus chinensis, Listroderes costirostris, Sitophilus zeamais, Anthonomus grandis, Lissorhoptrus oryzophilus, Aulacophora femoralis, Oulema oryzae, Phyllotreta striolata, Tomicus piniperda, Leptinotarsa ​​decemlineata, Epilachna varivesti s), Diabrotica sp., Agriotes sp., Psacothea hilaris, Anoplophora malas iaca; Diptera pests, such as Dacus (Bactrocera) dorsalis, Agromyza oryzae, Delia antiqua, Delia platura, Asphondylia sp., Musca domestica, Chromatomyia horticola, Liriomyza trifolii, Liriomyza bryoniae), mosquitoes (e.g. Anopheles gambiae, Anopheles arabiensis, Anopheles unlucky, Anopheles milas, Anopheles minutus, Anopheles dire, Anopheles stephensi, Anopheles sinensis, Anopheles albicans, Culex pipiens, Culex pipiens pallens, Culex tropicalis, Culex circumstianus, Culex pipiens tarsalis, Culex pipiens minutus, Culex tritaeniorhynchus, Aedes aegypti, Aedes albopictus, Aedes japonicus, Aedes irritans).

[0136] Hymenoptera, such as Athalia japonica, Athalia rosaeruficornis, Arge mali, Arge pagana, Dryocosmus kuriphilus, Formica japonica; Acarina, such as Polyphagotarsonemus latus, Steneotarsonemus pallidus, Tarsonemus waitei, Pyemotes ventricosus, Penthaleus major, Brevipalpus lewisi, Brevipalpus obovatus, Dolichotetranychus floridanus, Tenuipalpus zhizhilashvil iae), Brevipalpus phoenicis, Tuckerella pavoniformis, Bryobia praetiosa, Eotetranychus boreus, Ol igonychushondoensis, Panonychus citri, Panonychus ulmi, Tetranychuscin nabarinus, Tetranychus kanzawai, Tetranychus urticae, Tetranychus viennensis, Acaphyllatheae, Aceria tulipae, Aculops pelekassi, Aculus sternii schlechtendali), Calacarus carinatus, Calepitrimerus vitis, Epitrimerus pyri, Eriophyeschibaensi, Acarus siro, Aleuroglyphus ovatus, Rhizoglyphus siro,robini), Tyrophagusputre scentiae, Ornithonyssus bacot i, Leptotrom bidium akamushi, Leptotrombidium scutellaris, Leptotrombidium pallidum; Nematodes, such as Pratylenchus coffeae, Pratylenchus sp., Globodera rostochiens is, Globodera pallida, Heteroderasp., Meloidogyne sp., Tylemchulus semipenetrans, Aphelenchus avenae, Aphelenchoides chrysanthemum. ritzemabosi), Aphelenchoides besseyi; Thrips pests, such as Thrips palmi, Frankliniella oceidentalis, Scirtothrips dorsalis, Thrips flavus, Thrips tabaci; Isoptera pests, such as Cryptotermes domesticus, Coptotermes formosa nus, Reticulitermessperatus, Odontotermes formosanus; Orthoptera pests, such as Blattella germanica, Periplaneta americana, Oxya yezoensis, etc.

[0137] The compounds of the present invention represented by formula I as active ingredients have significant insecticidal effects on the above-mentioned pests that damage various lowland crops, highland crops, fruit trees, vegetables, other crops and horticultural products. Therefore, the insecticidal effect of the present invention can be obtained by treating the water of paddy fields, stems and leaves of plants, or soil of lowland crops, highland crops, fruit trees, vegetables, other crops, and flowers and ornamental plants during the season when such pests are expected to appear, or before or at the time of the appearance of the pests.

[0138] The compound represented by Formula I of the present invention is usually used in a suitable formulation form that is suitable for the purpose, and is prepared by a conventional method in the art for preparing agricultural and horticultural chemicals. It can be used in a suitable formulation form such as a suspension, emulsion, liquid formulation, water-dispersible powder, granules, dust, tablet, etc., and is prepared by mixing the aforementioned compound with at least one of a suitable inactive carrier and an adjuvant in a suitable ratio as required, and then dissolving, separating, suspending, mixing, impregnating, adsorbing, or attaching the components.

[0139] The inactive carrier that can be used in the application formulation of the present invention may be solid or liquid, and examples thereof include, in particular, soybean meal, grain meal, wood meal, bark meal, sawdust, tobacco stem meal, walnut shell meal, bran, cellulose powder, residues after plant extraction, synthetic polymers such as powdered synthetic resins, clays (e.g., kaolin, bentonite, acid clay, etc.), talcs (e.g., talc, pyrophyllite, etc.), silica (e.g., diatomaceous earth, silica sand, mica, white carbon (also known as hydrous silica powder, hydrous silica powder called synthetic highly dispersible silicic acid, certain products containing calcium silicate as the main component)), activated carbon, sulfur powder, pumice, sintered diatomaceous earth, brick crushed material, fly ash, sand, inorganic mineral powder (e.g., calcium carbonate, calcium phosphate), chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride), and compost, which may be used alone or in the form of a mixture of two or more.

[0140] Examples of materials that can be used as inactive carriers in liquid form include materials that function as solvents and materials that do not function as solvents but can disperse active ingredient compounds with the assistance of other auxiliary agents.

[0141] Examples of inactive carriers include water, alcohols (e.g., methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (e.g., diethyl ether, dioxane, cellosolve, diisopropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., kerosene, mineral oil, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, etc.), esters (e.g., ethyl acetate, butyl acetate, ethyl propionate, diisobutyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.), amides (e.g., dimethylformamide, diethylformamide, dimethylacetamide, etc.), and nitriles (e.g., acetonitrile, etc.), which may be used alone or in the form of a mixture of two or more.

[0142] Other adjuvants may be added to the formulation for use of the present invention, but no other adjuvants may be used.

[0143] Other exemplary adjuvants are as follows:

[0144] For the purpose of emulsification, dispersion, solubilization and / or wetting of the active ingredient compound, a surfactant may be used. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonates, naphthalene sulfonates, lignin sulfonates, and higher alcohol sulfonates.

[0145] Auxiliary agents that can be used for the purpose of dispersion stabilization, adhesion and / or binding of the active ingredient compound include casein, gelatin, starch, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, turpentine, bran oil, bentonite, xanthan gum, and lignin sulfonate.

[0146] Examples of adjuvants that can be used for the purpose of improving the fluidity of solid products include waxes, stearates, and alkyl phosphates. Adjuvants such as naphthalenesulfonate condensation products or condensed phosphates can be used as suspending agents in suspensions. Defoamers such as silicone oils can also be used as adjuvants.

