CN114605324A

CN114605324A - Isoxazoline substituted benzamide derivative and preparation method and application thereof

Info

Publication number: CN114605324A
Application number: CN202210314555.8A
Authority: CN
Inventors: 唐剑峰; 迟会伟; 刘莹; 吴建挺; 徐龙祥; 李文涛; 李颖
Original assignee: SHANDONG UNITED PESTICIDE INDUSTRY CO LTD
Current assignee: SHANDONG UNITED PESTICIDE INDUSTRY CO LTD
Priority date: 2022-03-28
Filing date: 2022-03-28
Publication date: 2022-06-10

Abstract

The invention belongs to the technical field of insecticides and acaricides, and particularly relates to isoxazoline substituted benzamide derivatives, and a preparation method and application thereof. Specifically disclosed is a compound represented by the formula (I) below or a salt thereof,

Description

Isoxazoline substituted benzamide derivative and preparation method and application thereof

Technical Field

The invention belongs to the technical field of insecticides and acaricides, and particularly relates to isoxazoline substituted benzamide derivatives, and a preparation method and application thereof.

Background

The insecticidal and acaricidal agent plays an extremely important role in solving the problem of human grain in agricultural production increase. With increasing demands for safety of chemical substances and environmental impact, development of safer pest control agents has been desired. Further, since pest control agents such as insecticides and acaricides are used throughout the years, the pests gradually develop resistance to these biological control agents, and the control effect is not satisfactory. Therefore, development of pest control agents having excellent safety, control effect, residual effect, and other properties is a trend in the future.

Patent document US7951828 discloses isoxazoline compounds CK shown below₁(Compound No. 5-008):

WO2005085216 discloses isoxazoline compounds CK shown below₂(Compound No. 6-007):

however, the biological activity of the above compounds is still to be further improved. The inventors have conducted intensive studies to find an insecticidal/acaricidal agent having more excellent properties.

Disclosure of Invention

In order to improve the above problems, the present invention provides a compound represented by the following formula (I), a stereoisomer, a racemate, a tautomer, a nitrogen oxide thereof, or a pharmaceutically acceptable salt thereof,

x is selected from halogen, cyano, C₁-C₆Alkyl or C₁-C₆Haloalkyl, each X may be the same or different;

m is selected from 1,2 or 3;

R₁selected from hydrogen, C₁-C₆Alkyl or C₃-C₆A cycloalkyl group;

n is selected from 0, 1,2, 3, 4 or 5;

R₂is selected from C₁-C₆Haloalkyl, C₃-C₆Cycloalkyl radical, C₃-C₆Cycloalkyl radical C₁-C₃Alkyl or C₃-C₆A halocycloalkyl group.

According to an embodiment of the invention: in the formula (I), the compound is shown in the specification,

x is selected from fluorine, chlorine, bromine, methyl or trifluoromethyl, each X may be the same or different;

m is selected from 2 or 3;

R₁selected from hydrogen, C₁-C₃Alkyl or cyclopropyl;

n is selected from 0, 1,2 or 3;

x is selected from fluorine or chlorine, each X may be the same or different, preferably attached in the 3-, 4-or 5-position;

m is selected from 2 or 3;

R₁selected from hydrogen, methyl or ethyl;

n is selected from 0, 1 or 2;

R₂is selected from C₃-C₆Cycloalkyl, fluoro C₃-C₆Cycloalkyl radical, C₃-C₆Cycloalkyl methyl, fluoro C₃-C₆Cycloalkyl methyl, fluoro C₁-C₆An alkyl group.

m is selected from 2 or 3;

when n is 1, R₁Is hydrogen, methyl or ethyl; when n is 2, R₁Is H;

n is 0, 1 or 2;

R₂selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-fluorocyclopropyl, cyclopropylmethyl, 2-fluoroethyl, 2, 2-difluoroethyl or 2,2, 2-trifluoroethyl.

By way of example, the compound of formula (I) is selected from the following compounds,

TABLE 1

The present invention also provides a process for the preparation of a compound of formula (I) as above, comprising the following step a) or step B):

step A): carrying out condensation reaction on the compound of the formula (II) and the compound of the formula (III) to obtain a compound of the formula (I);

step B):

B1) reacting the compound of the formula (II) with a halogenating agent to obtain a compound of a formula (IV);

B2) reacting a compound shown in a formula (IV) with a compound shown in a formula (III) to obtain a compound shown in a formula (I);

x, R therein₁、R₂M, n have the definitions described above; l is selected from a leaving group, such as Cl, Br, I or F.

According to an embodiment of the present invention, the reaction in step a) may be carried out in the presence of a condensing agent selected from at least one of N, N ' -Dicyclohexylcarbodiimide (DCC), N ' -Diisopropylcarbodiimide (DIC), 1-Hydroxybenzotriazole (HOBT), 2- (7-azabenzotriazole) -N, N ' -tetramethyluronium Hexafluorophosphate (HATU), benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate (PyBOP);

according to an embodiment of the present invention, the reaction in step a) may be carried out in the presence of a base, which may be an inorganic base, for example, at least one selected from pyridine, triethylamine, 4- (dimethylamino) pyridine (DMAP), Diisopropylethylamine (DIEA);

according to an embodiment of the invention, the reaction in step a) is carried out in a solvent selected from at least one of N, N-dimethylacetamide, N-dimethylformamide, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, acetonitrile, toluene, dichloromethane, 1, 2-dichloroethane;

according to an embodiment of the invention, the reaction temperature in step A) may be in the range of-5 to 120 deg.C, for example 0 to 50 deg.C, such as 15 to 30 deg.C.

According to an embodiment of the present invention, the halogenating agent in step B1) is selected from thionyl chloride, oxalyl chloride or thionyl chloride;

according to an embodiment of the invention, the temperature of the reaction in step B1) may be 0 to 100 ℃, e.g. 0 to 50 ℃, such as 0 to 30 ℃;

according to an embodiment of the present invention, the reaction in step B2) may be performed in the presence of a base, which may be selected from one, two or more of organic or inorganic bases, such as pyridine, triethylamine, 4- (dimethylamino) pyridine (DMAP), Diisopropylethylamine (DIEA), sodium carbonate, potassium carbonate, sodium hydroxide, potassium tert-butoxide, sodium hydride, or the like. Preferred solvents may be N, N-dimethylacetamide, N-dimethylformamide, dioxane, toluene, dichloromethane, 1, 2-dichloroethane;

according to an embodiment of the invention, the temperature of the reaction in step B2) may be in the range of 0 to 120 ℃, for example 0 to 50 ℃, such as 15 to 30 ℃.

The process for the preparation of the compound of formula (II) can be referred to the process described in the applicant's prior application CN111909143, which comprises the following steps:

(1) reacting the compound of the formula (VIII) with hydroxylamine or hydroxylamine hydrochloride to obtain a compound of the formula (VI);

(2) reacting the compound of formula (IX) with the compound of formula (X) to obtain a compound of formula (VII);

(3) reacting the compound of the formula (VI) with the compound of the formula (VII) to obtain a compound of the formula (V);

(4) hydrolyzing the compound of the formula (V) to obtain a compound of a formula (II);

wherein X, m has the definitions as described above; r is selected from alkyl of 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, tert-butyl;

according to an embodiment of the present invention, step (1) may be carried out in the presence of a base selected from an organic base such as triethylamine, sodium acetate, or an inorganic base such as sodium bicarbonate; the reaction solvent is selected from alcohol solvents such as methanol and ethanol, water or a mixture thereof; the reaction temperature can be 0-100 ℃, and preferably 15-30 ℃.

According to an embodiment of the present invention, step (2) may be carried out in the presence of a catalyst selected from tetrakis (triphenylphosphine) palladium, palladium acetate or bis (triphenylphosphine) palladium dichloride;

step (2) may be carried out in the presence of a base selected from sodium carbonate, potassium carbonate, pyridine, triethylamine or 4- (dimethylamino) pyridine; the solvent is selected from toluene, tetrahydrofuran, N-dimethylformamide or water; the reaction temperature may be 30 to 150 ℃, for example 50 to 120 ℃.

According to an embodiment of the present invention, step (3) may be performed in the presence of a halogenating agent, which may be N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS); the reaction temperature can be 0-100 ℃, for example 15-30 ℃;

according to an embodiment of the present invention, step (3) may be performed in the presence of a base selected from at least one of triethylamine, pyridine, sodium bicarbonate, sodium carbonate; the reaction temperature may be 0 to 100 ℃, for example 15 to 30 ℃.

According to an embodiment of the present invention, the step (4) may be performed in the presence of a base selected from at least one of sodium hydroxide, potassium hydroxide, or lithium hydroxide; or treatment with an acid such as trifluoroacetic acid in dichloromethane;

according to an embodiment of the present invention, the temperature of the reaction in step (4) may be 0 to 150 ℃, for example 15 to 80 ℃.

The amine represented by formula (III) can be purchased as a commercial product or can be produced by the method described in CN 111518094.

Wherein R is₁、R₂N has the definition as described above; l is selected from leaving groups, e.g.Such as Cl, Br, I or F.

According to an embodiment of the present invention, the reaction may be carried out in the presence of a base selected from sodium carbonate, potassium carbonate, pyridine, triethylamine, diisopropylethylamine or 4- (dimethylamino) pyridine; the solvent is selected from toluene, acetonitrile, tetrahydrofuran or N, N-dimethylformamide; the reaction temperature may be 20 to 150 ℃, for example 50 to 120 ℃.

The compounds of formula (VIII), formula (X) and formula (IX) may be purchased as commercial products or prepared by methods known to those skilled in the art.

The preparation of the compounds of the formula (I) and their starting materials here can be carried out, depending on the reaction conditions and the choice of starting materials which are suitable in each case, by replacing, for example, in a one-step reaction only one substituent by another substituent according to the invention or by replacing, in the same reaction step, a plurality of substituents by further substituents according to the invention.

If the individual compounds are not obtainable via the above routes, they can be prepared by derivatizing the other compounds or by routinely varying the synthetic routes described.

After completion of the reaction, the reaction mixture can be worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude product by chromatography, for example on alumina or silica gel.

The pharmaceutically acceptable salts of the compounds of formula (I) of the present invention can be prepared by known methods. For example by suitable acid treatment to give an acid addition salt of the compound of formula (I). The preparation method comprises the following steps: the pharmaceutically acceptable salts of the compounds of formula (I) can be conveniently obtained by reacting the compounds of formula (I) with an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, trifluoroacetic acid, malic acid or citric acid in a solvent such as water, diethyl ether or toluene.

The above preparation process allows to obtain an isomeric mixture of the compound of formula (I), if it is desired to obtain the pure isomers, which can be separated by conventional methods such as crystallization or chromatography.

All reactions described above may conveniently be carried out at atmospheric pressure or the autogenous pressure of the particular reaction, unless otherwise indicated.

The present invention also provides a pesticidal composition, such as an insecticidal and/or acaricidal composition, comprising, as an active ingredient, one, two or more of a compound represented by formula (I), a stereoisomer, a racemate, a tautomer, a nitrogen oxide, or a pharmaceutically acceptable salt thereof.

