CN112442026A - Mesoionic derivative and preparation method and application thereof - Google Patents

Abstract

The invention relates to a mesoion derivative and a preparation method and application thereof; in particular, the invention relates to mesoionic derivatives of formula (I) or stereoisomers, nitrogen oxides or salts thereof, and to processes for the preparation of the mesoionic derivatives, and their use in agriculture as pesticides, and to the form of pesticidal compositions thereof, and to methods of killing pests using these compounds or compositions; wherein R is¹、R²And R³Have the meaning as described in the present invention.

Description

Mesoionic derivative and preparation method and application thereof

Technical Field

The invention relates to the field of pesticides, in particular to a mesoion derivative, a preparation method of the mesoion derivative and application of the mesoion derivative as an insecticide in agriculture.

Background

Heterocyclic mesoionic compounds are known as pesticides and are described in the prior art WO09099929, WO11017334, WO11017347, WO11017342, WO12092115, WO12106495, WO12136724, WO14033244, WO14202582, WO14167084, WO16055431, WO16171053 and WO17093214, whereas the present invention relates to mesoionic derivatives which have not been reported in the prior art.

Disclosure of Invention

The invention relates to a novel mesoion derivative which has excellent control effects on pests in agriculture, particularly diamondback moth, armyworm, green peach aphid, brown planthopper and the like.

Specifically, the method comprises the following steps:

in one aspect, the present invention provides a novel mesoionic compound which is a compound having formula (I) or a stereoisomer, a nitroxide or a salt thereof of a compound having formula (I):

wherein:

R¹is hydrogen or C_1-6An alkyl group;

R²is a 5-6 membered heteroaryl; said 5-6 membered heteroaryl is optionally substituted by one or more groups selected from halogen, cyano, hydroxy, nitro, C_1-6Alkyl radical, C_1-6Alkoxy radical, C_1-6Alkylthio, halo C_1-6Alkyl, halo C_1-6Alkoxy or halo C_1-6Substituted by a substituent of alkylthio;

R³is C_6-10Aryl or 5-6 membered heteroaryl; said C_6-10Aryl and 5-6 membered heteroaryl optionally substituted with one or more substituents selected from halogen, cyano, hydroxy, nitro, C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkyl or halo C_1-6Substituent of alkoxy.

In some embodiments, R¹Is hydrogen or C_1-4An alkyl group.

In still other embodiments, R¹Is hydrogen, CH₃-or CH₃CH₂-。

In some embodiments, R²Is thiazolyl, pyridyl or pyrimidinyl; said thiazolyl, pyridyl and pyrimidinyl being optionally substituted by one or more groups selected from halogen, cyano, hydroxy, nitro, C_1-4Alkyl radical, C_1-4Alkoxy radical, C_1-4Alkylthio, halo C_1-4Alkyl, halo C_1-4Alkoxy or halo C_1-4And (3) substituent substitution of alkylthio.

In still other embodiments, R²Is thiazol-5-yl, pyridin-3-yl or pyrimidin-5-yl; the thiazol-5-yl, pyridin-3-yl and pyrimidin-5-yl groups are optionally substituted with one or more groups selected from halogen, cyano, hydroxy, nitro, C_1-4Alkyl radical, C_1-4Alkoxy radical, C_1-4Alkylthio, halo C_1-4Alkyl, halo C_1-4Alkoxy or halo C_1-4And (3) substituent substitution of alkylthio.

In still other embodiments, R²Is thiazol-5-yl, pyridin-3-yl or pyrimidin-5-yl; the thiazol-5-yl, pyridin-3-yl and pyrimidin-5-yl groups are optionally substituted with one or more groups selected from fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, CH₃-、CH₃O-、CH₃S-、CF₃-or CF₃And O-is substituted.

Yet in some embodiments, R²Is composed of

In some embodiments, R³Is phenyl or thienyl; said phenyl and thienyl being optionally substituted by one or more groups selected from halogen, cyano, hydroxy, nitro, C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkyl or halo C_1-4Substituent of alkoxy.

In still other embodiments, R³Is phenyl or thienyl; wherein said phenyl and thienyl are optionally substituted with one or more substituents selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, hydroxy,Nitro group, CH₃-、CH₃O-、CF₃-or CF₃And O-is substituted.

Yet in some embodiments, R³Is composed of

In still other embodiments, the invention relates to a compound that is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of a compound having one of the following structures:

in yet another aspect, the present invention provides a composition comprising at least one compound of the present invention.

Further, the composition comprises an agriculturally pharmaceutically acceptable auxiliary material.

In another aspect, the invention provides the use of a compound according to the invention or a composition according to the invention as a pesticide in agriculture.

In yet another aspect, the present invention provides a method of killing a pest in agriculture using a compound of the present invention or a composition of the present invention.

Further, the pests of the invention comprise diamondback moth, armyworm, alfalfa aphid and brown planthopper.

Detailed description of the invention

Definitions and general terms

Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. One skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.

It will be further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.

The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 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.

The articles "a," "an," and "the" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to one or to more than one (i.e., to at least one) of the objects. 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 embodiments of the described embodiments.

The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.

"stereoisomers" refers to compounds having the same chemical structure but differing in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.

"enantiomer" refers to two isomers of a compound that are not overlapping but are in mirror image relationship to each other.

"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.

The stereochemical definitions and rules used in the present invention generally follow the general definitions of S.P. 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.

