4-Substituted quinoline derivatives and preparation methods and applications thereof

Abstract

The present invention provides a 4-substituted quinoline derivative and a preparation method and application thereof. Specifically, the present invention relates to a compound represented by formula (I), a preparation method of the compound represented by formula (I), and application of a composition and / or preparation comprising the compound represented by formula (I) as an insecticide in agriculture, forestry and / or gardening; wherein, in formula (I), R 1 and R 2 are independently hydrogen, C 1‑6 Alkyl, etc.; R 3 , R 4 and R 5 are independently hydrogen, C 1‑6 Alkyl, etc.; R 6 , R 7 , R 8 , R 9 and R 10 are independently hydrogen, C 1‑6 Alkyl, C 1‑6 Alkoxy, halogenated C 1‑6 Alkoxy, etc.; Hy is pyrazolyl.

Description

Technical Field

[0001] The present invention relates to the field of pesticides, and in particular to a novel 4-substituted quinoline derivative, a method for preparing the 4-substituted quinoline derivative, and the use of a composition and / or preparation containing the 4-substituted quinoline derivative as a pesticide in agriculture, forestry and / or horticulture. Background Art

[0002] In agriculture, damage caused by pests to the growth and storage of crops can lead to a significant reduction in yield, while the continuous use of pesticides has led to problems such as pest resistance, the service life of pesticides, and environmental pollution. In order to alleviate the various problems existing in the current use of pesticides, it is necessary to continuously develop new pesticide compounds that are more efficient, less toxic, environmentally safe, and have different modes of action. Summary of the invention

[0003] The invention provides a novel quinoline derivative. The derivative has a novel structure, a simple preparation method, and has excellent control effect on pests, especially on armyworm, peach aphid, spider mite, rice brown planthopper, etc., and can be used as an insecticide in agriculture, forestry and / or gardening.

[0004] In order to achieve the purpose of the present invention, the following technical solutions are provided:

[0005] Specifically, on the one hand, the present invention provides a compound, which is a compound represented by formula (I), or a stereoisomer, nitrogen oxide or salt thereof of the compound represented by formula (I):

[0006]

[0007] in:

[0008] R 1 and R 2 are independently hydrogen, C 1-6 Alkyl or halogenated C 1-6 alkyl;

[0009] R 3 , R 4 and R 5 are independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C 1-6 Alkyl, halogenated C 1-6 Alkyl, C 1-6 Alkoxy or halogenated C 1-6 Alkoxy;

[0010] R 6 , R 7 , R 8 , R 9 and R 10are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, C 1-6 Alkyl, halogenated C 1-6 Alkyl, C 1-6 Alkoxy or halogenated C 1-6 Alkoxy;

[0011] Hy is pyrazolyl; wherein Hy is optionally substituted by 1, 2 or 3 groups selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, C 1-6 Alkyl, halogenated C 1-6 alkyl, phenyl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine or iodine, or pyridinyl optionally substituted by 1 or 2 groups selected from fluorine, chlorine, bromine or iodine.

[0012] In some embodiments, R 1 and R 2 are independently hydrogen, C 1-4 Alkyl or halogenated C 1-4 alkyl.

[0013] In other embodiments, R 1 and R 2 Each is independently hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CHF2, -CF3 or -CH2CHF2.

[0014] Preferably, in some embodiments, R 1 and R 2 Each independently is C 1-4 alkyl.

[0015] Further preferably, in some embodiments, R 1 and R 2 Each is independently -CH3 or -CH2CH3.

[0016] More preferably, in some embodiments, R 1 It is -CH3.

[0017] More preferably, in some embodiments, R 2 It is -CH2CH3.

[0018] In some embodiments, R 3 , R 4 and R 5 are independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C 1-4 Alkyl or halogenated C 1-4 alkyl.

[0019] In other embodiments, R 3 , R 4 and R 5Each is independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, -CH3 or -CF3.

[0020] Preferably, in some embodiments, R 3 , R 4 and R 5 are independently hydrogen or C 1-4 alkyl.

[0021] More preferably, in some embodiments, R 3 , R 4 and R 5 are independently hydrogen or C 1-4 Alkyl; wherein R 3 , R 4 and R 5 Not at the same time as hydrogen.

[0022] Further preferably, in some embodiments, R 3 and R 5 are each independently hydrogen; R 4 C 1-4 alkyl.

[0023] More preferably, in some embodiments, R 3 and R 5 are each independently hydrogen; R 4 It is -CH3.

[0024] In some embodiments, R 6 , R 7 , R 8 , R 9 and R 10 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 1-4 Alkoxy or halogenated C 1-4 Alkoxy.

[0025] In other embodiments, R 6 , R 7 , R 8 , R 9 and R 10 Each is independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -C(CH3)3, -CF3, -OCH3, -OCH2CH3 or -OCF3.

[0026] Preferably, in some embodiments, R 6 , R 7 , R8 , R 9 and R 10 are independently hydrogen, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 1-4 Alkoxy or halogenated C 1-4 Alkoxy.

[0027] More preferably, in some embodiments, R 6 , R 7 , R 8 , R 9 and R 10 Each is independently hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -C(CH3)3, -OCH3, -OCH2CH3 or -OCF3.

[0028] Further preferably, in some embodiments, R 6 , R 7 , R 9 and R 10 are each independently hydrogen; R 8 For hydrogen, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 1-4 Alkoxy or halogenated C 1-4 Alkoxy.

[0029] More preferably, in some embodiments, R 6 , R 7 , R 9 and R 10 are each independently hydrogen; R 8 It is hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -C(CH3)3, -OCH3, -OCH2CH3 or -OCF3.