According to an embodiment of the invention, the active ingredient is present in the composition in an amount of 0.1 to 99.9% by weight, for example 0.5 to 99% by weight.

According to an embodiment of the invention, one, two or more agriculturally and/or forestry and/or hygienically acceptable carriers are also included in the composition.

According to an embodiment of the invention, the composition may be administered in the form of a formulation.

For example, the compounds of formula (I) as active ingredients are dissolved or dispersed in a carrier or formulated so as to be more easily dispersible for insecticidal and/or acaricidal use.

According to an embodiment of the invention, the formulation includes, but is not limited to, the following forms: wettable powder, oil suspension, water suspension, aqueous emulsion, aqueous solution, missible oil or microcapsule and the like.

According to embodiments of the invention, a liquid or solid carrier, and optionally a surfactant, may also be added to the composition.

The invention also provides application of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof as pesticides, such as insecticides and/or acaricides.

The invention also provides application of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof in preparation of pesticides, such as insecticides and/or acaricides.

The invention also provides a method for controlling pests and/or harmful mites, which comprises applying an effective amount of one, two or more of the compounds shown in the formula (I), stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof or applying the composition to a growth medium of the pests and/or the harmful mites.

According to an embodiment of the invention, the effective amount is from 10 to 1000 grams per hectare, preferably from 20 to 500 grams per hectare.

The active substances according to the invention or the active substances to be used according to the invention are suitable, in view of good plant tolerance, favourable warm-blooded animal toxicity and good environmental compatibility, for protecting plants and plant organs, increasing harvest yields, improving the quality of the harvest and for controlling animal pests, mites and the like which occur, in particular, in agriculture, horticulture, animal husbandry, forestry, gardens and leisure facilities, in warehouse pest protection and material protection, and in the hygiene sector. They are preferably used as plant protection compositions. They are active against conventional sensitive and resistant species and against all or individual developmental stages. The pests and mites include but are not limited to:

arthropoda, in particular Arachnida, such as, for example, the genus Amycolatopsis (Acarus spp.), the genus Citrus gall (Aceraschedoni), the genus Dermatophagoides (Aculopsis sp.), the genus Acropyrium (Aculops spp.), the genus Acropyrium spp., the genus Bluella (Amblyomma spp.), the genus Tetranychus (Amphiyranthus flavus), the genus Argase (Arganella spp.), the genus Boophilus spp., the genus Brevurica (Brevipalpus spp.), the genus Bryopbiagrnaemophilus, the genus Bryopyratia (Bryopia spp.), the genus Deuteropyra (Bryopyratia spp.), the genus Detailus spp.), the genus Dermatophus (Dermatophus spp.), the genus Dermatophus spp., the genus Dermatophus spp (Hypoglyphosatus spp.), the genus Dermatophagoides (Hygrophytin), the genus Dermatophagoides (Hygrophytin), the genus Dermatophagoides), the genus Dermatophus spp.), the genus Dermatophagoides (Hygrophytylenchus spp.), the genus Dermatophus spp.), the genus Dermatophagoides (Hygrophytin (Dermatophus spp.), the genus Dermatophagoides (Dermatophus spp.), the genus Dermatophus (Dermatophus spp.), the genus Dermatophus (Hygrophytes) and the genus Dermatophus spp.), the genus Dermatophus (Hygrophytin (the genus Dermatophus spp.), the genus Dermatophus (Hygrophytes (the genus Dermatophus spp.), the genus Dermatophus (Dermatophus spp.), the genus Dermatophus (Hygrophys (Dermatophus (De, Venomous (Latrodectus spp.), Loxosceles spp, Tetranychus (Metatrenchus spp.), Neutratus, Nuphersa spp, Micronychus (Oligonchus spp.), Blastonella (Ornithodorous spp.), Ornithromycotus spp, Ornithronosus spp, Panonychus (Panonychus spp.), Phyllostachys citri (Phytocopterus spp.), Mitragus crenulata (Phytocopterus specvora), Tarsonemus laterosus (Polytarsonemus), Psortus (Psoroptes spp.), Phyllostachys flabellatus (Rhipicephalus spp.), Rhizopus spp., Rhizopus, Tetranychus (Rhynchus spp.), Tetranychus (Tetranychus spp.), Acarus sp., Tetranychus spus (Stepron spp.), Acarus sp., Tetranychus spp.), Tetranychus (Sterculia spyritus spp.), Acarus spp.);

coleoptera (Coleoptera) (beetle): bean species (Acanthoscelides spp.) (elephant), phaseolus vulgaris (Acanthoscelides obtectus) (common pisiform), Ceratoptera alba (Agrilus planipes) and Ceratopteris versicolor (Quadrifolia narrow Germin), Flammulina species (Agriotes spp.) (wireworm), Anoplophora glabripennis (Aphis longipes), Gomphytus species (Anthonoma spp.) (Arthrobacter flavidus), Gomphytus grandis (Anthronus grandis) (Arthrobacter asiaticus), Gomphytus species (Aphidius spp.) (Aprionus spp.) (Arthrospora), Cochlothiaoma sp. (Anacardia), Cochlothiajaponica (Aponia spp.) (grub), Cochlothuroides (Atacys specularis) (Black piss specula (Atanthus spec), Pieris versicolor (Pieris indica) (Pieris indica), Pieris indica (Pieris indica) (Pieris) and Pieris (Pieris indica) (Pieris chinensis (Pieris) of (Pieris) variety (Pieris illustrates (Pieris) and Pieris (Pieris) such as Pieris (Pieris sinensis (Pieris variety (Pieris) and Pieris (Pieris) such as (Pieris) A variety (Pieris) such as Pieris variety (Pieris) and Pieris variety (Pieris) including Pieris variety (Pieris) such, Pieris variety (Pieris) such as Pieris (Pieris variety (Pieris) such, Pieris (Pieris variety (Pieris) including Pieris) such as Pieris (Pieris variety, Pieris) and Pieris variety (Pieris) such), Pieris (Pieris) including Pieris variety (Pieris) and Pieris (Pieris) such), Pieris) such (Pieris) such), Pieris) such as (Pieris variety (Pieris) and Pieris variety (Pieris) such), Pieris variety (Pieris) variety (Pieris variety, Pieris (Pieris) and Pieris) including Pieris (Pieris) variety (Pieris) such) including Pieris variety (Pieris) such (Pieris variety (Pieris) including Pieris (Pieris variety, Pieris (Pieris variety (Pieris) including Pieris variety (Pieris) including Pieris, Cacoesia species (Cacoesia spp.), Callosobruchus maculatus (southern cowpea weevil), yellow spot dew beetle (carpophilus humilis) (xerophys), tortoise shell (Cassida witta), longicorn species (ccroscrna spp.), Ceratoma species (Ccrotoma spp.), Ceratoma species (Crotoma spp.), Ceratoma (chrysosporium), Ceratoma trifoliate (Ceratoma trifoliatus) (Ceratoma viridis), Ceratoma species (Ceratoma spp.), Ceratoma species (Ceratonia spp.), Chinese cabbage seed elephant (Ceratonia nigra), Chinese cabbage seed elephant (Ceratonia gigantea) (cabbage), Chinese cabbage weevil (Ceratonia rubra) (cabbage sepedodes), Brassica (Ceratonia), Ceratonia nigra (Ceratonia flava), Ceratoma spicata (Ceratonia flava), European red beetle (Ceratoma), Ceratonia nigra (Ceratonia flavus) (Colatodes), Ceratoma spicata (Coliotia spicata), Ceratoma (Coliotica), Ceratodes (Ceratodes spica) and Ceratodes (Colatodes (Junipes (Coliotica), Ceratodes (Junipes (Juniperus) and Ceratodes (Junipes), Ceratodes (Junipes (Juniperus) are), Brassica (Junipes (Juniperus), Brassica) and Brassica (Juniperus) Examples of such plants include, but are not limited to, Cryptolepis pusillus (Cryptolepis parvum), Cryptolepis pusillus (Cryptolepis granulosus), Cryptolepis species (Ctenora spp.) (nematodes), elephant species (Curculio spp.) (weevil), Rhinocephalus species (Cycleephora spp.) (Holotrichia dioides), Rhinocephalus pseudoptera (Cyclenophora spp.) (Holotrichia dioides), Rhinocephalus pseudoptera (Apolygus grandis), Rhinocephalus pseudoptera) (Rhinocephalus pseudoptera), Rhinocephalus pseudoptera (Deporus marginatus) (Rhinocephalus pseudoptera) (Mesorula-pectinifera), Rhinocephalus (Rhinocephalus pseudoptera), Rhinocephalus pseudoptera (Rhinocephalus) and Rhinocephalus pseudoptera (Membristylis), Rhinocephalus pseudoptera (Rhinocephalus) Pectinopsis), Rhinocephalus pseudoptera (Rhinocephalus) and Rhinocephalus (Pilus) Pilus chinensis (Membriae) or Rhinocephalus) Pilus (Pilus) Pilus chinensis), Rhinocarpus (Pilus) Pilus chinensis (Pilus) and Rhinocarpus) Pilus chinensis (Pilus) or Pilus chinensis (Pilus) Pilus chinensis) and Pilus chinensis (Pilus) or Pilus) Pilus chinensis (Pilus) or Pilus chinensis (Pilus) Pilus chinensis (Pilus) A. sp., Membriatus) A) Pilus) A) Pilus) or Pilus chinensis (Pilus) Pilus chinensis (Pilus) A. sp Alfalfa leaf weevil (Hypera stictica) (alfalfa weevil), Hyperdos species (Hyperdoss spp.) (argentina stem weevil (Hyperodes weevil)), coffee berry silly (Hypertenemus hamhei) (coffee fruit beetle), scotland species (Ips spp.) (echinacea), tobacco beetle (Lasioderma serricorne) (tobacco beetle), potato beetle (leptotarsia decemlineata) (colorado potato beetle), lipogyne fuscus, lipogynogenes suturalis, rice water weevil (lissorophiura) and silphigenia species (lycopus purpurea), common tortoise (megalophora), meldonia terrestris (Messostrea), Messostressostrea purpurea (Messochloes), Messochloesophagus spp (Messochloes grandis), Messochlothria spp. (Messochloesophagus spp.) (Messoides), Messochloesophagus spp. (Messoides albugineus spp.) (Messoensis, Mesloe beetle spochloes spp.) (Messochloes variety (Mesloe beetle), Mesloe beetle Rhinoceros rhynchophylla (oriycetes rhynchophylla) (date palm beetle), commerical saw beetle (O ryzaephilus beetle) (market saw beetle), cercaria castanea (elephant), cercaria subulata (odontobrama subulata) (saw beetle), rhynchophylla species (oxiphys spp.) (elephant), black horn mud insect (ocellumeyoplus subulata) (orange foot mud insect (cerolate)), rice negative mud insect (ocelluma oryzae), rose short beak elephant species (pandomous spp.) (elephant), phyllopodium parvus (phyllopodium parvum), phyllopomorpha (phyllopomorpha subulata) (ostriatus subulata), phyllopomorpha parva (phyllopomorpha), picrorhiza (ostriatus subulata), picrorhiza kura (ostriatus parvus (ostriatus spp.) (ostriatus parva), picria parva (ostriata), picria subulata (ostriata) species (ostriatus parva (ostriatus sp.) (picea mangle), picea mangle) and picea mangle (picrorhiza) (picea mangle) species (picrorhiza, picea mangle (picror) of picrorhiza, picea mangle (picrorhiza, picea sp. (picea) of picea mangle (picea sp. (picea) of picea sp. (picea) of picea mangle, picea sp. (picea) of picea (piceid, picea) of picrorhiza, picea sp. (picea) of picea mangle, picea (picea) of picea (picrorhiza, picea (picea) of picrorhiza, picea (picrorhiza, picea) of picea (picea) of piceid, picea) of picrorhiza, picea (picrorhiza, picea) of picrorhiza, picea (picrorhiza, picea (picea) of picrorhiza, picea) of picrorhiza, picea (picea) of picrorhiza, picea (picrorhiza, picea (picrorhiza, picea (picea) of picrorhiza, picea (picrorhiza, picea (picea) of pica) of picrorhiza, picea (picea) of pica) of picea (picrorhiza, pica) of pica, pic, Root gill species (rhizorgus spp.) (european scarab (european chafer), cryptorhynchophorus species (Rhynchophorus spp.) (elephant), silly species (Scolytus spp.) (wooddull moth), shonophorus species (shonophorus spp.) (cereal elephant), pea leaf elephant (Sitona linkuwana) (pea leaf elephant nail), rice weevil species (Sitophilus spp.) (cereal weevil), rice elephant (Sitophilus grandis) (paddy insect (granny weevil)), rice elephant (Sitophilus oryzae) (rice leaf), millet beetle (sterculus oryzae) (wheat leaf), maize beetle (sterculium), maize beetle (rice bark beetle) (Tribolium), and maize (Tribolium castrum) (Tribolium), maize beetle (Tribolium), and red beetle (Tribolium), maize (Tribolium (Tribolium), and red beetle (Tribolium), or brown beetle (Tribolium), or brown beetle (Tribolium), or brown rice.

