Substituted hydrazino compound as well as composition, preparation and application thereof

Abstract

The invention belongs to the technical field of pesticides, and relates to a substituted hydrazino compound as well as a composition, a preparation and application thereof. The substituted hydrazino compound provided by the invention has a structure as shown in a formula I. The compound disclosed by the invention has an excellent insecticidal effect at a low dosage and has a relatively good prevention and treatment effect on various pests. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides and relates to a substituted hydrazino compound, its composition, formulation and use. Background Art

[0002] In recent years, due to the long-term use of pest control agents, such as insecticides or fungicides, pests have acquired drug resistance and it has become difficult to control them with the currently used insecticides or fungicides. In addition, some of the known pest control agents are highly toxic or, due to their long-term persistence, damage the ecosystem. In this situation, although a large number of insecticides are known, for example, WO9310083A1 discloses insecticidal phenylhydrazine derivatives, there is still a need to develop new pest control agents that are highly effective, low in toxicity and low in residue. Summary of the Invention

[0003] Problems to be solved by the invention

[0004] In view of the above problems, the present invention provides a substituted hydrazino compound, its composition, formulation and use.

[0005] Solutions for solving the problems

[0006] In a first aspect, the present invention provides a compound of formula I or a pesticidally acceptable salt, stereoisomer or metabolite thereof,

[0007] wherein,

[0008] R is selected from -C1-C6 alkyl-, -C1-C6 haloalkyl-, -C1-C6 alkyl-C3-C6 cycloalkyl- and -C1-C6 haloalkyl-C3-C6 cycloalkyl; preferably, R is selected from -C1-C3 alkyl-, -C1-C3 haloalkyl-, -C1-C3 alkyl-C3-C6 cycloalkyl- and -C1-C3 haloalkyl-C3-C6 cycloalkyl; more preferably, R is selected from -C1-C3 alkyl-; further preferably, R is methylene.

[0009] In a second aspect, the present invention provides the following compounds or pesticidally acceptable salts, stereoisomers or metabolites thereof;

[0010]

[0011] In a third aspect, the present invention provides a pesticidal composition comprising an active ingredient and optionally at least one pesticidally acceptable carrier and / or adjuvant, wherein the active ingredient is the above compound or a pesticidally acceptable salt, stereoisomer or metabolite thereof.

[0012] Preferably, the content of the active ingredient in the above pesticide composition is 1 wt% - 99 wt%.

[0013] Fourthly, the present invention provides a pesticide preparation, which is made from the above compound or its agriculturally acceptable salt, stereoisomer or metabolite, or the above pesticide composition.

[0014] Preferably, the dosage form of the above pesticide preparation is emulsion, suspension, aqueous solution, microemulsion, water emulsion, wettable powder, soluble powder, water dispersible granule or microcapsule.

[0015] Fifthly, the present invention provides the use of the above compound or its agriculturally acceptable salt, stereoisomer or metabolite, or the above pesticide composition, or the above pesticide preparation in the preparation of a product for controlling agricultural pests.

[0016] Preferably, in the above use, the pests are at least one of mites, Lepidoptera, Homoptera, Diptera, Thysanoptera, Hemiptera, Isoptera, Coleoptera pests, preferably mites.

[0017] Sixthly, the present invention provides a method for controlling agricultural pests, which includes the following steps: applying an effective dose of the above compound or its agriculturally acceptable salt, stereoisomer or metabolite, or the above pesticide composition, or the above pesticide preparation to the agricultural pests to be controlled or their growth medium.

[0018] Preferably, in the above method for controlling agricultural pests, the effective dose is 10 grams to 1000 grams per hectare, preferably 20 grams to 500 grams per hectare.

[0019] Seventhly, the present invention provides a pesticide combination form, which contains the above compound or its agriculturally acceptable salt, stereoisomer or metabolite, or the above pesticide composition, or the above pesticide preparation, and at least one other pesticide active compound or fertilizer.

[0020] Preferably, in the above pesticide combination form, the other pesticide active compound is a fungicide, insecticide, acaricide, herbicide or plant growth regulator.

[0021] Effects of the invention

[0022] The present invention introduces an alkyl or haloalkyl structure between the benzene ring and the hydrazino group to obtain the compound of general formula I, which has an obvious difference in structure from the compounds of the prior art. This change is beneficial to the combination of the molecule with the target, so that the compound has excellent insecticidal effects at low doses. In addition, the compounds of the present invention have good control effects on a variety of pests, especially on pests that have developed resistance to existing drugs. Detailed implementation manners

[0023] In this specification, the meaning expressed by "may" includes the meanings of both performing a certain process and not performing a certain process.