[0147] In addition, the compound represented by formula I of the present invention is stable to light, heat, oxidation, etc., but a stabilizer can be added as needed to obtain a more stable composition. Examples of stabilizers include antioxidants, ultraviolet absorbers, phenol derivatives, such as BHT (2,6-di-tert-butyl-4-methylphenol), BHA (butylated hydroxyanisole), bisphenol derivatives, and arylamines, such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, condensates of aminophenethyl ether and acetone, and benzophenone compounds.

[0148] In addition, the effective amount of the compound represented by formula I of the present invention is generally 0.5-20% by weight in powders, 5-50% by weight in emulsions, 10-90% by weight in water-dispersible powders, 0.1-20% by weight in granules, and 10-90% by weight in flow agents. On the other hand, the amount of carrier in each formulation is generally 30-99% by weight in powders, 10-95% by weight in emulsions, 10-90% by weight in water-dispersible powders, 50-99% by weight in granules, and 5-90% by weight in flow agents. The amount of the above-mentioned auxiliary agents is generally 0.1-30% by weight in powders, 1-40% by weight in emulsions, 0.1-25% by weight in water-dispersible powders, 0.1-30% by weight in granules, and 0.1-40% by weight in flow agents.

[0149] In order to prevent and control various pests, a certain amount of the compound represented by formula I of the present invention as an effective active ingredient is directly, or appropriately diluted with water, or applied in the form of a suspension to the crops where the corresponding pests are expected to appear or the places where the pests are not expected to appear. The amount used depends on various factors, such as the purpose, the pests to be prevented, the growth state of the plant, the tendency of the pests to appear, the climate, environmental conditions, formulations, methods of use, places of use, time of use, etc. It is preferred to use the compound represented by formula I as an active ingredient at a concentration of 0.005 to 5000ppm (preferably 0.01 to 1000ppm). The dosage of the compound represented by formula I that can be used in about every hectare is usually within the range of 0.01 to 300g of the active ingredient.

[0150] The compound represented by formula I of the present invention as an active ingredient can be used alone in the control of various pests or sanitary pests or nematodes that damage rice, fruit trees, vegetables, other crops and flowers in agriculture, horticulture, and stored grain products. In addition, in order to obtain excellent control effects on various pests occurring simultaneously, the compound represented by formula I can be used in combination with at least one other insecticide and / or fungicide.

[0151] Regarding the mixed formulation (mixture) of the present invention for controlling pests, examples of insecticides, acaricides or nematicides that can be used as compounds in combination with the compound represented by formula I include compounds selected from the following: pyrethroid compounds, organophosphorus compounds, carbamate oxime compounds, carbamate compounds, neonicotin compounds, dihydrazide compounds, benzoyl urea compounds, juvenile hormone compounds, cyclodiene organochlorine compounds, 2-dimethylaminopropane-1,3-dithiol compounds, amidine compounds, phenylpyrazole compounds, organotin compounds, METI compounds, benzyl ester compounds, allylpyrrole compounds, dinitrophenol compounds, anthracene diamide compounds, oxadiazine compounds, semicarbazone compounds, tetronic acid compounds, carbamoyltriazole compounds, or tetrazine compounds. Examples of fungicides that can be combined with the compound represented by formula (1) include: strobilurin compounds, anilinopyrimidine compounds, azole compounds, azole compounds, dithiocarbamate compounds, phenylcarbamate compounds, organochlorine compounds, benzimidazole compounds, phenylamide compounds, sulfenic acid compounds, copper compounds, isoxazole compounds, organophosphorus compounds, N-halosulfanyl compounds, carboxyaniline compounds, morpholine compounds, organotin compounds, and cyanopyrrole compounds. Fumigants such as chloropicrin or natural product compounds such as nicotine can also be used in combination with the compound represented by formula I.

[0152] Specific examples of compounds that can be used in combination with the compound represented by Formula I include the following compounds:

[0153] Pyrethroid compounds and their various isomers, such as acrinathrin, allethrin [(1R) isomer], bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, β-cyfluthrin, cyhalothrin, λ-cyhalothrin, γ-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, cyphenothrin [(1R)-trans isomer] isomer]), deltamethrin, empenthrin [(EZ)-(1R) isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, methothrin, metofluthrin, permcthrin, phenothrin [(1R)-trans] isomer]), prallethrin, resmethrin, RU15525 (kadethrin), silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R) isomer], tralomethrin and transfluthrin, ZXI8901, biopermethrin, furamethrin, profluthrin, flubrocythrinate, and transfluthrin;

[0154] Organophosphorus compounds, such as acephate, azamethiphos, azinphos-methyl, azinphos-ethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, CYAP (cyanophos), demeton-S-Methyl, diazinon, inon), ECP (dichlofenthion), DDVP (dichlorvos), dicrotophos, dimethoate, dimethylvinphos, disulfoton (ethylthiometon), EPN (O-ethyl-O-4-nitrophenylphenylphosphonothioate), ethion, ethoprophos, famphur, fenamiphos, MEP (fenitrothion), MPP (fenthion), fosthiazate, heptenophos, isofenphos-methyl, isocarbophos (isopropyl-O-(methoxyaminethio-phosphino) salicylate), oxathiophos (isoxathion), malathion, mecarbam, methamidophos, DMTP (methidathion), mevinphos, monocrotophos, BRP (paled), omethoate, oxydemeton-methyl, parathion, parathion-methyl, PAP (phenthoate), ate), phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, te bupirimfos, temephos, terbufos, thiometon, triazophos, DEP (trichlorfon), vamidothion, Bayer 22 / 190 (chlorothion), bromfenvinfos, bromophos, bromophos-ethyl, butathiofos, carbophenothion, chlorphoxim, sulprofos, diamidafos, CVMP (tetrachlorvinphos), propaphos, mesulfenfos, dioxabenzofos (salithion), etrimfos, oxydeprofos, formothion, fensulfothion, chlorfenapyr (isazofos) or imicyafos (AKD3088), isamidofos, thiophosphine, and butythiocyclophosphine; carbamate oxime ester compounds, such as phosphocarb, alanycarb, butocarboxim, butoxycarboxim, thiodicarb, and Thiofanox;

[0155] Carbamate compounds, such as aldicarb, bendiocarb, benfuracarb, NAC (carbaryl), carbofuran, carbosulfan, ethiofencarb, BPMC (fenobucarb), Formetanate, furathiocarb, MIPC (isoprocarb), methiocarb, methomyl, cypermethrin oxamyl, pirimicarb, PHC (propoxur), trimethacarb, XMC (methoate), allyxycarb, aldoxycarb, bufencarb, butacarb, carbanolate, MTMC (metolcarb), MPMC (xylylcarb), fenothiocarb, xylylcarb, and bendiocarb;