Many organic compounds exist in an optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to denote the absolute configuration of a molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are the symbols used to specify the rotation of plane polarized light by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are dextrorotatory. A particular stereoisomer is an enantiomer and a mixture of such isomers is referred to as an enantiomeric mixture. A50: 50 mixture of enantiomers is referred to as a racemic mixture or racemate, which may occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.

Any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched forms, such as 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 the (R) -or (S) -configuration.

Depending on the choice of starting materials and methods, the compounds of the invention may exist as one of the possible isomers or as mixtures thereof, for example as racemates and mixtures of non-corresponding isomers (depending on the number of asymmetric carbon atoms). Optically active (R) -or (S) -isomers can 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 substituents of the cycloalkyl group may have cis or trans configuration.

Any resulting mixture of stereoisomers may be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers, depending on differences in the physicochemical properties of the components, for example, by chromatography and/or fractional crystallization.

The racemates of any of the resulting end products or intermediates can be resolved into the optical enantiomers by known methods using methods familiar to those skilled in the art, e.g., by separation of the diastereomeric salts obtained. The racemic product can also be separated by chiral chromatography, e.g., High Performance Liquid Chromatography (HPLC) using a chiral adsorbent. In particular, enantiomers can be prepared by asymmetric synthesis.

The compounds of the invention may be optionally substituted with one or more substituents, as described herein, in compounds of the general formula above, or as specifically exemplified, sub-classes, and classes of compounds encompassed by the invention. It is understood that the term "optionally substituted" may be 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 with a particular 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 formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently. Specifically, examples of "one or more" refer to 1,2,3, 4, 5, 6, 7, 8, 9, or 10. Wherein said substituent may be, but is not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxyl-substituted alkyl, hydroxyl-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkanoyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.

In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.

In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C₁-C₆Alkyl radical'Or "C_1-6Alkyl "means in particular independently disclosed methyl, ethyl, C₃Alkyl radical, C₄Alkyl radical, C₅Alkyl and C₆An alkyl group.

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

Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)₃) Ethyl group (Et, -CH)₂CH₃) N-propyl (n-Pr, -CH)₂CH₂CH₃) Isopropyl group (i-Pr, -CH (CH)₃)₂) N-butyl (n-Bu, -CH)₂CH₂CH₂CH₃) Isobutyl (i-Bu, -CH)₂CH(CH₃)₂) Sec-butyl (s-Bu, -CH (CH)₃)CH₂CH₃) Tert-butyl (t-Bu, -C (CH)₃)₃) N-pentyl (-CH)₂CH₂CH₂CH₂CH₃) 2-pentyl (-CH (CH)₃)CH₂CH₂CH₃) 3-pentyl (-CH (CH)₂CH₃)₂) 2-methyl-2-butyl (-C (CH)₃)₂CH₂CH₃) 3-methyl-2-butyl (-CH (CH)₃)CH(CH₃)₂) 3-methyl-1-butyl (-CH)₂CH₂CH(CH₃)₂) 2-methyl-1-butyl (-CH)₂CH(CH₃)CH₂CH₃) And so on.

The term "alkoxy" denotes 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, -OCH)₃) Ethoxy (EtO, -OCH)₂CH₃) 1-propoxy (n-PrO, n-propoxy, -OCH)₂CH₂CH₃) 2-propoxy (i-PrO, i-propoxy, -OCH (CH)₃)₂) And so on.

The term "alkylthio" means an alkyl group attached to the rest of the molecule through a sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, -SCH₃、-SCH₂CH₃、-SCH₂CH₂CH₃、-SCH(CH₃)₂And so on.

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

The term "heteroaryl" denotes monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5 to 7 atoms with one or more attachment points to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein. In one embodiment, a heteroaryl group of 5-10 atoms contains 1,2,3, or 4 heteroatoms independently selected from O, S, and N.

Examples of heteroaryl groups include, but are not limited to, furan-2-yl, furan-3-yl, N-imidazolyl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, N-pyrrolyl, pyrrol-2-yl, pyrrol-3-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridazinyl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, tetrazolyl, triazolyl, thiophen-2-yl, thiophen-3-yl, pyrazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 3-triazolyl, 1,2, 3-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, pyrazinyl, 1,3, 5-triazinyl, pyrimidinonyl, pyridonyl; the following bicyclic rings are also included, but are in no way limited to these: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), benzopiperidinyl, and the like.

The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms, examples of which include, but are not limited to, -CF₃，-CHF₂，-CH₂Cl，-CH₂CF₃，-CH₂CHF₂，-CH₂CH₂CF₃And the like.

The term "haloalkoxy" denotes an alkoxy group substituted with one or more halogen atoms, examples of which include, but are not limited to, -OCF₃，-OCHF₂，-OCHCl₂，-OCH₂CHF₂，-OCH₂CHCl₂，-OCH(CH₃)CHF₂And the like.

The term "haloalkylthio" denotes an alkylthio group substituted by one or more halogen atoms.

Salts of the compounds of the present invention include those derived from alkali or alkaline earth metals as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and those of formula N⁺(R^AAR^BBR^CCR^DD) Ammonium cation of (2), wherein R is^AA、R^BB、R^CCAnd R^DDIndependently selected from hydrogen, C₁-C₆Alkyl and C₁-C₆A hydroxyalkyl group. Salts of compounds having formula (I) may be prepared by treating a compound having formula (I) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine).

