Compounds of the formula (i) and their use

Abstract

This invention discloses a class of compounds and their uses, belonging to the field of agricultural technology. The compounds provided by this invention have excellent inhibitory activity against insect eggs, especially against the eggs of thrips, mites, lepidopteran moths, whiteflies, and ladybugs, and also have fungicidal activity. Compounds with this structure can be used to kill insect eggs and fungi, and have high research value in pesticides, with broad application prospects in the field of pesticide science.

Description

[0001] This application is a divisional application of Chinese patent application 202510266830.7. Technical Field

[0002] This invention relates to the field of agricultural technology, and in particular to a class of compounds and their uses. Background Technology

[0003] The pesticide market is vast and enormous, with a market capacity approaching 10 billion yuan. Typical agricultural pesticides mainly include Orthoptera such as locusts and mole crickets; Hemiptera such as stink bugs; Homoptera including aphids, leafhoppers, and planthoppers; Thysanoptera such as thrips; Coleoptera such as beetles; Lepidoptera such as moths and butterflies; Hymenoptera such as bees and ants; Diptera such as mosquitoes, flies, and horseflies; and Grylloides such as various spider mites.

[0004] In existing pest control practices, most insecticides focus on contact and stomach poison effects against adults, nymphs, or larvae. This aims to control the pest population by significantly reducing the number of insects on crops, thereby protecting crops from excessive damage and minimizing economic losses after infestations. While this method is generally effective in controlling pest populations in the environment, it often proves less effective against short-generation pests (such as various spider mites and thrips).

[0005] Taking spider mites as an example, there are numerous registered acaricides, including dozens of plant-derived, inorganic mineral, or chemical acaricides such as etoxazole, abamectin, triazophos, fenbutatin, spirodiclofen, etoxazole, veratrum root extract, and matrine. However, most of these acaricides target adult mites or nymphs, with only a few exhibiting good ovicidal activity. In the field, mites reproduce extremely rapidly, completing a generation cycle approximately every week, resulting in severe generational overlap. Therefore, if only acaricides without ovicidal activity are sprayed, although adult mites may be killed, new larvae will quickly hatch from the eggs and rapidly expand the population. While secondary applications can eliminate subsequently hatched mites, several problems arise in practical application. For example, overly frequent applications can lead to rapid development of mites' resistance. Simultaneously, the cost of pesticide application for farmers will increase exponentially. In the field, to save labor costs, traditional pesticide application methods tend to involve mixing multiple agents, such as acaricides, insecticides, fungicides, regulators, and foliar nutrients, in buckets. In actual mite control applications in the field, farmers often choose to use them in combination with ovicidal agents to extend the duration of effectiveness. However, among the registered acaricides, only etoxazole and spirodiclofen are explicitly used as ovicidal agents, making them relatively scarce. This scarcity and rising resistance are increasing the demand for new, effective dual-action acaricides that kill both mites and eggs. Simultaneously, multifunctional small-molecule acaricides are scarce. Farmers typically need to mix and apply multiple agents, such as regulators, foliar nutrients, fungicides, and ovicidal agents, in the field. Mixing multiple chemical agents with different mechanisms of action and formulations not only easily leads to antagonistic effects between agents but also easily damages the stability of the aqueous solution, causing precipitation, flocculation, and stratification, severely impacting the field application of the pesticides. At the same time, the mixing of large amounts of pesticides can easily lead to a further increase in target resistance and adverse environmental effects from pesticide residues.

[0006] Therefore, developing novel and highly effective insecticides and ovicides with novel structures and unique mechanisms of action is key to the control of agricultural pests. Summary of the Invention

[0007] The purpose of this invention is to provide a class of insecticidal oviposition compounds, which are prepared and isolated to obtain an absolute configuration, wherein one or more of the configurations are compounds to solve the problems existing in the prior art and achieve good inhibition and killing effects on insect eggs.

[0008] This invention provides a compound selected from one of the following compounds:

[0009]

[0010] .