[0030] Preferably, the pyridinyl group is pyridin-2-yl.

[0031] The phenyl group is

[0032] Indicates the location of connection to the rest of the molecule.

[0033] In other embodiments, Hy is the following sub-structure:

[0034]

[0035] Among them, R a , Ra1 and R a2 Each independently Among them, R a , R a1 and R a2 each independently optionally substituted with 1 or 2 groups selected from fluorine, chlorine, bromine or iodine;

[0036] R b , R c , R d , R e , R f and R g are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, C 1-4 Alkyl or halogenated C 1-4 alkyl.

[0037] In yet other embodiments, Hy is the following substructure:

[0038]

[0039] Among them, R a , R a1 and R a2 Each independently

[0040] R b , R c , R d , R e , R f and R g Each is independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, -CH3, -CH2CH3, -CHF2 or -CF3.

[0041] Preferably, in some embodiments, Hy is the following substructure:

[0042]

[0043] Among them, R a and R a2 Each independently Among them, R a and R a2 each independently optionally substituted with 1 or 2 groups selected from fluorine, chlorine, bromine or iodine;

[0044] R b , R c , R f and R g are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, C 1-4 Alkyl or halogenated C1-4 alkyl.

[0045] More preferably, in some embodiments, Hy is the following sub-structural formula:

[0046]

[0047] Among them, R a and R a2 Each independently

[0048] R b , R c , R f and R g Each is independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, -CH3, -CH2CH3, -CHF2 or -CF3.

[0049] Preferably, in some embodiments, Hy is the following substructure:

[0050]

[0051] Among them, R a and R a2 Each independently Among them, R a and R a2 Each is independently optionally substituted with 1 selected from fluorine, chlorine, bromine or iodine;

[0052] R b and R c each independently is hydrogen;

[0053] R f and R g are independently hydrogen, C 1-4 Alkyl or halogenated C 1-4 alkyl.

[0054] More preferably, in some embodiments, Hy is the following sub-structural formula:

[0055]

[0056] Among them, R a and R a2 Each independently Among them, R a and R a2 Each is independently optionally substituted with 1 selected from fluorine, chlorine, bromine or iodine;

[0057] R b and R c each independently is hydrogen;

[0058] R f and R g Each is independently hydrogen, -CH3, -CH2CH3, -CHF2 or -CF3.

[0059] In some embodiments, the present invention provides a compound, which is a compound represented by formula (II), or a stereoisomer, nitrogen oxide or salt thereof of the compound represented by formula (II):

[0060]

[0061] Among them, R 8 and Hy have the meanings as defined in the present invention.

[0062] In other embodiments, the present invention provides a compound, which is a compound represented by formula (II), or a stereoisomer, nitrogen oxide or salt thereof of the compound represented by formula (II):

[0063]

[0064] in:

[0065] R 8 For hydrogen, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 1-4 Alkoxy or halogenated C 1-4 Alkoxy;

[0066] Hy has the meaning defined in the present invention.

[0067] In some embodiments, R 8 is hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -C(CH3)3, -OCH3, -OCH2CH3 or -OCF3;

[0068] Hy has the meaning defined in the present invention.

[0069] In some embodiments, the present invention provides a compound, which is a compound having one of the following structures or a stereoisomer, nitrogen oxide or salt thereof of a compound having one of the following structures:

[0070]

[0071]

[0072]

[0073] In another aspect, the present invention provides a composition comprising at least one compound of the present invention and an adjuvant commonly used in pesticides.

[0074] In yet another aspect, the compounds of the present invention and / or the compositions of the present invention are used as pesticides in agriculture.

[0075] Detailed description of the invention

[0076] Definitions and general terms

[0077] Certain embodiments of the present invention are now described in detail, examples of which are illustrated by the accompanying structural formula and chemical formula. The present invention is intended to cover all substitutions, modifications and equivalent technical solutions, which are all included in the scope of the present invention as defined in the claims. It should be appreciated by those skilled in the art that many methods and materials similar or equivalent to those described in the present invention can be used to practice the present invention. The present invention is by no means limited to the methods and materials described in the present invention. In the event that one or more of the combined documents, patents and similar materials are different from or contradictory to the present application (including but not limited to defined terms, term applications, described technologies, etc.), the present application shall prevail.

[0078] It should be further appreciated that certain features of the invention, which for clarity are described in multiple separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which for brevity are described in a single embodiment, may also be provided separately or in any suitable sub-combination.

[0079] Unless otherwise specified, all technical terms used in the present invention have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. All patents and publications related to the present invention are incorporated herein by reference in their entirety.

[0080] Unless otherwise indicated, the following definitions used in the present invention shall apply. For purposes of the present invention, 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.

[0081] Unless otherwise specified or there is a clear conflict in context, the articles "a", "an", and "the" as used herein are intended to include "at least one" or "one or more". Therefore, these articles as used herein refer to articles that refer to one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in the implementation of the described embodiment.

[0082] The term "comprising" is an open expression, that is, including the contents specified in the present invention but not excluding other contents.

[0083] "Stereoisomers" refer to compounds that have the same chemical constitution but differ in the way the atoms or groups are arranged in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis / trans) isomers, atropisomers, and the like.

[0084] "Enantiomers" refer to two non-superimposable isomers of a compound that are mirror images of each other.

[0085] "Diastereoisomers" refer to stereoisomers that have two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereoisomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivity. Diastereomeric mixtures can be separated by high-resolution analytical procedures such as electrophoresis and chromatography, for example HPLC.

[0086] The stereochemical definitions and conventions used in the present invention generally follow those described in SP Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E. and Wilen, S., "Stereochemistry of Organic Compounds", John Wiley & Sons, Inc., New York, 1994.