When a compound of the invention comprises a base moiety, acceptable salts can be formed from organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, napthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.

Compositions and formulations of the compounds of the invention

The compound of the invention can be generally used as an insecticide active ingredient in a composition or a preparation, and usually also comprises an agriculturally and pharmaceutically acceptable auxiliary material, wherein the auxiliary material is a surfactant and/or a carrier, and the like, and the components meeting the use requirements of pesticides belong to the scope of the invention.

The surfactant may be any of various surfactants known in the art of pesticide formulation, and the present invention is preferably one or more of an emulsifier, a dispersant and a wetting agent.

The carrier other than the above surfactant may be any of various carriers known in the field of agricultural chemical preparations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetic carriers. Specifically, for example: white carbon black, kaolin, diatomite, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, an amine fertilizer, a mixture of urea and an 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.

The emulsifier can be various emulsifiers known in the field of pesticide preparations, and specifically, the emulsifier is one or more of calcium dodecyl benzene sulfonate, triphenyl ethyl phenol polyoxyethylene ether phosphate, fatty alcohol 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, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrylphenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.

The dispersing agent can be various dispersing agents known in the field of pesticide preparations, and specifically, the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl polyoxyethylene phenol phosphate, fatty alcohol polyoxyethylene ether phosphate and p-hydroxyphenyl lignosulfonate sodium salt.

The wetting agent is various wetting agents known in the field of pesticide preparations, and specifically, the wetting agent is one or more of sodium dodecyl sulfate, secondary alkyl sodium sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, alkyl naphthalene sulfonate and alkylphenol resin polyoxyethylene ether sulfate.

According to the pesticide composition, the pesticide composition can further contain various preparation auxiliaries commonly used in the field of pesticide preparation, and specifically, the auxiliaries are one or more of a solvent, a cosolvent, a thickening agent, an antifreezing agent, a capsule wall material, a protective agent, a defoaming agent, a disintegrating agent, a stabilizer, a preservative and a binder.

The solvent is various solvents well known in the field of pesticide preparation, and specifically, the solvent is one or more of organic solvent, vegetable oil, mineral oil, solvent oil and water.

Wherein the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N-dimethyldecanamide, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, dimethylbenzene, methylbenzene, octane, heptane, methanol, isopropanol, N-butanol, tetrahydrofurfuryl alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.

The vegetable oil comprises one or more of methylated vegetable oil, rosin-based vegetable oil, turpentine oil, epoxidized soybean oil, peanut oil, rapeseed oil, castor oil, corn oil and pine seed oil.

The mineral oil comprises one or more of liquid wax, engine oil, kerosene and lubricating oil.

Meanwhile, the solvent can also be used as a cosolvent.

The antifreezing agent is various antifreezing agents known in the field of pesticide preparation, and one or more of ethylene glycol, propylene glycol, glycerol and urea are preferably used in the invention.

The thickening agent is various known thickening agents in the field of pesticide preparations, and specifically, the thickening agent is one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, white carbon black, diatomite, kaolin, clay, sodium alginate, magnesium aluminum silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose and organic bentonite.

The capsule wall material is various capsule wall materials known in the field of pesticide preparation, and the invention is preferably one or more of polyurethane, polyurea and urea-formaldehyde resin.

The protective agent is various protective agents known in the field of pesticide preparation, and polyvinyl alcohol and/or polyethylene glycol are preferred in the invention.

The defoaming agent is various defoaming agents known in the field of pesticide preparation, and the invention is preferably one or more of organosiloxane, tributyl phosphate and silicone.

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

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

The invention also provides a preparation prepared from the pesticide composition, and the preparation is in the dosage form of missible oil, aqueous emulsion, microemulsion, soluble liquid, aqueous suspension, suspoemulsion, ultra-low volume spray, oil suspension, microcapsule suspension, water surface spreading oil, wettable powder, water dispersible granule, dry suspension, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, solid microcapsule preparation, effervescent tablet, effervescent granule, water floating dispersion granule or seed coating. The dosage forms may be prepared by methods conventional in the art.

The preparation method of the missible oil preparation can comprise, for example, mixing and stirring the active components, the solvent, the cosolvent and the emulsifier to form a uniform transparent oil phase, so as to obtain the missible oil preparation.

The preparation method of the aqueous emulsion can comprise the steps of mixing an active ingredient, an emulsifier, a cosolvent and a solvent to form a uniform oil phase; mixing water, thickener, antifreeze, etc. to obtain uniform water phase. Under high-speed shearing, adding the water phase into the oil phase or adding the oil phase into the water phase to form the aqueous emulsion with good dispersibility.

The microemulsion can be prepared, for example, by mixing and stirring the active ingredient, emulsifier and solvent into a uniform and transparent oil phase. Under stirring, water is gradually added to form a uniform and transparent microemulsion.

The preparation method of the water/oil suspending agent comprises the following steps: for example, water or oil can be used as a medium, and an auxiliary agent such as an active component and a surfactant is added into a sanding kettle, and after grinding to a certain particle size, filtration is performed. And adding the weighed thickening agent into the ground mother liquor, and uniformly shearing and dispersing. Making into oil suspension or water suspension.

The preparation method of the water dispersible granule and the soluble granule comprises the following steps: for example, the active ingredients, the dispersing agent, the wetting agent, the carrier and the like are uniformly mixed, then are pulverized into a certain particle size through air flow, are added with water for kneading, are finally added into a granulator for granulation, and are dried to obtain the water dispersible granules or the soluble granules.

