Pyripyropene derivative, and composition and use thereof

Abstract

The present invention belongs to the technical field of pesticides, and particularly relates to a pyripyropene derivative, and a composition and the use thereof. The compound is as represented by general formula I, wherein X1 represents hydrogen or fluorine, X2 represents hydrogen or fluorine, X3 represents hydrogen or fluorine, X4 represents hydrogen or fluorine, and X1, X2, X3 and X4 are not hydrogen simultaneously; R1 and R2 each independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl or -(CO)R3; Y1 represents hydroxyl, alkoxyalkyloxy, trialkylsilyloxy or -O(CO)R3; Y2 represents hydrogen or alkyl; or Y1 and Y2 together form = O. The compound has an excellent prevention and control effect on pests such as Myzus persicae, Apolygus lucorum, Rhopalosiphum padi and Bemisia tabaci.

Description

Pyripyropene derivatives and their compositions and uses Technical Field

[0001] The present invention belongs to the technical field of pesticides, and in particular relates to a pyripyropene derivative and a composition and use thereof. Background Art

[0002] To date, many pest control agents with insecticidal activity have been reported. However, some insect species have become resistant to these pest control agents or are difficult to control with these agents, and furthermore, there are safety concerns for humans and animals. Therefore, there is a continued desire to develop new pest control agents with potent insecticidal activity.

[0003] Summary of the Invention

[0004] To solve the above problems in the prior art, the present invention provides a pyripyropene derivative and its composition and use. The compound has excellent control effects on pests such as green myzus aphid, green stink bug, cereal aphid, and whitefly.

[0005] The technical solution adopted in the present invention is as follows:

[0006] A pyripyropene derivative as shown in formula I,

[0007] wherein X1 represents hydrogen or fluorine, X2 represents hydrogen or fluorine, X3 represents hydrogen or fluorine, and X4 represents hydrogen or fluorine, and X1, X2, X3 and X4 are not hydrogen at the same time;

[0008] R1 and R2 independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl or -(CO)R3;

[0009] Y1 represents hydroxy, alkoxyalkyloxy, trialkylsilyloxy or -O(CO)R3; Y2 represents hydrogen or alkyl; or Y1 and Y2 together form =O;

[0010] R3 each independently represents hydrogen, an alkyl, alkenyl or alkynyl group which is unsubstituted or substituted by at least one of halogen, alkoxy, alkoxycarbonyl or alkylthio, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group;

[0011] The aforementioned "cycloalkyl", "cycloalkenyl", "heterocyclyl" or "aryl" is optionally selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10)2 or -O-alkylene-(CO)OR 10 or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0012] R 10 Each is independently hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

[0013] In one embodiment,

[0014] R1 and R2 independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl or -(CO)R3;

[0015] Y1 represents hydroxy, C1-C8 alkoxy, C1-C8 alkyloxy, tri-C1-C8 alkylsilyloxy or -O(CO)R3; Y2 represents hydrogen or C1-C8 alkyl; or Y1 and Y2 together form =O;

[0016] R3 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl which is unsubstituted or substituted by at least one of halogen, C1-C8 alkoxy, C1-C8 alkoxycarbonyl or C1-C8 alkylthio, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl or heterocyclic group;

[0017] The aforementioned “C3-C8 cycloalkyl”, “C3-C8 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C8 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring form a fused ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0018] R 10are independently hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl, C1-C8 alkoxy or halogenated C1-C8 alkoxy.

[0019] In one embodiment,

[0020] R1 and R2 independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl or -(CO)R3;

[0021] Y1 represents hydroxy, C1-C6 alkoxy, C1-C6 alkyloxy, tri-C1-C6 alkylsilyloxy or -O(CO)R3; Y2 represents hydrogen or C1-C6 alkyl; or Y1 and Y2 together form =O;

[0022] R3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl which is unsubstituted or substituted by at least one of halogen, C1-C6 alkoxy, C1-C6 alkoxycarbonyl or C1-C6 alkylthio, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl or heterocyclic group;

[0023] The aforementioned “C3-C6 cycloalkyl”, “C3-C6 cycloalkenyl”, “heterocyclyl” or “aryl” is optionally selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C6 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-;

[0024] R 10Each of them is independently hydrogen, C1-C6 alkyl, halo-substituted C1-C6 alkyl, phenyl, or phenyl substituted by 1 to 3 groups selected from halogen, cyano, nitro, C1-C6 alkyl, halo-substituted C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halo-substituted C1-C6 alkoxy.

[0025] In one embodiment,

[0026] X1 represents hydrogen, X2 represents fluorine, X3 represents hydrogen, and X4 represents hydrogen; or X1 represents hydrogen, X2 represents hydrogen, X3 represents fluorine, and X4 represents hydrogen.

[0027] In one embodiment,

[0028] Y1 represents a hydroxyl group or -O(CO)R3; Y2 represents hydrogen; or Y1 and Y2 together form =O.

[0029] In the definition of the compounds represented by the above general formula and in all the following structural formulas, the technical terms used, whether used alone or in compound words, represent the following substituents: Alkyl groups with more than two carbon atoms can be straight-chain or branched. For example, the compound word "-O-alkylene-(CO)OR 10 " " in which the alkylene group can be -CH2-, -CH2CH2-, -CH(CH3)-, -C(CH3)2-, etc. The alkyl group is, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Similarly, alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl. The term "cycloalkyl" refers to a group consisting of cyclopentyl, cyclohexyl, cyclopentenyl, cyclohex ...

[0030] Unless otherwise specified, the "aryl" mentioned in the present invention includes but is not limited to phenyl, naphthyl, The "heterocyclic group" includes but is not limited to saturated or unsaturated non-aromatic cyclic groups etc., and also include but are not limited to heteroaryl, i.e. an aromatic cyclic group containing, for example, 3 to 6 ring atoms and optionally fused to a benzo ring, wherein 1 to 4 (e.g. 1, 2, 3 or 4) heteroatoms in the ring atoms are selected from oxygen, nitrogen and sulfur, for example

[0031] If a group is substituted by a group, this is understood to mean that the group is substituted by one or more identical or different groups selected from the groups mentioned. Furthermore, identical or different substituent characters contained in identical or different substituents are independently selected and may be identical or different. The same applies to ring systems formed from different atoms and units. At the same time, compounds known to those skilled in the art to be chemically unstable under standard conditions are excluded from the scope of the claims.

[0032] In addition, unless otherwise specified, the term "substituted by at least one group" as used herein refers to being substituted by 1, 2, 3, 4 or 5 groups; groups (including heterocyclic groups, aryl groups, etc.) without a specific connection position can be connected at any position, including the position connected to C or N; if it is substituted, the substituent can also be substituted at any position as long as it complies with the chemical bond connection rules. For example, a heteroaryl group substituted by 1 methyl group Can represent wait.

[0033] The types of pests against which the compound represented by Formula I or a salt thereof has an insecticidal effect as an active ingredient include, for example, lepidopteran pests, such as Spodoptera litura, Mamestra brassicae, Pseudaletia separata, green caterpillar, Plutella xylostella, Spodoptera exigua, Chilo suppressalis, Cnaphalocrocis medinalis, Tortricidae, Carposinidae, Lyonetiidae, Lymantriidae, Agrotis spp. pests, Helicoverpa spp. pests or Heliothis spp. pests. spp.), etc.; Hemipteran pests, for example, Aphididae, Adelgidae or Phylloxeridae, for example, Myzus percicae, Aphis gossypii Glover, Aphis fabae, Aphis maidis, Acyrthosiphon pisum, Aulacorthum solani, Aphis craccivora, Macrosiphum euphorbiae, Macrosiphum avenae, Metopolophium dirhodum, Rhopalosiphum padi, Schizaphis graminum, Brevicoryne brassicae, Lipaphis erysimi), Aphis citricola, Rosy apple aphid, Eriosoma lanigerum, Toxoptera aurantii or Toxoptera citricidus, Deltocephalae, for example Nephotettix cincticeps, leafhoppers,For example, the tea green leafhopper, the Delphacidae, for example, Laodelphax striatellus, Nilaparvata lugens or Sogatella furcifera, the Pentatomidae, for example, Eysarcoris ventralis, Nezaraviridula or Trigonotylus caelestialium, the Aleyrodidae, for example, Bemisia tabaci or Trialeurodes vaporariorum, the Coccoidea, for example, Pseudococcus comstocki, Planococcus citri Risso or Aonidiella spp. aurantii) (for example, Diaspididae, Margarodidae, Ortheziidae, Aclerdiae, Dactylopiidae, Kerridae, Pseudococcidae, Coccidae, Eriococcidae, Asterolecaniidae, Beesonidae, Lecanodiaspididae or Cerococcidae), and Psyllidae, for example, Diaphorina citri; pests of the order Coleoptera,For example, rice water weevil (Lissorhoptrus oryzophilus), mung bean weevil (Callosobruchus chinensis), yellow mealworm (Tenebrio molitor), corn rootworm (Diabrotica virgifera virgifera), cucumber beetle (Diabrotica undecimpunctata howardi), copper green beetle (Anomala cuprea), red copper beetle (Anomala rufocuprea), yellow flea beetle (Phyllotreta striolata), yellow melon (Aulacophora femoralis), potato beetle (Leptinotarsa ​​decemlineata), rice mudworm (Oulema oryzae), pear borer (Grapholita molesta) or Cerambycidae; Acari, for example, two-spotted spider mite (Tetranychus urticae), Kanzawa spider mite (Tetranychus truncatus) and other insects. kanzawai) or Panonychus citri; hymenopteran pests, such as Tenthredinoidea; Orthopteran pests, such as Acrididae; Dipteran pests, such as Musca domestica Linnaeus or Agromyzidae; Thysanopteran pests, such as Thrips palmi KARNY or Frankliniella occidentalis; and plant-parasitic nematodes, such as Meloidogyne hapla, Pratylenchus, Aphelenchoides besseyi or Bursaphelenchus xylophilus. Examples of animal parasites include the order Siphonaptera, for example Ctenocephalides felis or Pulex irritans, the order Anoplura, for example Pediculus spp. or Phtirus spp.; the order Acari,For example, Boophilus spp., Haemaphysalis longicornis, Rhipicephalus sanguineus, and Haemaphysalis spp.