[0087] Many organic compounds exist in optically active forms, i.e. they have the ability to rotate the plane of plane polarized light. When describing an optically active compound, the prefixes D and L or R and S are used to indicate the absolute configuration of the molecule about its chiral center(s). The prefixes d and l or (+) and (-) are the symbols used to designate the rotation of plane polarized light caused by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are right-handed. A specific stereoisomer is an enantiomer, and a mixture of such isomers is called a mixture of enantiomers. A 50:50 mixture of enantiomers is called a racemic mixture or racemate, which can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.

[0088] Any asymmetric atom (e.g., carbon, etc.) of the compounds disclosed herein can exist in a racemic or enantiomerically enriched form, such as in the (R)-, (S)-, or (R,S)-configuration. In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess in terms of the (R)- or (S)-configuration.

[0089] Depending on the choice of starting materials and process, the compounds of the invention may exist in the form of one of the possible isomers or a mixture thereof, such as a racemate and a diastereomeric mixture (depending on the number of asymmetric carbon atoms). Optically active (R)- or (S)-isomers may be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituents may be in the E or Z configuration; if the compound contains a disubstituted cycloalkyl group, the cycloalkyl substituents may be in the cis or trans configuration.

[0090] Any resulting mixture of stereoisomers can be separated into the pure or substantially pure geometric isomers, enantiomers, diastereomers on the basis of the differences in the constituent physicochemical properties, for example, by chromatography and / or fractional crystallization.

[0091] Any resulting racemate of the final product or intermediate can be separated into optical antipodes by known methods by methods familiar to those skilled in the art, such as by separation of the diastereoisomeric salts thereof obtained. The racemic product can also be separated by chiral chromatography, such as high performance liquid chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.

[0092] As described herein, the compounds of the present invention may be optionally substituted with one or more substituents, such as the general formula compounds above, or as specific examples in the embodiments, subclasses, and classes of compounds encompassed by the present invention. It should be understood that the term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted". 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 may be substituted at each substitutable position of the group. When more than one position in a given structural formula can be substituted by one or more substituents selected from a specific group, the substituents may be substituted at each position in the same or different manner. Specifically, examples of "one or more" refer to 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. The substituents may be, but are not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxy, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxy-substituted alkyl, hydroxy-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkylacyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amide, sulfonyl, aminosulfonyl and the like.

[0093] In addition, it should be noted that, unless explicitly stated otherwise, the description methods used in the present invention, "each... is independently" and "... are each independently" and "... are independently" can be interchanged and should be understood in a broad sense, which 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.

[0094] In various parts of this specification, substituents of compounds disclosed in the present invention are disclosed according to group types or ranges. It is particularly noted that the present invention includes each independent subcombination of the individual members of these group types and ranges. For example, the term "C1-C6 alkyl" or "C 1-6 "Alkyl" specifically refers to methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl and C6 alkyl as disclosed independently.

[0095] The term "alkyl" or "alkyl group" as used herein refers to a saturated straight or branched monovalent hydrocarbon group containing 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, the alkyl group contains 1-20 carbon atoms. In one embodiment, the alkyl group contains 1-12 carbon atoms; in one embodiment, the alkyl group contains 1-8 carbon atoms; in another embodiment, the alkyl group contains 1-6 carbon atoms; in another embodiment, the alkyl group contains 2-6 carbon atoms; in yet another embodiment, the alkyl group contains 1-4 carbon atoms; in yet another embodiment, the alkyl group contains 1-3 carbon atoms.

[0096] 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, -C(CH3)3), n-pentyl (-CH2C H2CH2CH2CH3), 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), neopentyl (C(CH3)3CH2-) and the like.

[0097] The term "alkoxy" means an alkyl group attached to the rest of the molecule via an oxygen atom, wherein the alkyl group has the meaning as described herein. Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH3), ethoxy (EtO, -OCH2CH3), 1-propoxy (n-PrO, n-propoxy, -OCH2CH2CH3), 2-propoxy (i-PrO, i-propoxy, -OCH(CH3)2), and the like.

[0098] The term "haloalkyl" means an alkyl group substituted by one or more halogen atoms, such examples include, but are not limited to, -CF3, -CHF2, -CH2Cl, -CH2CF3, -CH2CHF2, -CH2CH2CF3 and the like.

[0099] The term "haloalkoxy" means an alkoxy group substituted by one or more halogen atoms, such examples include, but are not limited to, -OCF3, -OCHF2, -OCHCl2, -OCH2CHF2, -OCH2CHCl2, -OCH(CH3)CHF2 and the like.

[0100] The term "halogen" refers to fluorine, chlorine, bromine, iodine.

[0101] The term "cyano" refers to -CN.

[0102] The term "nitro" refers to -NO2.

[0103] The term "hydroxy" refers to -OH.

[0104] The term "amino" refers to -NH2.

[0105] Salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and a salt having the formula N + (R AA R BB R CC R DD ) of an ammonium cation, wherein R AA , R BB , R CC and R DD Independently selected from hydrogen, C1-C6 alkyl and C1-C6 hydroxyalkyl. The salt of the compound of formula (I) or formula (II) can be prepared by treating the compound of formula (I) or formula (II) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).

[0106] When the compounds of the present invention contain a basic moiety, acceptable salts may be formed from organic and inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, and similarly known acceptable acids.

[0107] Compositions and preparations of the compounds of the present invention

[0108] The compounds of the present invention can generally be used as insecticide active ingredients in compositions or formulations. The formulations of the present invention are prepared from the compositions of the present invention.

[0109] The composition and / or formulation of the present invention generally further comprises adjuvants commonly used in pesticide science, and the adjuvants are surfactants and / or carriers acceptable in pesticide science.