[0024] In this specification, the "some specific / preferred implementation manners", "other specific / preferred implementation manners", "implementation manners", etc. mentioned refer to the specific elements (for example, features, structures, properties, and / or characteristics) related to the implementation manner, which are included in at least one of the implementation manners described herein, and may exist in other implementation manners or may not exist in other implementation manners. Additionally, it should be understood that the elements may be combined in any suitable manner in various implementation manners.

[0025] In this specification, the numerical range expressed by "numerical value A to numerical value B" refers to the range including the endpoint numerical values A and B.

[0026] In this specification, when "normal temperature" or "room temperature" is used, the temperature may be 15 - 25 °C.

[0027] Term definitions

[0028] Unless otherwise specified, the term "C1-C6 alkyl" refers to a saturated straight-chain or branched alkyl containing 1 to 6 (especially 1 to 3 carbon atoms) alone or in combination, including (but not limited to) methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl, 2,3-dimethyl-2-butyl, 3,3,-dimethyl-2-butyl, etc. Similarly, the term "C1-C3 alkyl" alone or in combination refers to a saturated straight-chain or branched alkyl containing 1 to 3 carbon atoms, including methyl, ethyl, propyl, isopropyl, etc.

[0029] Unless otherwise specified, the term "halogen" or "halogenated" refers to F, Cl, Br, I. The term "haloalkyl" refers to an alkyl in which one, two or more hydrogen atoms or all hydrogen atoms are replaced by halogen as defined above. Representative examples of haloalkyl include CCl3, CF3, CHCl2, CH2Cl, CH2Br, CH2I, CH2CF3, CF2CF3, etc.

[0030] The present invention encompasses "agronomically acceptable salts" of the compounds of the present invention, which can be generated by reacting the compounds of the present invention with acids or bases. Certain compounds, especially those having acidic or basic groups, can also exist in the form of salts, preferably agronomically acceptable salts. The term "agronomically acceptable salts" refers to those salts that retain the agronomic effectiveness and properties of the free base or free acid and are not undesirable either agronomically or otherwise. Agronomically acceptable salts generally include (but are not limited to) salts formed by reacting the compounds of the present invention with agronomically acceptable inorganic acids or organic acids, and such salts are also referred to as acid addition salts. Common inorganic acids include (but are not limited to) hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid (which can form sulfates or bisulfates), phosphoric acid (which can form phosphates or biphosphates), etc., and common organic acids include (but are not limited to) trifluoroacetic acid, citric acid (which can form mono-, di-, or trisodium citrate), maleic acid (which can form mono- or disodium maleate), fumaric acid (which can form mono- or disodium fumarate), succinic acid (which can form mono- or disodium succinate), tartaric acid (which can form mono- or disodium tartrate), oxalic acid (which can form mono- or disodium oxalate), lactic acid, pyruvic acid, salicylic acid, formic acid, acetic acid, propionic acid, benzoic acid, glycolic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. Agronomically acceptable salts can also include salts formed by reacting the compounds in the present invention with agronomically acceptable organic bases or inorganic bases, and such salts are also referred to as base addition salts. Common base addition salts include (but are not limited to) alkali metal salts, such as lithium, sodium, or potassium salts; alkaline earth metal salts, such as calcium or magnesium salts; organic base salts, such as ammonium salts formed by reacting with organic bases containing N + (C 1-6 alkyl)4 salts. Common inorganic or organic bases include (but are not limited to) lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, magnesium carbonate, calcium carbonate, ammonia water, triethylamine, or tetrabutylammonium hydroxide, etc. Agronomically acceptable salts can be synthesized by general chemical methods.

[0031] Unless otherwise specified, the term "stereoisomer" refers to compounds having the same chemical constitution but different arrangements of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotational isomers), geometric isomers (cis / trans isomers), atropisomers, etc. Any mixture of the resulting stereoisomers can be separated into pure or substantially pure geometric isomers, enantiomers, diastereomers based on the differences in the physicochemical properties of the components, for example, by chromatography and / or fractional crystallization.

[0032] Substituted hydrazine compounds

[0033] The present invention provides a compound of formula I or a pesticidally acceptable salt, stereoisomer or metabolite thereof,

[0034]

[0035] wherein,

[0036] R is selected from -C1-C6 alkyl-, -C1-C6 haloalkyl-, -C1-C6 alkyl-C3-C6 cycloalkyl- and -C1-C6 haloalkyl-C3-C6 cycloalkyl.

