Pyridazin compounds and pest control methods using these compounds.

Abstract

The invention proposes a pyridazin compound represented by formula (I) and a method for preparing this compound. This compound has very good activity against harmful insects and harmful mites in agriculture or other fields. In addition, these compounds can achieve very good control at very low doses, so they can be used to prepare insecticides and / or acaricides.

Description

Pyridazine compounds and their preparation methods and uses

[0001] This application claims priority from the following prior application: Patent application number 202311336414.7, filed with the State Intellectual Property Office of China on October 16, 2023, entitled “Pyridazine compounds, preparation methods and uses thereof.” The entire text of that application is incorporated herein by reference. Technical Field

[0002] The present invention belongs to the technical field of insecticides and acaricides, and particularly relates to pyridazine compounds and preparation methods and uses thereof. Background Art

[0003] Pesticides play a vital role in increasing agricultural production and addressing food security. With increasing demands for the safety and environmental impact of chemical substances, there is a growing desire for safer pest control agents. Furthermore, due to the long-term use of pesticides such as insecticides and acaricides, pests have gradually developed resistance to these agents, resulting in unsatisfactory pest control results. Therefore, the development of pest control agents with superior safety, control effectiveness, and residual effects is a future trend.

[0004] Patent document WO2010034737 discloses the following general formula compound and pyridazine compound CK1:

[0005] Patent document CN 103492378 A discloses the following general formula compound and pyridazine compound CK2:

[0006] However, the biological activity of the above compounds still needs to be further improved. In order to find insecticides and acaricides with better performance, the inventors conducted in-depth research.

[0007] Summary of the Invention

[0008] To improve the above problems, the present invention provides a compound represented by the following formula (I), its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof:

[0009] wherein R1 is selected from C1-C6 alkyl, halogenated C1-C4 alkyl, C3-C6 cycloalkyl or halogenated C3-C6 cycloalkyl;

[0010] R2 is selected from C1-C4 alkyl;

[0011] R3 is selected from H or C1-C4 alkyl;

[0012] R4 is selected from C1-C4 alkyl;

[0013] R5 is selected from C3-C6 cycloalkyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C2 alkyl, halogenated C3-C6 cycloalkylC1-C2 alkyl or C3-C6 epoxyalkylC1-C2 alkyl;

[0014] A is selected from CH or N;

[0015] X is selected from O or S.

[0016] According to an embodiment of the present invention: In formula (I),

[0017] R1 is selected from C2-C6 alkyl, halogenated C1-C4 alkyl, C3-C6 cycloalkyl or halogenated C3-C6 cycloalkyl;

[0018] R2 is selected from C1-C4 alkyl;

[0019] R3 is selected from H or C1-C4 alkyl;

[0020] R4 is selected from methyl or ethyl;

[0021] R5 is selected from C3-C6 cycloalkyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C2 alkyl, halogenated C3-C6 cycloalkylC1-C2 alkyl or C3-C6 epoxyalkylC1-C2 alkyl;

[0022] A is selected from N or CH;

[0023] X is selected from O or S.

[0024] According to an embodiment of the present invention: In formula (I),

[0025] R1 is selected from C2-C3 alkyl, halogenated C1-C3 alkyl, C3-C6 cycloalkyl or halogenated C3-C6 cycloalkyl;

[0026] R2 is selected from C1-C3 alkyl;

[0027] R3 is selected from H or methyl;

[0028] R4 is selected from methyl or ethyl;

[0029] R5 is selected from C3-C6 cycloalkyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C2 alkyl, halogenated C3-C6 cycloalkylC1-C2 alkyl or C3-C6 epoxyalkylC1-C2 alkyl;

[0030] A is selected from N or CH;

[0031] X is selected from O or S.

[0032] According to an embodiment of the present invention, the halogenated C3-C6 cycloalkyl group is the following group substituted by one, two or three F, Cl or Br: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

[0033] According to an embodiment of the present invention, the halogenated C3-C6 cycloalkyl C1-C2 alkyl group is the following group substituted by one, two or three F, Cl or Br:

[0034] As an example, the halogenated C3-C6 cycloalkyl C1-C2 alkyl group is selected from the following:

[0035] According to an embodiment of the present invention: In formula (I),

[0036] R1 is selected from ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, one, two or more fluorine or chlorine substituted groups: methyl, ethyl, n-propyl, isopropyl, cyclopropyl or cyclobutyl;

[0037] R2 is selected from methyl, ethyl or propyl;

[0038] R3 is selected from H or methyl;

[0039] R4 is selected from methyl or ethyl;

[0040] R5 is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,

[0041] A is selected from N or CH;

[0042] X is selected from O or S.

[0043] According to some embodiments of the present invention, formula (I) is selected from the structure shown in formula (IA):

[0044] wherein A, X, R4, and R5 have the same definitions as above.

[0045] According to an embodiment of the present invention, in Formula IA, A is selected from N or CH;

[0046] X is selected from O or S;

[0047] R4 is selected from methyl or ethyl;

[0048] R5 is selected from

[0049] As an example, the compound of formula (I) is selected from the following compounds,

[0050] Among the substituents listed above, Indicates the connection site.

[0051] The present invention also provides a method for preparing the compound represented by the above formula (I), which, when X is O, comprises the following step A) or step B):

[0052] Step A): a compound of formula (II) and a compound of formula (III) undergo condensation reaction to obtain a compound of formula (I);

[0053] Step B):

[0054] B1) reacting the compound of formula (II) with a halogenating agent to obtain a compound of formula (II-1);

[0055] B2) reacting the compound of formula (II-1) with the compound of formula (III) to obtain the compound of formula (I);

[0056] wherein R1, R2, R3, R4, R5, and A have the definitions given above; and L is selected from a leaving group, such as Cl, Br, I, or F.

[0057] According to an embodiment of the present invention, the reaction in step A) can be carried out in the presence of a condensing agent, such as at least one selected from N,N′-dicyclohexylcarbodiimide (DCC), N,N′-diisopropylcarbodiimide (DIC), 1-hydroxybenzotriazole (HOBT), 2-(7-azabenzotriazole)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (HATU), and benzotriazol-1-yl-oxytripyrrolidinophosphine hexafluorophosphate (PyBOP);

[0058] According to an embodiment of the present invention, the reaction in step A) can be carried out in the presence of a base, which can be an inorganic base, for example, at least one selected from pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP), and diisopropylethylamine (DIEA);

[0059] According to an embodiment of the present invention, the reaction in step A) is carried out in a solvent, and the solvent is, for example, at least one selected from N,N-dimethylacetamide, N,N-dimethylformamide, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, acetonitrile, toluene, dichloromethane, and 1,2-dichloroethane;

[0060] According to an embodiment of the present invention, the reaction temperature in step A) can be -5 to 120°C, for example, 0 to 50°C, such as 15 to 50°C.

[0061] According to an embodiment of the present invention, the halogenating agent in step B1) is, for example, selected from thionyl chloride, oxalyl chloride or thionyl chloride;

[0062] According to an embodiment of the present invention, the temperature of the reaction in step B1) may be 0-100°C, for example 0-50°C, such as 0-30°C;

[0063] According to an embodiment of the present invention, the reaction in step B2) can be carried out in the presence of a base, which can be selected from an organic base or an inorganic base, such as one, two or more of pyridine, triethylamine, 4-(dimethylamino)pyridine (DMAP), diisopropylethylamine (DIEA), sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide or sodium hydride. Preferred solvents include N,N-dimethylacetamide, N,N-dimethylformamide, dioxane, toluene, dichloromethane, and 1,2-dichloroethane.

[0064] According to an embodiment of the present invention, the reaction temperature in step B2) can be 0-120°C, for example 0-50°C, such as 15-30°C.