The preparation method of the soluble powder and the wettable powder comprises the following steps: for example, the active ingredients, various adjuvants and fillers such as other carriers can be thoroughly mixed and pulverized by a micronizer.

The pesticidal composition of the present invention may be provided in the form of a finished formulation, i.e., the substances in the composition have been mixed; or in separate formulations which are self-mixing in a tub or tank prior to use and optionally diluted by mixing with water depending on the concentration of active desired.

For additional information regarding The field of formulation, see "The formulations's Toolbox-Product Forms for model Agriculture" by T.S. woods, The Food-Environment Challenge, T.Brooks and T.R. Roberts eds, Proceedings of The 9th International conformation on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p.120. 133. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S. Pat. No. 3,309,192, column 5, column 43 to column 7, column 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 162, 164, 166, 167 and 169, 182; U.S.2,891,855 at column 3, line 66 to column 5, line 17 and examples 1-4; wed Control as a Science by Klingman, John Wiley and Sons, Inc., New York, 1961, pages 81-96; weed Control Handbook, 8 th edition, Blackwell Scientific Publications, Oxford, 1989, by Hance et al; and Developments in simulation technology, PJB Publications, Richmond, UK, 2000.

Application of the inventive compounds and compositions

The compounds according to the invention are particularly suitable for controlling animal pests such as arthropods, gastropods and nematodes in useful plants, including but not limited to:

hemiptera (Hemiptera): plant hoppers (Delphacidae) such as brown plant hoppers (Nilaparvata lugens), small brown plant hoppers (Laodelphax striatellus); leafhoppers (deltochalidae) such as green rice leafhopper (Nephotettix cincticeps); aphids (Aphididae)) such as cotton aphid (Aphis gossypii), alfalfa aphid (Aphis cracivora Koch); stinkbug (Pentatomidae) such as lygus lucorum (Nezara antennata); whiteflies (Aleyrodidae) such as greenhouse whitefly (Trialeurodes vaporariorum); scales (Coccidae) such as red mussel scale (Calformia red scale) (Aonidiella aurantii); lace bugs (Tingidae); psyllid (Homoptera, Psyllidea);

lepidoptera (Lepidoptera): snout moth (Pyralidae) such as Chilo suppersalis; noctuids (Noctuidae) such as Spodoptera litura (Spodoptera litura), armyworm (pseudolitea sepata), noctuid (Heliothis spp.) and noctuid (Helicoverpa spp.); pieridae (Pieridae) such as Pieris rapae; tortricid (Tortricidae) such as Trichinella fusca (Adoxophyes); fine moths (Gracillaridae) such as the tea-fine moth (Caloptilia theivora) and apple-fine moth (Phyllonorycter ringer Neella); moth (Carposinidae) such as peach moth (Carposina niponensis); plutella xylostella (lyonetidae) such as the genus plutella (Lyonetia spp.); moths (lymantriadae) such as the genus toxapha (Lymantria spp.) and the genus diaphora (Euproctis spp.); nest moths (Yponomeutidae) such as diamondback moth (Plutella xylostella); wheat moths (Gelechiidae) such as pink bollworm (Pectinophora gossypiella) and potato bollworm (photoria operculella); a fall webworm (arctiaceae) such as fall webworm (hypanthria cunea); and rice moths (Tineidae) such as clothiantus (tinearanspiens) and cottonta guianensis (Tineola bisseliella);

thysanoptera (Thysanoptera): frankliniella occidentalis, Frankliniella palmi (Thrips palmi), Frankliniella flavum (Scirtothrips dorsalis), Frankliniella tabacina (Thrips tabaci), Frankliniella quinquefolia (Frankliniella intonasa), and Frankliniella solani (Frankliniella fusca);

diptera (Diptera): houseflies (Musca domestica), Culex pipiens pallens (Culex pipiens pallens), Tabanus trifoliatus (Tabanus trigonus), allia fistulosa (hymexa annua), phaeophytes cinerea (hymexa platura), Anopheles sinensis (Anopheles sinensis), oryza sativa (agromiza oryzae), oryza sativa (hymeria griseola), oryza sativa (chlospora oryzae), oryza sativa (cucurbita cucurbitae), medfly (Ceratitis capitata), and trematopsis trifoliata (rhizomyza trifolii);

coleoptera (Coleoptera): the plant is selected from the group consisting of coccinella twenty-eight (Epilachna virginiocarpa), Phyllotreta striolata (phylotrita), mud worm of rice (Oulema oryzae), rice elephant (echinococcus squameus), rice water elephant (lissoropterus oryzae), cotton boll elephant (anthomonus grandis), green bean elephant (calorobucus chinensis), parasitic valley elephant (epheophorus ventratus), japanese beetle (Popillia japonica), ancient copper isocoryza turtles (Anomala cuprea), photinus pyralis (atrocerba), leptinotara (Leptinotarsa decemlineata), cottonwood beetle (cottonwood), bark beetle (bark beetle), white beetle (bark beetle) and white beetle (bark beetle) in the like;

orthoptera (Orthoptera): locusta migratoria (Locusta migratoria), mole cricket in africa (Gryllotalpa aficana), rice Locusta norhaii (Oxya yezoensis) and japanese rice Locusta (Oxya japonica);