[0011] The structures of the compounds of this invention can be confirmed using conventional methods well known to those skilled in the art. If this invention relates to the absolute configuration of a compound, then that absolute configuration can be confirmed using conventional techniques in the art. According to the literature (Absolute configuration of glycosyl sulfoxides, Tetrahedron: Asymmetry, Volume 21, Issue 15, 2010, Pages 1830-1832), if the lone pair electrons of the group and sulfur are on the same side, the group is shielded, the chemical shift decreases, and the chemical shift shifts to a higher field. If the group is on the same side as the oxygen atom, the group is unshielded, the chemical shift increases, and it shifts to a lower field. The absolute configuration of the compounds is obtained by comparing and analyzing the proton NMR spectra of chiral separation compounds and by testing their optical rotation.

[0012] The compound numbers listed above are for convenience in subsequent explanations only.

[0013] The present invention provides a method for controlling and / or killing insect eggs and / or sterilizing by applying one or more of the above-mentioned compounds to insect eggs and / or fungi.

[0014] The intermediate compounds of the present invention can be prepared by a variety of synthetic methods known to those skilled in the art, including the specific embodiments listed herein, embodiments formed by combining them with other chemical synthetic methods, and equivalent substitutions known to those skilled in the art. Preferred embodiments include, but are not limited to, the embodiments of the present invention.

[0015] The chemical reactions in the specific embodiments of this invention are carried out in a suitable solvent, which must be suitable for the chemical changes of this invention and the reagents and materials required therefor. To obtain the compounds of this invention, it is sometimes necessary for those skilled in the art to modify or select the synthesis steps or reaction flow based on existing embodiments.

[0016] As used in this application, the term "pest" refers to an organism that adversely affects a host (e.g., a plant or an animal such as a mammal) by parasitizing, damaging, attacking, competing with, or infecting them for nutrients.

[0017] Unless otherwise specified, pests include arthropods (including insects and arachnids), and include piercing-sucking pests and biting pests (such as bedbugs, mites, ticks, ants, lice, cockroaches, thrips, etc.).

[0018] Unless otherwise specified, the insect eggs are produced by insects of the orders Thysanoptera, Hemiptera, Lepidoptera, Coleoptera, Acari, Tetranychidae, Eriophyta, Tardiidae, Pyromitidae, Chrysophagidae, or Carnivorous mites; the fungi include fungi and bacteria.

[0019] The order "Thysanoptera" belongs to the class Insecta. Insects in this order are commonly known as thrips. They are small insects with slender, elongated bodies, generally yellowish-brown or black; they have well-developed eyes, piercing-sucking mouthparts, and are asymmetrical; their wings are narrow and long, with a few veins or no veins, and the wing edges are flat and long, with hairs of varying lengths; some species are wingless or only have vestigial hairs; they lack cerci. They generally suck plant sap, harming cereals, cotton, and tobacco, and some can transmit plant viruses, making them pests. Thrips are divided into the suborders Terebrantia and Tubulifera. The suborder *Thrips* includes: the superfamily *Aeolothripoidea* (comprising *Aeolothripidae*, *Orothripidae*, *Melanthripidae*, *Dactuliothripidae*, and *Franklinothripidae*), the superfamily *Merothripoidea* (comprising *Aeolothripoidea*), and the superfamily *Thripoidea* (comprising *Heterothripidae*, *Hemithripidae*, *Ceratothripidae*, *Panchaetothripidae*, and *Thripidae*). Among these, the family *Thripidae* is the largest and most important family within this order, containing 33 genera and approximately 200 species, such as *Frankliniella intonsa*, *Thripstabaci Lindeman* (cotton thrips), and *Taeniothrips distalis*. Karny, rice thrips (Stenchaeotothrips biformis), yellow-breasted thrips (Thrips hawaiiensis Morgan), palm thrips (Thrips palmi Karny), western flower thrips (Frankliniella occidentalis), loquat thrips (Thrips japonicus Bagnall), sugarcane thrips (Thripsserratus Kobus), rice thrips (Frankliniella tenuicornis Uzel), yellow hard thrips (Scirtothrips dorsalis Hood), greenhouse thrips (Heliothrips haemorrhoidalis Bouche), yellow thrips (Scirtothrips dorsalis Hood), and six-spotted thrips (Scolothrips sexmaculatus Pergande) are all common species in my country.The suborder *Phlaeothripoidea* includes: the superfamily *Phlaeothripoidea* (comprising Pypothripidae, Ecacanthothripidae, Eupatithripidae, Phlaeothripidae, Chirothripoididae, Hystricothripidae, Idolothripidae, and Megathripidae) and the superfamily *Urothripoidea* (comprising Urothripidae). The parentheses following each superfamily represent its subfamilies; similarly, all references to superfamilies in the following text will use this method.