[0065] According to the present invention, the compound represented by formula (I) can also be prepared by reacting the compound represented by (I-1) with the compound represented by (IV).

[0066] wherein R1, R2, R3, R4, R5, X, and A have the same definitions as above; and L' is selected from a leaving group, such as Cl, Br, I, or F.

[0067] The reaction can be carried out in the presence of a base, which can be an organic base or an inorganic base, for example, at least one selected from potassium tert-butoxide, sodium tert-butoxide, sodium hydride, cesium carbonate, 4-(dimethylamino)pyridine (DMAP), and diisopropylethylamine (DIEA);

[0068] According to an embodiment of the present invention, the reaction in step A) is carried out in a solvent, and the solvent is, for example, at least one selected from N,N-dimethylacetamide, N,N-dimethylformamide, 2-methyltetrahydrofuran, dioxane, acetonitrile, and toluene;

[0069] According to an embodiment of the present invention, the reaction temperature in step A) can be -5 to 120°C, for example, 20 to 80°C.

[0070] According to the present invention, when X in the compound represented by formula (I) is S, it can be obtained by reacting a carbonyl compound represented by formula (I) in which X is O with 2,4-bis(p-methoxyphenyl)-1,3-disulfide-2,4-diphosphatane-2,4-sulfide (Lawesson's reagent).

[0071] wherein R1, R2, R3, R4, R5, and A have the same definitions as above.

[0072] According to the present invention, the compound of formula (I) can exist in the following three isomeric forms, so the isomers described in this application include but are not limited to the following three forms:

[0073] wherein R1, R2, R3, R4, R5, X, and A have the same definitions as above.

[0074] According to an embodiment of the present invention, compounds II and III can be purchased as commercial products or can be prepared by methods known in the literature, for example, they can be prepared by referring to the methods described in patent documents WO2005040169, WO2008074824 or Journal of Fluorine Chemistry 132(11), page 995 (2011).

[0075] The preparation of the compounds of formula (I) and their starting materials herein can be selected according to the reaction conditions and starting materials that are suitable in each case, and it is possible, for example, to replace only one substituent with another substituent according to the invention in a single step, or to replace multiple substituents with other substituents according to the invention in the same reaction step.

[0076] If the respective compounds are not accessible via the routes described above, they can be prepared by derivatization of other compounds or by routine variations of the synthetic routes described.

[0077] 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 aluminum oxide or silica gel.

[0078] Pharmaceutically acceptable salts of the compounds of formula (I) of the present invention can be prepared by known methods. For example, acid addition salts of the compounds of formula (I) can be obtained by treatment with a suitable acid. The preparation method is as follows: the compound of formula (I) is reacted 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, ether, or toluene to conveniently obtain a pharmaceutically acceptable salt of the compound of formula (I).

[0079] The above preparation method can obtain an isomer mixture of the compound of formula (I). If pure isomers are required, they can be separated by conventional methods such as crystallization or chromatography.

[0080] Unless otherwise stated, all of the above reactions are conveniently carried out at atmospheric pressure or at the inherent pressure of the particular reaction.

[0081] The present invention also provides a pesticide composition, such as an insecticidal and / or acaricidal composition, comprising as an active ingredient one, two or more of the compound represented by formula (I), its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof.

[0082] According to an embodiment of the present invention, the weight percentage of the active ingredient in the composition is 0.1-99.9%, for example, 0.5-99%.

[0083] According to an embodiment of the present invention, the composition further comprises one, two or more agriculturally and / or forestry- and / or hygienically acceptable carriers.

[0084] According to an embodiment of the present invention, the composition may be administered in the form of a formulation.

[0085] For example, the compound represented by formula (I) is dissolved or dispersed in a carrier as an active ingredient or formulated into a preparation so as to be more easily dispersed when used as an insecticide and / or acaricide.

[0086] According to an embodiment of the present invention, the preparation includes but is not limited to the following forms: wettable powder, oil suspension, water suspension, aqueous emulsion, aqueous solution, emulsifiable concentrate or microcapsule, etc.

[0087] According to an embodiment of the invention, a liquid or solid carrier, and optionally a surfactant, may also be added to the composition.

[0088] The present invention also provides the use of one, two or more of the compound represented by formula (I), its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof as pesticides, such as insecticides and / or acaricides.

[0089] The present invention also provides the use of one, two or more of the compound represented by formula (I), its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof in the preparation of pesticides, such as insecticides and / or acaricides.

[0090] The present invention also provides a method for controlling pests and / or mites, comprising applying an effective amount of one, two or more of the compound represented by formula (I), its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts, or the composition to a growth medium of the pests and / or mites.

[0091] According to an embodiment of the present invention, the effective amount is 10 to 1000 grams per hectare, preferably the effective amount is 20 to 500 grams per hectare.

[0092] Due to their good plant tolerance, favorable homeothermic toxicity, and good environmental compatibility, the active substances according to the invention or the active substances to be used according to the invention are suitable for protecting plants and plant organs, increasing harvest yields, improving the quality of harvested products, and controlling animal pests, particularly pests and mites occurring in agriculture, horticulture, animal husbandry, forestry, gardens, leisure facilities, warehouse pest control, material protection, and the sanitary sector. They can preferably be used as plant protection compositions. They are active against conventional sensitive and resistant species and against all or individual developmental stages. These pests and mites include, but are not limited to:

[0093] From the phylum Arthropoda, in particular from the class Arachnida, for example, Acarus spp., Aceriasheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia graminum, Bryobia praetiosa, Centruroides spp., Chorioptes spp.), Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp., Metatetranychus spp.), Neutrombicula autumnalis, Nuphersa spp., Oligonychus spp., Ornithodorus spp., Ornithonyssus spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp.), Scorpiomaurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., Tetranychus spp., Trombicula alfreddugesi, Vaejovis spp., and Vasates lycopersici;

[0094] Coleoptera (Beetles): Acanthoscelides spp. (Weevils), Acanthoscelides obtectus (Common Pea Weevil), Agrilus planipennis (Willow Ash Borer), Agriotes spp. (Wireworms), Anoplophora glabripennis (Asian Longhorn Beetle), Anthonomus spp. (Curculidae), Anthonomus grandis (Cotton Bollworm), Aphidius spp., Apion spp. (Weevils), Apogonia spp. (Grubs), Atacnius sprctulus (Black Velvet Beetle), Atomaria linearis (pygmy mangold beetle), Aulacophore spp., Bothynoderes punctiventris (beetroot weevil), Bruchus spp. (weevils), Bruchus pisorum (pea weevil), Cacoesia spp., Callosobruchus maculatus (southern cowpea weevil), Carpophilus hemipteras (dried fruit beetle), Cassida vittata, Ccrostcrna spp., Ccrotoma spp. (chrysomcides), Cerotoma trifur cata (bean leaf beetle), Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis (cabbage seedpod weevil), Ceutorhynchus napi (cabbage curculio), Chaetocnema spp. (trichomoniasis), Colaspis spp.(earth beetle), Conoderus scalaris, Conoderus stigmosus, Conotrachelus nenuphar (Plum cone weevil), Cotinus nitidis (Green June beetle), Crioceris asparagi (Cypress beetle), Cryptolestes ferrugincus (Rusty grain beetle), Cryptolestes pusillus (Grain beetle), Cryptolestes turcicus (Turkish grain beetle), Ctenicera spp. (Nematodes), Curculio spp. (Weevils), Cyclocephala spp. (Grubs), Cylindrocpturus adspersus (sunflower stem weevil), Deporaus marginatus (mango leaf-cutting weevil), Dermestes lardarius (ham stem weevil), Dermestes maculates (white-bellied stem weevil), Diabrotica spp. (leaf beetles), Epilachna varivcstis (Mexican bean beetle), Raustinus cubae (stem borer), Hylobius pales (pales weevil), Hypera spp. (weevils), Hypera postica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil), Hypothenemus hampei) (coffee berry beetle), Ips spp.) (engravers), Lasioderma serricorne (tobacco beetle), Leptinotarsa ​​decemlinea ta (Colorado potato beetle), Liogenys fuscus, Liogenys suturalis, Lissorhoptrus oryzophilus (rice water weevil), Lyctus spp. (powder post beetles), Maecolaspis joliveti, Megascelis spp., Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle), Melolontha melolontha (common European beetle), Oberea brevis, Oberea linearis), Oryctes rhinoceros (date palm beetle), Oryzaephilus mercator (merchant grain beetle), Oryzaephilus surinamensis (sawtooth grain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cerealleaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp. (May / June beetles), Phyllophaga cuyabana, Phyllotreta spp.) (Trichomonas), Phynchites spp.), Popillia japonica (Japanese beetle), Prostephanus truncates (larger grain borer), Rhizopertha dominica (lesser grain borer), Rhizotrogus spp. (Eurpoean chafer), Rhynchophorus spp. (weevils), Scolytus spp. (wood moths), Shenophorus spp. (grain weevils), Sitona lincatus (pea leaf weevil), Sitophilus spp. (grain weevils), Sitophilus granaries (granary weevil), Sitophilus oryzae (rice weevil) weevil), Stegobium paniceum (drugstore beetle), Tribolium spp. (face weevil), Tribolium castaneum (red flour beetle), Tribolium confusum (confused flour beetle), Trogoderma variabile (warehouse beetle), and Zabrus tenebioides.