[0034] (Haemaphysalis flava), Sarcoptes spp., Dermanyssus spp., Ornithonyssus sylviarum, Ornithonyssus bacoti, and Leptotrombidium; Tabanidae; Diptera, for example Lucilia spp.; Mosquitoes, for example Stegomyia albopicta and Culex pipiens pallens; Simuliidae; Ceratopogonidae; Nematoda, for example Strongyloides, for example Strongyloides papillosus or Strongyloides stercoralis stercoralis, hookworms, for example A. caninum, Ancylostoma tubaeforme or Ancylostoma duodenale; Haemonchus spp.; Strongylida, for example Strongyloides mouse; hairworms; Metastrongyloidea, for example Metastrongylus spp., Angiostrongylus cantonensis or Aelurostrongylus cati; Oxyurida; Heterakidae, for example Heterakis gallinarum; Anisakis simplex; Ascaroidea, for example Ascaris suum. suum, Parascaris equorum, Toxicara canis, or Toxocara cati; Subuluridae;Spiruloidea, for example Gnathostoma spinigerum, Phys aloptera, Ascarops strongylina, Drashia megastoma, Acuaria or Ostertagia ostertagi; Filariidae, for example Dirofilaria or Onchocerca cervicalis; Order Dioctophymatida; Wipeworms and Trichinosis, for example Trichuris vulpis or Trichinella spiralis; Trematoda, for example Schistosoma japonicum, for example Schistosoma japonicum. aponicum or Fasciola hepatica; Acanthocephala, such as Macracanthorhynchus hirudinaceus or Moniliformis moniliformis; Cestoda, such as Bothriocephaloidea, such as Diphyllobothrium mansoni; Cyclophyllidea, such as Dipylidium caninum, Hymenolepis diminuta, Echinococcus multilocularis or Echinococcus granulosus; and protozoa. Preferred pest species include Hemiptera, Diptera, and Thysanoptera. Hemiptera pests are particularly preferred. ;

[0035] Preferred Hemiptera pests include Aphididae, Aphididae or Phylloxera (preferably Aphididae); Leafhoppers, Aleyrodidae, Pentatomidae or Coccoidea (Shield Scales, Arachnidae, Ichthyosauridae, Besmockidae, Coccoidea, Gumcopodidae, Mealycopodidae, Lecanopodidae, Meat Scales, Chain Scales, Beesonidae, Chain Scales or Cyperiidae); and Psyllidae, more preferably Myzus persicae, Cotton Aphid, Tea Green Leafhopper, Bemisia tabaci, Greenhouse Whitefly, Trigonotylus caelestialium or Cone's Mealycoides, Red Round Scale and Citrus Psyllid.

[0036] When the compound represented by Formula I is used as a pest control agent, the compound represented by Formula I can be used directly. Alternatively, the compound represented by Formula I can be mixed with suitable agricultural or animal husbandry acceptable carriers such as solid carriers, liquid carriers and gaseous carriers, surfactants, dispersants or other adjuvants for formulation to prepare any suitable formulation, such as emulsifiable concentrates, EW (oil-in-water emulsions), liquid formulations, suspensions, wettable powders, water-dispersible granules, dusts, DL powders, granules, granules, tablets, oils, aerosols, sols (floable), xerosols or microcapsules.

[0037] Solid carriers include, for example, talc, bentonite, clay, kaolin, diatomaceous earth, vermiculite, white carbon or calcium carbonate.

[0038] Liquid carriers include, for example, alcohols such as methanol, n-hexanol or ethylene glycol; ketones such as acetone, methyl ethyl ketone or cyclohexanone; aliphatic hydrocarbons such as n-hexane, kerosine or kerosene; aromatic hydrocarbons such as toluene, xylene or methylnaphthalene; ethers such as diethyl ether, dioxane or tetrahydrofuran; esters such as ethyl acetate; nitriles such as acetonitrile or isobutyronitrile; amides such as dimethylformamide or dimethylacetamide; vegetable oils such as soybean oil or cottonseed oil; dimethyl sulfoxide; or water.

[0039] Gaseous carriers include, for example, LPG, air, nitrogen, carbon dioxide, and dimethyl ether.

[0040] Surfactants or dispersants that can be used for, for example, emulsification, dispersion or spreading include, for example, alkyl sulfates, alkyl (aryl) sulfonates, polyoxyalkylene alkyl (aryl) ethers, polyol esters and lignin sulfonates. Auxiliary agents that can be used to improve formulation performance include, for example, carboxymethyl cellulose, gum arabic, polyethylene glycol and calcium stearate.

[0041] The above-mentioned carriers, surfactants, dispersants and adjuvants can be used alone or in combination as needed.

[0042] The content of the active ingredient in these formulations is not particularly limited, but is preferably 1-75% by weight for emulsifiable concentrates, 0.3-25% by weight for dusts, 1-90% by weight for wettable powders, and 0.5-10% by weight for granules.

[0043] According to another aspect of the present invention, there is provided a method for controlling pests, comprising applying an effective amount of a compound represented by Formula I or a salt thereof to a surface selected from the group consisting of water, soil, nutrient solution in nutrient solution culture, solid medium in nutrient solution culture, and seeds, roots, tubers, bulbs and rhizomes of plants.

[0044] According to one embodiment of the present invention, there is provided a method for controlling pests, the method comprising applying an effective amount of a compound represented by Formula I or a salt thereof to the pest or its habitat. According to a preferred embodiment of the present invention, there is provided a method for controlling pests, the method comprising applying an effective amount of a compound represented by Formula I or a salt thereof to plants or soil.

[0045] The compound represented by Formula I or its salt directly plays a strong control effect to harmful organism.In addition, it can be expected that the control effect that the compound is used to play as a mixture with other harmful organism control agents is higher than the control effect reached when only using the compound or other harmful organism control agents.Therefore, according to the present invention, a kind of harmful organism control composition comprising at least one compound represented by Formula I or its salt and at least one other harmful organism control agent is provided.In addition, according to another embodiment of the present invention, there is provided the purposes of the harmful organism control composition in protecting useful plants (cultivated plants) from harmful organisms.In addition, according to another embodiment, there is provided the purposes of the harmful organism control composition in the preparation for protecting useful plants (cultivated plants) from harmful organisms.

[0046] The compositions or compounds useful as pest control agents of the present invention, or blends thereof with other pest control agents, are used to control a wide variety of pests on various plants. Target plants include wheat and barley, coarse grains such as corn, millet, millet, barnyard grass, and edible sorghum, fruit trees such as oranges, apples, and grapes, vegetables such as cucumbers, pumpkins, melons, cabbage, eggplant, tomatoes, and strawberries, tubers such as potatoes, sweet potatoes, and taro, legumes such as red beans, kidney beans, and soybeans, oilseed crops such as rapeseed, fodder crops such as animal feed grasses, sorghum, and corn, ornamental plants, foliage plants, timber, tea, sugar beets, sugar cane, sunflowers, hops, cotton, tobacco, Arabic coffee, turf grasses, and edible mushrooms.

[0047] The compositions or compounds useful as pest control agents of the present invention or their blends with other pest control agents can be applied to pests, plants, and plant propagation materials, specifically, for example, seeds, plant leaves, roots, soil, water surfaces, planting materials, and spaces where pests should be prevented from entering. Treatment with the compounds, blends, and compositions of the present invention can be carried out before and after the entry of pests.

[0048] The present invention includes killing animal parasitic pests. Killing of pests can be carried out by applying to habitats, livestock farms, feed, plants, seeds, soil, materials and growth environments where animal parasitic pests grow or will grow, or to materials, plants, seeds, soil and water surfaces where animal parasitic pests should be prevented from entering.

[0049] Plant propagation materials to which the present invention is applied refer to plants that have the ability to reproduce during plant growth, including but not limited to seeds, branches or lops, and the pulled-out parts of a tuber, specifically seeds, roots, fruits, tubers, bulbs, underground stems, roots, branches, and buds. It also includes rice seedlings or seedlings that are transplanted after germination or rooting. For preventive purposes, plant protection agents are applied to these plant propagation materials during settled plating or transplanting.