[0110] The above-mentioned surfactant can be any surfactant known in the field of pesticide formulations. In the present invention, it is preferably one or more of an emulsifier, a dispersant and a wetting agent.

[0111] The other carriers except the above-mentioned surfactants can be various carriers known in the field of pesticide formulations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: one or more of white carbon black, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine fertilizer, a mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, anhydrous sodium bicarbonate, attapulgite, a mixture of anhydrous potassium carbonate and anhydrous potassium bicarbonate, and a mixture of anhydrous sodium carbonate and anhydrous sodium bicarbonate.

[0112] The emulsifier may be any emulsifier known in the field of pesticide formulations. Specifically, the emulsifier may be one or more of calcium dodecylbenzene sulfonate, triphenyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide adduct of fatty amide, fatty acid polyoxyethylene ester, rosin acid ethylene oxide adduct, polyol fatty acid ester and ethylene oxide adduct thereof, styrylphenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, terminal hydroxyl polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.

[0113] The above-mentioned dispersant can be various dispersants known in the field of pesticide formulations. Specifically, the dispersant is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, terminal hydroxyl polyoxyethylene polyoxypropylene ether block copolymer, triphenyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignin sulfonate sodium salt.

[0114] The wetting agent can be any wetting agent known in the field of pesticide formulations. Specifically, the wetting agent can be one or more of sodium dodecyl sulfate, sodium secondary alkyl sulfate, sodium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, alkyl naphthalene sulfonate, and alkylphenol resin polyoxyethylene ether sulfate.

[0115] According to the insecticide composition of the present invention, the insecticide composition may also contain various formulation adjuvants commonly used in the field of pesticide formulations. Specifically, the formulation adjuvant may be one or more of a solvent, a co-solvent, a thickener, an antifreeze agent, an encapsulating material, a protective agent, a defoaming agent, a disintegrant, a stabilizer, a preservative and a binder.

[0116] The above-mentioned solvent may be any solvent known in the field of pesticide formulations. Specifically, the solvent may be one or more of an organic solvent, vegetable oil, mineral oil, solvent oil and water.

[0117] The organic solvent includes one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethyldecylamide, N,N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1,4-dioxane and cyclohexanone.

[0118] The vegetable oil includes one or more of methylated vegetable oil, rosin-based vegetable oil, turpentine, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine nut oil.

[0119] The mineral oil includes one or more of liquid wax, motor oil, kerosene and lubricating oil.

[0120] At the same time, the above solvents can also be used as co-solvents.

[0121] The antifreeze agent may be any antifreeze agent known in the field of pesticide formulations. In the present invention, the antifreeze agent is preferably one or more of ethylene glycol, propylene glycol, glycerol and urea.

[0122] The thickener may be any thickener known in the field of pesticide formulations. Specifically, the thickener may be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatomaceous earth, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.

[0123] The capsule material may be any capsule material known in the field of pesticide formulations, and in the present invention, preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.

[0124] The protective agent can be any protective agent known in the field of pesticide formulations, and in the present invention, polyvinyl alcohol and / or polyethylene glycol are preferred.

[0125] The defoaming agent can be any defoaming agent known in the field of pesticide formulations. In the present invention, it is preferably one or more of organosiloxane, tributyl phosphate and silicone.

[0126] The stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.

[0127] The preservative is selected from one or more of benzoic acid, sodium benzoate, 1,2-benzisothiazolin-3-one (BIT for short), kasone and potassium sorbate.

[0128] The present invention also provides a preparation prepared from the above insecticide composition, wherein the preparation is in the form of emulsifiable concentrate, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspoemulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water film spreading oil, wettable powder, water dispersible granule, dry suspension, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, granule, solid microcapsule preparation, effervescent tablet, effervescent granule, water floating dispersible granule or seed coating. The above dosage forms can be prepared by conventional methods in the art.

[0129] The preparation method of the emulsifiable concentrate preparation may include, for example, mixing and stirring the active components, solvent, co-solvent and emulsifier to form a uniform and transparent oil phase, thereby obtaining the emulsifiable concentrate preparation.

[0130] The preparation method of the aqueous emulsion may include, for example, mixing the active ingredient, emulsifier, cosolvent and solvent to form a uniform oil phase; mixing water, thickener, antifreeze agent, etc. to form a uniform water phase. Under high-speed shearing, the water phase is added to the oil phase or the oil phase is added to the water phase to form an aqueous emulsion with good dispersibility.

[0131] The preparation method of the microemulsion is, for example, to mix and stir the active ingredient, emulsifier and solvent into a uniform and transparent oil phase, and then gradually add water under stirring to form a uniform and transparent microemulsion.

[0132] The preparation method of the water / oil suspension is as follows: for example, water or oil can be used as the medium, active components, surfactants and other auxiliary agents are added to a sand mill, ground to a certain particle size, and then filtered. Then, a measured thickener is added to the ground mother liquid, sheared and dispersed evenly, to prepare an oil suspension or a water suspension.

[0133] The preparation method of the above-mentioned water-dispersible granules and soluble granules is, for example, to mix the active components, dispersant, wetting agent, carrier, etc. uniformly, then pulverize to a certain particle size by air flow, then add water for kneading, and finally add to a granulator for granulation. After drying, water-dispersible granules or soluble granules can be obtained.

[0134] The preparation method of the above-mentioned soluble powder and wettable powder is, for example, to fully mix the active components, various adjuvants and other fillers such as carriers, and grind them with an ultra-fine grinder.

[0135] The insecticide composition of the present invention can be provided in the form of a finished preparation, that is, the various substances in the composition have been mixed; it can also be provided in the form of a separate preparation, which can be mixed in a bucket or tank before use and selectively mixed with water for dilution according to the required concentration of the active substance.