[0156] Neonicotinoid compounds, such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam;

[0157] Dihydrazide compounds, such as chromafenozide, halofenozide, methoxyfenozide and tebufenozide;

[0158] Benzoyl urea compounds, such as bistrifluron, chlortluazuron, ditlubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron;

[0159] Juvenile hormone compounds, such as fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxyfen, methoprene and hydroprene;

[0160] Cyclodiene organochlorine compounds, such as chlordane, endosulfan, lindane (gamma-HCH) and dienochlor;

[0161] 2-Dimethylaminopropane-1,3-dithiol compounds, such as cartap hydrochloride and thiocyclam;

[0162] Amidine compounds, such as amitraz;

[0163] Phenylpyrazole compounds, such as ethiprole, fipronil and acetoprole;

[0164] Organotin compounds, such as azocyclotin, cyhexatin and fenbutat in oxide;

[0165] Mitochondrial electron transport inhibitor (METI) compounds, such as fenazaquin, fenpyroximate, pyridaben, pyrimidifen, tebufenpyrad or tolfenpyrad;

[0166] Benzyl ester compounds, such as bromopropylate;

[0167] Allylpyrrole compounds, such as chlorfenapyl;

[0168] Dinitrophenol compounds, such as dinitro-ortho-cresol (DNOC (dinitro-ortho-cresol)) or binapacryl;

[0169] Anthracenediamide compounds, such as chlorantraniliprole and cyantraniliprole;

[0170] Oxadiazine compounds, such as indoxacarb;

[0171] Semicarbazone compounds, such as metaflumizone;

[0172] Tetronic acid compounds, such as spirodiclofen, spiromesifen and spirotetramat;

[0173] Carbamoyltriazole compounds, such as triazamate;

[0174] Tetrazine compounds, such as diflovidaz in;

[0175] Insecticides, acaricides and nematicides, such as abamectin, emamectinbenzoate, milbemectin, lepimectin, acequinocyl, azadirachtin, bensultap, benzoximate, bifenazate, buprofezin, CGA-50439, chinomethionate, clofentezine, cryolite, cyromazine, dazomet, DCIP, DDT, diafenuron thiuron), DD (1,3-dichloropropene), dicofol, dicyclanil, dinobuton, dinocap, ENT 8184, etoxazole, flonicamid, fluacrypyrim, flubendiamide, GE-81 (peroxycarbonate), hexythiazox, hydramethylnon, hydrogen cyanide, methyliodide, karanj in, MB-599 (verbutin), silver chloride, metam, methoxychlor, methyl isothiocyanate isothiocyanate), pentachlorophenol, phosphine, piperonyl butoxide, polynactins, BPPS (propargite), pymetrozine, pyrethrins, pyridalyl, rotenone, S421 (bis (2,3,3,3-tetrachloropropyl) ether)3-tetrachloropropyl)ether), sabadilla, spinosad, spinetoram, sulcofuron-sodium, sulfluramid, tetradifon, thiosultap, tribufos, aldrin, amidithion, amidothioate, aminocarb, amiton, aramite, athidathion, azothoate, barium polysulfide, Bayer 22408, Bayer 32394, benclothiaz, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohexyl-2-enone, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (1,1-bis(4-chlorophenyl)-2-ethoxyethanol), butonate, butopyronoxyl, 2-(2-butoxyethoxy)ethyl thiocyanate, camphechlor, chlorbenside, chlordecone, chlord imeform, chlorfenethol, chlorfenson, isopro thiolane), fluazuron, metaldehyde, phenisobromolate, fluazinam, bialaphos, benomyl, levamisol, pyrifluquinazon, cyflumetofen, amidoflumet, IKA-2005, cyenopyrafen, sulfoxaflor, pyrafluprole, pyriprole, tralopyril, flupyrazofos, diofenolan, chlorobenzilate, flufenzine, benzomate, flufenerim, tripropyl isocyanate isocyanurate (TPIC), albendazole, oxibendazole, fenbendazole, metam-sod ium, 1,3-dichloropropene, afidopyropen, flometoquin, pyflubumide, fluensulfone, tetraniliprole, cyclaniliprole, fluxametamide, broflanil ide, dicloromezotiaz, triflumezopyrim, fluazaindolizine, tioxazafen and fluhexafon;

[0176] Strobilurin compounds such as azoxystrobin, kresoxym-methyl, trifloxystrobin, metominostrobin, and orysastrobin;

[0177] Anilinopyrimidine compounds, such as mepanipyrim, pyrimethanil and cyprodinil;

[0178] Azoles, such as triadimefon, bitertanol, triflumizole, metoconazole, propiconazole, penconazole, flusilazole, myclobutanil, cyproconazole, tebuconazole, hexaconazole, prochloraz, and simeconazole;

[0179] Quinoxaline compounds, such as quinomethionate;

[0180] Dithiocarbamate compounds, such as maneb, zineb, mancozeb, polycarbamate, and propineb;

[0181] Phenyl carbamate compounds, such as diethofencarb;

[0182] Organochlorine compounds, such as chlorothalonil and quintozene; dibenzimidazole compounds, such as benomyl, thiophanate-methyl, and carbendazole;

[0183] Phenylamide compounds, such as metalaxyl, oxadixyl, ofurase, benalaxyl, furaxyl, and cyprofuram;

[0184] Sulfonic acid compounds, such as dichlofluanid;

[0185] Copper compounds, such as copper hydroxide and oxine-copper;

[0186] Isoxazole compounds, such as hydroxyisoxazole;

[0187] Organophosphorus compounds, such as fosetyl-aluminium and tolclofos-methyl;

[0188] N-halosulfanyl compounds, such as captan, captafol, and folpet;

[0189] Dicarboxylic imide compounds, such as procymidone, iprodione, and vinchlozolin;

[0190] Carboxyanilide compounds, such as flutolanil, mepronil, furamepyr, thifluzamide, boscalid, and penthiopyrad;

[0191] Morpholine compounds, such as fenpropimorph and dimethomorph;

[0192] Organotin compounds, such as triphenyltin hydroxide (fenthin hydroxide) and triphenyltin acetate (fenthinacetate);

[0193] Cyanopyrrole compounds, such as fludioxonil and fenpiclonil; fungicides, such as tricyclazole, pyroquilon, carpropamid, diclocymet, fenoxanil, fthalide, fluazinam, cymoxanil; l), triforine, pyrifenox, fenarimol, fenpropidin, pencycuron, ferimzone, cyazofamid, iprovalicarb, benthiavalicarb-isopropyl, iminoctadin-albesilate, cyflufenamid, kasugamycin, validamycin, streptomycin, oxolinic-acid, tebufloquin, probenazole, tiadinil, isot ianil, tolprocarb, or isofetamid, fenpicoxamid, quinofumelin, pydiflumetofen, dipymet itrone and pyraziflumid;