[0050] The term "cultivated plants" is to be understood as including plants that have been modified by breeding, mutagenesis and / or genetic engineering. Genetically modified plants (GMOs) are plants whose genetic material has been modified using recombinant DNA techniques that cannot readily be obtained under natural conditions by hybridization, mutation or natural recombination. One or more genes are usually incorporated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include, but are not limited to, targeted post-translational modifications of proteins (oligo- or polypeptides), for example by glycosylation or the addition of polymers such as prenylated, acetylated or farnesylated moieties or PEG moieties (e.g. as disclosed in Biotechnol Prog. 2001 Jul-Aug; 17(4):720-8., Protein Eng Des Sel. 2004 Jan; 17(1):57-66, Nat Protoc. 2007; 2(5):1225-35., Curr Opin Chem Biol. 2006 Oct; 10(5):487-91. Epub 2006 Aug 28, Biomaterials. 2001 Mar; 22(5):405-17, Bioconjug Chem. 2005 Jan-Feb; 16(1):113-21).

[0051] The term "cultivated plants" is to be understood as also including plants that have been made tolerant to the application of special classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, for example sulfonylureas (see, for example, US 6,222,100, WO 01 / 82685, WO 00 / 26390, WO 97 / 41218, WO 98 / 02526, WO 98 / 02527, WO 04 / 106529, WO 05 / 20673, WO 03 / 14357, WO 03 / 13225, WO 03 / 14356, WO 04 / 16073) or imidazolinones (see, for example, US 6,222,100, WO 01 / 82685, WO 00 / 26390, WO97 / 41218, WO 98 / 02526, WO 98 / 02527, WO 04 / 106529, WO 05 / 20673, WO 03 / 14357, WO 03 / 13225, WO 03 / 14356, WO 04 / 16073); Enolpyruvylshikimate 3-phosphate synthase (EPSPS) inhibitors, for example glyphosate (glyphosate) (see, for example, WO 92 / 00377); Glutamine synthetase (GS) inhibitors, for example glufosinate (glufosinate) (see, for example, EP-A-0 242 236, EP-A-242 246) or oxynil herbicides (see, for example, US Pat. No. 5,559,024). Plants tolerant to these herbicides can be obtained by conventional breeding or genetic engineering methods.

[0052] Several cultivated plants have been rendered tolerant to herbicides by conventional breeding (mutagenesis) methods, for example Clearfield (registered trademark) summer rapeseed (canola), which is tolerant to imidazolinones such as imazamox. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, sugar beet, and rapeseed tolerant to herbicides such as glyphosate and glufosinate, some of which are available under the trade names Roundup Ready (registered trademark) (tolerant to glyphosate) and LibertyLink (registered trademark) (tolerant to glufosinate).

[0053] The term "cultivated plants" is to be understood as also including plants that are capable, by the use of recombinant DNA technology, of synthesizing one or more insecticidal proteins, such as delta-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; asexual insecticidal proteins (VIPs), for example VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of nematode-colonizing bacteria, for example Photorhabdus spp. or Xenorhabdus spp. spp.); animal-derived toxins such as scorpion toxins, spider toxins, wasp toxins or other insect-specific neurotoxins; fungal toxins such as Streptomycetes toxins; plant lectins such as pea or barley lectins; lectins, protease inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cysteine ​​protease inhibitors or papain inhibitors, ribosome-inactivating proteins (RIPs) such as ricin, maize-RIP, abrin, luffain, saporin or bryodin; steroid metabolizing enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitor or HMG-CoA reductase; ion channel blockers such as sodium channel or calcium channel blockers; juvenile hormone esterase; helicokinin receptor; stilbene synthase, bibenzyl synthase, chitinase or glucanase.

[0054] In the context of the present invention, these insecticidal proteins or toxins are also to be understood in particular as pretoxins, hybrid proteins, truncated or otherwise modified proteins.

[0055] Hybrid toxins are produced by recombinant technology using novel combinations of protein domains (e.g., see WO 02 / 015701). Other examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A 374753, WO 93 / 007278, WO 95 / 34656, EP-A 427529, EP-A 451878, WO 03 / 018810, and WO 03 / 052073. Methods for producing such genetically modified plants are generally known to those skilled in the art and are, for example, described in the above-mentioned publications.

[0056] These insecticidal proteins contained in genetically modified plants confer tolerance to certain taxonomic arthropod pests, particularly beetles (Coleoptera), dipteran pests (Diptera), butterflies and moths (Lepidoptera), and plant-parasitic nematodes (Nematoda).

[0057] The term "cultivated plants" is to be understood as also including plants that are able to synthesize one or more proteins that increase tolerance to bacterial, viral or fungal pathogens using recombinant DNA technology. Examples of such proteins are so-called "pathogenesis-related proteins" (PR proteins, see, for example, EP-A 0 392 22), plant disease resistance genes (e.g., potato cultivars expressing resistance genes to Phytophthora infestans from the wild Mexican potato Solanum bulbocastanum) or T4 lysozyme (e.g., potato cultivars capable of synthesizing these proteins and having increased tolerance to bacteria such as Erwinia amylvora). Methods for producing such genetically modified plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications.

[0058] The term "cultivated plants" is to be understood as also including plants that are capable of synthesizing one or more proteins to increase their yield (for example biomass yield, grain yield, sugar content, oil content or protein content), tolerance to drought, salt or other growth-limiting environmental factors, or tolerance to pests and fungal, bacterial or viral pathogens by the use of recombinant DNA techniques.

[0059] The term "cultivated plants" is to be understood as also including plants which have altered or novel content of substances, in particular for improved human or animal nutrition, by the use of recombinant DNA technology, for example oil crops which produce health-promoting long-chain ω-3 fatty acids or unsaturated ω-9 fatty acids (e.g. Nexera (registered trademark) rapeseed).

[0060] The term "cultivated plants" is to be understood as also including plants which have altered or novel substance contents, in particular for improved raw material production, by the use of recombinant DNA techniques, for example potatoes with an increased amylopectin content (eg Amflora (registered trademark) potatoes).

[0061] The preferred method of applying the compound represented by Formula I or the composition comprising the compound as a pest control agent to plants or soil includes spreading treatment, soil treatment, surface treatment or fumigation. The example of spreading treatment includes spreading, spraying (spraying), spraying (misting), atomization (atomizing), granule application or water surface application. The example of soil treatment includes soil irrigation or soil mixing. The example of surface treatment includes coating, dust coating (dust coating) or covering. In addition, the example of fumigation treatment includes after injecting soil, covering soil with polyethylene film. Therefore, the control method of the present invention also includes wherein applying the compound represented by Formula I or the method comprising the preparation of the compound by fumigation treatment in a confined space.

[0062] Other pest control agents that can be incorporated into the compound represented by Formula I or its salt include insecticides, fungicides, acaricides or tickicides, herbicides, and plant growth regulators. Specific agents include, for example, those described in The Pesticide Manual, 13th edition, published by The British Crop Protection Council; and SHIBUYA INDEX, 14th edition, 2009, published by SHIBUYA INDEX RESEARCH GROUP. More specific examples thereof are M.1.-M.27. described below:

[0063] M.1. Organophosphate insecticides: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, and fenthione. hion), flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos,Pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon-methyl, triazophos, trichlorfon, and vamidothion;

[0064] M.2. Carbamate insecticides: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanafen e), furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, and triazamate;

[0065] M.3. Synthetic pyrethroid insecticides: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cypermethrin -Cyhalothrin, (RS) cyhalothrin, lambda-(RS) cyhalothrin, gamma-(RS) cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin thrin), empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tralomethrin, and transfluthrin;

[0066] M.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene, fenoxycarb, and pyriproxyfen;

[0067] M.5. Nicotinic receptor agonist / antagonist compounds: acetamiprid, bensultap, cartap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nicotine, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiacloprid, thiocyclam, thiosultap-sodium, and AKD 1022;

[0068] M.6. GABA-gated chloride channel antagonist compounds: chlordane, endosulfan, gamma-HCH, ethiprole, fipronil, pyraflprole, and pyriprole;

[0069] M.7. Chloride channel activators: abamectin, emamectin benzoate, milbemectin, lepimectin;

[0070] M.8.METI I compounds: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim, and rotenone;

[0071] M.9.METI II compounds: acequinocyl, fluacyprim, and hydramethylnon;

[0072] M.10. Oxidative phosphorylation uncouplers: chlorfenapyr, dinitrocresol (DNOC);

[0073] M.11. Other oxidative phosphorylation inhibitors: azocyclotin, cyhexatin, diafenthiuron, fenbutatin oxide, propargite, and tetradifon;

[0074] M.12. Moulting disruptors: cryomazine, chromafenozide, halofenozide, methoxyfenozide, and tebufenozide;

[0075] M.13. Synergists: piperonyl butoxide, tribufos;

[0076] M.14. Sodium channel blocker compounds: indoxacarb and metaflumizone;

[0077] M.15. Fumigants: methyl bromide, chloropicrin, sulfuryl fluoride

[0078] M.16. Selective feeding blockers: cryolite, pymetrozine, and flonicamid;

[0079] M.17. Mite growth inhibitors: clofentezine, hexythiazox, and etoxazole;

[0080] M.18. Chitin synthesis inhibitors: buprofezin, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, and triflumuron;

[0081] M.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, and spirotetramat;

[0082] M.20. Octapaminergic agonists: amitraz;