[0037] In a specific embodiment of the present invention, R is selected from -C1-C3 alkyl-, -C1-C3 haloalkyl-, -C1-C3 alkyl-C3-C6 cycloalkyl- and -C1-C3 haloalkyl-C3-C6 cycloalkyl.

[0038] In a specific embodiment of the present invention, R is selected from -C1-C3 alkyl-.

[0039] In a specific embodiment of the present invention, R is methylene-.

[0040] Specifically, the substituted hydrazine compounds of the present invention include (but are not limited to) the following compounds:

[0041]

[0042] The present invention also provides a method for preparing the above compound, which may include the following steps:

[0043] (1) Reacting compound II-1 with a hydrazine reagent to obtain compound II-2,

[0044]

[0045] (2) Reacting compound II-3 with compound II-2 under the action of a base to obtain compound I,

[0046]

[0047] (3) Reacting compound II-4 with II-2 in alcohol to obtain compound II-5,

[0048]

[0049] (4) Reacting compound II-5 with II-6 under the action of a catalyst and a base to obtain compound II-7,

[0050]

[0051] (5) Compound II-7 reacts with a reducing agent to obtain Compound I-3.

[0052]

[0053] In a specific embodiment of the present invention, in step (1) of the above preparation method, the hydrazine reagent can be hydrazine hydrate.

[0054] In a specific embodiment of the present invention, in step (2) of the above preparation method, the base can be selected from at least one of triethylamine, N,N-diisopropylethylamine, potassium carbonate, potassium phosphate, sodium carbonate, and sodium hydroxide.

[0055] In a specific embodiment of the present invention, in step (2) of the above preparation method, the base can be potassium carbonate.

[0056] In a specific embodiment of the present invention, in step (3) of the above preparation method, the alcohol can be selected from at least one of methanol and triethanol.

[0057] In a specific embodiment of the present invention, in step (3) of the above preparation method, the alcohol can be methanol.

[0058] In a specific embodiment of the present invention, in step (4) of the above preparation method, the catalyst can be selected from at least one of bis(triphenylphosphine)palladium dichloride, palladium acetate, and tetrakis(triphenylphosphine)palladium; the base can be selected from at least one of potassium carbonate, sodium carbonate, and potassium phosphate.

[0059] In a specific embodiment of the present invention, in step (4) of the above preparation method, the catalyst can be bis(triphenylphosphine)palladium dichloride; the base can be potassium carbonate.

[0060] In a specific embodiment of the present invention, in step (5) of the above preparation method, the reducing agent can be selected from at least one of sodium borohydride, sodium triacetoxyborohydride, and hydrogen-palladium / carbon system.

[0061] In a specific embodiment of the present invention, in step (5) of the above preparation method, the reducing agent can be hydrogen-palladium / carbon system.

[0062] Pesticide compositions

[0063] The present invention provides a pesticide composition, which comprises an active ingredient and optionally at least one pesticidally acceptable carrier and / or adjuvant, and the active ingredient is the above compound or its pesticidally acceptable salt, stereoisomer or metabolite.

[0064] In a specific embodiment of the present invention, the content of the active ingredient in the above pesticide composition can be 1 wt%-99 wt%.

[0065] In a specific embodiment of the present invention, in the above pesticide composition, the carrier can be a solid carrier or a liquid carrier.

[0066] In a specific embodiment of the present invention, in the above pesticide composition, the solid carrier can be natural or synthetic clays and silicates, for example, natural silica and diatomaceous earth, magnesium silicate (such as talc), magnesium aluminum silicate (such as kaolinite, kaolin, montmorillonite and mica), white carbon black, calcium salts (such as calcium carbonate, light calcium carbonate, calcium sulfate), sodium sulfate, amine salts (such as ammonium sulfate, hexamethylenediamine).

[0067] In a specific embodiment of the present invention, in the above pesticide composition, the liquid carrier can be aromatic hydrocarbons (such as benzene, xylene, toluene, etc.), chlorinated hydrocarbons (chlorobenzene, vinyl chloride, chloroform, dichloromethane, etc.), aliphatic hydrocarbons (such as petroleum fractions, cyclohexane, light mineral oil), alcohols (such as isopropyl alcohol, butanol, ethylene glycol, glycerol and cyclohexanol, etc.) and their ethers and esters, ketones (such as acetone, cyclohexanone and dimethylformamide and N-methyl-pyrrolidone).

[0068] In a specific embodiment of the present invention, in the above pesticide composition, the adjuvant can include a surfactant.