[0194] Fumigants, such as chloropicrin, ethylene dibromide (EDB), sulfonyl fluoride, acrylonitrile, bis(2-chloroethyl) ether, 1-bromo-2-chloroethane, 3-bromo-1-chloro-1-propene, bromocyclen, carbon disulfide, tetrachloromethane, sodium metham, nemadectin, and aluminum phosphide;

[0195] Natural compounds, such as Bacillus thuringiensis delta-endotoxin, borax, calcium polysulfide, cryolite, cytokinin, nicotine, 2-(octylthio)ethanol, potassium oleate, sodium oleate, motor oil, sulfur, tar, anabasine, morantel tartrate, pyrethrum, nicotine sulfate, rapeseed oil, soybean lecithin, starch, hydroxypropyl starch, capryloctanoylglycerol, propylene glycol fatty acid esters, diatomaceous earth, and Bacillus thuringiensis.

[0196] According to one embodiment, a horticultural or agricultural pesticide comprising a compound represented by Formula I as an active ingredient is provided. According to another embodiment, a method for protecting crops from harmful organisms is provided, the aforementioned method comprising treating the crops or soil for crops with an effective amount of a compound represented by Formula I.

[0197] When the compound represented by Formula I of the present invention is used in combination with at least one other insecticide and / or fungicide, a mixed composition of the compound represented by Formula I and other insecticides and / or fungicides can be used. Alternatively, the compound represented by Formula I can be mixed with other insecticides / fungicides for use when applied.

[0198] Preferably, the compound of formula I has a good synergistic effect in combination with the following insecticides and / or fungicides: neonicotinoid insecticides such as thiamethoxam, imidacloprid, clothianidin, thiacloprid, acetamiprid, nitenpyram, dinotefuran, and cycloheximide, or selected from flupyrazone, sulfoxaflor, flonicamid, pymetrozine, buprofezin, triflubenzuron, dichlorothiazide, afidopyropen, pyrifluquinazon, benzpyrimoxan, cyproconazole, tebuconazole, prothioconazole, cyproconazole, azoxystrobin, trifloxystrobin, pyraclostrobin, picoxystrobin, metalaxyl-M, metalaxyl, fludioxonil, prochloraz, and cyanostrobin.

[0199] Preferably, when the compound of formula I is combined with the preferred insecticide and / or fungicide, the ratio of the two is 0.01:100-100:0.01, or 0.1:100-100:0.1, or 1:100-100:1, or 1:10-10:1 (all by weight). In addition, any range obtained by replacing the upper or lower limit of the above range with the upper or lower limit of other ranges is also regarded as the mixing ratio range of the present invention.

[0200] In addition to or in place of the above-mentioned insecticides or fungicides, the compounds represented by formula I can also be mixed with plant protection agents, such as herbicides, fertilizers, soil conditioners, plant growth control agents, or any other materials expected to provide additive or synergistic effects to form multi-purpose compositions with high efficacy.

[0201] Alternatively, all application forms of the compounds described below as examples, such as free compounds, acid addition salts, base addition salts, esters, solvates such as hydrates, isomers such as stereoisomers, optical isomers, etc., can also be applied directly as active ingredients or in combination with existing insecticides, fungicides, herbicides, etc.

[0202] The compounds of the present invention have a wide range of applications, and the plants or ranges used mainly include the following categories: fruits and vegetables, including cucumbers, loofahs, watermelons, melons, pumpkins, hanging melons, spinach, celery, cabbages, cabbages, gourds, peppers, eggplants, tomatoes, onions, ginger, garlic, leeks, lettuce, kidney beans, cowpeas, broad beans, radishes, carrots, potatoes, and yams; cereals, including wheat, barley, corn, rice, and sorghum; fruit trees, including apples, pears, bananas, citrus, grapes, litchis, and mangoes; flowers, including peonies, roses, and flamingos; oil crops, including peanuts, soybeans, rapeseed, sunflowers, and sesame; sugar crops, including beets and sugarcane; other crops, such as strawberries, potatoes, sweet potatoes, tobacco, and tea; gardening, forestry, household hygiene, and public health areas, etc.; the plants or ranges listed above have no limiting effect on the scope of use of the compounds of the present invention.

[0204] The technical solution of the present disclosure will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary illustrations and explanations of the present disclosure and should not be construed as limiting the scope of protection of the present disclosure. All technologies implemented based on the above content of the present disclosure are included in the scope of protection intended by the present disclosure.

[0205] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods. The percentage content in this example refers to the percentage content by mass unless otherwise specified.

[0206] 1) Preparation Example of Intermediate Compound

[0207] Preparation Example 1: Synthesis of Intermediate 1

[0208]

[0209] Dissolve 2,2-difluorocyclopropylcarboxylic acid (10 g, 0.08 mmol) in tetrahydrofuran (200 ml), cool to 0°C, add lithium aluminum hydride (4.54 g, 0.12 mmol) in batches, continue stirring for 30 minutes, warm to room temperature, and stir for 4 hours. Cool in an ice-water bath, carefully drop water (13 ml), then drop 15% sodium hydroxide aqueous solution (4.5 ml), stir at room temperature for about 30 minutes, filter, and concentrate under reduced pressure (temperature is 30°C) to obtain a crude intermediate 1 (10 g), which is directly used in the next step.

[0210] Preparation Example 2: Synthesis of Intermediate 2

[0211]

[0212] Dissolve the crude intermediate 1 (10 g) in dichloromethane (400 ml), add N,N,N',N'-tetramethyl-1,6-hexanediamine (11.15 g, 0.065 mmol), cool to 0°C, add p-toluenesulfonyl chloride (26.48 g, 0.139 mmol) in batches, continue stirring for 30 minutes, warm to room temperature, and stir for 4 hours. Add saturated sodium chloride aqueous solution (500 ml), extract with dichloromethane, dry (sodium sulfate), filter, spin dry, and purify the residue by silica gel column chromatography to obtain intermediate 2 (15 g) for later use.

[0213] Preparation Example 3: Synthesis of Intermediate 3

[0214]

[0215] Under argon protection, 2-fluoro-3-nitrobenzoic acid (20 g, 0.108 mmol) was dissolved in methanol (200 ml), cooled to 0°C, thionyl chloride (25.7 g, 0.216 mmol) was slowly added dropwise, and stirred for 30 minutes, then heated to 60°C and stirred for 2 hours. The mixture was dried and the intermediate 3 (20 g, crude product) was obtained, which was used directly in the next step.