[0083] M.21. Ryanodine receptor modulators: flubendiamide and phtalamid compounds (R)-, (S)-3-chloro-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamide (M21.1);

[0084] M.22. Isoxazoline compounds: 4-[5-(3,5-dichlorophenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-pyridin-2-ylmethyl-benzamide (M22.1), 4-[5-(3,5-dichlorophenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-(2,2,2-trifluoroethyl)-benzamide (M22.2), 4 -[5-(3,5-dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoroethylcarbamoyl)-methyl]-benzamide (M22.3), 4-[5-(3,5-dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-naphthalene-1-carboxylic acid [(2,2,2-trifluoroethylcarbamoyl)-methyl]-amide (M22.4), .4), 4-[5-(3,5-dichlorophenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-N-[(methoxyimino)methyl]-2-methylbenzamide (M22.5), 4-[5-(3-chloro-5-trifluoromethyl-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoroethylcarbamoyl)-methyl]-benzamide (M22 .6), 4-[5-(3-chloro-5-trifluoromethyl-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-naphthalene-1-carboxylic acid [(2,2,2-trifluoroethylcarbamoyl)-methyl]-amide (M22.7) and 5-[5-(3,5-dichloro-4-fluorophenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-[1,2,4]triazol-1-yl-benzonitrile (M22.8);

[0085] M.23. Anthranilamide compounds: chloranthraniliprole, cyantraniliprole; 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-cyano-2-(1-cyclopropyl-ethylcarbamoyl)-6-methylphenyl]-amide (M23.1), 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-chloro-4-cyano-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.2), 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-chloro-4-cyano-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.3), 5-bromo-2-(3-chloro-pyridin-2-yl)- -2H-pyrazole-3-carboxylic acid [2-bromo-4-cyano-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.3), 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-chloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.4), 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2,4-dichloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.5), 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-chloro-2-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.6), 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2,4-dichloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.7), 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2,4-dichloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.8), 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2,4-dichloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.9), 5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2,4 2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methylbenzoyl)-N'-methylhydrazinecarboxylic acid methyl ester (M23.7), N'-(2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methylbenzoyl)-N'-methylhydrazinecarboxylic acid methyl ester (M23.8), N'-(2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methylbenzoyl)-N,N'-dimethyl Methyl hydrazinecarboxylate (M23.9), methyl N'-(3,5-dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-hydrazinecarboxylate (M23.10), methyl N'-(3,5-dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-N'-methylhydrazinecarboxylate (M23.11) and methyl N'-(3,5-dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-N,N'-dimethylhydrazinecarboxylate (M23.12);

[0086] M.24. Malononitrile compounds: 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)-malononitrile (CF2H-CF2-CF2-CF2-CH2-C(CN)2-CH2-CH2-CF3) (M24.1) and 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4-pentafluorobutyl)-malononitrile (CF2H-CF2-CF2-CF2-CH2-C(CN)2-CH2-CH2-CF2-CF3) (M24.2);

[0087] M.25. Microbial disruptors: Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;

[0088] M.26. Aminofuranone compounds: 4-{[(6-bromopyridin-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (M26.1), 4-{[(6-fluoropyridin-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-one (M26.2), 4-{[(2-chloro1,3-thiazol-5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (M26.3), 4-{[(6-chloropyridin-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (M26.4), 4-{[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5 H)-one (M26.5), 4-{[(6-chloro-5-fluoropyridin-3-yl)methyl](methyl)amino}furan-2(5H)-one (M26.6), 4-{[(5,6-dichloropyridin-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (M26.7), 4-{[(6-chloro-5-fluoropyridin-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-one (M26.8), 4-{[(6-chloropyridin-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-one (M26.9) and 4-{[(6-chloropyridin-3-yl)methyl](methyl)amino}furan-2(5H)-one (M26.10);

[0089] M.27. Other insecticides: aluminum phosphide, amidoflumet, benclothiaz, benzoximate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen, cyflumetofen, chinomethionate, dicofol, fluoroacetates, phosphine, pyridalyl, pyrifluquinazon, sulfur, organosulfur compounds, tartar emetic emetic), sulfoxaflor, N-R'-2,2-dihalo-1-R"cyclopropanecarboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazone or N-R'-2,2-bis(R"')propionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)-hydrazone, wherein R' is methyl, ethyl or a halogen selected from chlorine or bromine, R" is a hydrogen atom or a methyl group and R"' is methyl or ethyl, 4-but-2-ynyloxy-6-(3,5-dimethyl-piperidin-1-yl)-2-fluoropyrimidine (M27.1), cyclopropaneacetic acid, 1,1'-[(3S,4R,4a R,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl]ester (M27.2) and 8-(2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octane (M27.3).

[0090] Paraoxon and its preparation are described in Farm Chemicals Handbook, Vol. 88, Meister Publishing Company, 2001. Flupyrazofos is described in Pesticide Science 54, 1988, pp. 237-243 and US Pat. No. 4,822,779. AKD 1022 and its preparation are described in US Pat. No. 6,300,348. Anthranilamides M23.1-M23.6 are described in WO 2008 / 72743 and WO 200872783, and those M23.7-M23.12 are described in WO 2007 / 043677. Phthalic acid amide M 21.1 is known from WO 2007 / 101540. The alkynyl ether compound M27.1 is described, for example, in JP 2006131529. Organosulfur compounds are described in WO 2007060839. Isoxazolines M 22.1 to M 22.8 are described, for example, in WO 2005 / 085216, WO 2007 / 079162, WO 2007 / 026965, WO 2009 / 126668, and WO 2009 / 051956. Aminofuranones M 26.1 to M 26.10 are described, for example, in WO 2007 / 115644. Pyripyropene derivatives M 27.2 are described in WO 2008 / 66153 and WO 2008 / 108491. Pyridazine compounds M 27.3 are described in JP 2008 / 115155. Malononitrile compounds such as those (M24.1) and (M24.2) have been described in WO 02 / 089579, WO 02 / 090320, WO 02 / 090321, WO 04 / 006677, WO 05 / 068423, WO 05 / 068432 and WO 05 / 063694.

[0091] In one embodiment, the insecticidal composition comprises a biologically effective amount of at least one of the pyripyropene derivatives (component A), and at least one other active ingredient (component B) selected from the following compounds:

[0092] (1) Acetylcholinesterase (AChE) inhibitors: chlorpyrifos (CAS No.: 2921-88-2), acephate (CAS No.: 30560-19-1);

[0093] (2) γ-aminobutyric acid (GABA)-gated chloride channel antagonist: fipronil (CAS No.: 120068-37-3);

[0094] (3) Sodium channel modulators: highly effective chlorfenapyr (CAS No.: 91465-08-6), bifenthrin (CAS No.: 82657-04-3), deltamethrin (CAS No.: 52918-63-5), highly effective cypermethrin (CAS No.: 1224510-29-5), cis-cypermethrin (CAS No.: 67375-30-8);

[0095] (4) Competitive modulators of nicotinic acetylcholine receptor (nAChR): imidacloprid (CAS No.: 138261-41-3), thiamethoxam (CAS No.: 153719-23-4), acetamiprid (CAS No.: 135410-20-7), dinotefuran (CAS No.: 165252-70-0), clothianidin (CAS No.: 210880-92-5), sulfoxaflor (CAS No.: 946578-00-3), flupyralidone (CAS No.: 951659-40-8), thiamethoxam (CAS No.: 111988-49-9), trifluanid (CAS No.: 1263133-33-0), and pyrimidine (CAS No.: 948994-16-9);

[0096] (5) Glutamate-gated chloride channel (GluCl) allosteric modulators: avermectin (CAS No.: 71751-41-2), avermectin benzoate (CAS No.: 155569-91-8);

[0097] (6) Bionic juvenile hormone: pyriproxyfen (CAS No.: 95737-68-1);

[0098] (7) Nicotinic acetylcholine receptor (nAChR) channel blocker: cartap (CAS No.: 15263-53-3);

[0099] (8) Chitin biosynthesis inhibitors (type 1): buprofen (CAS No.: 69327-76-0), spiromesifen (CAS No.: 283594-90-1);

[0100] (9) Acetyl-CoA carboxylase inhibitors: spirotetramat (CAS No.: 203313-25-1), methoxyfenapyr (CAS No.: 1229023-00-0);

[0101] (10) Ryanodine receptor modulator: cyantraniliprole (CAS No.: 736994-63-1);

[0102] (11) String modulators - unknown target sites: flonicamid (CAS No.: 158062-67-0), anthracenesulfronil (CAS No.: 1403615-77-9);

[0103] (12) GABA-gated chloride channel allosteric modulators: bromofenac (CAS No.: 1207727-04-5), flufenac (CAS No.: 928783-29-3), isoxathiapiprole (CAS No.: 2061933-85-3), compound W (CAS No.: 2892524-05-7);

[0104] (13) Nicotinic acetylcholine receptor (nAChR) allosteric modulator: spinosad (CAS No.: 168316-95-8);

[0105] (14) Others: Metarhizium anisopliae.

[0106] In another specific embodiment, the weight ratio of the active ingredients A and B in the insecticidal composition is 1:150-150:1, 1:100-100:1, 1:80-80:1, 1:60-60:1, 1:40-40:1, 1:20-20:1, 1:10-10:1, 1:8-8:1, 1:5-5:1 or 1:3-1:1.