[0069] In a specific embodiment of the present invention, in the above pesticide composition, the surfactant can be at least one of ionic or non-ionic emulsifiers, dispersants, wetting agents. For example, the emulsifier can be polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty amine, and commercially available emulsifiers (such as agricultural emulsion 2201B, agricultural emulsion 0203B, agricultural emulsion 100#, agricultural emulsion 500#, agricultural emulsion 600#, agricultural emulsion 600-2#, agricultural emulsion 1601, agricultural emulsion 2201, agricultural emulsion NP-10, agricultural emulsion NP-15, agricultural emulsion 507#, agricultural emulsion OX-635, agricultural emulsion OX-622, agricultural emulsion OX-653, agricultural emulsion OX-667, Ning emulsion 36#); the dispersant can be sodium lignosulfonate, Nekal, calcium lignosulfonate, methylnaphthalenesulfonic acid formaldehyde condensate, etc.; the wetting agent can be sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonate, etc.

[0070] Pesticide formulations

[0071] The present invention provides a pesticide formulation which is made of the above compound or its agrochemically acceptable salt, stereoisomer or metabolite or the above pesticide composition.

[0072] In a specific embodiment of the present invention, the dosage form of the above pesticide formulation is emulsion, suspension, aqueous solution, microemulsion, water emulsion, wettable powder, soluble powder, water dispersible granule or microcapsule.

[0073] In a specific embodiment of the present invention, the dosage form of the above pesticide formulation can be an emulsion, a suspension, a wettable powder or a water dispersible granule. In a specific embodiment of the present invention, the above pesticide formulation can be prepared by a general method. For example, the active substance is mixed with a liquid solvent and / or a solid carrier, and at the same time a surfactant (such as an emulsifier, a dispersant, a stabilizer and a wetting agent) is added, and other auxiliaries (such as a binder, an antifoaming agent, an antioxidant, etc.) can also be added.

[0074] Pesticide uses

[0075] The present invention provides the use of the above compound or its agrochemically acceptable salt, stereoisomer or metabolite, or the above pesticide composition, or the above pesticide formulation in the preparation of a product for controlling agricultural pests.

[0076] In a specific embodiment of the present invention, the pests in the above use can be at least one of mites, Lepidoptera, Homoptera, Diptera, Thysanoptera, Hemiptera, Isoptera, Coleoptera pests.

[0077] In a specific embodiment of the present invention, the pests in the above use can be Lepidoptera pests, for example, Mythimna separata, Spodoptera exigua, Plutella xylostella, Agrotis ypsilon, Agrotis segetum, Diaphania indica, Anticarsia gemmatalis, Clepsis strigana, Choristoneura fumiferana, Chilo suppressalis, Adoxophyes orana, Dendrolimus punctatus, Sesamia inferens, Eldana saccharina, Elasmopalpus lignosellus, Grapholita molesta, Cydia pomonella, Helicoverpa armigera, Heliothis virescens, Helicoverpa zea, Hellula undalis, Hyphantria cunea, Yponomeuta malinellus, Tuta absoluta, Bucculatrix thurberiella, Scrobipalpula absoluta, Lobesia botrana, Hymenia recurvalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia furnacalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris rapae, Plusia gamma, Plutella xylostella, Pseudoplusia includens, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thera britannica and Trichoplusia ni, etc.

[0078] In a specific embodiment of the present invention, the pests in the above use can be Hemiptera pests (bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas), for example, pseudo-green stink bugs, corn stink bugs, black-spotted tobacco stink bugs, cotton red stink bugs, wheat flat shield stink bugs, tobacco stink bugs, cotton red stink bugs, American pasture stink bugs, pasture stink bugs, rice green stink bugs, beet net stink bugs, larch aphids, beet aphids, strawberry root aphids, apple aphids, cotton aphids, North American tea aphids, leaf roller aphids, pea aphids , potato aphid, silverleaf whitefly, apricot aphid, cabbage aphid, Caucasian fir aphid, spruce aphid, Jugend aphid, broad bean leafhopper, peach aphid, wheat aphid, euphorbia aphid, rose aphid, vetch aphid, wheat aphid, onion aphid, plum aphid, rice planthopper, stalk gall aphid, sugarcane planthopper, wart aphid, apple psyllid, pear psyllid, corn aphid, cereal aphid, wheat aphid, whitefly and grape root aphid, etc.