[0136] For additional information related to the formulation field, see "The Formulator's Toolbox - Product Forms for Modern Agriculture" by TS Woods, in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, edited by T. Brooks and TR Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, column 6, lines 16 to column 7, line 19, and Examples 10-41; U.S. Pat. No. 3,309,192, column 5, lines 43 to column 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. Pat. No. 2,891,855, column 3, lines 66 to column 5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pages 81-96; Hance et al., Weed Control Handbook, 8th edition, Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

[0137] Application of the compounds and compositions of the present invention

[0138] The compounds, compositions and formulations of the present invention are suitable for controlling animal pests such as arthropods, gastropods and nematodes in useful plants, including but not limited to:

[0139] Hemiptera: Planthoppers (Delphacidae) such as Nilaparvatalugens, Laodelphax striatellus; Leafhoppers (Deltocephalidae) such as Nephotettix cincticeps; Aphids (Aphididae) such as Aphis gossypii, Aphis craccivora Koch; Pentatomidae such as Nezaraantennata; Whiteflies (Aleyrodidae) such as Trialeurodes vaporariorum; Scales (Coccidae) such as Calformia red scale (Aonidiella aurantii); Tingidae; Homoptera, Psyllidea;

[0140] Lepidoptera: Pyralidae such as Chilo suppressalis; Noctuidae such as Spodoptera litura, Pseudaletia separata, Heliothis spp. and Helicoverpa spp.; Pieridae such as Pierisrapae; Tortricidae such as Adoxophyes; Gracilariidae such as Caloptilia theivora and Phyllonorycter ringoneella; Carposinidae such as Carposina niponensis; Lyonetiidae such as Lyonetia spp. spp.); Lymantriidae such as Lymantria spp. and Euproctis spp.; Yponomeutidae such as Plutella xylostella; Gelechiidae such as Pectinophora gossypiella and Phthorimaea operculella; Arctiidae such as Hyphantria cunea; and Tineidae such as Tinea translucens and Tineola bisselliella;

[0141] Thysanoptera: Frankliniella occidentalis, Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa and Frankliniella fusca.

[0142] Diptera: Musca domestica, Culex popienspallens, Tabanus trigonus, Hylemya anitqua, Hylemyaplatura, Anopheles sinensis, Agromyza oryzae, Hydrellia griseola, Chlorops oryzae, Dacus cucurbitae, Ceratitis capitata and Liriomyza trifolii.

[0143] Coleoptera: Epilachna vigintioctopunctata, Phyllotreta striolata, Oulema oryzae, Echinocnemus squameus, Lissorhoptrus oryzophilus, Anthonomus grandis, Callosobruchus chinensis, Sphenophorus venatus, Popillia japonica, Anomala cuprea, Diabrotica spp., Leptinotarsa ​​decemlineata, Agriotes spp., Lasioderma serricorne, Anthrenus grandis verbasci), Tribolium castaneum, Lyctus brunneus, Anoplophora malasiaca, and Tomicus piniperda;

[0144] Orthoptera: East Asian migratory locust (Locusta migratoria), African mole cricket (Gryllotalpaafficana), Hokkaido rice locust (Oxya yezoensis) and Japanese rice locust (Oxya japanica);

[0145] Hymenoptera: Athalia rosae, Acromyrmex spp., and Solenopsis spp.

[0146] Nematodes: Aphelenchoides besseyi, Nothotylenchus acris, Heterodera glycines, Meloidogyne incognita, Pratylenchus penetrans, and Nacobbus aberrans.

[0147] From the order Blattariae: Blattella germanica, Periplaneta fuliginosa, Periplaneta Americana, Periplaneta brunnea and Blatta orientalis.

[0148] Order Acarina: Tetranychidae (e.g., Tetranychus cinnabarinus, Tetranychu surticae, Panonychus citri, and Oligonychus spp.); Eriophyidae (e.g., Aculops pelekassi); Tarsonemidae; Tenuipalpidae; Tuckerellidae; Tuckerellidae Acaridae; Pyroglyphidae (e.g., Dermatophagoides farinae and Dermatophagoides ptrenyssnus); Cheyletidae, Cheyletus malaccensis; malaccensis and Cheyletusmoorei; and Dermanyssidae.

[0149] In the context of the present invention, useful plants include the following plant species: cereals (wheat, barley, rye, oats, rice, corn, sorghum and related species); beets (sugar beet and fodder beet); pome, stone and soft fruits (apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry); legumes (lentil, bean, pea, soybean); oil crops (rapeseed, mustard, olive, sunflower, coconut, castor oil plant, cocoa bean, peanut or soybean); cucurbit plants (squash, cucumber, melon); ); fiber plants (cotton, flax, jute); citrus fruits (oranges, lemons, grapefruits, mandarins); vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, red peppers); laurel plants (avocado, cinnamon, camphor) or plants such as tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grapevines, hops, bananas and natural rubber plants, as well as turf, ornamental and forest plants, such as flowers, shrubs, broad-leaved trees or evergreen trees, such as conifers, and plant propagation material.

[0150] The term "plant propagation material" should be understood as meaning reproductive parts of the plant, such as seeds, which can be used for the multiplication of the plant, and vegetative material, such as cuttings or tubers (for example potatoes).

[0151] The compounds, compositions and preparations of the present invention kill pests by an effective amount of active substances. Therefore, the present invention also relates to a method for controlling pests, which is carried out by applying an effective amount of a compound of the present invention, a composition or a preparation comprising an effective amount of a compound of the present invention to a seed, a plant or a plant part, a fruit or a soil where the plant grows. The application can be carried out before and after the seed, plant or plant part, fruit or soil where the plant grows is infested by the pest.