[0107] The term "biologically effective amount" refers to an amount of a biologically active compound (e.g., a compound of Formula I) sufficient to produce the desired biological effect when applied to (i.e., contacted with) the pest to be controlled or its environment, or the plant, the seed from which the plant grows, or the locus of the plant (e.g., the growth medium), thereby protecting the plant from damage by the pest or achieving other desired effects (e.g., increasing plant vigor). The compounds of the present invention can also be applied prophylactically to locations where pests or parasites are expected to appear.

[0108] The present invention also provides a method for preparing the pyripyropene derivative, which is Made for the intermediate system.

[0109] In one embodiment, the method comprises at least one of the following steps (the specific steps are selected according to the structure of the target product):

[0110] Wherein, the definitions of X1, X2, X3, X4, and R3 are as described above.

[0111] The reactions in steps 1 and 3 are both carried out in the presence of a solvent and a base; the reactions in steps 2, 5 and 9 are carried out in the presence of a solvent, preferably, a condensing agent is added during the reactions in steps 2, 5 and 9, with or without the addition of a base; the reaction in step 4 is carried out in the presence of an oxidant and a solvent; the reaction in step 6 is carried out in the presence of an acidic catalyst and a solvent; the reaction in step 7 is carried out in the presence of an organic base and a solvent; the reaction in step 8 is carried out in the presence of an acid (such as acetic acid) and a solvent; and the reaction in step 10 is carried out in the presence of pyridine hydrofluoride and a solvent.

[0112] In another embodiment, the solvent is selected from at least one of water, THF, pyridine, DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane (DCM) or ethyl acetate.

[0113] In another specific embodiment, the base is selected from at least one of an inorganic base (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KHCO3, KF, CsF, KI, NaI, K3PO4, K2HPO4, NaOH, KOH, NaH, KH, etc.) or an organic base (such as DBU, DMAP, imidazole, pyrazole, triethylamine, DIEA, potassium trimethylsilanolate, AcOK, AcONa, MeONa, EtONa, t-BuONa, etc.).

[0114] In another specific embodiment, the condensing agent is selected from at least one of Py-BOP, Py-AOP, HOBT (1-hydroxybenzotriazole), EDCI (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), DMAP (4-dimethylaminopyridine), DCC, HBTU or HATU.

[0115] In another embodiment, the oxidant is a Dess-Martin oxidant or a PCC oxidant.

[0116] In another embodiment, the acidic catalyst is pyridinium p-toluenesulfonate (PPTS) or p-toluenesulfonic acid.

[0117] In another specific embodiment, the compound II is prepared by fermenting Pseudomonas sartorii using 5-fluoronicotinic acid as a substrate.

[0118] In addition, the compounds of the present invention can also be prepared by referring to the methods described in WO2011093186, WO2010010955, WO2011148886, etc.

[0119] The present invention also provides an intermediate, as shown in Formula II.

[0120] The present invention also provides a method for preparing the pyripyropene derivative, comprising: It is prepared by reduction reaction, wherein X1, X2, X3, X4, Y1, Y2, R1 and R2 are as defined above.

[0121] In a specific embodiment, the reduction reaction is carried out in the presence of sodium borohydride and a solvent, and preferably, cerium trichloride can be added.

[0122] In another embodiment, the solvent is selected from at least one of THF, DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane or ethyl acetate.

[0123] The present invention also provides an intermediate, as shown in Formula III.

[0124] According to another aspect of the present invention, there is provided use of a compound represented by Formula I or an agriculturally or zootechnically acceptable salt thereof as a pest control agent. DETAILED DESCRIPTION

[0125] The following examples are provided to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights claimed in the present invention is described in the claims.

[0126] Given the economical efficiency and diversity of the compounds, we have selected and synthesized a number of compounds. A selection of these compounds is listed in Table 1 below. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are intended to better illustrate the present invention but are not intended to limit the present invention. Those skilled in the art should not interpret this as limiting the scope of the present invention to the following compounds.

[0127] Table 1 Compound structures and their 1 H NMR values

[0128] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or as described in detail. It will be understood by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific starting materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar starting materials and conditions, and these modifications or variations of the preparation methods of the present invention that result in various isomerizations of the compounds are included within the scope of the present invention. In addition, the preparation methods described below can be further modified according to the present disclosure using conventional chemical methods well known to those skilled in the art. For example, appropriate groups can be protected during the reaction, etc.

[0129] The following process examples are provided to facilitate a further understanding of the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthesis of the compounds shown in the table below are either commercially available or can be readily prepared by one of ordinary skill in the art.

[0130] Examples of representative compounds are shown below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0131] 1. Synthesis of compounds 5 and 38

[0132] (1) Fermentation production of compound 38

[0133] Fermentation of 5-fluoronicotinic acid using Pseudomonas satrophylla was performed, and the fermentation broth was filtered to collect the cells. Methanol was added, stirred, and filtered. The methanol extract was collected and concentrated under reduced pressure to obtain an oily concentrate. The oil was then purified by normal-phase silica gel column chromatography to obtain compound 38.

[0134] (2) Compound 38 (30 mg) was dissolved in methanol (2 ml), and 30% sodium methoxide solution (72 mg, 8 eq) was added, followed by stirring at room temperature overnight. The reaction was monitored by central control, and then an aqueous ammonium chloride solution (0.2 ml) was added to the system to quench the reaction. The reaction solution was spin-dried, and the resulting solid was dissolved in ethyl acetate (4 ml) and filtered. The filtrate was spin-dried to obtain a solid, which was then washed with a small amount of water to remove residual ammonium chloride. The resulting solid was dried to obtain compound 5-2 (23 mg, yield 97%).

[0135] (3) 5-2 (23 mg) was dissolved in dichloromethane (5 ml), and 4-dimethylaminopyridine (35 mg, 6 eq), triethylamine (29 mg, 6 eq), cyclopropionic acid (58 mg, 14 eq) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (110 mg, 12 eq) were added to the system in sequence under stirring at room temperature. After reacting for 1 hour, the reaction was monitored for completion. Water (2 ml) was added to the system, and the layers were separated. The dichloromethane phase was washed with 0.05 M hydrochloric acid, sodium bicarbonate, and sodium chloride in sequence. The resulting organic phase was spin-dried and purified by normal phase silica gel column chromatography to obtain compound 5-3 (32 mg, yield 97%).

[0136] (4) 5-3 (32 mg) was dissolved in methanol (5 ml), and a small amount of water and 1,8-diazabicyclo[5.4.0]undec-7-ene (8 mg, 1.1 eq) were added to the system in sequence. The reaction was stirred at room temperature for 2 h. The reaction of the raw material was monitored by central control until completion. The compound 5 (13 mg, yield 45%) was purified by normal phase silica gel column chromatography.

[0137] 2. Synthesis of Compound 9

[0138] (1) Under ice bath, TMEDA (0.1 eq) was added to a nitrogen-protected three-necked flask, and LHMDS (5 eq) was added dropwise. The mixture was kept warm for 10 minutes. A THF solution of compound 9-1 (1 g) was added. The mixture was kept warm for half an hour, then the temperature was raised to room temperature and the reaction was continued for 1 hour. Under ice bath, a THF solution of 9-2 (3 eq) was added to the system and the reaction was kept warm for 1 hour. After the reaction was completed, the reaction solution was poured into an aqueous ammonium chloride solution, extracted with ethyl acetate, and the organic phase was dried, concentrated, and purified by normal phase purification to obtain 430 mg of compound 9-3, with a yield of 34%.

[0139] (2) Compound 9-3 (430 mg) was reacted in an oil bath at 150°C under a negative pressure of 0 mmHg for 15 min to obtain a crude compound 9-4, which was directly used in the next reaction.

[0140] (3) The crude product of compound 9-4 was dissolved in 10 mL of THF, and 10 mL of 80% acetic acid solution was added. The mixture was stirred at room temperature. After the reaction of the raw materials was completed, the reaction solution was poured into a saturated sodium bicarbonate solution under ice bath, and extracted with ethyl acetate. The organic phase was dried and concentrated to obtain 380 mg of crude product of compound 9-5, with a crude product yield of 99%.

[0141] (4) Compound 9-5 crude product (380 mg), DMAP (6 eq), EDCI (4 eq) and cyclopropanecarboxylic acid (5 eq) were added to 10 mL of DCM in sequence and reacted at room temperature. After the reaction was completed, water was added for extraction. The organic phase was washed once with dilute hydrochloric acid, once with saturated sodium bicarbonate solution, and once with sodium chloride solution, and then dried and concentrated to obtain 460 mg of compound 9-6 crude product, with a crude yield of 98%.

[0142] (5) The crude product of compound 9-6 (460 mg) was dissolved in 10 mL of THF, and 3 mL of pyridine and 2 mL of hydrogen fluoride pyridine solution were added under ice bath. After the reaction was completed, the reaction solution was poured into ice water for extraction. The organic phase was washed with saturated sodium bicarbonate solution, dried and concentrated to obtain 240 mg of crude product of compound 9-7, with a crude product yield of 62%.