[0095] Dermaptcra (earwigs).

[0096] Dictyoptera (cockroaches): Blattella germanica (German cockroach), Blatta orientalis (Oriental cockroach), Parcoblatta pennylvanica, Periplaneta americana (American cockroach), Periplaneta australoasiae (Australian cockroach), Periplaneta brunnca (brown cockroach), Periplaneta fuliginosa (smoky brown cockroach), Pyncoselus suninamensis (Surinam cockroach), and Supella longipalpa) (brownbanded cockroach).

[0097] Diptera (Flies): Aedes spp. (Mosquitoes), Agromyza frontella (alfalfa blotch leafminer), Agromyza spp. (leafminers), Anastrepha spp. (fruit flies), Anastrepha suspensa (Caribbean fruit fly), Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies), Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (orange fruit fly), Ceratitis spp. (fruit flies), Ceratitis capitata (Mediterranean fruit fly), Chrysops spp. spp. (deer flies), Cochliomyia spp. (bloom fly larvae), Contarinia spp. (mosquitoes), Culex spp. (mosquitoes), Dasineura spp. (mosquitoes), Dasineura brassicae (cabbage midges), Delia spp., Delia pla tura (seed corn maggots), Drosophila spp. (vinegar flies), Fannia spp. (house flies), Fannia canicularis (little house fly), Fannia scalaris (gray-bellied toilet fly), Gasterophilus intestinalis (horse stomach fly), Gracillia perseae, Haematobia irritans (horn fly), Hylemyia spp. (root maggot), Hypoderma lineatum (common cattle grub), Liriomyza spp.) (leaf miner), Liriomyza brassica (serpentin eleafminer), Melophagus ovinus (sheep tick), Musca spp. (muscid fly), Muscaa utumnalis (face fly), Vusca domestica (house fly), Oestrusovis (sheep bot fly), Oscinella frit (Swedish straw fly), Pegomyia betae (beetle afminer), Phorbia spp., Psila rosae (carrot rust fly), Rhagoletis cerasi (cherry fruit fly), Rhagoletis spp. (apple fruit fly), pomonella (apple maggot), Sitodiplosism osellana (orange wheat blossom midge), stom oxyscalcitruns (stable fly), Tahanus spp. (horse flies), and Tipula spp. (crane flies).

[0098] Hemiptera (Stink Bugs): Acrosternum hilare (Green Stink Bug), Blissus leucopterus (Chinch Bug), Calocoris norvegicus (Potato Mirid), Cimex hemipterus (Tropical Bed Bug), Cimex lectularius (Bed Hug), Daghertus fasciatus, Dichelops furcatus, Dysdercus suturellus (Cotton Stainer), Edessa meditabunda, Eurygaster maura (Cereal Bug), Euschistus heros, Euschistus servus) (brown stink bug), Helopeltis antonii, Helopeltis theivora (tea blight plant bug), Lagynotomus spp. (stink bugs), Leptocorisa oratorius, Leptocorisa varicornis, Lygus spp. (plant bugs), Lygushesperus (western tarnished plant bug), Maconellicoccus hirsutus, Neurocolpus longirostris, Nezara viridula (southern green stink bug), PhyLocoris spp.) (lygus bug), Phytocoris californicus, Phytocoris relativus, Piezodorus guildingi, Poecilocapsus lineatus (fourlined plant bug), Psallus vaccinicola, Pseudacysta perseae, Scaptocoris castanea, and Triatoma spp. (bloodsucking conenose bugs / kissing bugs).

[0099] Homoptera (Aphids, Scale, Whitefly, Leafhoppers): Acrythosiphonpisum (pea aphid), Adelges spp. (adelg ds), Aleurodes proletella (cabbage whitefly), Aleurodicus di sperses, Aleurothrixus flccosus (woolly whitefly), Aluacaspis spp., Amrasca bigutella bigutella, Aphrophora spp. (leafhopper), Aonidiella aurantii (California redscale), Aphis spp. (aphids), Aphis gossypii (cotton aphid). aphid), Aphis pomi (apple aphid), Aulacorthitm solani (foxglove aphid), Bemisia spp. (whitefly), Bemisia argentifolii, Bemisia tabaci (sweetpotato whitefly), Bemisia tabaci (Gennadius), Brachycolus noxius (Russian aphid), Brachycorynclia asparagi (asparagus aphid), Brevennia rehi, Brevicoryne brassicae (cabbage aphid), Ceroplastes spp. (scale), Ceroplastes rubens (red wax scale). scale), Chionaspis spp. (scale), Chrysomphalus spp. (scale), Coccus spp. (scale), Dysaphis plantaginea (rosy apple aphid), Empoasca spp.) (leafhopper), Eriosoma lanigerum (woolly apple aphid), Icerya purchasi (cottony cushion scale), Idioscopus nitidulus (mango leafhopper), Laodelphax striatellus (smaller brown planthopper), Lepidosaphes spp., Macrosiphum spp., Macrosiphum euphorbiae (potato aphid), Macrosiphum granarium (English grain aphid), Macrosiphum rosae (rose aphid), Macrosteles quadrilin eatus (aster leafhopper), Mahanarva frimbiolata, Metopolophium dirhodum (rose grain aphid), Midis longicornis, Myzus persicae (green peach aphid), Nephotettix spp. (leafhopper), Nephotettix cinctipes (green leafhopper), Nilaparvata lugens (brown planthopper), Parlatoria pergandii (chaff scale), Parlatoriaziziphi (ebony scale), Peregrinus maidis (corn delphacid), Philaenus spp. (spraying insects), Phylloxera vitifoliae (grape phylloxera), Physokermes piceae (spruce bud scale), Planococcus spp. (mealybugs), Pseud ococcus spp.) (mealy bug), Pscudococcus brcvipcs (pincapple mcaly bug), Quad raspidiotus perniciosus (San Jose scale), Rhapalosiphum spp. (aphids), Rhapalosiphum maida (corn leaf aphid), Rhapalosiphum padi (oatbird-cherry aphid), Saissetia spp. (scale), Saissetiaoleae (black scale), Schizaphis graminum (green bug), Sitobion avenge (British wheat aphid), Sogatella furcifera (white-backed planthopper), furcifera (white-backed planthopper), Therioaphis spp. (aphids), Toumeyella spp. (scale), Toxoptera spp. (aphids), Trialeurodes spp. (whiteflies), Trialeurodes vaporariorum (greenhouse whitefly), Trialeurodes abutiloneus (bandedwing whitefly), Unaspis spp. (scale), Unaspis yanonensis (arrowhead scale), and Zulia entreriana.