hymenoptera (Hymenoptera): sinkiang vegetable wasps (Athalia rosae), Anthera incisa (Acromycex spp.) and Termite (Solenopsis spp.);

nematodes (nematodies): aphelenchoides besseyi (Aphelenchoides besseyi), strawberry bud nematode (Nothopylenchus acris), soybean cyst nematode (Heterodera glycines), Meloidogyne incognita (Meloidogyne incognita), Pratylenchus (Praytylenchus penatrans) and Heterodera micrantha (Nacobb aberrans);

blattaria (blattaria): blattella germanica (Blattella germanica), Blattella fuliginosa (Periplaneta fuliginosa), Periplaneta Americana (Periplaneta Americana), Blattella fusca (Periplaneta brunnea), and Blattella orientalis (Blattea orientalis);

acarina (Acarina): tetranyhidae (Tetranyhidae) (e.g., Tetranychus cinnabarinus (Tetranychus cinabaricus), Tetranychus urticae (Tetranychus urticae), Tetranychus citrullus (Pannychus citri) and Tetranychus spp.); gall mites (Eriophyidae) (e.g., citrus piercing gall mites (Aculops pelekassi)); tarsonemudae (Tarsonemidae); finesse family (tenuipipidae); duke mite family (Tuckerellidae); acarus family (Tuckerellidae Acaridae); pymetrophyceae (pyroxylidae) (e.g., dust mites (Dermatophagoides farinae) and house dust mites (Dermatophagoides ptrenyssnus)); carnivora (Cheyletidae), sarcophagidae (Cheyletus malaccensis) and sarcophagidae (Cheyletus moorei); and Dermanysidae (Dermanyssudae).

Within the scope of the present invention, useful plants include the following plant species: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); sugar beets (sugar radish and fodder beet); pome, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (lentils, binchou, peas, soybeans); oil crops (rape, mustard, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts or soybeans); cucurbits (squash, cucumber, melon); fiber plants (cotton, flax, hemp, jute); citrus fruits (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, red peppers); lauraceous plants (avocado, cinnamomum, camphor) or plants, such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, grapevine, hops, bananas and natural rubber plants, as well as turf, ornamental and forest plants, such as flowers, shrubs, broad-leaved trees or evergreens, such as conifers, and plant propagation material.

The term "plant propagation material" should be understood to mean the reproductive parts of the plant, such as seeds, which parts can be used for the propagation of the plant, as well as vegetative material, such as cuttings or tubers (e.g. potatoes).

The compounds or compositions of the present invention kill pests by an effective amount of the active substance. Wherein, the effective amount of the compound of the formula (I) is within 10g-5kg per hectare, the effect of controlling pests is better.

The invention also relates to a method for controlling pests by applying the active ingredients or compositions according to the invention to the seed, the plant or parts of the plant, the fruit or the soil in which the plant is growing. The application can be carried out before and after the seed, the plant or the plant part, the fruit or the soil in which the plant is growing is infested with pests.

The term "effective amount" as used denotes an amount of a compound or composition of the invention which is sufficient to control pests on cultivated plants or in the protection of materials without causing significant damage to the treated plants. The amount may vary within wide limits and depends on various factors such as the pest species, the cultivated plant or material being treated, the climatic conditions and the particular compound used.

The compound or the composition of the invention has simple use method, and the compound or the composition of the invention is applied to the pests or the growth medium thereof. The application dose of the compound or composition of the present invention varies depending on weather conditions, formulation, application timing, application method, application area, target disease, target crop, and the like.

General synthetic procedure

The following scheme describes the preparation of the compounds of the present invention. Unless otherwise indicated, the compounds of the invention may be prepared by the methods described herein. The starting materials, reagents and the like used in the preparation of the compounds of the present invention are commercially available or can be prepared by methods conventional in the art. In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In some embodiments, room temperature as described herein is 0-35 ℃ unless otherwise specified. In still other embodiments, the DMF is N, N-dimethylformamide.

The test conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: brookfield (Bruker) nuclear magnetic instrument at 400MHz or 600MHz in CDC1 at room temperature₃，d⁶-DMSO，CD₃OD or d⁶Acetone as solvent (reported in ppm) with TMS (0ppm) or chloroform (7.26ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublet), t (triplet), q (quatet, quartet), m (multiplet ), br (broadpeded, broad), dd (doublet of doublets), dt (doublet of triplets). Coupling constants are expressed in hertz (Hz).

The mass spectrum test conditions used in the invention are as follows: the conditions for low resolution Mass Spectrometry (MS) data determination were: agilent 6120Quadrupole HPLC-MS (column model: Zorbax SB-C18,2.1X 30mm,3.5 μm,6min, flow rate 0.6mL/min, mobile phase 5% -95% (CH with 0.1% formic acid)₃CN) in (H containing 0.1% formic acid)₂Proportion in O)), at 210/254nm with UV detection, using electrospray ionization mode (ESI).

Synthetic schemes

The target compound I can be prepared by the above synthetic scheme. Reacting the intermediate A compound with the intermediate B compound under the condition of heating (80-160 ℃) to obtain a target compound I;

wherein R is¹、R²And R³Have the meaning as described in the present invention.