[0216] Preparation Example 4: Synthesis of Intermediate 4

[0217]

[0218] Under argon protection, intermediate 3 (20 g, crude product) was dissolved in anhydrous ethanol (300 ml), acetic acid (10 ml) was added, and zinc powder (32 g) was slowly added in batches. Stir at room temperature for 2 h. Celite was spread and filtered, the filtrate was spin-dried, saturated sodium chloride aqueous solution (500 ml) was added, extracted with ethyl acetate, dried (sodium sulfate), filtered, and spin-dried. The residue was purified by silica gel column chromatography to obtain intermediate 4 (15 g) for standby use.

[0219] Preparation Example 5: Synthesis of Intermediate 5

[0220]

[0221] Under argon protection, intermediate 4 (2 g, 0.012 mmol) was dissolved in toluene (20 ml), p-fluorobenzoyl chloride (2.05 g, 0.013 mmol) and 4-dimethylaminopyridine (0.14 g, 0.001 mmol) were added in sequence, the temperature was raised to 100°C, and stirred for 2 h. Saturated sodium chloride aqueous solution (50 ml) was added, extracted with ethyl acetate, dried (sodium sulfate), filtered, and spin-dried, and the residue was purified by silica gel column chromatography to obtain intermediate 5 (3.1 g).

[0222] Preparation Example 6: Synthesis of Intermediate 6

[0223]

[0224] Under argon protection, intermediate 5 (3.1 g, 0.011 mmol) was dissolved in N, N-dimethylformamide (50 ml), intermediate 2 (3.34 g, 0.013 mmol) and cesium carbonate (6.92 g, 0.022 mmol) were added, the temperature was raised to 100 ° C, and stirring was continued for 3 h. Water (200 mL) was added, extracted with ethyl acetate, and the organic phases were combined. The organic phase was washed with saturated brine, dried (sodium sulfate), filtered, and dried, and the residue was purified by silica gel column chromatography to obtain intermediate 6 (3.5 g).

[0225] Preparation Example 7: Synthesis of Intermediate 7

[0226]

[0227] Intermediate 6 (2 g, 0.005 mmol) was dissolved in a mixed solution of methanol (3 ml) and tetrahydrofuran (3 ml), and an aqueous sodium hydroxide solution (4 M, 3 ml) was added, and the temperature was raised to 40°C, and stirring was continued for 1 h. Water (10 mL) was added, and the mixture was extracted with ethyl acetate, and dilute hydrochloric acid (1 M) was slowly added dropwise to the aqueous phase to adjust the solution pH to 3, and stirring was continued for 30 min, and the mixture was filtered and dried to obtain intermediate 7 (1.5 g).

[0228] Preparation Example 8: Synthesis of Intermediate 8

[0229]

[0230] Under argon protection, intermediate 7 (1.5 g, 0.004 mmol) was dissolved in dry toluene (20 ml), cooled to 0°C, thionyl chloride (0.97 g, 0.008 mmol) and N,N-dimethylformamide (one drop) were added, the temperature was raised to 80°C, and stirring was continued for 3 h. The reaction solution was concentrated under reduced pressure to obtain a crude product of intermediate 8 (1.4 g), which was directly used in the next step.

[0231] Preparation Example 9: Synthesis of Intermediate 9

[0232]

[0233] Under argon protection, intermediate 4 (2 g, 0.012 mmol) was dissolved in toluene (20 ml), and benzoyl chloride (1.82 g, 0.013 mmol) and 4-dimethylaminopyridine (0.14 g, 0.001 mmol) were added in sequence, and the temperature was raised to 100°C and stirred for 2 h. Saturated sodium chloride aqueous solution (50 ml) was added, and the mixture was extracted with ethyl acetate, dried (sodium sulfate), filtered, and spin-dried. The residue was purified by silica gel column chromatography to obtain intermediate 9 (2.8 g).

[0234] Preparation Example 10: Synthesis of Intermediate 10

[0235]

[0236] Under argon protection, intermediate 9 (2.8 g, 0.010 mmol) was dissolved in N, N-dimethylformamide (50 ml), intermediate 2 (3.22 g, 0.012 mmol) and cesium carbonate (10.02 g, 0.31 mmol) were added, the temperature was raised to 100 ° C, and stirring was continued for 3 h. Water (200 mL) was added, extracted with ethyl acetate, and the organic phases were combined. The organic phase was washed with saturated brine, dried (sodium sulfate), filtered, and dried, and the residue was purified by silica gel column chromatography to obtain intermediate 10 (3.4 g).

[0237] Preparation Example 11: Synthesis of Intermediate 11

[0238]

[0239] Intermediate 10 (3.4 g, 0.009 mmol) was dissolved in a mixed solution of methanol (5 ml) and tetrahydrofuran (5 ml), and an aqueous sodium hydroxide solution (4 M, 5 ml) was added, and the temperature was raised to 40°C, and stirring was continued for 1 h. Water (20 mL) was added, and the mixture was extracted with ethyl acetate, and dilute hydrochloric acid (1 M) was slowly added dropwise to the aqueous phase to adjust the solution pH to 3, and stirring was continued for 30 min, and the mixture was filtered and dried to obtain intermediate 11 (3.0 g).

[0240] Preparation Example 12: Synthesis of Intermediate 12

[0241]

[0242] Under argon protection, intermediate 11 (1.5 g, 0.004 mmol) was dissolved in dry toluene (20 ml), cooled to 0°C, and then thionyl chloride (1.02 g, 0.008 mmol) and N,N-dimethylformamide (one drop) were added, and the temperature was raised to 80°C, and stirring was continued for 3 h. The reaction solution was concentrated under reduced pressure to obtain a crude product of intermediate 12 (1.5 g), which was directly used in the next step.

[0243] II) Compound Preparation Example

[0244] Example 1: Preparation of 3-(N-(2,2-difluorocyclopropyl)methyl)-4-fluorobenzamide)-2-fluoro-N-(4-(perfluoropropan-2-yl)-2-(trifluoromethyl)phenyl)benzamide (Compound 1)

[0245]

[0246] Under argon protection, the crude product of intermediate 8 (1.4 g) was dissolved in toluene (20 ml), and 2-trifluoromethyl-4-(heptafluoroisopropyl)aniline (1.48 g, 0.004 mmol) and 4-dimethylaminopyridine (0.05 g, 0.0004 mmol) were added in sequence, and the temperature was raised to 100°C and stirred for 2 h. A saturated sodium chloride aqueous solution (50 ml) was added, and the mixture was extracted with ethyl acetate, dried (sodium sulfate), filtered, and spin-dried. The residue was purified by silica gel column chromatography to obtain compound 1 (2.2 g).