Dermaptera (Dcrmaptcra) (earwigs).

Vein winged order (Dictyoptera) (cockroach): german cockroach (Blattella germanica) (German cockroach), Blatta orientalis (Blatta orientalis), Blatta palustris (cocitria pennymannica), Periplaneta americana (peritland americana) (americana), Blatta australiana (peritland australoache), Blatta australiana (Australia nckroloach), Periplaneta fusca (pcriparia) brown cockroach (brown cockroach), Periplaneta smokaria (perilanta fuliginosa) (black chest cockroach (smoothckn), and Blatta subclinica (brown cockroach)), Blatta green cockroach (brown cockroach), and Periplaneta fuliginosa (brown cockroach) (Periplaneta subclinica cockroach (brown cockroach)).

Diptera (Diptera) (flies): mosquito species (Aedes spp.) (mosquito), lucerne fly larvae (Agromyza frontella) (alfa blotcheminensis), agromyzis species ((Agromyza spp.) (leaf miner), trypetid species (anastrep spp.) (fruit fly), garleria persica (anastrep persica), garleria persica (garleria persica) (garleria persica (calibrella fufly), mosquito species (anophes spp.) (mosquito), fruit fly species (Bactrocera spp.) (fruit fly), melon fly (Bactrocera persica) (melon), citrus fruit fly (Bactrocera persica), mosquito species (deer spp.) (mosquito), mosquito fly larvae (sartoria midges) (sea fly), sea fly larvae (sea fly larvae) (midges), sea fly larvae (sea fly larvae) (grub.) (cubensis), mosquito species (deer spp.) (fruit fly, deer spp.) (mosquito fly, mosquito fly larvae (sea fly), mosquito fly larvae (sea fly larvae) (sea fly) (mosquito larvae) (sea fly, seed, bird fly, bird fly, bird, pig, leaf of rape mosquito (Dasineura brassicae) (cabbage mosquito), Dimochi species (Delia spp.), Grapholitha californica (Delia platura) (root maggot (seed corn flag)), Drosophila species (Drosophila spp.) (vinegar fly), Musca species (Fannia spp.) (housefly), yellow belly fly (Fannia canthus) (summer fly (litter fly)), Grey belly fly (grey belly fly) (Grey belly fly), Gasterophilus intestinalis (Gasterous intestinalis) (horse bot), Gracillia persea, Haematobia irutans (Haematobia irritans) (Hymenophila), Blastus species (Hymenophila maggot) (root maggot (skin maggot)), Musca (common fly) (Merista typhus (Musca), Musca melanogaster (Musca), Musca species (Merista spongia) and Musca (Musca), Musca fly (leaf fly) (Merista spossius), Musca fly (Musca fly) (Merista) and Musca (leaf), Musca fly (Musca) and Musca (Musca) are included in the genus, Musca variety (Musca) and Musca, and Musca, such as the same, and their preparation, Fall flies (Muscaa utumnalis) (face flies), house flies (vusca domastica) (house flies), sheep flies (oesterussivis) (sheep nose flies), european wheat straw flies (Oscinella fructica) (sweden wheat straw flies), beet spring flies (pegomyces betaeus) (spinach leaf miner), musca spp (P horbia spp.), carrot stem flies (Psila rosea) (carrot flies (carrotrus domestica)), cherry fruit flies (cherry fruit fly (cherry fruit fly)), apple fruit flies (rhaponticum (apple maggot) (apple maggot)), red mud flies (Sidipterospodoptera) (white flies (wheat grass), and cattle fly (grass fly (cattle grass)), and cattle fly (cattle grass) species).

Hemiptera (Hemiptera) (stinkbug): apolygus lucorum (Acrosteronum hieron) (green stink bug), Oryza sativa (Blissus leucopterus) (long stink bug), Oryza sativa (Caloris norvegicus) (potato stink bug), Tropical stink bug (Cimex hemipterus) (tropical stink), stinkbug (Cimex leucopterus) (bed bug), Daghertussis fasciatus, Dichelops furcatus, Oryza sativa (Euonymus sutus), Edessa meditibetus (Euonymus), Oryza sativa (Leyopteris), Oryza sativa (Leiplus), Oryza sativa (Oryza sativa), Oryza sativa (Oryza sativa) and/Oryza sativa (Oryza sativa) for treating, Lygus hesperus (lygushineus) (western tarnished plant bug), hibiscus syriacus (macrocytoericcus hirsutus), neuroolpus longirostris, rice green bugs (Nezara viridula) (southern green stink bug), lygus planticola (phytolocoris spp.) (lygus), california blind bugs (phytoorius californicus), phytoorius relatus, pisoruszodorus guildingii, lygus tetragonorrhoea (Poiococcus lineus) (neurolylindus bug), Psychicola, Pseudactyla, Scotococcus and trypanosoma species (nose cone)/trypanosoma (nose cone).

Homoptera (Homoptera) (aphid, scale, whitefly, leafhopper): piper pisum (Acrythosiphopkinsum) (pea aphid)), Coccinum species (Adelges spp.) (adelg ds), Beeuglena brassicae (Aleurodes proteella) (Beeuglena cabbage whitefly), Aleurodicus spiralis (Aleuroderus di spores), Beeurothyrius filiformis (Aleurothrix luteus) (gloomy whitlys), Begonia alba (Aluaspis spp.), Amrasa biguella, Laodermata species (Aphrophophora ra spp.) (leafhopper)), Rhodococcus aurantii (Amadonis nigrella aurantii) (Begonia aphid), Begonia nilaparvata (Begonia), Begonia nilaparvata (Begoniothiaca), Begoniothiaspora (Begoniothiaspora aphid), Begoniothrix gloea (Begoniothrix), Begonia indica (Begoniothiaspora indica), Begonia indica (Begonia), Begoniothiaspora (Begonia), Begonia (Begonia), Begonioth (Begonia), Begonia) and Begonia (Begonia) Aphis viride (Begonia) are (Begonia), Begonia (Begoniothrix) species (Begonia), Begonia (Begonia, Begoniothrix) of Begonia (Begonia), Begonia, Begoniothiaca, Begonia (Begoniothiaca, Begonia, Begoni, Wheat-tail aphid (Brachycolus noxius) (Russian aphid), asparagus tubular aphid (brachycorythrix asparagi) (asparagus aphid), Brevennia rehi, cabbage aphid (brevicornus brassicae) (cabbage aphid), Ceroplastes sp (Ceroplastes spp.), red Ceroplastes (Ceroplastes rubens) (red wax scale), snow shield plant (chilblastes spp.) (scale), round shield plant (chrysomyrod plant sp.) (scale), soft wax plant (cocussp.) (pink leaf fly), red leaf plant (apple leaf plant), green leaf plant (apple leaf plant), apple leaf plant, apple, euphorbia magna (Macrosiphum eupatoria) (potato aphid), Myzus avenae (Malcoprinus grandiflorum) (English grazing), Long-pipe aphid (Macrosiphum rosa) (rose aphid), Tetranychus tetragonolobus (Macrostemma quadratus) (purple leaf cicada (ash leaf hopper)), Mahanarafrimota, Metaplexis tetragonolobus (Methodophyllum dirhodorium) (rose aphid), Midis locorins, Myzus persicae (Myzus persicae), Myzus nigra (Netephrix paraphyllus) (Phosphophylum), Phytophthora nigra (leaf aphid), Phytophthora nigra (leaf hopper), Phytophthora nigra grandis (leaf), Phytophthora nigra (leaf aphid), Phytophthora nigra (leaf aphid), Phytophus nigra (leaf), Phytophthora grandis (leaf, Phytophthora grandis (P. sp), Phytophthora grandis (Phoma) and Phytophthora grandis (Phoma) A (Phocticola (leaf, Phytophthora grandis (P. sp), Phytophthora grandis (P. grandis), Phytophthora grandis (P. sp), Phytophthora grandis (P. sp), Phytophthora grandis (P. niphylum) and (P. sp), Phytophthora grandis (P. niphylum) of the), Phytophthora grandis (P. sp), Myzus (P. niphylum) of Mipanopluria grandis (P. sp), Myzus (Taurophylum) of Myzus (Mitsu (P. sp), Myzus (Mitsu (P. niphylum) of Myzus), Myzus (Mitsu. sp), Myzus (Mitsu (Mitsuma) of Mitsu), Myzus (Mitsu), Myzus (Mitsuba) of Myzus), Myzus (Mitsu), Myzus (Mitsu) of Myzus (Mitsu, Myzus (Mitsuma variety (Mitsu, Myzus), Myzus (Mitsu), Myzus (Mitsuba) of Myzus (Mitsu, The plant diseases of the species lecanicillium (Physioderma piceae) (sport scale), the species Leptococcus sp (Plasmococcus spp.), the species Leptococcus sp (Leptococcus spp.), the species Leptococcus sp (Pseudococcus spp.), the species Bectonus sp (Pseudococcus spp.), the species Leptococcus sp (Pseudococcus spp.), the species Phryptococcus sp), the species Leptococcus sp (Rhapococcus spp.), the species Leptococcus sp (Pseudomonadaceae spp.), the species Leptococcus sp (Phytophagus spp.), the species Leptococcus spp (Phytophagus spp.), the species Leptococcus spp (Pseudophaga (Pseudophagus spp.), the species Leptococcus spp (Phytophagus spp.), the species Leptococcus spp (Tripterus sp (Tripterus spp.), the species Leptococcus spp (Tripterus sp (Tripterus spp.), the species Leptococcus spp), the species Leptococcus sp (Tripterus spp.), the species (Tripterus spp), the species Leptococcus spp.), the species (Tripterus sp), the species Leptococcus spp), the species (Tripterus sp (Tripterus sp), the species (Tripterus sp), the species (Tripterus sp), the species of the genus Leptococcus spp), the genus Leptococcus sp (Tripterus sp), the species of the genus Leptococcus spp), the species of the genus Leptococcus sp), the genus Leptococcus sp (Tripterus sp), the species of the genus Leptococcus spp), and the species of the genus Leptococcus sp (Tripterus sp), the species of the genus Leptococcus spp), the genus Leptococcus sp (Tripterus (Tri, Whitefly species (Trialeurodes spp.) (whitefly), greenhouse whitefly (Trialeurodes vaporariorum) (greenhouses whitefly), brown wing whitefly (Trialeurodes abutiloneus) (bandtwing whitefly), cupula species (Unaspis spp.) (scale), arrowhead (Unaspis yanonensis) (arrowhead scale), and Zulia entreriana.