Examples

Intermediate 1: synthesis of N- ((2-chlorothiazol-5-yl) methyl) pyridin-2-amine

The first step is as follows: synthesis of pyridin-2-ylcarbamic acid tert-butyl ester

2-aminopyridine (4.70g,0.05mol), Boc anhydride (14.17g,0.65mol) and triethylamine (7.55g,75mmol) were added in this order to dichloromethane (47mL) and the reaction was stirred at room temperature for 12 hours; filtration, spin-drying of the solvent, addition of water (45mL), extraction with ethyl acetate (50mL x 3), combination of the organic phases, washing of the organic phases with saturated brine (30mL x 3), drying, filtration, concentration of the filtrate, and separation of the residue by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 5/1] gave the title compound (white solid, 2.31g, yield: 24%).

The second step is that: synthesis of N- ((2-chlorothiazol-5-yl) methyl) pyridin-2-amine

Pyridine-2-ylcarbamic acid tert-butyl ester (1.94g,0.01mol) was dissolved in DMF (30mL) at room temperature, sodium hydride (0.36g,15mmol) was added portionwise at 0 ℃ over 30 minutes, after which reaction was continued with stirring at 0 ℃ for 30 minutes, the reaction temperature was raised to room temperature, a solution of 2-chloro-5-chloromethylthiazole (1.68g,0.01mol) in DMF (10mL) was slowly added dropwise, and the reaction was then carried out at room temperature for 8 hours. To the reaction solution was added 25mL of ice water, extracted with ethyl acetate (40mL x 3), the organic phases were combined, washed with saturated brine (20mL x 3), dried over magnesium sulfate, filtered, and concentrated to give an oil. The oily substance obtained above was dissolved in dichloromethane (20mL), and trifluoroacetic acid (2.3g,0.01mol) was slowly added dropwise at room temperature, after the dropwise addition was completed, the reaction was raised to 40 ℃ and refluxed for 8 hours; the reaction was concentrated, an aqueous potassium carbonate solution was added, pH was adjusted to 8, ethyl acetate (30mL x 3) was extracted, the organic phase was washed with water (10mL x 3), dried, filtered, the filtrate was concentrated, and the residue was separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 7/3] to give the title compound (yellow oil, 0.78g, yield: 34%).

¹H NMR(400MHz,CDCl₃)δ(ppm):8.19(d,1H),7.45-7.42(m,2H),7.65(t,1H),6.42(d,1H),4.80(s,1H),4.68(d,2H)；

MS(ES-API,pos.ion)m/z:226.10[M+1]⁺。

The intermediate compounds in table 1 can be prepared according to the above synthesis of intermediate 1 using the corresponding starting materials.

TABLE 1

Intermediate 4: synthesis of N- ((6- (methylthio) pyridin-3-yl) methyl) pyridin-2-amine

The first step is as follows: synthesis of 6- (methylthio) pyridine-3-carbaldehyde

6-Chloronicotinal (7.05g,50.00mmol), sodium thiomethoxide (17.5g,250mmol) and DMF (100mL) were added to a 250mL single neck flask, heated to reflux in a 70 ℃ oil bath and stirred for 12 hours. After the reaction was completed, the reaction was stopped, and after cooling to room temperature, the mixture was poured into ice water (300mL) and stirred vigorously at room temperature for 10 minutes. A precipitate precipitated out of the solution, and the precipitate was filtered off and washed with 50mL of water to obtain the title compound (off-white solid, 4.8g, yield: 62.7%).

The second step is that: synthesis of N- ((6- (methylthio) pyridin-3-yl) methyl) pyridin-2-amine

6- (methylthio) pyridine-3-carbaldehyde (2.4g,16.00mmol), o-aminopyridine (1.5g,16.00mmol) and methylene chloride (20mL) were added to a 100mL single-neck flask, stirred at room temperature for 10 minutes, the reaction solution was concentrated by distillation under reduced pressure, and the residue was heated in an oil bath at 90 ℃ while stirring under vacuum for 4 hours. After the reaction was completed, tetrahydrofuran (10mL) and methanol (20mL) were added to dissolve, and the mixture was stirred at room temperature, then sodium borohydride (608mg,16.00mmol) was added slowly in portions over 30 minutes, and after the addition was completed, the reaction was stirred at room temperature for 12 hours. The reaction solution was concentrated by distillation under the reduced pressure, washed with water (100mL), extracted with ethyl acetate (100 mL. times.3), the organic phases were combined, and the organic phase was dried over anhydrous magnesium sulfate for 1 hour. Filtration and distillation of the filtrate under reduced pressure followed by column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 2/1] gave the title compound (white solid, 2g, yield: 54%).

¹H NMR(400MHz,CDCl₃)δ(ppm):8.58(s,1H),8.24(d,J＝7.3Hz,1H),7.85-7.65(m,2H),7.42(s,1H),7.13(dd,J＝7.3Hz,4.6Hz,1H),6.62(s,1H),4.36(s,2H),4.0(s,1H),2.55(s,3H)；

MS(ES-API,pos.ion)m/z:232.30[M+1]⁺。

The intermediate compounds in table 2 can be prepared according to the synthesis of intermediate 4 above, using the corresponding starting materials.