[0247] 1 H NMR(400MHz, CDCl3)δ7.95(s,1H),7.89–7.75(m,2H),7.39(dd,J=8.2,5.5Hz,2H),7.28(s,1H),7.27–7.19(m,1H),7.16(d,J=8.3H z,1H),6.93(t,J=8.4Hz,2H),4.44(s,1H),3.60(dd,J=14.3,8.2Hz,1H),2.07(s,1H),1.67(d,J=5.0Hz,1H),1.13(d,J=3.7Hz,1H).

[0248] Example 2: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(2,2-difluorocyclopropyl)methyl)-4-fluorobenzamide)-2-fluorobenzylamine (Compound 2)

[0249]

[0250] Under argon protection, compound 1 (1 g, 0.0014 mmol) was dissolved in dichloromethane (10 ml), and an aqueous solution (1 ml) of sodium bromide (0.228 g, 0.0022 mmol) and sodium hydroxide (0.029 g, 0.0007 mmol) was added, and the temperature was raised to 40°C, and sodium hypochlorite solution (4 ml) was added, and stirred for 1 h. A saturated sodium chloride aqueous solution (50 ml) was added, and the mixture was extracted with dichloromethane, and the organic phases were combined. The organic phase was washed with a saturated sodium sulfite aqueous solution, dried (sodium sulfate), filtered, and spin-dried, and the residue was purified by silica gel column chromatography to obtain compound 2 (0.7 g).

[0251] 1 H NMR (400MHz, DMSO) δ10.58(d,J=39.9Hz,1H),8.43(s,1H),7.96(s,1H),7.70(d,J=64.2Hz,2H),7.25(d, J=115.5Hz,5H),4.28(s,1H),3.58(s,1H),2.14–2.01(m,1H),1.63(dd,J=6.8,4.0Hz,1H),1.24(s,1H).

[0252] Example 3: Preparation of 3-(N-(2,2-difluorocyclopropyl)methyl)-4-fluorobenzamide)-2-fluoro-N-(2-methyl-4-(perfluoropropan-2-yl)phenyl)benzamide (Compound 3)

[0253]

[0254] Under argon protection, the crude product of intermediate 8 (1.4 g) was dissolved in toluene (20 ml), and 2-methyl-4-(heptafluoroisopropyl)aniline (1.11 g, 0.004 mmol) and 4-dimethylaminopyridine (0.05 g, 0.0004 mmol) were added in sequence, and the temperature was raised to 100°C and stirred for 2 h. A saturated sodium chloride aqueous solution (50 ml) was added, and the mixture was extracted with ethyl acetate, dried (sodium sulfate), filtered, and spin-dried. The residue was purified by silica gel column chromatography to obtain compound 3 (1.8 g).

[0255] 1H NMR (400MHz, CDCl3) δ8.38(d,J=8.6Hz,1H),8.09(d,J=7.0Hz,2H),7.61–7.44(m,3H),7.44–7.32(m,3H),6.92(t,J=7.9Hz, 2H), 4.63 (d, J = 100.4Hz, 1H), 3.42 (d, J = 130.4Hz, 1H), 2.34 (d, J = 5.8Hz, 3H), 2.17 (s, 1H), 1.54 (s, 1H), 1.18–1.05 (m, 1H).

[0256] Example 4: Preparation of 3-(N-(2,2-difluorocyclopropyl)methyl)benzamido)-2-fluoro-N-(4-(perfluoropropan-2-yl)-2-(trifluoromethyl)phenyl)benzamide (Compound 4)

[0257]

[0258] Under argon protection, the crude product of intermediate 12 (1.5 g) was dissolved in toluene (20 ml), and 2-trifluoromethyl-4-(heptafluoroisopropyl)aniline (1.48 g, 0.004 mmol) and 4-dimethylaminopyridine (0.05 g, 0.0004 mmol) were added in sequence, and the temperature was raised to 100°C and stirred for 2 h. A saturated sodium chloride aqueous solution (50 ml) was added, and the mixture was extracted with ethyl acetate, dried (sodium sulfate), filtered, and spin-dried. The residue was purified by silica gel column chromatography to obtain compound 4 (2.2 g).

[0259] 1 H NMR (400MHz, CDCl3) δ7.94 (s, 1H), 7.83 (d, J = 8.2Hz, 1H), 7.74 (t, J = 6.8Hz, 1H), 7.36 (d, J = 7.3Hz, 3H), 7.30(s,1H),7.26–7.08(m,4H),4.44(s,1H),3.61(s,1H),2.06–1.95(m,1H),1.63(s,1H),1.12(s,1H).

[0260] Example 5: Preparation of N-(2-bromo-4-(perfluoropropan-2-yl)-6-(trifluoromethyl)phenyl)-3-(N-(2,2-difluorocyclopropyl)methyl)benzamido)-2-fluorobenzamide (Compound 5)

[0261]

[0262] Step 1: Synthesis of compound 5

[0263] Under argon protection, compound 4 (1 g, 0.0015 mmol) was dissolved in dichloromethane (10 ml), and an aqueous solution (1 ml) of sodium bromide (0.224 g, 0.0023 mmol) and sodium hydroxide (0.03 g, 0.0008 mmol) was added, and the temperature was raised to 40°C, and sodium hypochlorite solution (4 ml) was added, and stirred for 1 h. A saturated aqueous sodium chloride solution (50 ml) was added, and the mixture was extracted with dichloromethane, and the organic phases were combined. The organic phase was washed with a saturated aqueous sodium sulfite solution, dried (sodium sulfate), filtered, and spin-dried, and the residue was purified by silica gel column chromatography to obtain compound 5 (0.8 g).

[0264] 1 H NMR (400MHz, DMSO) δ10.59(d,J=37.2Hz,1H),8.43(s,1H),7.96(s,1H),7.68(d,J=53.4Hz,2H),7 .30(d,J=21.4Hz,6H),4.23(s,1H),3.53(s,1H),2.02(d,J=7.2Hz,1H),1.64(s,1H),1.24(s,1H).

[0265] Example 6: Preparation of 3-(N-(2,2-difluorocyclopropyl)methyl)benzamido)-2-fluoro-N-(2-methyl-4-(perfluoropropan-2-yl)phenyl)benzamide (Compound 6)

[0266]

[0267] Under argon protection, the crude product of intermediate 12 (1.4 g) was dissolved in toluene (20 ml), and 2-methyl-4-(heptafluoroisopropyl)aniline (1.05 g, 0.004 mmol) and 4-dimethylaminopyridine (0.05 g, 0.0004 mmol) were added in sequence, and the temperature was raised to 100°C and stirred for 2 h. A saturated aqueous sodium chloride solution (50 ml) was added, and the mixture was extracted with ethyl acetate, dried (sodium sulfate), filtered, and spin-dried. The residue was purified by silica gel column chromatography to obtain compound 6 (1.7 g).