[0143] (6) The crude product of compound 9-7 (240 mg) was dissolved in 10 mL of THF, and cerium chloride heptahydrate (1.2 eq) and sodium borohydride (2.4 eq) were added in sequence. The reaction was allowed to proceed at room temperature. After the reaction was completed, the reaction solution was filtered through celite, and the filtrate was mixed with silica gel and purified by normal phase purification to obtain 60 mg of compound 9 (light yellow solid, yield 25%).

[0144] 3. Synthesis of Compound 9

[0145] (1) Compound 9-6 (950.0 mg, 1.62 mmol) was dissolved in 5 ml of dichloromethane. Triethylamine (TEA, 1.32 g, 12.96 mmol), cyclopropanecarboxylic acid (696.6 mg, 8.10 mmol), 4-dimethylaminopyridine (DMAP, 395.3 mg, 3.24 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 1.55 g, 8.10 mmol) were added sequentially under ice-water bath and stirred at room temperature for 30 min. LCMS showed that the reaction was complete. Water and dichloromethane were added to the reaction solution to dilute it. The organic phase was washed with saturated ammonium chloride solution and saturated brine in sequence, dried and concentrated to obtain compound 9-8 (600.0 mg, yield 51%, light yellow solid).

[0146] (2) Compound 9-8 (300.0 mg, 0.41 mmol) was dissolved in a pyridine / tetrahydrofuran (2 ml / 10 ml) mixed solvent, and pyridine hydrofluoride (5 ml) was added dropwise at 0°C. The mixture was stirred at room temperature for 12 h. LCMS monitored the reaction to be complete. The reaction solution was quenched with saturated aqueous sodium bicarbonate solution, the aqueous phase was extracted with ethyl acetate, the organic phase was washed with saturated brine, dried, and concentrated, and the residue was purified by column chromatography (EA / PE = 30-60%) to give compound 9 (150.0 mg, 59.6 mmol, 60% yield, as a white solid).

[0147] 4. Synthesis of Compound 43

[0148] Compound 9 (20 mg, 0.03 mmol) was dissolved in 1 ml of dichloromethane, and triethylamine (32 mg, 0.06 mmol), acetic anhydride (6.1 mg, 0.06 mmol), and 4-dimethylaminopyridine (2 mg, 0.03 mmol) were added. The mixture was allowed to react at room temperature for 0.5 h. LCMS monitored the reaction to completion. The reaction solution was quenched with aqueous sodium bicarbonate solution and extracted with ethyl acetate. The organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 1 / 2) to afford compound 43 (10 mg, 47% yield, as a light yellow solid).

[0149] 5. Synthesis of Compound 61

[0150] Compound 5 (100 mg, 0.16 mmol) was dissolved in 1 ml of DMF, and triethylamine (32 mg, 0.32 mmol), 61-1 (67 mg, 0.32 mmol), and 4-dimethylaminopyridine (2 mg, 0.016 mmol) were added. The mixture was allowed to react at room temperature for 0.5 h. LCMS monitored the reaction for completion. The reaction solution was quenched with aqueous sodium bicarbonate solution and extracted with ethyl acetate. The organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (MeOH:DCM = 1:15) to afford compound 61 (10 mg, 9% yield, as a light yellow solid).

[0151] 6. Synthesis of Compound 95

[0152] Compound 5 (0.50 g, 0.82 mmol) was added to a 100 ml three-necked flask and dissolved in 5 ml of dichloromethane. The reaction was placed in an ice-salt bath and Dess-Martin periodinane (0.52 g, 1.22 mmol) was slowly added, maintaining the temperature at no more than 5°C. The reaction was then allowed to react at room temperature for 4 h. After completion of the reaction, as monitored by LCMS, a small amount of saturated sodium thiosulfate solution was added to quench the reaction. The product was extracted three times with dichloromethane, the organic phase dried over anhydrous sodium sulfate, and concentrated. The residue was purified by column chromatography (PE:EA = 1:1) to afford compound 95 (0.11 g, 22% yield, as a yellow solid).

[0153] 7. Synthesis of Compound 126

[0154] (1) Preparation of Compound 126-1: Refer to Compound 9-7. Compound 126-1 (300 mg, 0.48 mmol) was dissolved in 2 ml of 1,2-dichloroethane, and bromomethyl methyl ether (306 mg, 2.46 mmol), TBAI (48 mg, 0.39 mmol), and DIEA (906 mg, 2.46 mmol) were added sequentially. The mixture was allowed to react at room temperature for 12 h. LCMS monitored the reaction until complete. The reaction solution was diluted with water and dichloromethane, and the organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA:PE = 1:5) to give Compound 126-2 (150 mg, 47% yield, as a light yellow solid).

[0155] (2) Compound 126-2 (150 mg, 0.23 mmol) was dissolved in 2 ml of anhydrous ethanol. CeCl3·7H2O (85 mg, 0.23 mmol) and NaBH4 (16 mg, 0.46 mmol) were added sequentially under an ice-water bath and reacted at room temperature for 30 min. LCMS monitored the reaction to be complete. The reaction solution was quenched with saturated aqueous NaHCO3 solution and extracted with ethyl acetate. The organic phase was washed with water and saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA:PE = 1:1) to obtain compound 126 (59 mg, 38% yield, as a light yellow solid).

[0156] 8. Synthesis of Compound 128

[0157] (1) Compound 5-2 (25.0 g crude product) was dissolved in 200 mL DMF, and 128-1 (64.3 mL, 526.3 mmol) and 4-methylbenzenesulfonate pyridinium (6.6 g, 26.3 mmol) were added under ice-water bath, and stirred at room temperature for 30 min. LCMS monitored the reaction completion. The reaction solution was quenched by adding saturated sodium bicarbonate aqueous solution, extracted with dichloromethane, and the organic phase was washed with water and saturated brine, dried and concentrated to obtain a crude product. The crude product was slurried with PE:EA = 10:1, and the filter cake was collected and dried in vacuo to obtain crude compound 128-2 (28.0 g, light yellow solid), which was used directly in the next reaction.

[0158] (2) Compound 128-2 (28.0 g, crude product) was dissolved in 150 mL of DMF. Tert-butyldimethylsilyl chloride (TBSCl, 16.4 g, 108.8 mmol) and imidazole (7.4 g, 108.8 mmol) were added sequentially under an ice-water bath, and the mixture was stirred at room temperature for 12 h. LCMS monitored the reaction completion. The reaction solution was quenched by adding saturated aqueous ammonium chloride solution, extracted with dichloromethane, and the organic phase was washed with water and saturated brine, dried, and concentrated to obtain a crude product. The crude product was slurried with petroleum ether, and the filter cake was collected and dried under vacuum to obtain crude compound 128-3 (28 g, light yellow solid), which was used directly in the next reaction.

[0159] (3) Compound 128-3 (28.0 g, crude product) was dissolved in 100 mL of THF. 1500 mL of 80% AcOH aqueous solution was added under an ice-water bath and stirred at room temperature for 24 h. LCMS confirmed the reaction was complete. The pH was adjusted to 7-8 with saturated sodium bicarbonate aqueous solution. The aqueous phase was extracted with ethyl acetate, and the organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA:PE = 1:5 to 3:5) to give compound 128-4 (21.0 g, 35.6 mmol, light yellow solid).

[0160] (4) Compound 128-4 (500 mg, 0.85 mmol) was dissolved in 2 ml of dichloromethane, and 4-dimethylaminopyridine (104 mg, 0.85 mmol) and 128-5 (110 mg, 0.85 mmol) were added. The mixture was allowed to react at room temperature for 10 h. LCMS confirmed the completion of the reaction. The reaction solution was quenched with aqueous sodium bicarbonate solution and extracted with dichloromethane. The organic phase was washed with water and saturated brine, dried, and concentrated. The residue was purified by column chromatography (THF:PE = 1:4) to give compound 128-6 (500 mg, 91% yield, as a light yellow solid).

[0161] (5) Compound 128-6 (500 mg, 0.77 mmol) was dissolved in 2 ml of dichloromethane. Triethylamine (623 mg, 6.16 mmol), cyclopropanecarboxylic acid (265 mg, 3.08 mmol), EDCI (590 mg, 3.08 mmol), and 4-dimethylaminopyridine (188 mg, 1.54 mmol) were added at room temperature and allowed to react for 2 h. LCMS monitoring confirmed the completion of the reaction. The reaction solution was diluted with water and dichloromethane, and the organic phase was washed with saturated ammonium chloride and saturated brine, dried, and concentrated. The residue was purified by column chromatography (THF:PE = 1:1) to give compound 128-7 (450 mg, 82% yield, as a light yellow solid).

[0162] (6) Compound 128-7 (450 mg, 0.63 mmol) was dissolved in 1 ml of tetrahydrofuran. Pyridine (0.5 ml, 6.3 mmol) and hydrofluoric acid / pyridine (0.5 ml, 5.0 mmol) were added under an ice-water bath and allowed to react at room temperature for 12 h. LCMS monitored the reaction to be complete. The reaction solution was quenched with aqueous sodium bicarbonate solution and extracted with ethyl acetate. The organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (MeOH:DCM = 1:20) to give compound 128 (49 mg, 13% yield, as a light yellow solid).