[0152] The term "effective amount" used means an amount of the compound of the present invention that is sufficient to control pests on cultivated plants or in material protection and does not cause significant damage to the treated plants. This amount can vary within a wide range and depends on various factors such as pest species, cultivated plants or materials treated, climatic conditions and the specific compound used.

[0153] The compounds, compositions and preparations of the present invention are simple to use, and the compounds, compositions and preparations of the present invention are applied to the pests or their growth medium. The application dosage of the compounds, compositions and preparations of the present invention varies according to weather conditions, dosage form, application timing, application method, application area, target disease, target crop, etc.

[0154] General synthesis process

[0155] The following scheme describes the preparation of the compounds of the present invention. Unless otherwise specified, the compounds of the present invention can be prepared by the methods described in the present invention. The raw materials, reagents, etc. used to prepare the compounds of the present invention are all commercially available, or can be prepared by conventional methods in the art. In this specification, if there is any difference between the chemical name and the chemical structure, the structure is dominant. In addition, in some embodiments, unless otherwise specified, the reaction described in the present invention is carried out at room temperature, and the term "room temperature" refers to the natural temperature around the location of the object, and the ambient temperature may vary depending on the region, season, and time, generally between -20°C and 45°C or at about 18°C ​​to 30°C, or about 20°C to 25°C or about 22°C. The term "react overnight" generally refers to 8-20 hours.

[0156] Synthesis scheme

[0157] Synthesis Scheme 1

[0158]

[0159] The target compound shown in formula (I) can be prepared by the method of synthesis scheme 1. Intermediate N and intermediate M undergo nucleophilic substitution reaction under alkaline conditions (such as cesium carbonate, etc.) to obtain the target compound shown in formula (I);

[0160] Among them, intermediate N and intermediate M can be purchased commercially, or prepared using corresponding raw materials by known preparation methods;

[0161] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and Hy have the meanings as defined in the present invention. Example

[0162] Intermediate M-1: Synthesis of 3-(2-bromoethoxy)-1-(4-chlorophenyl)-1H-pyrazole

[0163]

[0164] Dissolve 1-(4-chlorophenyl)-1H-pyrazole-3-ol (3.89 g, 20 mmol) in 30 mL of anhydrous N,N-dimethylformamide, add potassium carbonate (2.76 g, 20 mmol), stir for 30 min, add 1,2-dibromoethane (7.51 g, 40 mmol), heat to 100 ° C under nitrogen protection and react for 12 hours until the raw material is completely converted. Cool to room temperature, add water (50 mL), extract with ethyl acetate (40 mL x 3), combine the organic phases, concentrate the organic phases under reduced pressure, and separate the residue by column chromatography [petroleum ether / ethyl acetate (v / v) = 3 / 1] to obtain 2.3 g of orange-yellow solid with a yield of 40.1%.

[0165] LC-MS: (M+1) m / z=301.1.

[0166] Intermediate 1: Synthesis of 3-methyl-1-phenyl-1H-pyrazol-5-ol

[0167]

[0168] Ethyl acetoacetate (6.05 g, 50 mmol) and phenylhydrazine hydrochloride (7.23 g, 50 mmol) were dissolved in 20 mL of anhydrous ethanol and heated to 90°C for reflux reaction for 8 hours. After the reaction was completed, the solvent was removed under reduced pressure using a rotary evaporator, and the residue was washed with water (30 mL), filtered, and the filter cake was dried (dried at 80°C for 5 hours) to obtain 5.30 g of a white solid with a yield of 60.8%.

[0169] LC-MS: (M+1) m / z=175.1.

[0170] The corresponding ethyl acetoacetate, ethyl 2-methyl-3-oxopentanoate, ethyl difluoroacetoacetate, ethyl trifluoroacetoacetate and phenylhydrazine hydrochloride or 2-hydrazinepyridine hydrochloride are used as raw materials, and the preparation method of intermediate 1 is referred to to obtain the intermediate compounds in Table 1.

[0171] Table 1

[0172]

[0173] The intermediate compounds in Table 2 can be obtained by using the corresponding intermediate compounds in Table 1 and 1,2-dibromoethane as reaction raw materials and referring to the preparation method of intermediate M-1.

[0174] Table 2

[0175]

[0176]

[0177] Intermediate N-1: Synthesis of 2-ethyl-3,7-dimethyl-6-(4-(trifluoromethoxy)phenoxy)-quinolin-4-ol

[0178]

[0179] Step 1: Synthesis of 5-fluoro-4-methyl-2-nitrobenzoic acid

[0180] Add nitric acid (20mL, 65%) and sulfuric acid (50mL, 98%) to a 250mL round-bottom flask, cool to -10°C with an ice-salt bath, dissolve 3-fluoro-4-methylbenzoic acid (15.00g, 97.4mmol) in concentrated sulfuric acid (50mL), slowly dropwise add to the above mixed acid, control the temperature in the reaction system between -10 and 0°C, remove the ice-salt bath after the addition is complete, and react at 25°C for 2.5 hours. Pour the crude product into ice water, filter out the precipitate, rinse with water, and dry to obtain 15.91g of white solid, yield: 82.1%.

[0181] LC-MS: (M+1) m / z=200.0.

[0182] Step 2: Synthesis of isopropyl 5-fluoro-4-methyl-2-nitrobenzoate

[0183] Dissolve 5-fluoro-4-methyl-2-nitrobenzoic acid (10 g, 50.2 mmol) in isopropanol (60 mL), slowly add concentrated sulfuric acid (10 mL, 98%) at 0°C, and heat to 105°C and reflux for 20 hours after the addition is complete. Remove excess isopropanol with a rotary evaporator under reduced pressure, then extract with ethyl acetate (60 mL x 3), wash the organic phase with water (30 mL), saturated brine (30 mL), dry over anhydrous magnesium sulfate, and concentrate under reduced pressure to obtain 9.63 g of red liquid, with a yield of 79.6%.