[0100] Hymenoptera (Ants, Wasps and Bees): Acromyrrmex spp., Athalia rosae, Atta spp. (leafcutting ants), Camponotus spp. (carpenter ants), Diprion spp. (saw flies), Formica spp. (ants), Iridomyrmex humilis (Argentine ants), Monomorium spp., Monomorium minumum (little black ant), Monomorium pharaonis (Pharaoh ant), Neodiprion spp. (saw flies), Pogonomyrmex humilis (Argentine ants), spp. (harvester ants), Polistes spp. (paper wasps), Solenopsis spp. (fire ants), Tapoinoma sessile (odorous house ants), Tetranomorium spp. (pavement ants), Vespula spp. (yellow jackets), and Xylocopa spp. (carpenter bees).

[0101] Isoptera (Termites): Coptotermes spp., Coptotermes curvignathus, Coptotermes frenchii, Coptotermes formosanus (Formosan subterranean termite), Cornitermes spp. (nasute termite), Cryptotermes spp. (drywood termite), Heterotermes spp. (desert subterranean termite), Heterotermes aureus, Kalotermes spp. (drywood termite), Incistitermes spp. (drywood termite), Macrotermes spp. spp. (fungus-growing termites), Marginitermes spp. (drywood termites), Microcerotermes spp. (harvester termites), Microtermes obesi, Procornitermes spp., Reticulitermes spp. (soil-dwelling termites), Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermes flavipes (Eastern soil-dwelling termites), Reticulitermes hageni, Reticulitermes hesperus (Western soil-dwelling termites), Reticulitermes santonensis, Reticulitermes speratus), Reticulitermes tibialis, Reticulitermes virginicus, Schedorhinotermes spp., and Zootermopsis spp. (wood-destroying termites).

[0102] Lepidoptera (Moths and Butterflies): Achoea janata, Adoxophyes spp., Adoxophyes orana, Agrotis spp. (cutworms), Agrotis ipsilon (black cutworm), Alabama argillacea (cottonleaf worm), Amorbia cuneana, Amyelosi transitella (navel orange worm), Anacamptodes defectaria, Anarsia lineatella (peach twig borer), Anomis sabulijera (jute looper), Anticarsia emmatalis (velvet bean caterpillar), Archips argyrospila (fruit tree leafroller), Archips rosana (rose leafroller), leafroller), Argyrotaenia spp. (tortricid moths), Argyrotaenia citrana (orange tortrix), Autographa gamma, Bonagota cranaodcs, Borbocinnara (rice leaffolder), Buccula trix thurberiella (cottonleaf perforator), Caloptilia spp. (leafminers), Capua reticulana, Carposina niponensis (peach fruit moth), Chilo spp., Chlumetia transversa (mango shoot borer), Choristoneura rosaceana (oblique-banded leaf roller), Chrysodeixis spp.), Cnaphalocerus medinalis (grass leafroller), Colias spp., Conpomorpha cramerella, Cossus cossus (wood moth), Crambus spp. (Sod webworms), Cydia funebrana (plum fruit moth), Cydia molesta (oriental fruit moth), Cydia nignicana (pea moth), Cydia pomonella (apple codling moth), Darna diducta, Diaphania spp. (stem borer), Diatraea spp. (stalk borer), Diatraea saccharalis (sugarcane borer), Diatraea graniosella (southwester cornborer), Earias spp. (cotton bollworm), Earias insulata (Egyptian bollworm), Earias vit.ella (rough northern bollworm), Ecdytopophaaurantianum, Elasmopalpus lignosellus (lesser cornstalk borer), Epiphysias postrutta na (light brown apple moth), Ephestia spp. (meal borer), Ephestia cautella (almond moth), Ephestia elutella) (tobbaco moth), Ephestia kuehniella (Mediterranean flour moth), Epimeces spp.), Epinotia aporema, Erionota thrax (banana skipper), Eupoecilia ambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltia spp. (cutworms), Gortyna spp. (stem borers), Grapholita molesta (oriental fruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp. (snoctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpazea (corn borer / cotton bollworm), Heliothis spp. (spotworm), Heliothis virescens (tobacco budworm), Hellula undalis (cabbage web worm), Indarbela spp. (root borer), Keiferia lycopersicella (tomato pinworm), Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella, Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp. (spotworm), Loxagrotis albicosta (western bean cutworm), cutworm), Lymantria dispar (gypsy moth), Lyonetia clerkella (apple leafminer), Mahasena corbetti (oil palm bagworm), Malacosoma spp.) (tent caterpillars), Mamestra brassicae (cabbage armyworm), Maruca testulalis (bean borer), Metisa plana (grassworm), Mythimna unipuncta (true armyworm), Neoleucinodes elegantalis (small tomato borer), Nym phulade punctalis (rice leafroller), Operophthera brumata (winter moth), Ostrinianubilalis (European corn borer), Oxydia vesulia, Pandemiscerasana (common grape leafroller), Pandemis heparana (brown apple tortrix), Papilio demodocus, Pectinophoragossypiella (pink bollworm), Peridroma spp. (cutworm), Peridroma saucia (variegated cutworm), Perileucopte ra coffeella (white coffee leafminer), Phthorimaea operculella (potato tuber moth), Phyllocnisitis citrella, Phyllonorycter spp.(Leafminer), Pieris rapae (Imported Cabbageworm), Plathypena scabra, Plodia interpunctella (Indian Meal Moth), Plutella xylostella (Diamondback Moth), Polychrosis viteana (Grape Berry Moth), Prays endocarps, Prsys oleae (Olive Moth), Pseudaletia spp. (Snow Moth), Pseudaletia unipunctata (Army Bug), Pseudoplusia includens (Soybean Looper), Rachiplusia nu (Groundworm), Chilo suppressalis (Striped Stem Borer), Scirpophaga incertulas (Striped Stem Borer), Sesamia spp. (Stalk Borer), spp. (stem borer), Sesamia inferens (pink rice stemborer), Sesamianona grioides, Setora nitens, Sitotroga cerealella (Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp. (armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugipcrda (fall armyworm), Spodoptera oridania (southern armyworm), Synanthedon spp.(root borer), Thecla basilides, Thermisia gemmatalis, Tineola bisselliella (webbingclothes moth), Trichoplusia ni (cabbage looper), Tutsabsoluta, Yponomeuta spp., Zeuzera coffeae (red branchborer), Zeuzera pyrina (pear leopard moth), and Spodoptera litura (Fabricius).

[0103] Mallophaga (Mallophaga chewing lice): Bovicola ovis (sheep biting louse), Menacanthus stramineus (chicken body louse), and Menopon gallinea (common hen house).

[0104] Orthoptera (grasshoppers, locusts and crickets): Anabrus simplex (Mormon cricket), Gryllotalpidae (mole cricket), Locusta migratoria, Melanoplus spp. (grasshoppers), Microcentrum retinerve (angular winged katydid), Pterophylla spp. (katydids), chistocerca gregaria, Scudderia furcata (fork-tailed bush katydid) and Valanga nigricorni.