TABLE 2

Intermediate 8: synthesis of bis (2,4, 6-trichlorophenyl) 2- (2-nitro-1-phenylethyl) malonate

The first step is as follows: synthesis of (2-nitroethylene) benzene

Benzaldehyde (4.24g,40mmol) and nitromethane (7.32g,120mmol) are dissolved in methanol (8mL), 10mL of 48% sodium hydroxide (4.80g,120mmol) aqueous solution is added dropwise at-8 ℃, the temperature is controlled below 15 ℃, reaction is carried out for 15 minutes after the dropwise addition, and precipitate is generated. Adding 50mL of ice water, and reacting for 20 minutes at 0 ℃; slowly adding the reaction solution into hydrochloric acid (6M,30mL), controlling the temperature at 0 ℃ and stirring for 5 minutes to generate yellow precipitate; suction filtration was performed, and the filter cake was washed with ice water (20 mL. times.2) and dried to give the title compound (yellow solid, 3.38g, yield: 57%).

The second step is that: synthesis of dimethyl 2- (2-nitro-1-phenylethyl) malonate

(2-Nitroethylene) benzene (3.28g,22mmol) and dimethyl malonate (1.64g,11mmol) were dissolved in toluene (20mL), and triethylamine (2.22g,22mmol) was added to react at room temperature for 8 hours. To the reaction solution was added 50mL of water, stirred, extracted with ethyl acetate (30mL × 2), the organic phase was dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, and the residue was separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 4/1] to give the title compound (yellow oil, 3.56g, yield: 58%).

The third step: synthesis of 2- (2-nitro-1-phenylethyl) malonic acid

Sodium hydroxide (1.60g,40mmol) was dissolved in 10mL of water, a solution of dimethyl 2- (2-nitro-1-phenylethyl) malonate (1.41g,5mmol) in methanol (10mL) was added, the reaction temperature was raised to 60 ℃, and the reaction was stirred for 2 hours. After cooling to room temperature, the reaction mixture was poured into ice water (20mL), stirred, adjusted to pH 1 with dilute hydrochloric acid, insoluble material was formed, extracted with ethyl acetate (30mL × 2), and the organic phases were combined and rotary evaporated to dryness to give the title compound (yellow solid, 1.09g, yield: 86%).

The fourth step: synthesis of bis (2,4, 6-trichlorophenyl) 2- (2-nitro-1-phenylethyl) malonate

2- (2-Nitro-1-phenylethyl) malonic acid (1.26g,5mmol) was dissolved in 20mL of dichloromethane, 0.2mL of DMF was added dropwise, the reaction temperature was lowered to-5 ℃ and oxalyl chloride (1.27g,10mmol) was slowly added dropwise, and the reaction was carried out at 0 ℃ for 10 hours. 2,4, 6-trichlorophenol (0.39g,2mmol) was added to the reaction mixture, and the reaction was continued with stirring at 0 ℃ for 12 hours. The reaction mixture was concentrated, cooled to room temperature, methanol (15mL) was added, and the precipitate was precipitated, filtered, and the filter cake was washed with methanol (10 mL. times.2) and dried to give the title compound (white solid, 1.06g, yield: 35%).

¹H NMR(400MHz,CDCl3)δ(ppm):7.40(s,4H),7.38-7.26(m,3H),7.18(t,J＝7.3Hz,2H),5.24(dd,J＝13.4,9.8Hz,1H),5.07(dd,J＝13.5,3.8Hz,1H),4.73(d,J＝8.7Hz,1H),4.55(td,J＝9.2,3.8Hz,1H)；

MS(ES-API,pos.ion)m/z:612.87[M+1]⁺。

The intermediate compounds in table 3 can be prepared according to the above synthesis of intermediate 8 using the corresponding starting materials.

TABLE 3

Example 1: synthesis of 1- ((2-chlorothiazol-5-yl) methyl) -3- (2-nitro-1-phenylethyl) -4-oxo-4H-pyrido [1,2-a ] pyrimidin-1-ium-2-ol salt

N- ((2-Chlorothiazol-5-yl) methyl) pyridin-2-amine (0.24g,0.5mmol) and bis (2,4, 6-trichlorophenyl) 2- (2-nitro-1-phenylethyl) malonate (0.31g,0.5mmol) were dissolved in 15mL of a toluene solution and reacted at 110 ℃ for 12 hours. The reaction was stopped, and the reaction solution was concentrated and then separated by silica gel column chromatography [ petroleum ether/ethyl acetate (v/v) ═ 1/3] to give the objective compound (yellow solid, 0.120g, yield: 54%).

MS(ES-API,pos.ion)m/z:442.9[M+1]⁺；

¹H NMR(400MHz,CDCl₃)δ(ppm):9.08(d,J＝7.1Hz,1H),7.88–7.79(m,1H),7.63(s,1H),7.57(d,J＝8.8Hz,1H),7.47(d,J＝7.2Hz,2H),7.32–7.29(m,1H),7.28–7.16(m,3H),5.63(s,2H),5.61–5.57(m,1H),5.32–5.24(m,1H),5.21–5.16(m,1H).

Intermediate compounds 1 to 7 and corresponding intermediate compounds 8 to 11 were prepared by a similar method to that of example 1 to give the target compounds in table 4.

TABLE 4

Test example

1) Test targets: diamondback moth

Leaf soaking method: and (3) fully soaking a proper amount of cabbage leaves in the prepared liquid medicine, naturally drying in the shade, putting into a culture dish filled with filter paper, inoculating 10 heads/dish of 2-3 instar middle-stage larvae of the plutella xylostella, culturing in an observation room at 24-27 ℃, and investigating the result after 3 days. The body of the insect is touched by a writing brush, no response is regarded as dead insect, and the test concentration is 200 mg/L.