[0184] 1 H NMR (400MHz, CDCl3) δ (ppm): 7.81 (d, 1H), 7.33 (d, 1H), 5.26 (m, 1H), 2.39 (s, 3H), 1.35 (d, 6H);

[0185] LC-MS: (M+1) m / z=242.2.

[0186] Step 3: Synthesis of isopropyl 4-methyl-2-nitro-5-(4-(trifluoromethoxy)phenoxy)benzoate

[0187] Isopropyl 5-fluoro-4-methyl-2-nitrobenzoate (9.60 g, 39.8 mmol), p-trifluoromethoxyphenol (7.12 g, 40.0 mmol) and potassium carbonate (5.52 g, 40.0 mmol) were added to a 250 mL round-bottom flask, and N,N-dimethylformamide (100 mL) was added. The temperature was quickly raised to 80°C under nitrogen protection and reacted for 18 hours. Ice water (100 mL) was added, and the mixture was extracted with ethyl acetate (60 mL x 3). The organic phase was washed with a saturated aqueous solution of sodium bicarbonate (50 mL x 3), and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain 12.0 g of a yellow oil with a yield of 75.6%.

[0188] LC-MS: (M+1) m / z=400.3.

[0189] Step 4: Synthesis of isopropyl 2-amino-4-methyl-5-(4-(trifluoromethoxy)phenoxy)benzoate

[0190] Under nitrogen protection, iron powder (5.60g, 100.0mmol), ethanol (100mL), water (20mL) and hydrochloric acid (1.0mL, 35%) were added to a 500mL round-bottom flask, heated to 90℃ and stirred, and a solution of 4-methyl-2-nitro-5-(4-(trifluoromethoxy)phenoxy)benzoic acid isopropyl ester (12.0g, 30.0mmol) in ethanol (100mL) was slowly added dropwise. After the addition was complete, the mixture was reacted at 90℃ for 12 hours. Solid impurities were removed by filtration, and the filtrate was concentrated by rotary evaporator, and ethyl acetate (150mL) was added. The mixture was washed with brine (30mL x 3), the organic phases were combined and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 10 / 1] to obtain 10.5g of yellow oil, with a yield of 94.6%.

[0191] 1 H NMR (400MHz, CDCl3) δ (ppm): 7.60-7.51 (m, 1H), 7.25-7.15 (m, 2H), 6.91-6. 80(m,2H),6.20(s,1H),5.69(s,2H),5.21(m,1H),2.11(s,3H),1.35(d,6H);

[0192] 19 F NMR (100MHz, CDCl3) δ (ppm): -58.4;

[0193] LC-MS: (M+1) m / z=370.3.

[0194] Step 5: Synthesis of 2-ethyl-3,7-dimethyl-6-(4-(trifluoromethoxy)phenoxy)-quinolin-4-ol

[0195] Under nitrogen protection, 2-amino-4-methyl-5-(4-(trifluoromethoxy)phenoxy)benzoic acid isopropyl ester (10.0 g, 27.1 mmol), 3-pentanone (4.3 g, 50.0 mmol), zinc chloride (6.82 g, 50.0 mmol) and xylene (100 mL) were added to a 500 mL round-bottom flask and refluxed at 160°C for 18 hours. After the reaction was completed, xylene was evaporated with a rotary evaporator to obtain a yellow-brown viscous substance, which was cooled to 25°C and then added with water (50 mL) and ethyl acetate (50 mL) and stirred to form a suspension, which was filtered and dried to obtain 6.76 g of a white solid with a yield of 66.2%.

[0196] 1 H NMR (400MHz, CDCl3) δ (ppm): 11.4 (s, 1H), 7.51 (s, 1H), 7.28 (s, 1H), 7.22 (m, 2H), 7.01 (m, 2H), 2.72 (q, 2H), 2.31 (s, 3H), 2.03 (s, 3H), 1.25 (t, 3H);

[0197] LC-MS: (M+1) m / z=377.1.

[0198] The intermediate compounds in Table 3 can be obtained by using the corresponding materials as reaction raw materials and preparing them according to the preparation method of the intermediate N-1.

[0199] Table 3

[0200]

[0201]

[0202] Example 1: Synthesis of 4-(2-((1-(4-chlorophenyl)-1H-pyrazol-3-yl)oxy)ethoxy)-2-ethyl-3,7-dimethyl-6-(4-(trifluoromethoxy)phenoxy)quinoline

[0203]

[0204] 2-Ethyl-3,7-dimethyl-6-(4-(trifluoromethoxy)phenoxy)-quinolin-4-ol (566 mg, 1.50 mmol) was dissolved in 15 mL of anhydrous N,N-dimethylformamide, cesium carbonate (733 mg, 2.25 mmol) was added, and after stirring for 10 min, 3-(2-bromoethoxy)-1-(4-chlorophenyl)-1H-pyrazole (497 mg, 1.65 mmol) was added, and the temperature was raised to 100°C and reacted for 12 hours under nitrogen protection. After the reaction was completed, it was cooled to room temperature, and the mixture was poured into water (50 mL), extracted with ethyl acetate (50 mL x 3), and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The residue was separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 10 / 1] to obtain 485 mg of light yellow solid, with a yield of 54.1%.