[0105]

[00145] From the order Phthiraptera (sucking louse): Haematopinus spp. (cattle and pig lice), Linognathus ovillus (sheep louse), Pediculus humanus capitis (body louse), Pediculus humanus humanus (body louse), and Pthirus pubis (crab louse).

[0106] Siphonaptera (Fleas): Ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea), and Pulex irritans (human flea).

[0107] Thysanoptera (Thrips): Frankliniella fusca (tobacco thrip), Frankliniella occidentalis (western flower thrips), Frankliniella shultzei, Frankliniella williamsi (corn thrip), Ieliothrips haemorrhaidalis (greenhouse thrip), Riphiphorothrips cruentatus, Scirtothrips spp., Scirtothrips cirri (citrus thrip), Scirtothrips dorsalis (yellow tea thrips), Taeniothrips rhopalantennalis, and Thrips spp.

[0108] From the order Thysanura (bristletails): Lepisma spp. (silverfish) and Thermobia spp. (bristlefish).

[0109] Acarina (mites and ticks): Acarapsis woodi (tracheal mite of honeybee), Acarus spp. (food mite), Acarus siro (grain mite), Aceria mangiferae (mango bud mite), Aculops spp., Aculops lycopersici (tomato russetmite), Aculops pelekasi, Aculus pelekassi, Aculus schlechtendali (apple rust mite), Amblyomma amcricanum (lone star tick), Boophilus spp. (ticks), Brevipal pusobovatus (privet mite), Brevipalpus phoenicis (red and black flat mite), Demodex spp. (mange mites), Dermacentor spp. (hard ticks), Dermacentor variabilis (American dog tick), Dermatophagoides pteronyssinus (house dust mite), Eotetranycus spp., Eotetranychus carpini (yellow spider mite), Epitimerus spp., Eriophyes spp., Ixodes spp. (ticks), Metatetranycus spp. spp.), Notoedres cati, Oligonychus spp., Oligonychus coffee, Oligonychus ilicus (southernred mite), Panonychus spp.), Panonychus cirri (citrus red mite), Panonychus ulmi (European red mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemun latus (broad mite), Rhipicephalus sanguineus (brown dog tick), Rhizoglyphus spp. (bulb mite), Sarcoptes scabiei (itch mite), Tegolophus perseaflorae, Tetranychus spp., Tetranychus urticae (twospotted spider mite), mite)) and Varroa destructor (honey bee mite).

[0110] Nematodes (Nematodes): Aphelenchoides spp. (bud and leaf & pine wood nematodes), Belonolaimus spp. (sting nematodes), Criconemella spp. (ring nematodes), Dirofilaria immitis (dog heartworm), Ditylenchus spp. (stem and bulb nematodes), Heterodera spp. (cyst nematode), Heterodera zeae (corn cyst nematode), Hirschmanniella spp. (root nematodes), Hoplolaimus spp. (lance nematodes), Meloidogyne spp.) (root-knot nematode), Meloidogyne incognita (root-knot nematode), Onchocerca volvulus (hook-tail worm), PraLylenchus spp. (lesion nematode), Radopholus spp. (burrowing nematode), and Rotylenchus reniformis (kidney-shaped nematode).

[0111] Synecdoche (Insect Class): White pine borer (Scutigerella immaculata).

[0112] As an example, the pest is selected from green peach aphid, whitefly, scale insect, brown planthopper or tea green leafhopper.

[0113] As an example, the harmful mite is selected from Tetranychus cinnabarinus or Tetranychus urticae.

[0114] Due to their positive properties, the compounds of formula (I) can be used for protecting important agricultural and horticultural crops, domestic and breeding animals, and the environment frequented by humans from pests and / or acarids.

[0115] To obtain the desired effect, the amount of the compound of formula (I) to be used varies depending on various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infestation, climatic conditions, the method of application and the formulation employed.

[0116] The selection of ingredients for the dosage forms or compositions described herein should be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, moisture, and temperature.

[0117] Useful dosage forms include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspensions), etc., which may optionally be thickened into a jelly-like substance. Useful dosage forms also include solids such as dusts, powders, granules, tablets, pills, films, etc., which may be water-dispersible ("wettable") or water-soluble. The active ingredient can be microencapsulated and then made into a suspension or solid dosage form; in addition, the entire dosage form of the active ingredient can also be encapsulated. Encapsulation can control or delay the release of the active ingredient. Sprayable dosage forms can be diluted in an appropriate medium, and the spray volume used is about one hundred to several hundred liters per hectare. High-concentration compositions are mainly used as intermediates for further processing.

[0118] Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. Surfactants and recommended applications are listed in McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, and Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964. All formulations may contain small amounts of additives to reduce foaming, corrosion, microbial growth, etc., or thickeners to increase viscosity.

[0119] Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfonated succinates, alkyl sulfates, alkylbenzene sulfonates, organosilanes, N,N-dialkyl taurates, lignin sulfonates, condensates of naphthalene sulfonates with aldehydes, polycarboxylates and polyoxyethylene / polyoxypropylene block copolymers.

[0120] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silicon dioxide, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate, and liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfone, 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 butter, 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 tetrahydrofuranol.

[0121] Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and fine powders can be prepared by mixing and grinding, usually in a hammer mill or fluid energy mill. Suspensions are generally prepared by wet grinding; see, for example, U.S. Pat. No. 3,060,084. Granules and pellets are prepared by spraying the active substance onto a freshly prepared granular carrier or by granulation techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp. 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, Pages 8-57 and following, and WO 91 / 13546. Pellets are prepared as described in U.S. Pat. No. 4,172,714, and water-dispersible and water-soluble granules are prepared as described in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, and DE 3,246,493. Tablets can be prepared as described in US 5180587, US 5232701 and US 5208030. Films can be prepared by the methods described in GB 2095558 and US 3299566.

[0122] More information on processing can be found in U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19, and Examples 10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17, and 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.

[0123] Herein, for certain applications of the composition, for example, in agriculture, one, two or more other fungicides, insecticides and acaricides, herbicides, plant growth regulators or fertilizers may be added to the insecticidal and / or acaricidal composition of the present invention, thereby producing additional advantages and effects. Beneficial effects

[0124] The compounds of formula (I) described in the present invention exhibit excellent control activity against various insect pests and mites in agriculture and other fields. Furthermore, these compounds can achieve excellent control effects at very low dosages and are therefore useful in the preparation of insecticides and / or miticides.

[0125] Definitions and Explanations of Terms

[0126] Unless otherwise defined, all technical and scientific terms herein have the same meanings as commonly understood by persons skilled in the art to which the claimed subject matter belongs. Unless otherwise indicated, all patents, patent applications, and publications cited herein are incorporated by reference in their entirety. If multiple definitions of a term are used herein, the definitions in this section shall prevail.

[0127] It should be understood that references to the invention can be found in the literature including Carey and Sundberg "ADVANCED ORGANIC CHEMISTRY 4 THDefinitions of standard chemical terms can be found in Chemical Synthesis, Chemical Analysis, Pharmaceutical Preparation, Formulation and Delivery, and Treatment of Patients. For example, the manufacturer's instructions for use of the kits can be used, or reactions and the like can be performed in a manner known in the art or as described herein. Purification is performed. The above techniques and methods can generally be implemented according to conventional methods well known in the art, based on the descriptions in the multiple general and more specific literature cited and discussed in this specification. In this specification, groups and substituents thereof can be selected by those skilled in the art to provide stable structural parts and compounds. When substituents are described by conventional chemical formulas written from left to right, the substituents also include chemically equivalent substituents obtained when the structural formula is written from right to left, as long as they comply with the valence bond rules. For example, CH2O is equivalent to OCH2, and the substitution position can be connected with an oxygen atom or a methylene carbon atom.