Hymenoptera (Hymenoptera) (ants, wasps and bees): incised leaf ant species (Acromyrmex spp.), Sinkiang leaf beehive (Athalia rosae), leaf ant species (Atta spp.) (Ieafcutting ants), black ant species (Camponotus spp.) (carpenter ant)), pine leaf bee species (Diprion spp.) (leaf beehive (saw fly)), ant species (Formica spp.) (Ant), Argentina ant species (Iridogyrmex pollicis) (Argentina), Carcinia subnata (Monorium spp.) (Monocorium little) (littleberlac), Monomerium termite (Monomerium spp.) (Monomerium kummer.) (Monomerinum), termite leaf ant species (Neomerium spp.) (Melissa), and bee species (Solomonus spp.) (Polonella), and bee species (Solomone spp.) (Melilotus spp.) (Legione), and species (Melilotus spp.) (Melilotus spp (Solomon) (Melilotus spp.) (Carya) and Sina) are harvested, Wasp species (vespela spp.) (yellow jack) and trichogramma species (Xylocopa spp.) (carpenter bee).

Isoptera (Isoptera) (termites): coptotermes spp, Coptotermes curcus, Coptotermes curcumine, Coptotermes frutus, Coptotermes formosanus, Formosan subcoternum, Corniteus spp, Coptotermes formosanus, Coptotermes spp, Coptotermes formosanus, Coptotermes formotermes spp, Heterotermes spp, Coptotermes formotermes spp, Coptotermes formosanus spp, Coptotermes formosanus termes spp, Coptotermes formosanus spp, Coptotermes termes formosanus termes spp, Coptotermes termes spp, Coptotermes termes formosanus termes, Coptotermes termes, Coptotermes termes, Coptotermes termes, Coptotermes, Cotermes termes, Cotermes termes, Cotermes termes, Cotermes termes, Cotermes, Reticulitermes banyulensis, Spodoptera grassland (Reticulitermes grassei), Reticulitermes flavipes (Reticulitermes f la vi pes) (eastern soil-dwelling termites), Reticulitermes flavenii (Reticulitermes hagenii), West soil-dwelling termites (Reticulitermes heperus) (West soil-dwelling termites), Moraxella (Reticulitermes santonensis), North-dwelling soil-dwelling termites (Reticulitermes speratus), Reticulitermes nigripes (Reticulitermes tibialis), Reticulitermes virginicus (Reticulitermes virginicus), Reticulitermes formosanus species (Schedorthes spp.) and Zootes spp.

Lepidoptera (Lepidoptera) (moths and butterflies): achoea janata, Trichosporon species (Adoxophyceae spp.), Trichosta gossypii (Adoxophyes orana), Gekko sp (Agrotis spp.), cutworm (Agrotis ipsilon) (Black cutworm), Alabama virescens (Alabama argillaceae) (Cotton leaf worm (cottonleaf worm), Amorbia cuneata, Amylosis tradiatricella (Na orange), Anacamptodia fectaria, Spodoptera punctata (Antarctica Lineata) (peach twig borreria), Heliothis virescens (Anomia sibirica), Pseudocera erecta (Ostrinia), Pseudocera kummer (Ostrinia), Pseudocera punctata (Ostrinia), Pseudocera kummer (Bodinia), Pseudocera armorida (Ostrinia), Spodoptera punctata (Ostrinia), Spodoptera frugiella punctifera (Ostrinia), Spodoptera (Ostrinia) and leaf (Ostrinia) varieties, Spodoptera (Ostrinia) and leaf The species of the genus Spodoptera (Caloptilia spp.) (Spodoptera exigua), Capua reticulana, peach fruit moth (Carposina nipponensis) (peach fruit moth)), Bombycis gramineus (Chilo spp.), mango transverse-thread Philippine moth (Chuumetia transversa) (mango shoot front borner), Rose color cabbage moth (Choristeurosaana) (oblitera) (obliquus)) and Spodoptera species (Chrysodexis p.)), rice leaf roller (Cnaphalous medius) (grass leaf roller)), Bean flour species of the genus Pieris (Colias spp.)), Yao-punctifera (Conmopora reticulata), Spodoptera litura (apple leaf moth) (apple moth), Spodoptera frugiperda (apple moth (Plutella), Spodoptera xylostella), Spodoptera litura (Spodoptera frugiperda (apple moth) (apple moth (Plutella), Spirochaeta (Spirochaeta.) (Chorista), Spodoptera frugiperda (Spodoptera), Spirochaeta) (apple moth (Plutella), Spirocha) (apple moth (Plutella) species (Plutella) and Spirochaeta (moth (Plutella) A) and Spirogra (Plutella) in the family of the family Choristocarpus (Plutella) species (Plutella) and Spiritis sinensis (Plutella) and Spirilis (Spirilis) of the family, Spiritis sinensis (Sporica) and Sporica) species (Sporina) of the family Gracilaria) and Gracilaria (Plutella) of the family Gray moth (Plutella) species (Plutella) and Gracilaria) of the family, Plutella variety (Plutella) of the family, Plutella) and Gracilaria (Plumbum variety (Plutella) of the family, Plumbus (Plumbum variety (Plumbum frugium) and Plumbum variety (Plumbum, Plumbum variety (Plumbum) including the family, Plumbum variety (Plumbum species (Plumbum) including Plumbum variety (Plumbum) including the family, Plumbum species (Plumbum variety (Plumbum) including the family, Plumbum variety (Plumbum species (Plumbum variety (Plumbum) including the family, Plumbum species (Plumbum variety (Plumbum) including the family, Plumbum species (Plumbum) including the family, Plumbum species (Plumbum) such as, Plumbum species (Plumbum) including the family, Plumbum variety (Plumbum ) including the family, Plumbum variety (Plumbum, Plumbum species (Plumbum, Plumbum variety (Plumbum, Plumbum species (Plumbum, the species Darna diducta, Diaphania sp (Diaphania spp.) (stem borer)), borer sp (diaphraea spp.) (stem borer)), borer (diaphraea saccharalis) (sungar borer), southwestern corn stalk (diaphraea grandiosella) (southwester cornborer), diamond-back seed (eared leaf borer), diamond-back seed (eared leaf spot.) (cotton bollworm), diamond-back (earia insulata) (egg yellow diamond-back borm), diamond-back diamond-worm (ear diamond-back) (egg diamond-back diamond), diamond-back (ear diamond-back) of (ear diamond-back) (egg white moth), diamond-back (egg), south phaea larva (stem borer), stem borer (yellow leaf borer), yellow meadow (yellow meadow), yellow meadow (stem borer, yellow borer), yellow meadow (stem borer), yellow borer (yellow borer) (egg borer) (yellow borer) (egg white borer) (egg borer) (yellow borer), yellow borer) (yellow borer), yellow borer (yellow borer) (yellow borer), yellow borer (yellow leaf) (yellow borer), yellow leaf borer (yellow leaf borer), yellow leaf borer) (yellow leaf borer (yellow leaf) (yellow leaf borer), yellow leaf borer (yellow leaf borer), yellow leaf borer (yellow leaf borer), yellow leaf borer (yellow leaf borer), yellow leaf) (yellow leaf borer), yellow leaf borer (yellow leaf borer), brown leaf borer), yellow leaf borer (yellow leaf borer), brown leaf borer (yellow leaf borer), brown leaf borer) (yellow leaf borer), brown leaf borer (yellow leaf borer), brown leaf borer) (yellow leaf borer), banana skipper (eriionota thrax) (banana skipper), glossy privet (eupoiecia ambiguella) (grape berry moth)), primitive root cutting insect (Euxoa auxiliaris) (armyworm), cutworm species (felia spp.) (rhizopus dicus), hornworm species (Gortyna spp.) (stem borer), oriental fruit moth (grapholitha molesta) (peach (apricot) fruit borer (oriental fruit moth)), trilobata (hedylea heloca) indica (bean leaf borer (bean leaf webber)), cyan worm species (woodworm spp.) (cabbage moth), cotton bollworm (Helicoverpa armigera) (corn borer), cotton bollworm (cabbage moth) (cabbage moth)) and cabbage moth (cabbage moth) (cabbage moth) larva (cabbage moth), cotton bollworm (cabbage moth) (corn borer), cotton bollworm (cabbage moth) (cabbage moth) and cotton moth (cabbage moth) (corn borer) species), cotton bollworm (cabbage moth) (corn borer (cabbage moth) species (cabbage moth) and corn borer (cabbage moth) (corn borer) moth (cabbage moth) species (cabbage moth) moth (cabbage moth), cotton moth (cabbage moth) moth (cabbage moth) species (cabbage moth) moth (cabbage moth) moth (cabbage moth) moth, cotton moth (cabbage moth) moth (moth) moth (cabbage moth) moth (moth) or moth) moth (moth) or moth (moth) moth (cabbage moth (moth) or corn borer) moth (moth) moth (cabbage moth (moth) variety, cotton leaf moth (cabbage moth) or corn borer) variety, cotton leaf moth (moth) or corn borer (moth) or moth (moth) variety, cotton leaf moth (moth) or corn borer) variety, cotton leaf moth (moth) variety (moth) or corn borer) variety (moth) or corn borer (moth) variety (moth) or corn borer (moth) or (moth) or corn borer) or (moth) or corn borer (moth) variety (moth) or moth (moth) or corn moth) or moth (corn borer) or moth (moth) or corn moth (moth) or (moth) variety (moth) or (moth) or corn borer (moth) or (corn borer (moth) or corn borer (moth) or (corn borer) or corn borer (corn borer) or (moth) or corn borer (moth) or (moth) or rice, corn borer) or rice, white-fin eggplant borer (Leucinodes orbornalis) (eggplantfront borre), spiderworm moth (Leuciptera malifoliella), fine moth species (Lithocolletis spp.), grape leaf roller moth (Lobesia borna) (grape fruit moth), Loxagra gruotis species (Loxagrutissp.) (Spodoptera frugiperda), soybean-line root cutting insect (Loxagrus albicans) (western bean fruit moth), gypsy moth (Lymantria dispar) (gypsy moth), peach leaf roller (Lyonetherella), apple leaf roller (apple leaf moth (apple leaf miner)), oil palm moth (Mahasa coreticum) (tomato leaf moth), cabbage (cabbage), cabbage (Mallotus leaf borer), cabbage moth (apple leaf borer) (cabbage caterpillar), cabbage caterpillar (apple leaf borer), cabbage (cabbage caterpillar), cabbage caterpillar (cabbage caterpillar), cabbage caterpillar (cabbage caterpillar) leaf borer (cabbage caterpillar), cabbage caterpillar (cabbage caterpillar, moth (cabbage caterpillar, moth) moth (cabbage caterpillar, rice stem borer, moth (cabbage caterpillar, moth (cabbage caterpillar, moth, cabbage caterpillar, moth, cabbage caterpillar, moth, cabbage caterpillar, moth, cabbage caterpillar, rice stem borer, moth, rice stem borer, moth, rice stem borer, moth, rice, moth, rice stem borer, moth, rice, moth, rice stem borer, moth, rice, moth, rice, moth, rice stem borer, rice stem borer, rice stem, rice, European corn borer (Ostrinia nubilalis) (European corn borer)), Oxydia vesulia, Ostrinia (Pandemiscarana) (common grape leaf moth (common currant torrex)), Spodoptera frugiperda (Pandemia hepes) (brown apple torrex), Pneumoniella africana (Papilio demoduloca), Spodoptera litura (Pectinophora grandiflora) (red bell bollworm (pink bollworm)), Spodoptera species (Peridroma spp.) (root cutting insect), Philobium japonicum (Peridroma saucia) (variegated cutworm), Spodoptera coffea (Perileria lutea), Plutella xylostella (Plumbum xylostella), Plumbum xylostella (Plumbum xylostella) (white moth (Plumbum xylostella), Plumbum xylostella (Plumbum xylostella) (Pimenta) (Plumbum xylostella), Plumbum xylostella (Plumbum xylostella) and Plumbum xylostella (Plumbum xylostella) A), Grape berry moth (polychrosia viteana) (grapple berry sport), citrus fruit moth (Prays endocarps), olive moth (prasys oleae) (olive sport), armyworm species (pseudoglenia spp.) (noctuid), pseudoglenoid unicata (marchantia virescens), soybean looper (pseudoglena includens) (soybe looper), inchworm (rachidia nu), Chilo suppressalis (Chilo supressalis), tryporyza incertulas (Scophhaga incertulas), stem borer (Sesamia spp.) (moth), rice stem borer (Sesamia infusoriana snellensis) (pink rice stem borer), pink stem borer (sempervirula, Sesamia brownia punctifera) (Spodoptera), southern Spodoptera (Spodoptera), Spodoptera terreus (Spodoptera), Spodoptera litura (Spodoptera) (Spodoptera), Spodoptera (Spodoptera (Spodoptera) and Spodoptera (Spodoptera) are used as Spodoptera fructialis, the Spodoptera fructinatura (Spodoptera) as the Spodoptera, Spodoptera, Spodoptera (Spodoptera) for preventing rice stem borer, Spodoptera (Spodoptera) and Spodoptera) including Spodoptera, Spodoptera (Spodoptera) including Spodoptera, Spodoptera (Spodoptera) including Spodoptera (Spodoptera) and Spodoptera (Spodoptera) including Spodoptera (Spodoptera) including Spodoptera) and Spodoptera (Spodoptera) including Spodoptera (Spodoptera) including Spodoptera (Spodoptera including Spodoptera) including Spodoptera (Spodoptera) including Spodoptera (Spodoptera) including Spodoptera (Spodoptera) including Spodoptera (Spodoptera) including Spodoptera (Spodoptera including, The species Heliothis virescens (Synanthon spp.) (root borer), Therla basilides, Thermia gemmatalis, Chlamydia armyworms (Teneola bisseliella) (webbingclotheshes moth), Trichoplusia ni (cab looper), Tomatomyza sativa (Tutsassolutita), Phlebia nidulans (Yonomeuta spp.), Cochlothuria coffea arabica (Zeuzearocoffea) (red branchborer), Zeuzera pyrina (Leopard moth (Leopboard moth)), and Spodoptera litura (Fabricius)).