[0079] In a specific embodiment of the present invention, the pests in the above use can be Thysanoptera pests (thrips), for example, orchid thrips, tobacco brown thrips, alfalfa flower thrips, oriental flower thrips, platycodon thrips, rice thrips, palm thrips, western flower thrips, cotton thrips, yellow thrips and tobacco thrips, etc.

[0080] In a specific embodiment of the present invention, the pests in the above use can be dipteran pests (flies, mosquitoes), for example, Aedes aegypti, Aedes albopictus, Aedes harassing, Mexican fruit fly, Anopheles quinquefasciatus, Anopheles malariae, Anopheles white-legged, Anopheles malariae, Anopheles microplus, Anopheles four-spotted, Red-headed blowfly, Mediterranean fruit fly, Maggot disease golden fly, deer fly, sorghum gall midge, Culex pipiens, Aedes aegypti, Culex quinquefasciatus, Aedes mosquito, Melon fly, Olive fruit fly, Rapeseed Leaf gall midge, onion fly, wheat field fly, gray field fly, cabbage root fly, human skin fly, small toilet fly, horse fly, tsetse fly, palpi tsetse fly, peanut field gray field fly, pattern fly, vegetable leafminer, American leaf miner, copper green fly, silk green fly, wheat gall midge, fall housefly, housefly, stable fly, sheep mad fly, European wheat straw fly, henbane spring fly, radish fly, cherry fruit fly, apple fruit fly, red tailed meat fly, stable fly, gadfly, red horsefly and European crane fly, etc.

[0081] In a specific embodiment of the present invention, the pests in the above-mentioned use can be Orthoptera pests (crickets, grasshoppers, locusts), for example, house crickets, mole crickets, migratory locusts, two-striped black locusts, red-footed black locusts, Mexican black locusts, migratory black locusts, stone-dwelling black locusts, striped red locusts, American desert locusts, African desert locusts, Moroccan scutellaria, court grasshoppers, Senegalese car locusts, smelly glandular locusts, Italian locusts, Australian plague locusts and brown migratory locusts, etc.

[0082] In a specific embodiment of the present invention, the pests in the above uses can be hymenopteran pests (ants, bees, wasps, sawflies), for example, Athalia rosae japanensis, leafcutter ants, Crematogaster spp., Lasius niger, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, red ants, Pheidole megacephala, velvet ants, Bombus spp., Vespa mandarinia, Vespula germanica, Polistes rothneyi, and Argentine ants, etc.

[0083] In a specific embodiment of the present invention, the pests in the above uses can be coleopteran pests (beetles), for example, Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Anthonomus grandis, Anthonomus pomorum, Cryptophagus surinamensis, Tomicus piniperda, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Anthonomus quadrigibbus, Cassida nebulosa, Cetonia aurata, Ceutorhynchus assimilis, Meloe violaceus, Crioceris asparagi, Phratora vitellinae, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Hypera postica, Hylobius abietis, Hypera brunneipennis, Sitona lineatus, Ips typographus, Lema melanopus, Lema decempunctata, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Meligethes aeneus, Melolontha hippocastani, Oulema oryzae, Otiorhynchus sulcatus, Otiorhynchus ovatus, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granarius, etc.

[0084] In a specific embodiment of the present invention, the pests in the above uses can be blattodean pests (cockroaches), for example, Blattella germanica, Periplaneta americana, Periplaneta japonica, Blattella asahinai, Periplaneta australasiae, and Blatta orientalis, etc.

[0085] In a specific embodiment of the present invention, the pests in the above uses can be isopteran pests (termites), for example, Reticulitermes flaviceps, Reticulitermes speratus, Reticulitermes lucifugus, Reticulitermes chinensis, and Coptotermes formosanus, etc.

[0086] In a specific embodiment of the present invention, the pests in the above uses can be siphonapteran pests (fleas), for example, Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, etc.

[0087] In a specific embodiment of the present invention, the pests in the above uses can be thysanuran pests (silverfish, firebrats), for example, Lepisma saccharina and Thermobia domestica.

[0088] In a specific embodiment of the present invention, the pests in the above uses can be chilopod pests (e.g., centipedes) or millipedes.

[0089] In a specific embodiment of the present invention, the pests in the above uses can be collembolan pests, for example, Folsomia candida, etc.