[0128] The term "pharmaceutically acceptable salt" as used herein refers to a salt that retains the biological efficacy of the free acid and free base of the specified compound and has no adverse effects in biological or other aspects. The compounds of the present application also include pharmaceutically acceptable salts, such as nitrates, hydrochlorides, sulfates, phosphates, acetates, trifluoroacetates, malates or citrates, etc., which are generally used in the field of agriculture and horticulture. Pharmaceutically acceptable salts refer to the form in which the basic group in the parent compound is converted into a salt. Pharmaceutically acceptable salts include, but are not limited to, inorganic or organic acid salts of basic groups such as amine (amino) groups. The pharmaceutically acceptable salts of the present application can be synthesized from the parent compound, that is, the basic group in the parent compound is reacted with 1-4 equivalents of acid in a solvent system. Suitable salts are listed in Remington's Pharmaceutical Scicences, 17 th ed., Mack Publishing Company, Easton, Pa., 1985, p. 1418 and Journal of Pharmaceutical Science, 66, 2 (1977), for example the hydrochloride salt.

[0129] As used herein, "stereoisomer" refers to isomers resulting from differences in the spatial arrangement of atoms in a molecule. Compounds of formula (I) contain asymmetric or chiral centers and, therefore, exist in different stereoisomeric forms. All stereoisomeric structures of formula (I), as well as mixtures, including racemic mixtures, are intended to be part of the present application. Diastereomeric mixtures can be separated into individual diastereomers based on their differing physicochemical properties using well-known methods. For example, enantiomers can be resolved by reaction with an appropriate optically active substance (e.g., chiral alcohol or Mosher's acid chloride) to convert them into diastereomers, which are separated and converted (e.g., by hydrolysis) to the corresponding individual isomers. Some compounds of formula (I) may exist as atropisomers (e.g., substituted aryl groups) and are also intended to be part of the present application. Enantiomers can also be separated using chiral chromatographic columns. Compounds of formula (I) may exist in different tautomeric forms, and all such forms are intended to be included within the scope of the present application. For example, compounds in the keto-enol and imine-enamine forms are intended to be included within the scope of the present application. DETAILED DESCRIPTION

[0130] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope of protection that the present invention is intended to protect.

[0131] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0132] The following chromatographic conditions were used for LC-MS analysis in the following examples:

[0133] Chromatographic column: Agilent ZORBAX SB-C18 150 mm × 4.6 mm, 5 μm (id);

[0134] Detection wavelength: 254 nm; flow rate: 0.8 mL / min; column temperature: 30°C;

[0135] Gradient elution conditions:

[0136] Synthesis Example

[0137] Example 1: Preparation of N-(cyclopropylmethyl)-5-methyl-1-(3-methylbutan-2-yl)-N-(pyridazin-4-yl)-1H-pyrazole-4-carboxamide (Compound 1)

[0138] Step 1: Preparation of (3-methylbutan-2-ylidene)hydrazine: At room temperature, 8.61 g (0.10 mol) of 3-methyl-2-butanone, 50 ml of ethanol and 3.84 g (0.025 mol) of barium oxide were added to a flask, and 7.5 g (0.12 mol) of 80% hydrazine hydrate was added dropwise. After the addition was complete, the temperature was raised to 50°C for reaction. After the raw materials reacted completely, heating was stopped, the reaction solution was filtered, the filtrate was concentrated, ethyl acetate was added, the separated liquid was washed with water, and concentrated to obtain 9.5 g of the product.

[0139] GC-MS m / z = 100.10.

[0140] Second step reaction: Preparation of ethyl 2-((2-(-3-methylbutan-2-ylidene)hydrazino)methylene)-3-oxobutanoate: At room temperature, 9.5 g (0.05 mol) of ethyl 2-(ethoxymethylene)-3-oxobutanoate was added to a flask, and a solution of 6 g (0.06 mol) (3-methylbutan-2-ylidene)hydrazine and 60 ml of methyl tert-butyl ether was added dropwise. After the addition was complete, stirring was continued at room temperature. After the reaction ceased, the mixture was concentrated under reduced pressure to obtain 11.7 g of the product;

[0141] LC-MS[M+H] + =241.16, [M+Na] + =263.14, [M+K] + =279.11.

[0142] The third step reaction: Preparation of 5-methyl-1-(3-methylbutan-2-yl)-1H-pyrazole-4-carboxylic acid ethyl ester: 11.7g (0.0488mol) of 2-((2-(-3-methylbutan-2-ylidene)hydrazino)methylene)-3-oxobutanoic acid ethyl ester, 6.5g of acetic acid and 50ml of methanol were added to a flask at room temperature, 3.4g (0.054mol) of sodium cyanoborohydride was added under stirring, and the mixture was stirred at room temperature for 12h after the addition. The reaction solution was concentrated to remove methanol, 100ml of water was added to the concentrate, and then extracted three times with 50ml of ethyl acetate. The organic phases were combined, washed once with 50ml of water, and the organic phase was concentrated to obtain 10.3g of the product;

[0143] LC-MS[M+H] + =225.16, [M+Na] + =247.14, [M+K] + =263.11.

[0144] Step 4: Preparation of 5-methyl-1-(3-methylbutyl-2-yl)-1H-pyrazole-4-carboxylic acid: 10 g (0.045 mol) of ethyl 5-methyl-1-(3-methylbutyl-2-yl)-1H-pyrazole-4-carboxylate was added to 40 ml of 5N aqueous sodium hydroxide solution at room temperature, diluted with 20 ml of ethanol. The reaction mixture was stirred for 12 hours. After the raw materials reacted completely, the reaction solution was concentrated to remove ethanol. The residue was added to 50 ml of water and extracted once with 30 ml of ethyl acetate. The aqueous phase was adjusted to a pH of 3-4 with 2N hydrochloric acid, then extracted three times with 100 ml of ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and filtered and concentrated to obtain 8.6 g of the product.

[0145] LC-MS[M+H] + =197.13, [M+Na] + =219.11, [M+K] + =235.08.

[0146] Step 5: Preparation of 5-methyl-1-(3-methyl-2-butyl)-1H-pyrazole-4-carbonyl chloride: 1 g (0.005 mol) of 5-methyl-1-(3-methylbutyl-2-yl)-1H-pyrazole-4-carboxylic acid, 0.05 g of N,N-dimethylformamide, and 0.84 g (0.007 mol) of thionyl chloride were added sequentially to 10 ml of 1,2-dichloroethane at room temperature. The mixture was heated to 80°C and stirred for 2 hours. After the reaction, the solution was concentrated under reduced pressure at 40°C. 1.1 g of the product was obtained as a yellow oil.

[0147] Step 6: Preparation of 3,5-dichloro-N-cyclopropylmethylpyridazin-4-amine and 4,5-dichloro-N-cyclopropylmethylpyridazin-3-amine: Dissolve 18.5 g (0.1 mol) of 3,4,5-trichloropyridazine in a mixture of 21.4 g (0.3 mol) of cyclopropylmethylamine and 100 ml of ethyl acetate at room temperature. Heat to 40°C and stir for 3 hours. Dilute with ethyl acetate and aqueous solution, and separate the phases. Wash the organic layer with saturated brine and concentrate to yield 21 g of the product.

[0148] LC-MS[M+H] + =218.03, [M+Na] + =240.01, [M+K] + =255.98.