Mallophaga ((Mallophaga) feather louse (chewing lice)): ovine feather louse (Bovicola ovis) (sheet biting louse), turkey short horn feather louse (chicken feather louse), and chicken feather louse (Menopon gallina) (common henhouse).

Orthoptera (Orthoptera) (grasshopper, locust and cricket): arana nigra (anacrus simplex) (Mormon grass-hopper (Mormon cricket)), mole cricket (Gryllotalpidae) (mole cricket)), eastern asia migratory locust (Locusta migratoria), grasshopper species (Melanoplus spp.) (grasshopper), acephala wing spurs (microcentrumretrierve) (angular wing grasshopper), pterophora species (Pterophylla spp.) (grasshopper), steleophaga egr, chianus furcifera (scuddermatus furcatata) (fork tailed bush tree (fork tailed bushy didid)), and tuberous ridge (vanilloida).

Phthiraptera (Phthiraptera) (sucking lice): the blood sucking lice species (haemattopinus spp.) (cattle and pig lice), sheep jaw lice (sheep lice), head lice (pedigree capitis) (body lice), human body lice (pedigree humanus (body lice) and crab lice (crab lice)).

Siphonaptera (daphnaptera) (fleas): ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea) and human flea (Pulex irutans) (human flea).

Thysanoptera (thrips): frankliniella fusca (Frankliniella fusca) (tobaco third), Frankliniella occidentalis (western flower) Frankliniella hultrias (western flower), Frankliniella shultzii (Frankliniella williamsii) (corn Thrips), Frankliniella glasshouse Thrips (IIelothrips hamoralidis) (greenhous third), Riphisprothrips cruentus, Scirpus sp (Sciroththrips spp), Platycodon grandiflorum (Scirthricirris) (citrus trough), Frankliniella tabacum (Scirthrips spp), Talothriparia (yellow Thrips spp), and Throughthrips (Thripus spp).

Thysanoptera (Thysanura) (bristletail): chlamydomonas species (Lepisma spp.) (silverfish) and locusta species (Thermobia spp.) (locusta spp.).

From the order of Acarina (Acarina) (mites (mite) and cicadas (tick)): woodbee scutellariae (acarapis woodi) (parasitic mites in the trachea of bees), dermatophagoides (Acarus spp.) (food mites), Acarus macrorhynchophylla (Acarus srorona) (grain mite), mango bud mite (Aceria mangifera) (mango bud mite), acanthophyrus sp. (Acarus spp.), acanthophysalis scabrosoides (acanthophyceae), acanthophysalis lycopersici (acanthophysalis septemporosa) (tomato bud mite), acanthophysalis pelekasi, acanthophysalis citri (acanthophysalis peekatsi) (acanthophysalis peeka), acanthophysalis dermalis (acanthophysalis spindalii) (apple gall mite (decapili mite), american tick (acanthophysalis tick (mangifer sporus sp.), Chinese tick (amygdalus persicum), short tick (mangiferous tick (mangifer), or mangiferous tick (mangifer sp.), or mangiferous tick (mangiferous tick) and mangiferous tick (mangiferous tick) species), mangiferous tick (mangiferous tick) and mangiferous tick (mange sp.) including mangiferous tick (mange variety), mange sp.) including mange variety), mange variety (mange variety), mange variety (mange variety), mange variety (mange variety), mange variety (mange variety), mange variety (mange variety), mange variety (mange variety), mange variety (mange variety), mange variety of mange variety (mange variety), mange variety (mange variety), mange variety (mange variety) and mange variety (mange variety), mange variety (mange variety of mange variety (mange variety), mange variety of mange variety (mange variety), mange variety (mange variety), mange variety (mange variety of mange variety (mange variety), mange variety (mange variety), mange variety of mange variety (mange variety of, House dust mite (Dermatophagoides pteronyssinus) (house dust mite), Tetranychus sp (Eotetranus spp.), hornbeam Tetranychus carpesii (Eotetranthus carpini (yellow spider mite), Tetranychus sp.), Gephyrus sp (Epithromyces sp.), Gephylus sp (Eriophenous spp.), hard tick sp (I.D.; es sp.), ticks (tick), Tetranychus sp (Notederus sp.), Microphyrus sp.), Microphycus sp. sp.Ohiophagus (Ochrophycus sp.), Tetranychus sp (Notoednes. cati), Microphycus sp (Oligonychus sp.), Calonychus (Ocynidae) coffee, Tetranychus parvus (Ocigo nuciferus), Tetranychus wintergreen (Oligonychus (Ochrotus) and Tetranychus (Ochrotus sp.), Tetranychus (Tetranychus urticae (Tetranychus), Tetranychus urticae (Tetranychus urticae) (Tetranychus sp.), Tetranychus urticae (Tetranychus), Tetranychus (Tetranychus) and Tetranychus (Tetranychus) or Tetranychus (Tetranychus) or Tetrasticus (Tetrasticus) or (Tetrasticus) or Tetrasticus (Tetrasticus) or Tetrasticus (Tetrasticus) or Tetrasticus (Tetrasticus) or (Tetrasticus) or Tetrasticus (Tetrasticus) or Tetrasticus (Tetrasticus) or Tetrasticus (Tetrasticus) or Tetrasticus (Tetrasticus) or Tetrasticus (Tetrasticus) or Tetrasticus (Tetrasticus) or Tetrasticus, Rhizomorpha species (rhizomorph spp.) (root mite (bulb mite)), Sarcoptes scabies (Sarcoptes scabies) (itch mite), coronaria avocado (tetragonophys perseafarae), Tetranychus species (Tetranychus spp.), Tetranychus urticae (Tetranychus urticae) (twospoked spider mite)) and Varroa destructor (Varroa destructor) (honey bee mite).

Nematoda (nematodes): the species Aphelenchoides (Aphelenchoides spp.) (bud and leaf and pine wood nematodes (bud and leaf & pine wood nematodes)), the species nematodiasis (Belonolaevis spp.) (sting nematodes), the species Cyclotella minor (Criconella spp.) (ring nematodes), the species Dirofilaria immitis (dog heartword), the species Ditylenchus spp. (stem and bulb nematodes), the species Trichophythora (Heterodera spp.) (Cytospora spp.), the species Heterocladia (Heterocladia zeyla) (maize nematodide), the species Melilodinia spp. (Hichlamyella spp.) (Neurospora spp.) (Melilotus spp.)), the species Heterocladospora spp. (Melilotus spp.)), the species Melilotus spp.) (Melilotus spp.)), the species (Melilotus spp.) (Melilotus, Melilotus spp.) (Melilotus spp.)) and Melilotus spp.) (Melilotus spp.)) and Melilotus spp.) (Melilotus, Melilotus spp.) (Melilotus, Melilotus spp.) (Melilotus, Melilotus spp.) (Melilotus spp.)) and Melilotus, Melilotus spp.) (Melilotus spp.)) and Melilotus spp.) (Melilo, The species of the genus Rapholus (Rapholus spp.) (Burrowing nematode) and the species of the Leptochloa (Rotylenchus reniformis) (kidney-shaped nematode).