2) Test targets: sticky insect

Leaf soaking method: and (3) fully soaking a proper amount of corn leaves in the prepared liquid medicine, naturally drying in the shade, placing the corn leaves into a culture dish filled with filter paper, inoculating 10 heads/dish of armyworm larvae in the 3-instar middle period, placing the armyworm larvae in an observation room at 24-27 ℃, culturing after 72 hours, investigating the result, and testing the concentration to be 200 mg/L.

3) Test targets: alfalfa aphid

Spraying method: selecting cowpea leaves with consistent growth, making leaf disks by using a puncher, placing wet sponge blocks in a culture dish, placing the leaf disks on the sponge, and adding water to flush the leaf disks for later use. Inoculating 2-3-year-old alfalfa aphids raised indoors to prepared leaf disks, wherein the number of the leaf disks is more than 15. The spray tower is adopted for treatment, and the amount of the sprayed liquid medicine is 0.5mL per treatment. The test material after the medicament treatment is placed in an observation room, and the result is observed after 48 hours. The body of the insect is touched by a writing brush, no response is regarded as dead insect, and the test concentration is 200 mg/L.

4) Test targets: 2-3 years old brown planthopper

Stem and leaf spraying method: selecting healthy plants with roots (2-3 leaf stage of rice seedlings), carefully cleaning the roots, fixing the plants in a culture dish by quartz sand, carrying out spray treatment on the rice seedlings in different concentrations of medicaments under a Potter spray tower, airing and inoculating insects on the plants, and covering a plastic cup. The blank control was treated first and then the above procedure was repeated in the order of the test doses, with no less than 2 replicates per treatment. Each treated seedling has about 5 roots and 15 worms. Placing the test material treated by the medicament in an observation room, dripping water into a culture dish at regular time for moisturizing, and observing the result after 96 hours. The body of the insect is touched by a writing brush, no response is regarded as dead insect, and the test concentration is 200 mg/L.

The test results show that: the lethality of example 5, example 12, example 14 and example 18 to diamondback moth is above 90% at the concentration of 200 mg/L;

under the concentration of 200mg/L, the lethality of example 11 and example 14 to the green peach aphids is more than 80%;

the mortality rate of examples 4 and 9 to brown planthopper is 100% at a concentration of 200 mg/L.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

Claims (10)

1. A compound which is a compound having formula (I) or a stereoisomer, a nitroxide or a salt thereof:

wherein:

R¹is hydrogen or C_1-6An alkyl group;

R²is a 5-6 membered heteroaryl; said 5-6 membered heteroaryl is optionally substituted by one or more groups selected from halogen, cyano, hydroxy, nitro, C_1-6Alkyl radical, C_1-6Alkoxy radical, C_1-6Alkylthio, halo C_1-6Alkyl, halo C_1-6Alkoxy or halo C_1-6Substituted by a substituent of alkylthio;

R³is C_6-10Aryl or 5-6 membered heteroaryl; said C_6-10Aryl and 5-6 membered heteroaryl optionally substituted with one or more substituents selected from halogen, cyano, hydroxy, nitro, C_1-6Alkyl radical, C_1-6Alkoxy, halo C_1-6Alkyl or halo C_1-6Substituent of alkoxy.

2. The compound of claim 1, wherein:

R¹is hydrogen or C_1-4An alkyl group; or

Preferably R¹Is hydrogen, CH₃-or CH₃CH₂-。

3. The compound of claim 1, wherein:

R²is thiazolyl, pyridyl or pyrimidinyl; wherein said thiazolyl, pyridyl or pyrimidinyl is optionally substituted with one or more substituents selected from haloElement, cyano, hydroxy, nitro, C_1-4Alkyl radical, C_1-4Alkoxy radical, C_1-4Alkylthio, halo C_1-4Alkyl, halo C_1-4Alkoxy or halo C_1-4Substituted by a substituent of alkylthio; or

Preferably, R²Is thiazol-5-yl, pyridin-3-yl or pyrimidin-5-yl; wherein said thiazol-5-yl, pyridin-3-yl and pyrimidin-5-yl are optionally substituted with one or more groups selected from fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, CH₃-、CH₃O-、CH₃S-、CF₃-or CF₃And O-is substituted.

4. A compound according to claim 3, wherein:

R²is composed of

5. The compound of claim 1, wherein:

R³is phenyl or thienyl; wherein said phenyl and thienyl are optionally substituted with one or more substituents selected from halogen, cyano, hydroxy, nitro, C_1-4Alkyl radical, C_1-4Alkoxy, halo C_1-4Alkyl or halo C_1-4Substituent substitution of alkoxy; or

Preferably, R³Is phenyl or thienyl; wherein said phenyl and thienyl are optionally substituted with one or more substituents selected from the group consisting of fluoro, chloro, bromo, iodo, cyano, hydroxy, nitro, CH₃-、CH₃O-、CF₃-or CF₃And O-is substituted.

6. The compound of claim 5, wherein:

R³is composed of

7. The compound according to any one of claims 1 to 6, which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of a compound having one of the following structures:

8. a composition comprising a compound of any one of claims 1-7.

9. Use of a compound according to any one of claims 1 to 7 or a composition according to claim 8 as a pesticide in agriculture.

10. A method of killing pests in agriculture of a compound according to any one of claims 1 to 7 or a composition according to claim 8.