[0090] In a specific embodiment of the present invention, the pests in the above uses can be nematodes. For example, plant parasitic nematodes such as Meloidogyne spp., M. hapla, M. incognita, M. javanica and other Meloidogyne spp.; cyst-forming nematodes, Globodera rostochiensis and other Globodera spp.; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii and other Heterodera spp.; Anguina tritici; Anguina spp.; Aphelenchoides spp., Aphelenchoides besseyi and other Aphelenchoides spp.; Bursaphelenchus spp., Bursaphelenchus xylophilus and other Bursaphelenchus spp.; Criconemella spp., Criconemella spp., Criconemella spp., Criconemella spp., Criconemella spp.; Ditylenchus spp., Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus spp.; Dolichodorus spp., Dolichodorus spp.; Helicotylenchus spp.; Hemicycliophora spp. and Hemicriconemoides spp., Hemicycliophora spp. and Hemicriconemoides spp.; Hemicriconemoides spp.; Hoplolaimus spp., Hoplolaimus spp.; Merlinius spp., Merlinius spp.; Paratylenchus spp., Pratylenchus penetrans, Pratylenchus neglectus and other Pratylenchus spp.; Radopholus spp., Radopholus similis and other Radopholus spp.; Rotylenchulus spp., Rotylenchulus spp. and other Rotylenchulus spp.; Trichodorus spp., Trichodorus primitivus and other Trichodorus spp.; Paratrichodorus spp.; Tylenchorhynchus spp., Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus spp.; Tylenchulus spp., Tylenchulus semipenetrans and other Tylenchulus spp.; Xiphinema spp., Xiphinema spp.; and other plant parasitic nematodes.

[0091] In a specific embodiment of the present invention, the pests in the above uses can be arachnid pests. For example, Araneae, such as Latrodectus mactans and Loxosceles reclusa, etc.; Argasidae, Ixodidae and Sarcoptidae of Acarina, such as Ixodes hexagonus, Amblyomma variegatum, Argas persicus, Boophilus microplus, Rhipicephalus annulatus, Dermacentor andersoni, Ornithonyssus bacoti, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Sarcoptes scabiei, Eriophyidae (such as Aculus schlechtendali); Tenuipalpidae (such as Polyphagotarsonemus latus); Tenuipalpidae (such as Brevipalpus phoenicis); and Tetranychidae (such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus truncatus, Tetranychus urticae, Panonychus ulmi and Panonychus citri, etc.).

[0092] Methods for controlling agricultural pests

[0093] The present invention provides a method for controlling agricultural pests, which comprises the following steps: applying an effective dose of the above compound or its agrochemically acceptable salt, stereoisomer or metabolite, or the above pesticide composition, or the above pesticide formulation to the agricultural pests to be controlled or their growth medium.

[0094] In a specific embodiment of the present invention, the effective dose in the above method for controlling agricultural pests can be 10 grams to 1000 grams per hectare.

[0095] In a specific embodiment of the present invention, the effective dose in the above method for controlling agricultural pests can be from 20 grams to 500 grams per hectare.

[0096] Pesticide combination forms The present invention provides a pesticide combination form, which comprises the above-mentioned compound or its pesticidally acceptable salt, stereoisomer or metabolite, or the above-mentioned pesticide composition, or the above-mentioned pesticide formulation, and at least one other pesticidally active compound or fertilizer. In a specific embodiment of the present invention, the other pesticidally active compound in the above pesticide combination form is a fungicide, insecticide, acaricide, herbicide or plant growth regulator.

[0097] Examples

[0098] The technical solutions of the present invention will be described in detail below in conjunction with examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those not specified in the examples, they are carried out under conventional conditions or conditions recommended by the manufacturer. For reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0099] The various exemplary embodiments, features and aspects of the present invention will be described in detail below. The special word "exemplary" here means "serving as an example, embodiment or illustration". Any embodiment described as "exemplary" here does not have to be construed as superior to or better than other embodiments.

[0100] In addition, in order to better illustrate the present invention, numerous specific details are given in the following specific embodiments. Those skilled in the art should understand that the present invention can also be implemented without some specific details. In other instances, methods, means, equipment and steps well-known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.

[0101] Unless otherwise stated, the units used in this specification are all international standard units, and the numerical values and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0102] Abbreviation: TLC thin layer chromatography.

[0103] Example 1: Preparation of isopropyl carbazate (II-2)

[0104]

[0105] Dissolve compound II-1 (40 g, 0.326 mol) in dichloromethane (200 ml), cool to 0 °C, and add hydrazine hydrate dropwise (41.8 g, 0.8 mol). After the addition is complete, allow the temperature to rise to 25 °C naturally and stir for 3 hours. Then add water (200 ml) to the reaction solution, extract with dichloromethane (100 ml × 2), wash the aqueous phase with sodium chloride, dry over sodium sulfate, evaporate to dryness, and purify by column chromatography to obtain colorless oily substance II-2 (24.5 g, yield 63%). 1 1H NMR: (400 MHz, CDCl3) δ 6.17 (s, 1H), 4.95 - 4.89 (m, 1H), 3.74 (s, 2H), 1.22 (d, J = 6.4 Hz, 6H).