[0149] Step 7: Preparation of N-cyclopropylmethylpyridazin-4-amine: A mixture of 21 g (0.096 mol) of 3,5-dichloro-N-cyclopropylmethylpyridazin-4-amine and 4,5-dichloro-N-cyclopropylmethylpyridazin-3-amine was added to a pressure reactor containing 200 ml of ethanol. 1.5 g (0.001 mol) of 10% Pd / C was then added, and the pressure reactor was purged with nitrogen. The pressure reactor was pressurized to 0.02 MPa with hydrogen and heated to 35°C. After 5 hours, the reaction was complete. The reaction solution was filtered, and the filtrate was concentrated to remove the ethanol. The residue was made alkaline with saturated potassium carbonate solution and then extracted three times with 200 ml of dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated to yield 13.3 g of the product.

[0150] LC-MS[M+H] + =150.11, [M+Na] + =172.09, [M+K] + =188.06.

[0151] Step 8: Preparation of N-(cyclopropylmethyl)-5-methyl-1-(3-methylbutan-2-yl)-N-(pyridazin-4-yl)-1H-pyrazole-4-carboxamide: To a dichloroethane solution of 0.75 g (0.005 mol) of N-cyclopropylmethylpyridazin-4-amine and 0.76 g (0.0075 mol) of triethylamine was added dropwise 1.1 g (0.005 mol) of 5-methyl-1-(3-methyl-2-butyl)-1H-pyrazole-4-carbonyl chloride at 0° C. After stirring at room temperature for 24 h, the mixture was diluted with 100 ml of dichloroethane, washed with 3×50 ml of saturated saline solution, dried over magnesium sulfate and concentrated. The residue was purified by column chromatography (CH 2 Cl 2 / MeOH) to give 1.12 g of the product.

[0152] LC-MS[M+H] + =328.22, [M+Na] + =350.20, [M+K] + =366.17.

[0153] 1 H-NMR (400MHz, solvent CDCl3) δ (ppm): 9.06 (1H, s), 8.98 (1H, s), 7.27 (1H, d), 6.94 (1H, s), 3.84 (2H, d), 3.81 (1H, m),2.41(3H,s),1.41(3H,d),1.15(1H,m),0.98(3H,d),0.68(1H,m),0.61(3H,d),0.52(2H,d),0.23(2H,d).

[0154] Example 2: Preparation of N-((2-chlorocyclopropyl)methyl)-5-methyl-1-(3-methylbutan-2-yl)-N-(pyridazin-4-yl)-1H-pyrazole-4-carboxamide (Compound 9)

[0155] To a dichloroethane solution of 0.92 g (0.005 mol) of N-((2-chlorocyclopropyl)methyl)pyridazin-4-amine and 0.76 g (0.0075 mol) of triethylamine was added dropwise 1.1 g (0.005 mol) of 5-methyl-1-(3-methyl-2-butyl)-1H-pyrazole-4-carbonyl chloride at 0° C. After stirring at room temperature for 24 h, the mixture was diluted with 100 ml of dichloroethane, washed with 3×50 ml of saturated saline solution, dried over magnesium sulfate and concentrated. The residue was purified by column chromatography (CH 2 Cl 2 / MeOH) to give 1.18 g of the product.

[0156] LC-MS[M+H] + =362.18, [M+Na] + =384.16, [M+K] + =400.13.

[0157] 1 H-NMR (400MHz, solvent CDCl3) δ (ppm): 9.06 (1H, s), 8.98 (1H, s), 7.27 (1H, d), 6.94 (1H, s), 3.86 (2H, d), 3.81 (1H, m), 2. 58(1H,m),2.41(3H,s),1.79(1H,m),1.41(3H,d),1.15(1H,m),1.12(1H,d),0.98(3H,d),0.84(1H,d),0.61(3H,d).

[0158] The present invention also synthesized the following compounds with reference to the method in the above examples:

[0159] Table 1

[0160] Formulation Examples

[0161] In the following examples, all percentages are by weight and all dosage forms were prepared using conventional methods.

[0162] Example 3:

[0163] This example uses the compound obtained in the above example to prepare a wettable powder, specifically using the following raw material composition ratio for preparation:

[0164] Compound 1 50.0%, dodecylphenol polyethoxyglycol ether 4.0%, sodium lignin sulfonate 6.0%, sodium aluminosilicate 8.0%, montmorillonite (calcined) 32.0%.

[0165] Example 4:

[0166] In this example, the compound obtained in the above example was used to prepare granules, specifically using the following raw material composition ratios:

[0167] Compound 9 20.0%, other components are sodium lauryl sulfate 2.0%, calcium lignin sulfonate 6.0%, potassium chloride 10.0%, polydimethylsiloxane 1.0%, and soluble starch is used to make up to 100%.

[0168] Example 5:

[0169] In this embodiment, the compound obtained in the above embodiment is used to prepare extruded pellets, specifically using the following raw material composition ratio:

[0170] Compound 11 30.0%, anhydrous calcium sulfate 9.0%, crude calcium lignin sulfonate 4.0%, sodium alkylnaphthalene sulfonate 1.0%, calcium / magnesium bentonite 56.0%.

[0171] Example 6:

[0172] This example uses the compound obtained in the above example to prepare emulsifiable concentrate, specifically using the following raw material composition ratio for preparation:

[0173] Compound 12 25.0%, solvent 150 60%, PEG 400 5%, Rhodacal 70 / B 3%, Rhodameen RAM / 77%.

[0174] Example 7:

[0175] In this example, the compound obtained in the above example was used to prepare an aqueous suspension concentrate, specifically using the following raw material composition ratios for preparation:

[0176] Compound 13 30.0%, POE polystyrene phenyl ether sulfate 5.0%, xanthan gum 0.5%, polyethylene glycol 5%, triethanolamine 1%, sorbitol 0.5% and water to 100.0%.

[0177] Biological activity assay

[0178] Example 8:

[0179] 1. Determination of insecticidal activity

[0180] In this example, the compounds prepared in the above examples were used to carry out insecticidal activity tests on several insects.

[0181] Insecticidal Activity Assay: The test method is as follows: a sample of the test compound is dissolved in a suitable solvent (e.g., acetone, methanol, DMSO, etc., selected based on its solubility for the sample) to prepare a test solution of the desired concentration. The test unit consists of a small open container containing 12-15 day-old radish plants. The test plant is pre-infested by placing 30-40 insect pests on a leaf cut from the plant (cut leaf method). As the test plant leaves dehydrate, the pests migrate across the plant. After pre-infestation, the soil in the test unit is covered with a layer of sand.

[0182] The test method is as follows: The test is repeated three times. After spraying the test plants with the prepared test compound, each test unit is allowed to dry for 1 hour, and then a black mesh cover is placed on top of the small open container. The test unit is maintained in a growth chamber at 25°C and 70% relative humidity for 6 days. The insect mortality (lethality) of each test unit is then visually evaluated. The mortality rate is calculated as follows:

[0183] (1) Test results of exemplary compounds for controlling green peach aphids

[0184] At a dose of 100 ppm, the compounds with a mortality rate of more than 80% to green peach aphid are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 45, 48, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116;

[0185] At a dose of 20 ppm, the compounds with a mortality rate of more than 80% to green peach aphid are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116;

[0186] At a dosage of 5 ppm, the compounds with a mortality rate of more than 80% to peach aphid are: 1, 9, 10, 11, 12, 13, 21, 29, 30, 31, 32, 33, 50, 51, 54, 55, 56, 57, 58, 61, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 113, 114, and 116.

[0187] (2) Test results of exemplary compounds for controlling whiteflies

[0188] At a dose of 100 ppm, the compounds with a mortality rate of more than 80% to Bemisia tabaci are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 45, 48, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116;

[0189] At a dose of 20 ppm, the compounds with a mortality rate of more than 80% to Bemisia tabaci are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116;

[0190] At a dose of 5 ppm, the compounds with a mortality rate of more than 80% to whitefly are: 1, 9, 10, 11, 12, 13, 21, 29, 30, 31, 32, 33, 50, 51, 54, 55, 56, 57, 58, 61, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 113, 114, and 116.