[0020] The term "Hemiptera" refers to insects with a slightly flattened and rigid body; piercing-sucking mouthparts; filiform or club-shaped antennae; two ocelli or none; a well-developed pronotum with triangular scutels; forewings that are hemolecular and hindwings that are membranous, with some species having vestigial or wingless wings; most species have scent glands; the tarsi often have claws at the end, with claw pads below the claws; the abdomen has 9-11 segments, usually 10; and no cerci; it is named for its hemolecular forewings. The order Hemiptera is divided into the suborders Auchenorrhyncha and Sternorrhyncha. Auchenorrhyncha includes the superfamily Cicadodea (Cicadidae, Membracidae, Machearotidae, Cercopidae, Cicadellidae) and the superfamily Fulgoroidea (Tettigometridae, Delphacidae, Fulgoridae, Eurybrachydidae, Cixiidae, Meenoplidae, Dictyopharidae, Achilidae, Tropiduchidae, Derbidae, Lophopididae). ae, Issidae, Flatidae, Ricaniidae; the suborder Ricaniidae includes the superfamily Psylloidea, Aleyrodoidea, Aphidoidea (including Adelgidae, Phyloxeridae, Pemphigidae, and Aphididae) and the superfamily Coccoidea (including Margarodidae, Ortheziidae, Kerridae, Kermidae, Dactylopiidae, Pseudococcidae, Asterolecaniidae, Coccidae, and Diaspididae).

[0021] The "Lepidoptera" mentioned above belong to the class Insecta and have a very wide distribution, with the most abundant species in the tropics. The larvae of most species damage various cultivated plants. The larger ones often eat all the leaves or bore into the branches and trunks. The smaller ones often roll leaves, clump leaves together, form sheaths, spin webs, or burrow into plant tissues to feed. The adults mostly supplement their nutrition with nectar, or their mouthparts degenerate and they no longer feed. Lepidoptera includes the suborder Zeugloptera (family Micropterygidae), the suborder Monotrysia (superfamilies Eriocraniidea, Hepialoidea, Stigmelloidea, Incurvarioidea), and the suborder Ditrhysia (superfamilies Tinaeoidea, Cossoidea, Psychoidea, Castnioidea, Tortricoidea, Pyraloidea, Bombycoidea, Calliduloidea, Geometridae, Sphingoidea, Noctuoidea, Hesperioidea, and Papilionoidea).

[0022] The order Coleoptera is the largest and most diverse order in the class Insecta and even the animal kingdom. It is divided into three suborders: Adephaga, Polyphaga, and Rhynchophora. The Adephaga suborder includes: Caraboidea (including Cicindelidae, Carabidae, Amphizoidae, Omophronidae, Hygrobiidae, Haliplidae, and Dytiscidae), Gyrinoidea (including Gyrinidae), and Paussoidea (including Paussoidea). The superfamily Paussidae, superfamily Cupesoidea, and superfamily Rhysodoidea are included. The suborder Polyphagous includes: superfamily Hydrophiloidea, superfamily Staphylinoidea, family Silphidae, family Leiodidae, family Clambidae, family Scydmaenidae, family Orthoperidae, family Phaenidae. ocephalidae, Discolomidae, Platypsyllidae, Cantharoidea (including Lycidae, Lampyridae, Cantharidae, Drilidae, Malachiidae, Phloeophilidae, Prionoceridae, Dasytidae), Lymexyloidea (including Lymexylidae, Atrium) Actoceridae), Elateroidea (including Rhipiceridae, Cebrionidae, Elateridae, Eucinmidae, Throscidae), Dryopoidea (including Psephenidae, Dryopidae, Helmidae, Georyssidae, Heteroceridae), Dascilloidea (including Dascilloidea)(Dascillidae), Tenebrionoidea (Alleculidae, Tenebrionidae), Ptinidae (Lyctidae, Bostrychidae, Anobiidae, Ptinidae), Scarabaeoidea (Scarabaeidae, Aegialiidae, Aphodiidae, Ochodaeidae, Geotrupidae, Trogidae, Melolonthidae, Rutelidae, Dynastidae, Cetoniidae, Trichiidae, Passalidae) The superfamily Cerambycoidea includes Prionidae, Cerambycidae, Lamiidae, and Sagridae; the superfamily Brentoidea includes Brentidae; the superfamily Curculionoidea includes Anthribidae, Aglycyderidae, Proterhiniidae, Cyladidae, and Curculionidae; the suborder Curculionoidea includes: the superfamily Curculionoidea. Common insects (common names): ladybug, longhorn beetle, firefly, dung beetle, blister beetle, rhinoceros beetle, jewel beetle, blister beetle, scarab beetle, stag beetle, click beetle, water beetle, rice weevil.