[0106] (2) Preparation of (E)-2-(5-bromo-2-methoxybenzylidene)hydrazino-1-isopropyl carboxylate (II-5)

[0107]

[0108] Add compound II-4 (10.75 g, 50 mmol) and compound II-2 (5.9 g, 50 mmol) to a reaction flask, dissolve in solvent methanol (60 mL), stir the reaction at room temperature, and a white solid will precipitate continuously. After 2 hours, TLC detects that the reaction is complete, filter and dry to obtain the crude product II-5, and directly proceed to the next step.

[0109] (3) Preparation of (E)-2-((4-methoxy-[1,1'-biphenyl]-3-yl)methylene)hydrazino-1-isopropyl carboxylate (II-7)

[0110]

[0111] Add the crude product of II-5, potassium carbonate (20.7 g, 150 mmol) and II-6 (9.15 g, 75 mmol) to a reaction flask, solvent dioxane / water (120 / 40 mL), bis(triphenylphosphine)palladium dichloride (1.4 g, 2 mmol), protect with nitrogen, heat to 100 °C and react overnight. Cool, pour into 80 ml of water, extract with ethyl acetate twice, combine the organic layers, wash successively with water and saturated brine, separate the organic phase, dry the organic phase over anhydrous sodium sulfate, filter, concentrate to obtain the crude product, and purify by column chromatography (petroleum ether:ethyl acetate = 5:1) to obtain white solid II-7 (13.5 g, two-step yield 86.5%).

[0112] (4) Preparation of 2-((4-methoxy-[1,1'-biphenyl]-3-yl)methyl)hydrazino-1-isopropyl carboxylate (I-3)

[0113]

[0114] Dissolve II-7 (3.65 g, 11.6 mmol) in a reaction flask containing methanol (60 ml), add palladium / carbon (400 mg, 5%), and react overnight at room temperature under hydrogen. Filter through diatomaceous earth to obtain the crude product, and wash it by stirring with a mixture of petroleum ether and ethyl acetate for 2 hours to obtain white solid I-3 (2.3 g, yield 62%).

[0115] Meanwhile, other compounds represented by general formula I can also be prepared and obtained in the manner described above.

[0116] Preparation of the preparation:

[0117] Example 2: Preparation of an emulsion

[0118] Uniformly mix 20 parts of the compound of the present invention represented by general formula I, 10 parts of polyoxyethylene styryl phenyl ether, and 70 parts of xylene to obtain an emulsion.

[0119] Example 3: Preparation of a wettable powder

[0120] Uniformly stir and mix 10 parts of the compound of the present invention represented by general formula I, 2 parts of sodium dodecyl sulfate, 2 parts of dialkyl sulfosuccinate, 1 part of sodium salt of β-naphthalene sulfonic acid formaldehyde condensate, and 85 parts of diatomaceous earth to obtain a wettable powder.

[0121] Example 4: Preparation of a suspension

[0122] Uniformly stir and mix 10 parts of the compound of the present invention represented by general formula I, 3 parts of sodium salt of β-naphthalene sulfonic acid formaldehyde condensate, 1 part of triphenylethylphenol, 5 parts of propylene glycol, 0.5 part of a silicone defoamer, and 33.5 parts of water. Then mix 0.3 part of xanthan gum and 46.7 parts of water, and finally stir and mix the substances obtained from the two mixtures to obtain a suspension.

[0123] Example 5: Preparation of a water dispersible agent

[0124] Uniformly pulverize and mix 20 parts of the compound of the present invention represented by general formula I, 6 parts of metal salt of naphthalene sulfonic acid formaldehyde condensate, 1 part of metal salt of dialkyl sulfosuccinate, and 73 parts of calcium carbonate, then add water for kneading and granulate and dry to obtain water dispersible granules.

[0125] Biological activity determination

[0126] Example 6: Insecticidal activity determination experiment against adult Tetranychus cinnabarinus

[0127] Perform greenhouse acaricidal activity determination with the compound of the present invention. The determination method is as follows: According to the solubility of the test compound, dissolve it with acetone or dimethyl sulfoxide, and prepare 50 ml of the test solution with the required concentration using a 0.1% Tween 80 solution. The content of acetone or dimethyl sulfoxide in the solution does not exceed 10%.