[0268] 1 H NMR (400MHz, CDCl3) δ8.37(d,J=8.4Hz,1H),8.05(s,2H),7.68–7.41(m,3H),7.34(t,J=14.6Hz,3H),7.22(s,2H), 4.62(d,J=112.2Hz,1H),3.44(d,J=136.1Hz,1H),2.49–2.23(m,3H),2.24–2.06(m,1H),1.54(s,1H),1.11(s,1H).

[0269] Refer to the synthesis method of Examples 1-6 for the following compounds

[0270] Table 1 Example compounds 7-24 of the present invention and comparative example compounds 2 and 3

[0271]

[0272]

[0273]

[0274]

[0275]

[0276] 2. Preparation Examples

[0277] Preparation Example 1: 10% emulsifiable concentrate of the compound of the present invention

[0278] The compound of the present invention is 10%, fast T is 5%, castor oil polyoxyethylene ether is 5%, methyl oleate is 2%, and xylene is less than 100%.

[0279] According to the above formula, the above materials are weighed and mixed evenly to obtain 10% emulsifiable concentrate of the compound of the present invention, and samples are packaged after they are qualified.

[0280] Formulation Example 2: 20% wettable powder of the compound of the present invention

[0281] The compound of the present invention is 20%, sodium dodecylbenzene sulfonate is 5%, sodium lignin sulfonate is 5%, and kaolin makes up to 100%.

[0282] According to the above formula, the above materials are weighed and mixed evenly, and then crushed to less than 10 microns using a jet mill. Samples are taken and packaged after passing the test.

[0283] 3. Biological Activity Test Example

[0284] (I) Indoor bioactivity test against Spodoptera litura

[0285] 1. Test samples

[0286] Compounds 1-26 and reference compounds 1-3 in the biological test of the present invention were prepared in this laboratory, wherein reference compound 1 (ciprofloxacin) was prepared according to the method disclosed in CN109497062B, and the structure of reference compound 1 is as follows:

[0287] (Ciprofenamide)

[0288] The compounds of the present invention and reference compounds 1 to 3 obtained above were tested against various pests.

[0289] The sample preparation method is to weigh 10 mg of the original drug of the sample to be tested, dissolve it in 1 mL of DMF, prepare a 10000 ppm mother solution, and dilute the mother solution to the required concentration with 0.05% Tween-80 water for activity testing.

[0290] 2. Test target: Spodoptera litura

[0291] 3. Test methods

[0292] The activity test was conducted by the leaf disc feeding method. The leaf disc was immersed in the drug solution for 10 seconds, and then placed in a culture dish after drying, with 4 discs per dish and filter paper placed in the culture dish to keep it moist. 20-30 Spodoptera litura test insects were placed in each dish, and repeated 3 times. The insects were placed in a light incubator at a temperature of 25°C and a light intensity of 14hL:10hD for cultivation. The number of dead Spodoptera litura insects was investigated 1, 2, and 3 days after the drug was applied, and the mortality rate was calculated.

[0293] The mortality rate is the mortality rate that causes the death of pests at the test concentration of the compound.

[0294] The calculation formula is: mortality rate (%) = number of dead insects / total number of insects*100.

[0295] The insecticidal activities of the compounds of the present invention and the control compounds against Spodoptera litura are as follows:

[0296] When the concentration of the compounds 1-26 of the present invention is 1 ppm, the control effect on the Spodoptera litura is ≥80% 12 hours after the application, while the control effect of the reference compounds 1, 2, and 3 is ≤20%. The control effect of the compounds 1-26 of the present invention on the Spodoptera litura is 100% 72 hours after the application, while the control effect of the reference compounds 1, 2, and 3 is ≤80%.

[0297] When the concentration of the compounds 1, 2, 3, 4, 5, 6, 9, 12, 13, 15, 17, 21, 24 and 26 of the present invention is 0.5 ppm, the control effect on the Spodoptera litura is ≥60% 12 hours after the application of the drug, while the control effect of the control compounds 1, 2, 3 and 4 is ≤20%. The control effect of the compounds 1, 2, 3, 4, 5, 6, 9, 12, 13, 15, 17, 21, 24 and 26 of the present invention on the Spodoptera litura is ≥90% 72 hours after the application of the drug, while the control effect of the control compounds 1, 2 and 3 is ≤30%.

[0298] (II) Field effect test of rose, cowpea and watermelon:

[0299] 1. Materials and methods 1.1 Test agents

[0300] Compound 1, compound 2, compound 3, compound 4, compound 5, compound 6, reference compounds 1-3 and acetamiprid.

[0301] 1.2 Test targets and crops

[0302] Target: Thrips, Yellow Thrips, Western Flower Thrips

[0303] Crops: Rose (variety: Aisha), cowpea, watermelon

[0304] 1.3 Test methods

[0305] 1.3.1 Field trial for the control of rose thrips (Kunyang Street, Jinning District, Kunming City, Yunnan Province, August 4, 2024)

[0306] The test site is located in Kunyang Street, Jinning District, Kunming City, Yunnan Province. The test crop is rose, and the variety is Aisha. The test agent compounds 1-6 are configured to a mass concentration of 66.7ppm, the control agent control compound 1 (Cyprofenoxam), control compound 2, and control compound 3 are configured to a mass concentration of 66.7ppm, and acetamiprid is configured to a mass concentration of 667ppm. A clear water blank control is also set. The test treatment area is 4㎡, each treatment is repeated 4 times, and the random block group arrangement is arranged.

[0307] Use Huayou brand electric backpack sprayer for conventional spraying. Investigate the insect population before spraying, and investigate once 14 and 24 hours after spraying, check and record the number of active thrips on the marked leaves. Count the thrips reduction rate and calculate the control effect.

[0308] Calculation method of drug efficacy:

[0309] Thrips reduction rate (%) = [(number of insects before medication - number of insects after medication) / number of insects before medication] × 100

[0310] Control effect (%) = [(thrips reduction rate in treatment area - thrips reduction rate in blank control area) / (100 - thrips reduction rate in blank control area)] × 100

[0311] 1.3.2 Field trial for controlling yellow thrips on cowpea (Ledong Li Autonomous County, Hainan Province, July 13, 2024)

[0312] The test site is located in Ledong Li Autonomous County, Hainan Province. The test crop is cowpea, and the local yellow thrips are highly resistant. The test agent compounds 1-6 are configured to a mass concentration of 66.7ppm, the control agent control compound 1 (Cyprofenoxam), control compound 2 and control compound 3 are configured to a mass concentration of 66.7ppm, and acetamiprid is configured to a mass concentration of 667ppm. A clear water blank control is also set. The test treatment area is 4㎡, each treatment is repeated 4 times, and the random block group is arranged.