[0023] The "mites" mentioned in this application mainly include agricultural pests, most of which belong to the families Tetranychidae, Tenuipalpidae, Eriophyidae, Tarsonemidae, Pyemotidae, Penthhaleidae, and Cheyetidae of the class Acachnidae.

[0024] The family Tetranychus is divided into several genera: *Oligonychus* (e.g., *Oligonychus baipisongis*, *Oligonychus karamatus*, *Oligonychus rubicundus*), *Eotetranychus* (e.g., *Eotetranychus albus*, *Eotetranychus bailae*, *Eotetranychus camelliae*), *Tetranychus* (e.g., *Tetranychus neocaledonicus*, *Tetranychus phaselus*, *Tetranychus surticae*, *Tetranychus cinnabarinus*), and *Schizotetranychus* (e.g., *Schizotetranychus baltazarae*, *Schizotetranychus basilica*). * *Schizotetranychus elongatus*, etc.; *Mixonychus* (e.g., *Mixonychus (Bakerina) aestiva*, *Mixonychus (Mixonychus) ganjuis*, *Mixonychus (Bakerina) murrayae*, etc.); *Panonychus* (e.g., *Panonychus citri*, *Panonychus caglei*, *Panonychus ulmi*, etc.); *Allonychus* (e.g., *Allonychus bambusae*, *Allonychus wuyinicus*); *Stigmaeopsis* (e.g., *Stigmaeopsis*). Celarius, Stigmaeopsis nanjingensis, Monocyllus (e.g., Monocyllus georicus), Acanthonychus (e.g., Acanthonychus jiangfengensis), Amphitetranychus (e.g., Amphitetranychus hawthorn)* *Viennensis*, *Sonotetranychus* (e.g., *Sonotetranychus neosalix*), *Xinella* (e.g., *Xinella huangshanensis*), *Yunonychus* (e.g., *Yunonychus daliensis*), *Neotetranychus* (e.g., *Neotetranychus lek*), *Eurytetranychus* (e.g., *Eurytetranychus glycyrrhizae*, *Eurytetranychus wuyishanensis*), *Aponychus* (e.g., *Aponychus equilibris*, *Aponychus corpuzae*), and *Eutetranychus* (e.g., *Eutetranychus orientalis*, *Eutetranychus xi'anensis*). * *Stylophoronychus* (e.g., *Stylophoronychus baghensis*), *Eurytetranychoides* (e.g., *Eurytetranychoides japonicus*), *Tenuipalpoides* (e.g., *Tenuipalpoides hastata*, *Tenuipalpoides zizyphus*), *Bryobia* (e.g., *Bryobia borealis*, *Bryobia exserta*), *Sinobryobia* (e.g., *Sinobryobia chinensis*), *Petrobia* (e.g., *Petrobia xinjiangensis*, *Petrobia (Tetranychina) zachvatkini*), and *Tetranycopsis* (e.g., *Tetranycopsis*). hystriciformis, Tetranycopsis spiraeae, etc.), and the genus Aplonobia (e.g., Aplonobia salsa).The genera *Alpha alkalisalinae*, *Mesobryobia* (e.g., *Mesobryobia terpoghossiani*), and *Dolichonobia* (*Dolichonobia altaiensis*).