[0191] (3) Test results of exemplary compounds for controlling tea green leafhoppers

[0192] At a dose of 100 ppm, the compounds with a mortality rate of more than 80% to tea green leafhopper are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 45, 48, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116;

[0193] At a dose of 20 ppm, the compounds with a mortality rate of more than 80% to tea green leafhopper are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116;

[0194] At a dose of 5 ppm, the compounds with a mortality rate of more than 80% to tea green leafhopper are: 1, 9, 10, 11, 12, 13, 21, 29, 30, 31, 32, 33, 50, 51, 54, 55, 56, 57, 58, 61, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 113, 114, and 116.

[0195] (4) Test results of exemplary compounds for controlling scale insects

[0196] At a dose of 100 ppm, the compounds with a mortality rate of more than 80% to scale insects are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 45, 48, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116;

[0197] At a dose of 20 ppm, the compounds with a mortality rate of more than 80% to scale insects are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116;

[0198] At a dosage of 5 ppm, the compounds with a mortality rate of more than 80% to scale insects are: 1, 9, 10, 11, 12, 13, 21, 29, 30, 31, 32, 33, 50, 51, 54, 55, 56, 57, 58, 61, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 113, 114, and 116.

[0199] (5) Illustrative Example Compounds Test Results for Controlling Brown Planthoppers

[0200] At a dose of 100 ppm, the compounds with a mortality rate of more than 80% to brown planthopper are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 45, 48, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116;

[0201] At a dosage of 20 ppm, the compounds with a mortality rate of more than 80% to brown planthoppers are: 1, 9, 10, 11, 12, 13, 21, 29, 30, 31, 32, 33, 50, 51, 54, 55, 56, 57, 58, 61, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 103, 113, 114, and 116.

[0202] 2. Determination of acaricidal activity

[0203] In this example, the compounds prepared in the above examples were used to carry out acaricidal activity tests on several types of mite pests.

[0204] The test method is as follows: Dissolve the test compound sample in a suitable solvent (e.g., acetone, methanol, DMSO, etc., selected based on its solubility for the sample) to prepare a test solution of the desired concentration. Cut double-sided tape into 2-3 cm lengths and affix it to one end of a microscope slide. Use tweezers to remove the paper from the tape. Using a size 0 brush, select uniformly sized, brightly colored, and active female adult mites. Attach their backs to the double-sided tape (be careful not to cover the legs, antennae, or mouthparts). Attach 10 mites per row, four rows per strip.

[0205] The test method is as follows: Repeat the test three times, place in a biochemical incubator at a temperature of (25+1)°C and a relative humidity of about 85% for 4 hours, observe with binoculars, and remove dead or inactive individuals. Immerse one end of the mite-carrying glass slide in the test liquid, gently shake for 5 seconds, then remove it. Quickly dry the mite body and the excess test liquid around it with absorbent paper. Place it in the above-mentioned biochemical incubator, and check the results with binoculars after 24 hours. Use a brush to gently touch the mite body. Mites whose legs are motionless are considered dead, and the mortality rate is calculated. The mortality rate is calculated as follows:

[0206] The results of the test on Tetranychus cinnabarinus are as follows:

[0207] At a dosage of 200 ppm, the compounds with a mortality rate of more than 80% to Tetranychus cinnabarinus are: 1, 2, 3, 9, 10, 11, 12, 13, 21, 22, 29, 30, 31, 32, 33, 41, 45, 48, 50, 51, 52, 54, 55, 56, 57, 58, 61, 63, 65, 69, 71, 72, 73, 81, 85, 86, 87, 88, 89, 97, 98, 101, 103, 104, 105, 113, 114, 116.

[0208] 3. Test results of exemplary compounds and control agents

[0209] This example conducted a comparative test on the insecticidal activity of the exemplary compounds and a control agent (prepared according to the method reported in the literature, and the insecticidal testing method is the same as above). The test results are shown in Tables 2 and 3 below.

[0210] Table 2

[0211] Table 3

[0212] In addition to the compounds listed in the table above, the other exemplary compounds of the present invention all showed significantly better control activity against pests and mites than the control agents. Therefore, the compounds of formula (I) of the present invention exhibited excellent activity against a variety of pests and mites in the agricultural field.

[0213] The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A compound represented by formula (I), its stereoisomer, racemate, tautomer, nitrogen oxide or a pharmaceutically acceptable salt thereof, in, R1 is selected from C1-C6 alkyl, halogenated C1-C4 alkyl, C3-C6 cycloalkyl or halogenated C3-C6 cycloalkyl; R2 is selected from C1-C4 alkyl; R3 is selected from H or C1-C4 alkyl; R4 is selected from C1-C4 alkyl; R5 is selected from C3-C6 cycloalkyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C2 alkyl, halogenated C3-C6 cycloalkylC1-C2 alkyl or C3-C6 epoxyalkylC1-C2 alkyl; A is selected from CH or N; X is selected from O or S.

2. The compound according to claim 1, characterized in that R1 is selected from C2-C6 alkyl, halogenated C1-C4 alkyl, C3-C6 cycloalkyl or halogenated C3-C6 cycloalkyl; R2 is selected from C1-C4 alkyl; R3 is selected from H or C1-C4 alkyl; R4 is selected from methyl or ethyl; R5 is selected from C3-C6 cycloalkyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C2 alkyl, halogenated C3-C6 cycloalkylC1-C2 alkyl or C3-C6 epoxyalkylC1-C2 alkyl; A is selected from N or CH; X is selected from O or S.

3. The compound according to claim 1 or 2, characterized in that R1 is selected from C2-C3 alkyl, halogenated C1-C3 alkyl, C3-C6 cycloalkyl or halogenated C3-C6 cycloalkyl; R2 is selected from C1-C3 alkyl; R3 is selected from H or methyl; R4 is selected from methyl or ethyl; R5 is selected from C3-C6 cycloalkyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C2 alkyl, halogenated C3-C6 cycloalkylC1-C2 alkyl or C3-C6 epoxyalkylC1-C2 alkyl; A is selected from N or CH; X is selected from O or S.

4. The compound according to any one of claims 1 to 3, characterized in that R1 is selected from ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, one, two or more fluorine or chlorine substituted groups: methyl, ethyl, n-propyl, isopropyl, cyclopropyl or cyclobutyl; R2 is selected from methyl, ethyl or propyl; R3 is selected from H or methyl; R4 is selected from methyl or ethyl; R5 is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, A is selected from N or CH; X is selected from O or S.

5. The compound according to any one of claims 1 to 4, characterized in that Formula (I) is selected from the structure shown in the following formula (IA): Wherein, A, X, R4 and R5 have the definitions as described in any one of claims 1-4.

6. The compound according to claim 5, characterized in that In Formula IA, A is selected from N or CH; X is selected from O or S; R4 is selected from methyl or ethyl; R5 is selected from 7. The compound according to any one of claims 1 to 3, characterized in that The compound of formula (I) is selected from the following compounds, 8. Use of one, two or more of the compound of formula (I) according to any one of claims 1 to 7, its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof as pesticides, such as insecticides and / or miticides.

9. Use of one, two or more of the compound of formula (I) according to any one of claims 1 to 7, its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof in the preparation of pesticides, such as insecticides and / or miticides.

10. A method for controlling pests, comprising applying an effective amount of one, two or more of the compound of formula (I) according to any one of claims 1 to 7, its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof, or the composition to a growth medium of pests and / or mites.