[0205] 1 H NMR(400MHz,DMSO-d6)δ(ppm):8.31(t,1H),7.922(s,1H),7.74(d,2H),7.55(d,2H),7.48(s,1H),7.31-7.29(m,1H),7.2 1(s,1H),6.89(d,1H),6.71-6.67(m,2H),4.42(t,2H),3.67(t,2H),3.02(q,2H),2.42(s,3H),2.30(s,3H),1.37(t,3H);

[0206] LC-MS: (M+1) m / z=598.5.

[0207] Any intermediate compound among intermediates N-1 to N-6 can be used as a reaction raw material with the corresponding intermediate compound among intermediates M-1 to M-6, and the target compound in Table 4 can be obtained by referring to the preparation method of Example 1.

[0208] Table 4

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216] Bio-test

[0217] Test targets: armyworm, green peach aphid, spider mite, rice brown planthopper;

[0218] Experimental treatment: Compounds were dissolved in DMF to 1% EC for later use;

[0219] 1) Sticky insect prevention test

[0220] Leaf dipping method: The target for the test is armyworm. A proper amount of corn leaves are fully soaked in the prepared liquid and then dried naturally in the shade. They are placed in a culture dish lined with filter paper, and 10 3rd instar larvae of armyworm are added to each dish. The dish is placed in an observation room at 24-27℃ for cultivation. The results are investigated after 72 hours. The insect body is touched with a brush. If there is no reaction, it is considered dead. The test concentration is 200mg / L.

[0221] 2) Green peach aphid control test

[0222] Spray method: The target is peach aphid. The cabbage leaves infected with peach aphid are sprayed under the Potter spray tower. The leaves infected with peach aphid are placed in an observation room at 20-22℃ for cultivation. The results are investigated after 48 hours. The insect body is touched with a brush. If there is no reaction, it is considered dead. The test concentration is 200mg / L.

[0223] 3) Test on the efficacy of preventing spider mites

[0224] Spray method: The target is spider mites. The broad bean leaves infected with spider mites are sprayed under a Potter spray tower. After treatment, the leaves infected with spider mites are placed in an observation room at 24-27℃ for cultivation. The results are investigated after 48 hours. The insect body is touched with a brush. If there is no reaction, it is considered dead. The test concentration is 200mg / L.

[0225] 4) Rice brown planthopper control test

[0226] Spray method: The test target is rice brown planthopper, that is, rice seedlings inoculated with rice brown planthopper are sprayed under the Potter spray tower, and the rice brown planthopper is cultured in an observation room at 24-27℃ after treatment. The results are investigated after 72 hours. The insect body is touched with a brush, and no reaction is considered dead. The test concentrations are 200mg / L, 100mg / L, 50mg / L, and 25mg / L.

[0227] The test results are:

[0228] At a dosage of 200 mg / L, the mortality rates of Example 1, Example 2, Example 4, Example 6, Example 7, Example 8, Example 9, Example 11, Example 12, Example 13, Example 15, Example 16, Example 17, Example 18, Example 19, Example 20, and Example 21 to armyworms were ≥80%.

[0229] At a dosage of 200 mg / L, the mortality rates of Examples 6, 8, 9, 12, 13, 15, 16, and 18 against green peach aphids were ≥ 80%.

[0230] At a dosage of 200 mg / L, the mortality rate of Example 2, Example 3, Example 4, Example 5, Example 6, Example 7, Example 8, Example 9, Example 10, Example 11, Example 12, Example 13, Example 14, Example 15, Example 16, Example 17, Example 18, Example 19, Example 20, and Example 21 to rice brown planthopper is ≥80%; at a dosage of 100 mg / L, the mortality rate of Example 6, Example 7, Example 8, Example 9, Example 11, Example 12, Example 13, Example 15, Example 16, Example 17, Example 18, Example 20, and Example 21 to rice brown planthopper is ≥80%; at a dosage of 50 mg / L, the mortality rate of Example 8, Example 9, Example 12, Example 13, Example 15, Example 16, and Example 18 to rice brown planthopper is ≥80%; in addition, at a dosage of 25 mg / L, the mortality rate of Example 13 to rice brown planthopper is ≥80%.

[0231] The test results show that the compounds of the present invention have significant control effects on pests, especially on armyworms, green peach aphids and rice brown planthoppers, and can be further developed for use as insecticides.

[0232] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

Claims

1. A compound, which is a compound represented by formula (I) or a salt thereof: in: R 1 and R 2 Each independently represents -CH3, -CH2CH3; R 3 , R 4 and R 5 are each independently hydrogen, -CH3; R 6 , R 7 , R 9 and R 10 each independently is hydrogen; R 8 For hydrogen, -C 1-4 Alkyl, -C 1-4 Alkoxy or -halogenated C 1-4 Alkoxy; Hy is the following substructure: Among them, R a , R a2 Each independently Among them, R a , R a2 Each is independently optionally substituted with 1 selected from fluorine, chlorine, bromine or iodine; R b , R c , R f and R g are independently hydrogen, -C 1-4 Alkyl or -halogenated C 1-4 alkyl.

2. The compound according to claim 1, wherein: R 8 It is hydrogen, -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3, -C(CH3)3, -OCH3, -OCH2CH3 or -OCF3.

3. The compound according to claim 1, wherein: Hy is the following substructure: Among them, R a , R a2 Each independently R b , R c , R f and R g Each is independently hydrogen, -CH3, -CH2CH3, -CHF2 or -CF3.

4. A compound having one of the following structures or a salt thereof:

5. A composition comprising the compound according to any one of claims 1 to 4 and an adjuvant in pesticide science.

6. Use of the compound according to any one of claims 1 to 4 or the composition according to claim 5 as an insecticide against armyworm, green peach aphid and / or rice brown planthopper in agriculture.

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