[0163] 9. Synthesis of Compound 5

[0164] (1) Compound 128-4 (21.0 g, 35.6 mmol) was dissolved in 150 mL of DCM. Triethylamine (TEA, 28.7 g, 284.8 mmol), cyclopropanecarboxylic acid (15.3 g, 178.0 mmol), 4-dimethylaminopyridine (DMAP, 8.7 g, 71.2 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 27.2 g, 142.4 mmol) were added sequentially under ice-water bath and stirred at room temperature for 12 h. LCMS showed that the reaction was complete. The reaction solution was diluted with water and dichloromethane. The organic phase was washed with saturated ammonium chloride solution and saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 10-50%) to give compound 5-4 (17.5 g, 24.1 mmol, white solid).

[0165] (2) Compound 5-4 (17.5 g, 24.1 mmol) was dissolved in a pyridine / tetrahydrofuran (20 mL / 100 mL) mixed solvent, and pyridine hydrofluoride (30 mL) was added dropwise at 0°C. The mixture was stirred at room temperature for 24 h. LCMS monitored the reaction to be complete. The reaction solution was quenched with saturated aqueous sodium bicarbonate solution, the aqueous phase was extracted with ethyl acetate, and the organic phase was washed with water and saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 30-60%) to give compound 5 (13.4 g, 21.9 mmol, white solid).

[0166] 10. Synthesis of Compound 131

[0167] (1) Compound 9-7 (120.0 mg, 0.25 mmol) was dissolved in 2 ml of 1,2-dichloroethane, and bromomethyl methyl ether (31.0 mg, 0.25 mmol), TBAI (11.0 mg, 0.03 mmol), and DIEA (32.3 mg, 0.25 mmol) were added sequentially. The mixture was allowed to react at room temperature for 3 h. LCMS monitored the reaction to be complete. The reaction solution was diluted with water and dichloromethane, and the organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 1 / 5) to give compound 131-1 (30.0 mg, 47% yield, as a light yellow solid).

[0168] (2) Compound 131-1 (30.0 mg, 0.05 mmol) was dissolved in 1 ml of tetrahydrofuran. CeCl3·7H2O (18.6 mg, 0.05 mmol) and NaBH4 (3.8 mg, 0.10 mmol) were added sequentially under an ice-water bath and allowed to react at room temperature for 30 min. LCMS monitored the reaction to be complete. The reaction solution was quenched with saturated aqueous NaHCO3 solution and extracted with ethyl acetate. The organic phase was washed with water and saturated brine, dried, and concentrated. The residue was purified by column chromatography (EA / PE = 1 / 1) to give compound 131 (8.0 mg, yield 27%) as a light yellow solid.

[0169] 11. Synthesis of Compound 133

[0170] (1) Compound 9-5 (350 mg, 0.60 mmol) was dissolved in 2 ml of dichloromethane, and 4-dimethylaminopyridine (77.5 mg, 0.60 mmol) and propionic anhydride (72.8 mg, 0.60 mmol) were added. The mixture was allowed to react at room temperature for 30 min. LCMS monitored the reaction to be complete. The reaction solution was quenched with aqueous sodium bicarbonate solution and extracted with dichloromethane. The organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (THF / PE = 1 / 4) to give compound 133-1 (140 mg, 37% yield, as a light yellow solid).

[0171] (2) Compound 133-1 (140 mg, 0.22 mmol) was dissolved in 2 ml of dichloromethane. Triethylamine (175 mg, 1.74 mmol), cyclopropanecarboxylic acid (73.5 mg, 0.87 mmol), EDCI (164.5 mg, 0.87 mmol), and 4-dimethylaminopyridine (52.5 mg, 0.43 mmol) were added at room temperature and reacted for 2 h. LCMS monitored the reaction to be complete. The reaction solution was diluted with water and dichloromethane, and the organic phase was washed with saturated ammonium chloride and saturated brine, dried, and concentrated. The residue was purified by column chromatography (THF / PE = 1 / 3) to give compound 133-2 (80 mg, 52% yield, as a light yellow solid).

[0172] (3) Compound 133-2 (80 mg, 0.63 mmol) was dissolved in 1 ml of tetrahydrofuran. Pyridine (0.5 ml, 6.3 mmol) and hydrofluoric acid / pyridine (0.5 ml, 5.0 mmol) were added under an ice-water bath and allowed to react at room temperature for 12 h. LCMS confirmed the completion of the reaction. The reaction solution was quenched with aqueous sodium bicarbonate solution and extracted with ethyl acetate. The organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (THF / PE = 1 / 1) to afford compound 133-3 (50 mg, 75% yield, as a light yellow solid).

[0173] (4) Compound 133-3 (50 mg, 0.08 mmol) was dissolved in 1 ml of tetrahydrofuran. CeCl3·7H2O (30 mg, 0.08 mmol) and NaBH4 (6.5 mg, 0.17 mmol) were added under ice-water bath and reacted at room temperature for 30 min. LCMS monitored the reaction to be complete. The reaction solution was quenched with aqueous sodium bicarbonate solution and extracted with ethyl acetate. The organic phase was washed with saturated brine, dried, and concentrated. The residue was purified by column chromatography (THF / PE = 1 / 1) to give compound 133 (30 mg, 40% yield, as a light yellow solid).

[0174] DETAILED DESCRIPTION

[0175] Biological activity evaluation:

[0176] (1) Insecticidal activity test:

[0177] 1.1) Spray treatment test

[0178] After the original drug is dissolved in acetone, the solution is diluted with distilled water to a gradient dose. Select potted radish seedlings with insects of the same age as the peach aphids and seedlings, use a handheld sprayer to spray, spray evenly on both sides, spray 8-10 times per pot of radish, use clean water as the control, repeat 3 times, and transfer to breeding conditions after application. Select 3-year-old green stink bug test insects with the same physiological state raised indoors, put them in disposable transparent plastic cups, inoculate 20 test insects into each cup, and put 4 fruit corn kernels, then use a spray tower to spray, cover the cup mouth with the cup after spraying, repeat 3 times, use clean water as the control, and transfer to breeding conditions after application. Select potted wheat seedlings with the same age as the cereal aphids and seedlings, use a handheld sprayer to spray, spray evenly on both sides, spray 8-10 times per pot of wheat, use clean water as the control, repeat 3 times, and transfer to breeding conditions after application. After n days, the results were investigated and the mortality of each treatment was counted to calculate the mortality rate: mortality rate (%) = (number of dead insects / number of test insects) * 100.

[0179] Table 2 Insecticidal test results

[0180] Note: N stands for no data; Reference compound A:

[0181] 1.2) Top conduction ability test

[0182] Infested radish seedlings were planted in disposable transparent plastic cups, with three seedlings per cup. The plants were drought-treated for 24 hours before the experiment. 20 mL of the prepared solution was then injected into the roots of the seedlings. Three replicates were added for each treatment, with a water control provided. Normal lighting and culture conditions were maintained. Six days after treatment, the results were assessed. Mortalities were counted for each treatment, and mortality rates were calculated. Representative experimental results are shown in Table 3.

[0183] Mortality rate = (number of dead insects / number of test insects) × 100%

[0184] Table 3 Test results of top conduction capacity

[0185] Note: Control compound B: acyclovir.

[0186] (2) Composition insecticide activity determination test:

[0187] 2.1) Test conditions and operating steps

[0188] Test targets: Myzus persicae, Bemisia tabaci

[0189] Green peach aphid: Dissolve the original drug in acetone and dilute the solution with distilled water to a gradient dosage. Select potted radish seedlings with infested aphids and seedlings of the same age. Use a handheld sprayer to spray evenly from both sides, spraying 8-10 times per pot of radish. Use clean water as a control. Repeat this three times. After application, transfer the plants to rearing conditions. After 6 days, investigate the results and count the mortality rate for each treatment. Calculate the mortality rate: Mortality rate (%) = (number of dead insects / number of insects tested) * 100.

[0190] Bemisia tabaci: After dissolving the original drug in acetone, dilute the solution with distilled water to a gradient dose. Use a one-liter plastic cup with a lid as a test vessel. Cut two true leaves from the Beibei pumpkin and insert them on a plastic sponge. Add an appropriate amount of water to the sponge to moisturize the pumpkin seedlings. Place the treated pumpkin seedlings in the plastic cup to make a test device. Gather about 200 adult Bemisia tabaci and place them in the test device. Use a handheld electric sprayer to evenly spray the prepared drug solution from the hole cover on the top. Repeat 3 times for each treatment. After the application is completed, place the treatment room at a temperature of 25°C and a humidity of 60%. Investigate the results after 3 days. Count the deaths of each treatment separately and calculate the mortality rate: Mortality rate (%) = (number of dead insects / number of test insects) * 100.

[0191] 2.2) Qualitative evaluation of efficiency

[0192] Toxicity tests were performed at different ratios within the selected range, and the optimal ratio was selected based on the synergistic effect. A synergistic effect > 0 indicates a synergistic effect; a synergistic effect close to 0 indicates an additive effect; and a synergistic effect < 0 indicates an antagonistic effect.

[0193] Synergistic effect = actual mortality rate - theoretical mortality rate

[0194] Theoretical mortality rate = 1-(1-P1)(1-P2)

[0195] Where, P1, P2 are the mortality rates of each single dose in the mixture.