[0025] Furthermore, the eggs are produced by the following species: flower thrips (Frankliniella intonsa), tobacco thrips (Thripstabaci Lindeman), bean thrips (Taeniothrips distalis Karn), rice thrips (Stenchaeotothrips biformis), yellow-breasted thrips (Thrips hawaiiensis Morgan), palm thrips (Thrips palmi Karny), western flower thrips (Frankliniella occidentalis), loquat thrips (Thrips japonicus Bagnall), sugarcane thrips (Thrips serratus Kobus), rice thrips (Frankliniella tenuicornis Uzel), tea thrips (Scirtothrips dorsalis Hood), greenhouse thrips (Heliothrips haemorrhoidalis Bouche), tea thrips (Scirtothrips dorsalis Hood), and six-spotted thrips (Scolothrips). The following are listed: *Sexmaculatus Pergande*, *Cnaphalocrocis medinalis*, *Spodoptera exigua*, *Spodoptera litura*, *Carposina sasakii*, *Helicoverpaarmigera*, *Plutella xylostella*, *Diaphania indica*, *Marucatestulalis Geyer*, *Bemisia tabaci Gennadius*, *Trialeurodesvaporariorum*, *Aleurocanthus spiniferus*, *Dialeurodes citriAshm*, *Bemisia myricae Kuwana*, *Aleurocybotus indicus*, *Aleurodicus dispersus*, and *Oligonychus*. baipisongis), larch small claw mite (Oligonychus karamatus), carmine small claw mite (OligonychusRubicundus, longhorn beetle (Cerambycidae), ladybug (Coccinellidae), firefly (Lampyridae), dung beetle (Scarabaeidae), blister beetle (Mylabris phalerata), rhinoceros beetle (Allomyrina dichotoma), jewel beetle (Buprestidae), blister beetle (Melyridae), scarab beetle (Scarabaeidae), stag beetle (Lucanidae), click beetle (Elateridae), water beetle (Dytiscidae), rice weevil (Sitophilus oryzae), ladybug (Harmonia axyridis), white spider mite (Eotetranychus albus), white wax spider mite (Eotetranychus bailae), camellia spider mite (Eotetranychus camelliae), cabbage mite (Tetranychus neocaledonicus), bean spider mite (Tetranychus phaselus), two-spotted spider mite (Tetranychus * *Schizotetranychus urticae*, *Tetranychus cinnabarinus*, *Schizotetranychus baltazarae*, *Schizotetranychus bambusae*, *Schizotetranychus elongatus*, *Mixonychus (Bakerina) aestiva*, *Mixonychus (Mixonychus) ganjuis*, *Panonychus citri*, *Panonychus caglei*, *Allonychus bambusae*, *Allonychus wuyinicus*, *Stigmaeopsis celarius*, *Mononychellus georgicus*, *Acanthonychus jiangfengensis*, *Amphitetranychus* viennensis).

[0026] The fungi mentioned are selected from fungi.

[0027] The term "control" as used in this invention refers to, but is not limited to, the arbitrary killing of insect eggs, regulation of hatching, inhibition / interference with egg activity, and prevention of hatching; the term "prevention of hatching" refers to preventing or delaying the hatching of larvae from the eggs.

[0028] The term "kill" in this invention refers to the insect eggs permanently losing their ability to grow and hatch.

[0029] The "sterilization" described in this invention refers to the direct killing or inhibition of the growth of plant pathogens, including fungi and bacteria. The sterilization includes protective sterilization and systemic sterilization. Protective sterilization involves direct contact with pathogens outside or on the surface of the plant, killing or inhibiting the pathogens and preventing them from entering the plant, thereby protecting the plant from the harm of pathogens. Systemic sterilization, on the other hand, can be absorbed by the plant and transported within the plant to the site of pathogen infection to eliminate the pathogens.

[0030] In this invention, the compound is used to make agricultural products, which further include one or more of the following: excipient dispersants, wetting agents, binders, surfactants, stabilizers, and solvents.

[0031] Suitable surfactants can be selected by those skilled in the art based on actual usage requirements. Examples of surfactants that may be used in some embodiments of the invention include, but are not limited to, ethoxylated castor oil, sodium lauryl sulfate, saponins, ethoxylated alcohols, ethoxylated fatty esters, alkoxylated diols, ethoxylated fatty acids, carboxylated alcohols, carboxylic acids, fatty acids, ethoxylated alkylphenols, fatty esters, sodium dodecyl sulfide, other fatty acid-based surfactants, other natural or synthetic surfactants, and combinations thereof. In some embodiments, the surfactant is a nonionic surfactant. In some embodiments, the surfactant is an ionic surfactant. The selection of a suitable surfactant depends on the relevant application and usage conditions, and suitable surfactants are known to those skilled in the art.