[0128] Take two true-leaf kidney bean seedlings, inoculate them with adult mites of Tetranychus cinnabarinus resistant to bifenazate, and after investigating the base number, use a hand-held sprayer to conduct a whole-plant spraying treatment. Each treatment has 3 replicates. After treatment, place them in a standard observation room. After 72 hours, investigate the number of surviving mites and calculate the mortality rate.

[0129] Among some of the test compounds, at a concentration of 10 ppm, the insecticidal mortality rate of Compound I-3 against adult mites of Tetranychus cinnabarinus resistant to bifenazate was 100%. And for the compound bifenazate used as the positive control: (from Patent WO9310083A1) at a concentration of 10 ppm, the insecticidal mortality rate against Tetranychus cinnabarinus that has developed resistance is less than 10%.

[0130] It can be seen that among the test compounds, Compound I-3 has excellent insecticidal activity and has an obvious advantage over the positive control compound.

[0131] As described above, the substituted hydrazine-based compounds of the present invention have a new structure and excellent insecticidal activity.

[0132] It should be noted that although the technical solutions of the present invention are introduced by specific examples, those skilled in the art can understand that the present invention should not be limited thereto.

[0133] The embodiments of the present invention have been described above. The above description is exemplary and not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations are obvious to those of ordinary skill in the art in the technical field without departing from the scope and spirit of the described embodiments. The choice of terms used herein is intended to best explain the principles of the embodiments, practical applications, or improvements to the technology in the market, or to enable other ordinary skilled persons in the technical field to understand the embodiments disclosed herein.

Claims

1. A compound of formula I or a pesticidally acceptable salt, stereoisomer or metabolite thereof, wherein, R is selected from -C1-C6 alkyl-, -C1-C6 haloalkyl-, -C1-C6 alkyl-C3-C6 cycloalkyl- and -C1-C6 haloalkyl-C3-C6 cycloalkyl.

2. The compound according to claim 1, or a pesticidally acceptable salt, stereoisomer or metabolite thereof, characterized in that, R is selected from -C1-C3 alkyl-, -C1-C3 haloalkyl-, -C1-C3 alkyl-C3-C6 cycloalkyl- and -C1-C3 haloalkyl-C3-C6 cycloalkyl; Preferably, R is selected from -C1-C3 alkyl-; More preferably, R is methylene.

3. The following compounds or pesticidally acceptable salts, stereoisomers or metabolites thereof; 4. A pesticidal composition comprising an active ingredient and optionally at least one pesticidally acceptable carrier and / or adjuvant, wherein the active ingredient is the compound of any one of claims 1 to 3 or a pesticidally acceptable salt, stereoisomer or metabolite thereof.

5. The pesticidal composition according to claim 4, characterized in that the content of the active ingredient in the pesticidal composition is 1 wt% - 99 wt%.

6. A pesticidal preparation made from the compound of any one of claims 1 to 3 or a pesticidally acceptable salt, stereoisomer or metabolite thereof or the pesticidal composition according to claim 4 or 5; Preferably, the dosage form of the pesticidal preparation is emulsion, suspension, aqueous solution, microemulsion, water emulsion, wettable powder, soluble powder, water dispersible granule or microcapsule.

7. Use of the compound of any one of claims 1 to 3 or a pesticidally acceptable salt, stereoisomer or metabolite thereof or the pesticidal composition according to claim 4 or 5 or the pesticidal preparation according to claim 6 in the preparation of a product for controlling agricultural pests; Preferably, the pests are at least one of mites, Lepidoptera, Diptera, Thysanoptera, Hemiptera, Isoptera, Coleoptera pests, preferably mites.

8. A method for controlling agricultural pests, comprising the following steps: Applying an effective dose of the compound of any one of claims 1 to 3 or a pesticidally acceptable salt, stereoisomer or metabolite thereof or the pesticidal composition according to claim 4 or 5 or the pesticidal preparation according to claim 6 to the agricultural pests to be controlled or their growth medium; Preferably, the effective dose is 10 grams to 1000 grams per hectare, preferably 20 grams to 500 grams per hectare.

9. A pesticidal combination comprising the compound of any one of claims 1 to 3 or a pesticidally acceptable salt, stereoisomer or metabolite thereof or the pesticidal composition according to claim 4 or 5 or the pesticidal preparation according to claim 6, and at least one other pesticidal active compound or fertilizer; Preferably, the other pesticidal active compound is a fungicide, insecticide, acaricide, herbicide or plant growth regulator.

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