General class (general classes of insects): white pine worm (Scutigerella immaculata).

Owing to their positive properties, the compounds of the formula (I) can be used advantageously for protecting crops, domestic animals and livestock animals of agricultural and horticultural importance, as well as the environment customary for humans, against pests and/or mites.

The amount of the compound of formula (I) to be used to obtain the desired effect will vary depending on various factors such as the compound used, the crop to be protected, the type of pest, the extent of infection, the climatic conditions, the method of application and the dosage form employed.

The ingredients of the dosage forms or compositions described herein are selected in accordance with the physical properties of the active ingredient, the mode of application and environmental factors such as soil type, moisture and temperature.

Useful dosage forms include solutions such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspensions), and the like, which may optionally be viscous jellies. Useful dosage forms also include solids such as powders, granules, tablets, pills, films, and the like, which may be water dispersible ("wettable") or water soluble. The effective components can be microencapsulated and made into suspension or solid dosage form; in addition, the whole dosage form of the effective components can be encapsulated. The capsule can control or delay the release of the effective components. Sprayable formulations can be diluted in a suitable medium using spray volumes of about one to several hundred liters per hectare. The compositions in high concentrations are mainly used as intermediates for further processing.

Typical solid Diluents are described in Watkins et al, Handbook of insulation Dual ingredients and Cariers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solventsguide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers annular, Allured pub. Corp., Ridgewood, New Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended applications. All formulations may contain small amounts of additives to reduce foaming, coalescence, corrosion, microbial growth, etc., or thickeners to increase viscosity.

Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, sulfonated dialkyl succinates, alkyl sulfates, alkyl benzene sulfonates, organosilanes, N, N-dialkyl taurates, lignosulfonates, aldehyde condensates for naphthalenesulfonates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starches, sugars, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate, liquid diluents include, for example, water, N-dimethylformamide, dimethylsulfone, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, olive oil, castor oil, linseed oil, tung oil, sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and cocoa oil, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, dodecanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the components. Powders and fines can be prepared by mixing and typically by grinding in a hammer mill or liquid energy mill, typically by wet milling; see, for example, U.S. Pat. No. 3060,084, granules and pellets are prepared by spraying the active substance onto freshly prepared granular carriers or by granulation techniques. See Browning, "Aggloration," Chemical Engineering, Decumber 4, 1967, pp147-48, Perry's Chemical Engineering's Handbook, 4TH Ed., McGraw-Hill, New York, 1963, Pages 8-57and following, and WO 91/13546. The preparation of pellets is described in U.S.4172714, water dispersible and water soluble granules are described in U.S.4144050, U.S.3920442 and DE 3246493 to prepare tablets as described in US 5180587, U.S.5232701 and U.S. 5208030. Films may be prepared by the methods described in GB2095558 and u.s.3299566.

For more information on processing see U.S.3,235,361, col.6, line 16through chol.7, line 19and Examples 10-41; U.S. Pat. No. 3,309,192, Col.5, line 43through Col.7, line 62and EXAMPLES 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 140, 162, 164, 166, 167and 169-182; U.S.2,891,855, col.3, line 66through col.5, line 17and Examples 1-4; klingman, Weed Control as a Science, John Wiley and Sons, inc., New York 1961, pp 81-96; and Hance et al, Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

Herein, for certain applications of the composition, for example in agriculture, one, two or more other bactericides, acaricides, herbicides, plant growth regulators or fertilizers and the like may be added to the insecticidal and/or acaricidal composition of the invention, whereby additional advantages and effects may be produced.

Advantageous effects

The compound of formula (I) shows good activity to various pests and mites in agriculture or other fields. Furthermore, these compounds can be used for the preparation of insecticides and/or acaricides because of their excellent control effect at very low doses.

Definition and description of terms

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 the claimed subject matter belongs. All patents, patent applications, and publications cited herein are incorporated by reference in their entirety unless otherwise indicated. If there are multiple definitions of terms herein, the definition in this section controls.

It is understood that reference may be made to (including Carey and Sundberg "ADVANCED ORGANIC CHEMISTRY 4)^THED. "Vols.A (2000) and B (2001), Plenum Press, New York). Unless otherwise indicated, conventional methods within the skill of the art are employed, such as mass spectrometry, NMR, IR and UV/Vis spectroscopy, and pharmacological methods. Unless a specific definition is set forth, the terms used herein in the pertinent description of analytical chemistry, organic synthetic chemistry, and pharmaceutical chemistry are known in the art. Standard techniques can be used in chemical synthesis, chemical analysis, pharmaceutical preparation, formulation and delivery, and treatment of patients. For example, the reaction and purification can be carried out using the manufacturer's instructions for use of the kit, or in a manner known in the art or as described herein. The techniques and methods described above can generally be practiced according to conventional methods well known in the art, as described in various general and more specific documents referred to and discussed in this specification. In the present specification, groups and substituents thereof may be selected by one skilled in the art to provide stable moieties and compounds. When a substituent is described by a general formula written from left to right, the substituent also includes chemically equivalent substituents obtained when a formula is written from right to left, as long as it complies with the valence rules. For example, CH₂O is equivalent to OCH₂The substitution position may be bonded with an oxygen atom or a carbon atom of a methylene group.

The term "pharmaceutically acceptable salt" as used herein refers to salts that retain the biological effectiveness of the free acid and free base of the specified compound and that are not biologically or otherwise undesirable. Filing of the present applicationThe compound also includes pharmaceutically acceptable salts, such as nitrate, hydrochloride, sulfate, phosphate, acetate, trifluoroacetate, malate or citrate, which can be generally used in the field of agriculture and horticulture. Pharmaceutically acceptable salts refer to the form in which the base group in the parent compound is converted to a salt. Pharmaceutically acceptable salts include, but are not limited to, inorganic or organic acid salts of basic groups such as amine (amino) groups. Pharmaceutically acceptable salts of the present application can be synthesized from the parent compound by reacting a basic group in the parent compound with 1-4 equivalents of an acid in a solvent system. Suitable salts are listed in Remingtong's Pharmaceutical sciences, 17^thed., Mack Publishing Company, Easton, Pa.,1985, p.1418 and Journal of Pharmaceutical Science,66,2(1977), for example the hydrochloride salt.

"stereoisomers" as used herein refers to isomers resulting from the different arrangement of atoms in a molecule in space. The compounds of formula (I) contain asymmetric or chiral centers and, therefore, exist in different stereoisomeric forms. All stereostructures and mixtures of formula (I) are as such, including racemic mixtures, as part of the present application. Diastereomeric mixtures can be separated into the individual diastereomers, based on their different physicochemical properties, by well-known means, e.g., resolution of the enantiomers can be converted into the diastereomers by reaction with a suitable optically active substance (e.g., a chiral alcohol or Mosher's moylchloride), which can be separated and converted (e.g., hydrolyzed) into the corresponding individual isomers. Some of the compounds of formula (I) may be atropisomers (e.g., substituted aryl) are also part of this application. Enantiomers can also be separated using a chiral chromatography column. The compounds of formula (I) may exist in different tautomeric forms, which forms are included within the scope of the present application. For example, keto-enol and imine-enamine forms of the compounds.

The term "C_1-6Alkyl "denotes a straight or branched chain saturated hydrocarbon group having 1,2, 3, 4,5 or 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and,Isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, and the like, or isomers thereof.

The term "C_3-6Cycloalkyl "is understood to mean a saturated monocyclic hydrocarbon ring having 3, 4,5, or 6 carbon atoms. For example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

The term "haloalkyl" refers to a straight-chain, branched-chain alkyl group substituted with one or more halogen substituents. Preferably C₁-C₆Haloalkyl being a straight-chain, or branched, C substituted by one or more halogens, e.g. 1,2, 3, 4,5 halogens₁-C₆An alkyl group.

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

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

The following chromatographic conditions were used for the LC-MS detection analysis in the examples below:

a chromatographic column: agilent ZORBAX SB-C18150 mm X4.6 mm, 5 μm (i.d);

detection wavelength: 254 nm; flow rate: 0.8 mL/min; column temperature: 30 ℃;

gradient elution conditions:

time (min)	Methanol (%)	0.1 aqueous formic acid solution (% by volume)
			0.00	50	50
5.00	50	50
			15.00	90	10
20.00	90	10
			25.00	90	10

Synthetic examples

Example 1: preparation of N- (cyanomethyl) -N-cyclopropyl-4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzamide (Compound 1)

The first step of reaction: preparation of methyl (Z) -4- ((oxime) methyl) -2-methylbenzoate: 26.70g (0.15mol) of methyl 4-formyl-2-methylbenzoate, 12.53g (0.18mol) of hydroxylamine hydrochloride and 18.45g (0.225mol) of sodium acetate were dissolved in this order in a mixed solution of 75ml of water and 300ml of ethanol at room temperature. The reaction solution was stirred for 6 hours. The reaction mixture was concentrated, diluted with ethyl acetate and aqueous sodium hydroxide (2M) and the phases separated. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. And (5) carrying out suction filtration and drying to obtain 25.76g of a product with the yield of 89%.

LC-MS[M+H]⁺＝194.08、[M+Na]⁺＝216.06、[M+K]⁺＝232.03。

The second step of reaction: preparation of 1, 3-dichloro-5- (3,3, 3-trifluoroprop-1-en-2-yl) benzene: 5.72g (0.03mol) of 3, 5-dichlorophenylboronic acid, 10.35g (0.075mol) of potassium carbonate, 0.53g (0.00075mol) of bis (triphenylphosphine) palladium chloride and 120ml of toluene are placed in a three-necked flask at room temperature under nitrogen and stirred. To the above mixture was added 7.87g (0.045mol) of 2-bromo-3, 3, 3-trifluoroprop-1-ene in portions. After the addition, the reaction was stirred at 80 ℃ for 9 hours. The reaction solution was cooled to room temperature, and 75ml of water was added to the reaction solution. And (4) phase separation. The aqueous layer was extracted with toluene (2 x 45ml) and the organic phases were combined. Washing with saturated salt water. Dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure and column chromatography was carried out (eluent: ethyl acetate: petroleum ether (1: 8)) to give 5.13g of a product with a yield of 71%.