[0196] Table 4 Qualitative evaluation test results of the composition synergistic effect

[0197] At the same time, after many tests, it was found that the compounds and compositions of the present invention have good control effects on piercing-sucking mouthpart pests (such as aphids, whiteflies, stink bugs, psyllids, scale insects, mealybugs and leafhoppers, etc.), can reduce the occurrence of viral diseases and bacterial diseases transmitted by insect vectors, are suitable for economic crops, field crops and ornamental plants, etc., can be used for foliar treatment, seed treatment or soil treatment, and have little impact on beneficial arthropods such as natural enemy insects and pollinating insects, can effectively reduce the environmental burden of sustainable agricultural development, are suitable for pest resistance management and integrated pest control, and have certain commercial value.

Claims

1. A pyripyropene derivative as shown in formula I, in, X1 represents hydrogen or fluorine, X2 represents hydrogen or fluorine, X3 represents hydrogen or fluorine, X4 represents hydrogen or fluorine, and X1, X2, X3 and X4 are not hydrogen at the same time; R1 and R2 independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl or -(CO)R3; Y1 represents hydroxy, alkoxyalkyloxy, trialkylsilyloxy or -O(CO)R3; Y2 represents hydrogen or alkyl; or Y1 and Y2 together form =O; R3 each independently represents hydrogen, an alkyl, alkenyl or alkynyl group which is unsubstituted or substituted by at least one of halogen, alkoxy, alkoxycarbonyl or alkylthio, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group; The aforementioned "cycloalkyl", "cycloalkenyl", "heterocyclyl" or "aryl" is optionally selected from oxo, halogen, cyano, nitro, alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, cycloalkyl substituted by alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-alkylene-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 Each is independently hydrogen, alkyl, haloalkyl, phenyl, or phenyl substituted by at least one group selected from halogen, cyano, nitro, alkyl, haloalkyl, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkoxy or haloalkoxy.

2. The pyripyropene derivative according to claim 1, characterized in that R1 and R2 independently represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkylC1-C8 alkyl or -(CO)R3; Y1 represents hydroxyl, C1-C8 alkoxy, C1-C8 alkyloxy, tri-C1-C8 alkylsilyloxy or -O(CO)R3; Y2 represents hydrogen or C1-C8 alkyl; or Y1 and Y2 together form =O; R3 each independently represents hydrogen, C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl which is unsubstituted or substituted by at least one of halogen, C1-C8 alkoxy, C1-C8 alkoxycarbonyl or C1-C8 alkylthio, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, aryl or heterocyclic group; The aforementioned "C3-C8 cycloalkyl", "C3-C8 cycloalkenyl", "heterocyclyl" or "aryl" is optionally selected from oxo, halogen, cyano, nitro, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, halogenated C1-C8 alkyl, halogenated C2-C8 alkenyl, halogenated C2-C8 alkynyl, halogenated C3-C8 cycloalkyl, C3-C8 cycloalkyl substituted by C1-C8 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C8 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 are independently hydrogen, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, or selected from halogen, cyano, nitro The phenyl group is substituted by at least one of a C1-C8 alkyl group, a C1-C8 alkyl group, a halogenated C1-C8 alkyl group, a C1-C8 alkoxycarbonyl group, a C1-C8 alkylthio group, a C1-C8 alkylsulfonyl group, a C1-C8 alkoxy group or a halogenated C1-C8 alkoxy group.

3. The pyripyropene derivative according to claim 1 or 2, characterized in that: R1 and R2 independently represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC1-C6 alkyl or -(CO)R3; Y1 represents hydroxyl, C1-C6 alkoxy, C1-C6 alkyloxy, tri-C1-C6 alkylsilyloxy or -O(CO)R3; Y2 represents hydrogen or C1-C6 alkyl; or Y1 and Y2 together form =O; R3 each independently represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, aryl or heterocyclic group which is unsubstituted or substituted by at least one of halogen, C1-C6 alkoxy, C1-C6 alkoxycarbonyl or C1-C6 alkylthio; The aforementioned "C3-C6 cycloalkyl", "C3-C6 cycloalkenyl", "heterocyclyl" or "aryl" is optionally selected from oxo, halogen, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, halogenated C1-C6 alkyl, halogenated C2-C6 alkenyl, halogenated C2-C6 alkynyl, halogenated C3-C6 cycloalkyl, C3-C6 cycloalkyl substituted by C1-C6 alkyl, -OR 10 、-SR 10 、-(CO)OR 10 、-(SO2)R 10 、-N(R 10 )2 or -O-(C1-C6 alkylene)-(CO)OR 10 or two adjacent carbon atoms on the ring form a condensed ring with unsubstituted or halogen-substituted -OCH2CH2- or -OCH2O-; R 10 Each of them is independently hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, or phenyl substituted by 1 to 3 groups selected from halogen, cyano, nitro, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

4. The pyripyropene derivative according to any one of claims 1 to 3, characterized in that: X1 represents hydrogen, X2 represents fluorine, X3 represents hydrogen, and X4 represents hydrogen; or X1 represents hydrogen, X2 represents hydrogen, X3 represents fluorine, and X4 represents hydrogen; Preferably, the compound is selected from Table 1 of the specification.

5. A method for preparing a pyripyropene derivative according to any one of claims 1 to 4, characterized in that: Its obtained by an intermediate; or Prepared by reduction reaction; or Includes at least one of the following steps: Wherein, the definitions of X1, X2, X3, X4, and R3 are as described in any one of claims 1 to 4; Wherein, the reactions in step 1 and step 3 are both carried out in the presence of a solvent and a base; the reactions in step 2, step 5 and step 9 are carried out in the presence of a solvent, preferably, a condensing agent is added during the reactions in step 2, step 5 and step 9, with or without the addition of a base; the reaction in step 4 is carried out in the presence of an oxidant and a solvent; the reaction in step 6 is carried out in the presence of an acidic catalyst and a solvent; the reaction in step 7 is carried out in the presence of an organic base and a solvent; the reaction in step 8 is carried out in the presence of an acid (such as acetic acid) and a solvent; the reaction in step 10 is carried out in the presence of pyridine hydrofluoride and a solvent; More preferably, the solvent is selected from at least one of water, THF, pyridine, DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane or ethyl acetate, the base is selected from at least one of an inorganic base or an organic base, the condensing agent is selected from at least one of Py-BOP, Py-AOP, HOBT, EDCI, DMAP, DCC, HBTU or HATU, the oxidant is a Dess-Martin oxidant or a PCC oxidant, or the acidic catalyst is pyridine p-toluenesulfonate (PPTS) or p-toluenesulfonic acid; Preferably, the reduction reaction is carried out in the presence of sodium borohydride and a solvent, more preferably, cerium trichloride may be added; or the solvent is selected from at least one of THF, DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane or ethyl acetate.

6. The method according to claim 5, characterized in that The compound II is prepared by fermenting Pseudomonas saturnalis with 5-fluoronicotinic acid as a substrate.

7. An insecticidal composition, characterized in that: Comprising a biologically effective amount of at least one of the pyripyropene derivatives according to any one of claims 1 to 4; preferably, further comprising a formulation adjuvant; more preferably, further comprising other active ingredients; further preferably, the other active ingredients are selected from at least one of the following compounds: (1) Acetylcholinesterase (AChE) inhibitors: chlorpyrifos, acephate; (2) GABA-gated chloride channel antagonist: fipronil; (3) Sodium channel regulators: highly effective chlorfenapyr, bifenthrin, deltamethrin, highly effective cypermethrin, cis-cypermethrin; (4) Competitive modulators of nicotinic acetylcholine receptors (nAChR): imidacloprid, thiamethoxam, acetamiprid, dinotefuran, clothianidin, sulfoxaflor, flupyralidone, thiamethoxam, trifluanid, and pyrimidine; (5) Allosteric modulators of glutamate-gated chloride channels (GluCl): avermectin, avermectin benzoate; (6) Bionic juvenile hormone: pyriproxyfen; (7) Nicotinic acetylcholine receptor (nAChR) channel blockers: cartap; (8) Chitin biosynthesis inhibitors (type 1): buprofezin, spiromesifen; (9) Acetyl CoA carboxylase inhibitors: spirotetramat, methoxyfentamethylenetetramine; (10) Nicotinic acid receptor modulators: cyantraniliprole; (11) String modulators - unknown target sites: flonicamid, anthracene; (12) GABA-gated chloride channel allosteric modulators: bromofenac, fluoxathiapiprolin, isoxathiapiprolin, and compound W (CAS No. 2892524-05-7); (13) Nicotinic acetylcholine receptor (nAChR) allosteric modulators: spinosad; (14) Others: Metarhizium anisopliae. More preferably, the weight ratio of the pyriproxypyrimidine derivative to other active ingredients in the insecticidal composition is 1:150-150:1, 1:100-100:1, 1:80-80:1, 1:60-60:1, 1:40-40:1, 1:20-20:1, 1:10-10:1, 1:8-8:1, 1:5-5:1 or 1:3-1:

1.

8. A method for controlling pests, characterized in that: The method comprises contacting the pest or its environment with a biologically effective amount of the pyripyropene derivative according to any one of claims 1 to 4 or the composition according to claim 7.

9. Use of the pyripyropene derivative according to any one of claims 1 to 4 or the composition according to claim 7 in controlling pests.

10. An intermediate as shown in formula II or III of claim 5.

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