[0313] Use Huayou brand electric backpack sprayer for conventional spraying. Investigate the insect population before spraying, and investigate once 1d (1 day) and 2d (2 days) after spraying, check and record the number of active yellow thrips on the marked leaves. Count the reduction rate of yellow thrips and calculate the control effect. The calculation method of drug efficacy is the same as 1.3.1.

[0314] 1.3.3 Field trial for the control of western flower thrips in watermelon (Taizhou City, Zhejiang Province, August 1, 2024)

[0315] The test site is located in Taizhou City, Zhejiang Province. The test crop is watermelon, and the local western flower thrips is highly resistant. The test agent compounds 1-6 are configured to a mass concentration of 66.7ppm, the control compound 1 (Cyprofenoxam), the control compound 2 and the control compound 3 are configured to a mass concentration of 66.7ppm, and the acetamiprid is configured to a mass concentration of 667ppm. A clear water blank control is also set. The test treatment area is 4㎡, each treatment is repeated 4 times, and the random block arrangement is arranged.

[0316] Use Huayou brand electric backpack sprayer for conventional spraying. Investigate the insect population before spraying, and investigate once 1d (1 day) and 2d (2 days) after spraying, check and record the number of active western flower thrips on the marked leaves. Count the reduction rate of western flower thrips and calculate the control effect. The calculation method of drug efficacy is the same as 1.3.1.

[0317] 2 Results Analysis

[0318] Table 2 Results of the test on controlling rose thrips

[0319]

[0320]

[0321] Note: The protective efficacy (%) in the table is the average value of each replicate.

[0322] Table 3 Test results for controlling yellow thrips on cowpea

[0323]

[0324] Note: The protective efficacy (%) in the table is the average value of each replicate.

[0325] Table 4 Test results for controlling western flower thrips in watermelon

[0326]

[0327]

[0328] Note: The protective efficacy (%) in the table is the average value of each replicate.

[0329] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A compound represented by formula I: ， or its stereoisomers, nitrogen oxides, isotopes and pesticide-acceptable salts, in, Q is selected from the following groups: ， in, Indicates the connection end; W1 and W2 are independently selected from oxygen or sulfur; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each of the groups is independently selected from one or more of hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl and optionally substituted alkynyl.

2. The compound of formula (I) according to claim 1, its stereoisomers, nitrogen oxides, isotopes and pesticide-acceptable salts, characterized in that: The W1 and W2 are both oxygen.

3. The compound of formula (I) according to claim 1, its stereoisomers, nitrogen oxides, isotopes and pesticide-acceptable salts, characterized in that: R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 They are independently selected from one or more of hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl and halogenated C2-C6 alkynyl.

4. The compound of formula (I) according to claim 1, its stereoisomers, nitrogen oxides, isotopes and pesticide-acceptable salts, characterized in that Formula I is selected from the following compounds:

5. The compound of formula (I) according to claim 1, its stereoisomers, nitrogen oxides, isotopes and pesticide-acceptable salts, characterized in that: Formula I is selected from the following compounds:

6. An insecticidal composition, characterized in that: Contains the compound represented by formula I, its stereoisomers, nitrogen oxides, isotopes and pesticide-acceptable salts as active ingredients, Wherein, Q is selected from the following groups: ， in, Indicates the connection end; W1 and W2 are independently selected from oxygen or sulfur; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 are independently selected from one or more of hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl and optionally substituted alkynyl.

7. The insecticidal composition according to claim 6, characterized in that The W1 and W2 are both oxygen.

8. The insecticidal composition according to claim 6, characterized in that R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 They are independently selected from one or more of hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl and halogenated C2-C6 alkynyl.

9. The insecticidal composition according to claim 6, characterized in that , Formula I is selected from the following compounds:

10. The insecticidal composition according to claim 6, characterized in that: Formula I is selected from the following compounds:

11. The insecticidal composition according to any one of claims 6 to 10, characterized in that It also contains another active ingredient, B.

12. The insecticidal composition according to claim 11, characterized in that The other active ingredient B is a neonicotinoid insecticide such as thiamethoxam, imidacloprid, clothianidin, thiacloprid, acetamiprid, nitenpyram, dinotefuran, cycloheximide, or is selected from flupyrazone, sulfoxaflor, flonicamid, pymetrozine, buprofezin, triflubenzuron, dichlorothiazide, afidopyropen, pyrifluquinazon, benzpyrimoxan, cyproconazole, tebuconazole, prothioconazole, cyproconazole, azoxystrobin, trifloxystrobin, pyraclostrobin, picoxystrobin, metalaxyl-M, metalaxyl, fludioxonil, prochloraz, cyanamide, one or more of cyanostrobin. Preferably, the mass ratio of the compound of formula I to B is 1:100 to 100:1, more preferably 1:10 to 10:

1.

13. A compound of formula II, characterized in that The structure of the compound of formula II is as follows: Among them, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each of them is independently selected from hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl, and optionally substituted alkynyl.

14. The compound of formula II according to claim 13, characterized in that R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 are independently selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, optionally substituted alkynyl; preferably one or more of hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl and halogenated C1-C6 alkylsulfonyl, preferably, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 are independently selected from one or more of hydrogen, halogen, cyano, nitro, C1-C6 alkyl and halogenated C1-C6 alkyl. Preferably, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 They are independently selected from one or more of hydrogen, F, Cl, Br, methyl and trifluoromethyl.

15. A compound of formula III, characterized in that The structure of the compound of formula III is as follows: Wherein, Q is selected from the following groups: ， in, Indicates the connection end; W1 and W2 are independently selected from oxygen or sulfur; R1, R2, R3, R4, R5, R6, R7, R8, R9 are independently selected from hydrogen, halogen, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylcarbonyl, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkenyl, optionally substituted alkynyl; L is a leaving group, preferably a halogen.

16. The compound of formula III according to claim 15, characterized in that in, W1 and W2 are both oxygen.

17. The compound of formula III according to claim 15, characterized in that R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl and optionally substituted alkynyl; preferably hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 The invention relates to one or more of alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, C1-C6 alkylcarbonyl, halogenated C1-C6 alkylcarbonyl, C1-C6 alkylsulfinyl, halogenated C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl and halogenated C1-C6 alkylsulfonyl. Preferably, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from one of hydrogen, halogen, cyano, nitro, C1-C6 alkyl and halogenated C1-C6 alkyl. Particularly preferably, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from one of hydrogen, F, Cl, Br, methyl and trifluoromethyl.

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