LC-MS[M+H]⁺＝240.98、[M+Na]⁺＝262.96、[M+K]⁺＝278.93。

The third step of reaction: preparation of methyl 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoate: 5.79g (0.03mol) of methyl (Z) -4- ((oxime) methyl) -2-methylbenzoate, 6.68g (0.05mol) of N-chlorosuccinimide and 55ml of N, N-dimethylformamide were added to a three-necked flask at room temperature, and the reaction was stirred at 40 ℃ for 2.5 hours. The reaction solution was cooled to room temperature, and a solution of 6.03g (0.025mol) of 1, 3-dichloro-5- (3,3, 3-trifluoroprop-1-en-2-yl) benzene and 5.05g (0.05mol) of triethylamine in 30ml of N, N-dimethylformamide was added to the mixture, followed by stirring at room temperature for 20 hours. The reaction mixture was diluted with water and ethyl acetate and the phases separated. The organic phase was washed twice with water and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine and dried over anhydrous sodium sulfate. Filtering, and concentrating the filtrate under reduced pressure. Column chromatography of the residue (eluent: ethyl acetate: petroleum ether (1: 6)) gave 4.05g of product in 36% yield.

LC-MS[M+H]⁺＝432.04、[M+Na]⁺＝454.02、[M+K]⁺＝469.99。

The fourth step of reaction: preparation of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid: 3.24g (0.0075mol) of methyl 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoate are added at room temperature to 15ml of 2N aqueous sodium hydroxide solution and diluted with 15ml of tetrahydrofuran. The reaction mixture was stirred for 2 hours and the pH adjusted to 2 with 1M dilute hydrochloric acid. And (4) carrying out suction filtration, washing a filter cake with water, and drying to obtain 2.91g of a product with the yield of 93%.

LC-MS[M+H]⁺＝418.02、[M+Na]⁺＝440、[M+K]⁺＝455.97。

The fifth step of reaction: preparation of 2- (cyclopropylamino) acetonitrile: 1.71g (0.03mol) of cyclopropylammonia, 3.0g (0.025mol) of bromoacetonitrile and 20ml of acetonitrile were charged into a three-necked flask at room temperature, and the reaction was stirred at 60 ℃ for 7.5 hours. The reaction solution was desolventized under reduced pressure. To the residue was added 60ml of water, extracted with ethyl acetate (3 × 20ml) and the organic phases combined. Washing with saturated salt water. Dried over anhydrous magnesium sulfate. The organic phase is decompressed and the solvent is removed to obtain 2.20g of the product with the yield of 92 percent.

The sixth reaction step: preparation of N- (cyanomethyl) -N-cyclopropyl-4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzamide: 1.67g (0.004mol) of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid, 1.03g (0.008mol) of di (isopropyl) ethylamine and 2.29g (0.0044mol) of benzotriazol-1-yl hexafluorophosphate, oxytripyrrolidinylphosphine were dissolved in this order in 30ml of dichloromethane at 0 ℃. The reaction mixture was stirred for 2 hours. To the above solution was added 0.46g (0.0048mol) of 2- (cyclopropylamino) acetonitrile at room temperature. Stirring was continued at room temperature for 15 hours. 20ml of water was added to the reaction system and the phases were separated. The aqueous phase was extracted twice with dichloromethane. The organic phases were combined, washed with saturated brine and dried over anhydrous magnesium sulfate. The organic phase is decompressed and desolventized, and column chromatography is carried out (eluent: ethyl acetate: petroleum ether (1: 4)) to obtain 1.31g of product with 66 percent of yield.

LC-MS[M+H]⁺＝496.08、[M+Na]⁺＝518.06、[M+K]⁺＝534.03。

¹H-NMR (400MHz, solvent CDCl₃)δ(ppm):7.86(1H,s),7.62(2H,d),7.54(2H,d),7.28(1H,d),4.47(2H,s),4.11(1H,d),3.71(1H,d),2.73(1H,s),2.35(3H,s),0.61(4H,d)。

Example 2: preparation of N- (cyanomethyl) -4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -N- (2, 2-difluoroethyl) -2-methylbenzamide (Compound 5)

The first step of reaction: preparation of 2- ((2, 2-difluoroethyl) amino) acetonitrile: 2.43g (0.03mol) of 2, 2-difluoroethylamine, 3.0g (0.025mol) of bromoacetonitrile and 20ml of acetonitrile were put into a three-necked flask at room temperature, and the reaction was stirred at 60 ℃ for 8 hours. The reaction solution was desolventized under reduced pressure. To the residue was added 60ml of water, extracted with ethyl acetate (3 × 20ml) and the organic phases combined. Washing with saturated salt water. Dried over anhydrous magnesium sulfate. The organic phase is decompressed and the solvent is removed to obtain 2.46g of product with 82 percent of yield.

The second step of reaction: preparation of N- (cyanomethyl) - -4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -N- (2, 2-difluoroethyl) -2-methylbenzamide: 1.67g (0.004mol) of 4- (5- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid, 1.03g (0.008mol) of di (isopropyl) ethylamine and 2.29g (0.0044mol) of benzotriazol-1-yl hexafluorophosphate, oxytripyrrolidinylphosphine were dissolved in this order in 30ml of dichloromethane at 0 ℃. The reaction mixture was stirred for 2 hours. To the above solution was added 0.58g (0.0048mol) of 2- ((2, 2-difluoroethyl) amino) acetonitrile at room temperature. Stirring was continued at room temperature for 12 hours. 20ml of water was added to the reaction system and the phases were separated. The aqueous phase was extracted twice with dichloromethane. The organic phases were combined, washed with saturated brine and dried over anhydrous magnesium sulfate. The organic phase is decompressed and desolventized, and the product is obtained by column chromatography (eluent: ethyl acetate: petroleum ether (1: 3)) with the yield of 78 percent, 1.62 g.

LC-MS[M+H]⁺＝520.06、[M+Na]⁺＝542.04、[M+K]⁺＝558.01。

¹H-NMR (400MHz, solvent CDCl₃)δ(ppm):7.86(1H,s),7.62(2H,d),7.54(2H,d),7.28(1H,d),5.72(1H,t),4.56(2H,s),4.11(1H,d),3.71(1H,d),3.48(2H,d),2.36(3H,s)。

Example 3: preparation of N- (cyanomethyl) -N-cyclopropyl-4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzamide (Compound 13)

LC-MS[M+H]⁺＝194.08、[M+Na]⁺＝216.06、[M+K]⁺＝232.03。

The second step of reaction: preparation of 1, 3-dichloro-2-fluoro-5- (3,3, 3-trifluoroprop-1-en-2-yl) benzene: 6.27g (0.03mol) of 3, 5-dichloro-4-fluorobenzeneboronic acid, 10.35g (0.075mol) of potassium carbonate, 0.53g (0.00075mol) of bis (triphenylphosphine) palladium chloride and 120ml of toluene are stirred at room temperature under nitrogen in a three-necked flask. To the above mixture was added 7.87g (0.045mol) of 2-bromo-3, 3, 3-trifluoroprop-1-ene in portions. After the addition, the reaction was stirred at 80 ℃ for 9 hours. The reaction solution was cooled to room temperature, and 75ml of water was added to the reaction solution. And (6) phase separation. The aqueous layer was extracted with toluene (2 x 45ml) and the organic phases were combined. Washing with saturated salt water. Dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure and column chromatography was carried out (eluent: ethyl acetate: petroleum ether (1: 8)) to give 5.28g of product in 68% yield.

LC-MS[M+H]⁺＝258.97、[M+Na]⁺＝280.95、[M+K]⁺＝296.92。

The third step of reaction: preparation of methyl 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoate: 5.79g (0.03mol) of methyl (Z) -4- ((oxime) methyl) -2-methylbenzoate, 6.68g (0.05mol) of N-chlorosuccinimide and 55ml of N, N-dimethylformamide were added to a three-necked flask at room temperature, and the reaction was stirred at 40 ℃ for 2.5 hours. The reaction solution was cooled to room temperature, and a solution of 6.60g (0.025mol) of 1, 3-dichloro-2-fluoro-5- (3,3, 3-trifluoroprop-1-en-2-yl) benzene and 5.05g (0.05mol) of triethylamine in 30ml of N, N-dimethylformamide was added to the mixture, followed by stirring at room temperature for 20 hours. The reaction mixture was diluted with water and ethyl acetate and the phases separated. The organic phase was washed twice with water and the aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed with saturated brine and dried over anhydrous sodium sulfate. Filtering, and concentrating the filtrate under reduced pressure. Column chromatography of the residue (eluent: ethyl acetate: petroleum ether (1: 6)) gave 4.05g of product in 36% yield.

LC-MS[M+H]⁺＝450.03、[M+Na]⁺＝472.01、[M+K]⁺＝487.98。

And a fourth step of reaction: preparation of 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid: 3.38g (0.0075mol) of methyl 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoate are added at room temperature to 15ml of 2N aqueous sodium hydroxide solution and diluted with 15ml of tetrahydrofuran. The reaction mixture was stirred for 2 hours and the pH was adjusted to 2 with 1M dilute hydrochloric acid. And (4) carrying out suction filtration, washing a filter cake with water, and drying to obtain 2.93g of a product with the yield of 90%.

LC-MS[M+H]⁺＝436.02、[M+Na]⁺＝458、[M+K]⁺＝473.97。

The sixth reaction step: preparation of N- (cyanomethyl) -N-cyclopropyl-4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzamide: 1.75g (0.004mol) of 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid, 1.03g (0.008mol) of di (isopropyl) ethylamine and 2.29g (0.0044mol) of benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate are dissolved in succession in 30ml of dichloromethane at 0 ℃. The reaction mixture was stirred for 2 hours. To the above solution was added 0.46g (0.0048mol) of 2- (cyclopropylamino) acetonitrile at room temperature. Stirring was continued at room temperature for 12 hours. 20ml of water was added to the reaction system and the phases were separated. The aqueous phase was extracted twice with dichloromethane. The organic phases were combined, washed with saturated brine and dried over anhydrous magnesium sulfate. The organic phase is decompressed and desolventized, and the product is obtained by column chromatography (eluent: ethyl acetate: petroleum ether (1: 3)) with the yield of 76 percent of 1.56 g.

LC-MS[M+H]⁺＝514.07、[M+Na]⁺＝536.05、[M+K]⁺＝552.02。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.60(2H,d),7.54(2H,d),7.28(1H,d),4.47(2H,s),4.11(1H,d),3.71(1H,d),2.73(1H,s),2.35(3H,s),0.61(4H,d)。

Example 4: preparation of N- (cyanomethyl) -N- (cyclopropylmethyl) -4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzamide (Compound 15)

1.75g (0.004mol) of 4- (5- (3, 5-dichloro-4-fluorophenyl) -5- (trifluoromethyl) -4, 5-dihydroisoxazol-3-yl) -2-methylbenzoic acid, 1.03g (0.008mol) of di (isopropyl) ethylamine and 2.29g (0.0044mol) of benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate are dissolved in succession in 30ml of dichloromethane at 0 ℃. The reaction mixture was stirred for 2 hours. To the above solution was added 0.53g (0.0048mol) of 2- ((cyclopropylmethyl) amino) acetonitrile at room temperature. Stirring was continued at room temperature for 10 hours. 20ml of water was added to the reaction system and the phases were separated. The aqueous phase was extracted twice with dichloromethane. The organic phases were combined, washed with saturated brine and dried over anhydrous magnesium sulfate. The organic phase is decompressed and desolventized, and the product is obtained by column chromatography (eluent: ethyl acetate: petroleum ether (1: 3)) with the yield of 1.67g and 79 percent.

LC-MS[M+H]⁺＝528.09、[M+Na]⁺＝550.07、[M+K]⁺＝566.04。

¹H-NMR (400MHz, solvent CDCl)₃)δ(ppm):7.60(2H,d),7.54(2H,d),7.28(1H,d),4.47(2H,s),4.11(1H,d),3.71(1H,d),3.09(2H,d),2.35(3H,s),1.06(1H,t),0.32(4H,d)。

The present invention also synthesizes the following compounds by reference to the methods in the above examples:

TABLE 2

Formulation examples

In the following examples, all percentages are by weight and all dosage forms are prepared using conventional methods.

Example 5:

in this example, the compound obtained in the above example is used to prepare a wettable powder, which is specifically prepared by using the following raw material compositions in proportion:

150.0% of compound, 4.0% of dodecylphenol polyethoxy glycol ether, 6.0% of sodium lignosulfonate, 8.0% of sodium aluminosilicate and 32.0% of montmorillonite (calcined).

Example 6:

in this example, granules were prepared using the compounds obtained in the above examples, specifically using the following raw materials:

520.0% of compound, 2.0% of sodium dodecyl sulfate as other components, 6.0% of calcium lignosulfonate, 10.0% of potassium chloride, 1.0% of polydimethylsiloxane and soluble starch to be 100%.

Example 7:

in this example, the compound obtained in the above example is used to prepare an extruded pellet, specifically using the following raw material composition:

1330.0% of compound, 9.0% of anhydrous calcium sulfate, 4.0% of crude calcium lignosulfonate, 1.0% of sodium alkyl naphthalene sulfonate and 56.0% of calcium/magnesium bentonite.

Example 8:

in this example, the compound obtained in the above example is used to prepare emulsifiable concentrate, and specifically, the emulsifiable concentrate is prepared by using the following raw material compositions:

1425.0% of compound, 15060% of solvent, PEG 4005% of Rhodacal 70/B3% of Rhodameen RAM/77%.

Example 9:

in this example, the compound obtained in the above example is used to prepare an aqueous suspension, specifically, the following raw material composition is used to prepare the aqueous suspension:

1530.0%, POE polystyrene phenyl ether sulfate 5.0%, xanthan gum 0.5%, polyethylene glycol 5%, triethanolamine 1%, sorbitol 0.5% and water to 100.0%.

Biological activity assay

Example 10:

1. determination of insecticidal Activity

In this example, several insects were tested for insecticidal activity using the compounds prepared in the above examples.

And (3) testing the insecticidal activity: the test method is as follows, a test solution with a desired concentration is prepared by dissolving a test compound sample in a suitable solvent (the kind of solvent is acetone, methanol, DMSO, etc., and is selected according to its dissolving ability for the sample). The test unit is composed of a small open container filled with 12-15-day old radishes (suitable for plutella xylostella, Pieris brassicae, Spodoptera litura, striped flea beetle, armyworm and the like) or tillering stage rice (suitable for Chilo suppressalis, Cnaphalocrocis medinalis guenee, Frankliniella occidentalis and the like). The plants were pre-infested by placing 30-40 pests on a leaf of the test plant that was cut from a cultivated plant (leaf cutting method). As the leaves dehydrate, the pests move on the test plants. After pre-dip dyeing, the soil of the test cell was covered with a layer of sand.

The test method is as follows: the test was repeated three times, and after spraying the formulated test compound, each test unit was allowed to dry for 1 hour, and then a black mesh cap was placed on top. The test cells were kept in a growth chamber at 25 ℃ and 70% relative humidity for 6 days. The mortality rate (mortality) of the insects was then visually assessed for each test unit, the mortality rate being calculated as,

(1) test results for controlling frankliniella occidentalis by exemplary example Compounds

At a dose of 25ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 10ppm, the compounds with the fatality rate of more than 80 percent to frankliniella occidentalis have the following characteristics: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 1ppm, the compounds with the fatality rate of over 80 percent to frankliniella occidentalis have the following characteristics: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87.

(2) Test results for exemplary example Compounds against Plutella xylostella

At a dose of 10ppm, the compounds with a mortality rate of more than 80% to plutella xylostella are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 1ppm, the compounds with a mortality rate of more than 80% to plutella xylostella are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 0.1ppm, the compounds with the mortality rate of more than 80 percent on the plutella xylostella comprise: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87.

(3) Test results of the exemplary embodiment Compounds for controlling Pieris rapae

At a dose of 10ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 1ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 0.1ppm, the compounds with a fatality rate of more than 80% to pieris rapae are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87.

(4) Exemplary example Compounds control armyworm test results

At a dose of 10ppm, the compounds with a lethality rate of more than 80% to armyworm are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 1ppm, the compounds with a lethality rate of more than 80% to armyworm are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 0.1ppm, the compounds with a lethality of more than 80% to armyworm are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87.

(5) Exemplary example Compounds control Prodenia litura test results

At a dose of 10ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 1ppm, the compounds with a mortality rate of more than 80% to prodenia litura comprise: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 0.1ppm, the compounds with a mortality rate of more than 80% to prodenia litura have the following characteristics: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87.

(6) Test results for exemplary example Compounds to control Chilo suppressalis

At a dose of 10ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 1ppm, the compounds with the lethality rate of more than 80 percent to chilo suppressalis comprise: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at the dose of 0.1ppm, the compounds with the lethality rate of above 80% to chilo suppressalis are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87.

(7) Test results for the control of rice leaf rollers by exemplary example Compounds

At a dose of 10ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 1ppm, the compounds with the lethality rate of more than 80 percent to rice leaf roller comprise: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 0.1ppm, the compounds with a lethality rate of more than 80% to cnaphalocrocis medinalis are: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87.

(8) Test results for the control of phyllotreta striolata with exemplary example compounds

At a dose of 10ppm, the compounds with the fatality rate of more than 80 percent to phyllotreta striolata comprise: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

the compound with the fatality rate of over 80 percent to phyllotreta striolata at the dosage of 1ppm comprises the following components: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

the compounds with the fatality rate of over 80 percent to phyllotreta striolata at the dosage of 0.1ppm comprise: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87.

2. Acaricidal Activity assay

In this example, several mite-killing activity tests were carried out using the compounds prepared in the above examples.

The test method is as follows: dissolving a compound sample to be detected with a suitable solvent (the kind of the solvent is acetone, methanol, DMSO, etc., and is selected according to the dissolving capacity of the solvent on the sample), and preparing the solution to be detected with the required concentration. The double-sided adhesive tape is cut into 2-3 cm long pieces, the pieces are attached to one end of a microscope slide, paper pieces on the adhesive tape are removed by tweezers, female adult mites which are consistent in size, bright in body color and lively in action are selected by a zero-number brush pen, the backs of the female adult mites are adhered to the double-sided adhesive tape (paying attention to the fact that the female adult mites do not stick to the mite feet, the mite beards and a mouth tool), 4 lines of the double-sided adhesive tape are adhered to each piece, and 10 heads of the double-sided adhesive tape are adhered to each line.

The test method is as follows: the test was repeated three times, and after 4 hours in a biochemical incubator at a temperature of (25+1) ° c and a relative humidity of about 85%, the dead or inactive individuals were removed by binocular observation. Soaking one end of the glass sheet with the mites into the liquid medicine, slightly shaking for 5s, taking out, and quickly sucking off the mites and the redundant liquid medicine around the mites with absorbent paper. And (4) placing the mites in the biochemical incubator, checking the result by using binoculars after 24 hours, slightly touching the mite bodies by using a writing brush, taking the mites with sufficient immobility as death, and calculating the mortality. The mortality rate was calculated as follows:

the following results were obtained for the Tetranychus cinnabarinus part:

at a dose of 25ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 10ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87;

at a dose of 1ppm, the compounds with the lethality rate of more than 80 percent to tetranychus cinnabarinus have the following components: 1. 2,3, 4,5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 26, 31, 32, 33, 34, 35,36, 37, 38, 39, 40, 41, 42, 43, 44, 49, 50, 51, 55, 59, 61, 67, 68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 82, 83, 84, 85, 86, 87.

3. Test results for exemplary example compounds and control agents

This example performs a comparative test of the activity of an exemplary compound of the examples versus a control agent (Compound CK)₁Compound CK being number 5-008 in patent document US7951828₂Number 6-007 in patent document WO2005085216, prepared according to literature reported methods). The test results are shown in table 3 below.

TABLE 3

In addition to the compounds listed in the above table, other exemplary compounds of the present invention have better control activity against pests and mites than the control agents. Therefore, the compound shown as the formula (I) shows good activity to various pests and mites in the agricultural field.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A compound shown in a formula (I), a stereoisomer, a racemate, a tautomer, a nitrogen oxide or a pharmaceutically acceptable salt thereof,

wherein, the first and the second end of the pipe are connected with each other,

m is selected from 1,2 or 3;

R₁selected from hydrogen, C₁-C₆Alkyl or C₃-C₆A cycloalkyl group;

n is selected from 0, 1,2, 3, 4 or 5;

2. The compound of claim 1, wherein, in formula (I),

m is selected from 2 or 3;

R₁selected from hydrogen, C₁-C₃Alkyl or cyclopropyl;

n is selected from 0, 1,2 or 3;

3. The compound of claim 1, wherein, in formula (I),

m is selected from 2 or 3;

R₁selected from hydrogen, methyl or ethyl;

n is selected from 0, 1 or 2;

4. The compound of claim 1, wherein, in formula (I),

m is selected from 2 or 3;

when n is 1, R₁Is hydrogen, methyl or ethyl; when n is 2, R₁Is H;

n is 0, 1 or 2;

5. A compound according to any one of claims 1 to 4, wherein the compound of formula (I) is selected from the group consisting of,

6. a process for the preparation of a compound according to any one of claims 1 to 5, comprising the following step A) or step B):

step B):

x, R therein₁、R₂M, n have the definitions as defined in any one of claims 1 to 5; l is selected from a leaving group, such as Cl, Br, I or F.

7. A pesticidal composition, such as an insecticidal and/or acaricidal composition, characterized in that it comprises, as an active ingredient, one, two or more of the compounds of formula (I) according to any one of claims 1 to 5, stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof.

8. Use of one, two or more of the compounds of formula (I), their stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof according to any one of claims 1 to 5 as pesticides, such as insecticides and/or acaricides.

9. Use of one, two or more of the compounds of formula (I), their stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof as claimed in any one of claims 1 to 5 for the preparation of a pesticide, e.g. an insecticide and/or an acaricide.

10. A method for controlling pests and/or mites, which comprises applying an effective amount of one, two or more of the compounds of formula (I), its stereoisomers, racemates, tautomers, nitroxides or pharmaceutically acceptable salts thereof as described in any one of claims 1 to 5, or applying a composition as described in claim 7 to a growth medium for pests and/or mites.