[0032] In this invention, the dosage forms include, but are not limited to, emulsifiable concentrates, soluble powders, soluble granules, solutions, dispersible liquids, water-in-oil emulsions, microemulsions, microcapsule suspensions, seed treatment liquids, aerosols, etc.

[0033] Emulsifiable concentrates (ECs) are a type of pesticide formulation. They are liquids made by dissolving a high concentration of the active ingredient in a solvent and adding an emulsifier. They are typically diluted with a large amount of water to form a stable emulsion before being sprayed using a sprayer. Low-volume spraying and even ultra-low-volume spraying are also possible. They can be used directly or diluted with water before spraying.

[0034] Wettable powder is a very fine dry agent obtained by mixing and pulverizing the active ingredient, filler, surfactant and other adjuvants together.

[0035] Suspension concentrates are formulations in which solid active pharmaceutical ingredients are uniformly dispersed in water as particles smaller than 4 micrometers. Their international code is SC. They have fine particle sizes, typically 0.1–3 μm, and high suspension rates. Suspension concentrates are divided into two types: aqueous suspensions and oil suspensions. Aqueous suspensions use water as the suspension medium, while oil suspensions use oils as the suspension medium and do not contain water. Commonly used oils are vegetable oils, such as corn oil and rapeseed oil. Suspension concentrates can be used without organic solvents, making them a good dosage form for processing solid active pharmaceutical ingredients. Suspension concentrates are mixtures of solid powder and liquid suspended in water. They need to be shaken well before use and then diluted with water before spraying. Suspension concentrates are easy to carry and dilute, can be sprayed evenly, and have good adhesion and long-lasting effect.

[0036] Powder formulations refer to the original powder of the pesticide, or powder prepared by adding a certain diluent. They can be sprayed directly using a simple duster, resulting in high work efficiency, minimal adhesion to crops, low residue, and minimal risk of pesticide damage.

[0037] Granules, also known as granules, are a solid dosage form obtained by mixing and granulating the active pharmaceutical ingredient with carriers, binders, dispersants, wetting agents, stabilizers, and other adjuvants. Their performance requirements mainly include fineness, uniformity, storage stability, hardness, and disintegration properties. Granules have the largest particle size among solid dosage forms, ranging from 300 to 1700 μm in diameter, and offer advantages such as ease of use, minimal outward diffusion, and long-lasting efficacy.

[0038] Aqueous solutions are solutions of the active pharmaceutical ingredient. The drug is uniformly dispersed in water in an ionic or molecular state. The concentration of the drug depends on the water solubility of the active pharmaceutical ingredient, which is generally its maximum solubility. It is then diluted with water before use.

[0039] In this invention, the compound can be used in combination with most commercially available agricultural formulations such as insecticides, acaricides, and fungicides to achieve synergistic effects.

[0040] Furthermore, when using the compound to control and / or kill pest eggs and / or sterilize, the compound concentration is not less than 0.1 ppm. Even further, the compound concentration is not less than 1 ppm.

[0041] The concentration of the compound used is 0.1 to 10000 ppm, or it can be 0.1 to 500 ppm, 0.1 to 200 ppm, 0.1 to 100 ppm, 0.1 to 50 ppm, 1 to 500 ppm, 1 to 200 ppm, 1 to 100 ppm, 1 to 50 ppm, 1 to 10 ppm, 1 to 5 ppm, 2 to 200 ppm, 2 to 100 ppm, 2 to 50 ppm, 2 to 10 ppm, 3 to 200 ppm, 3 to 100 ppm, 3 to 50 ppm, 3 to 10 ppm, 4 to 200 ppm, 4 to 100 ppm, 4 to 50 ppm, 4 to 10 ppm, or 10 to 1000 ppm. Specific options include, but are not limited to: 0.1ppm, 0.2ppm, 0.3ppm, 0.4ppm, 0.5ppm, 0.6ppm, 0.7ppm, 0.8ppm, 0.9ppm, 1ppm, 1.1ppm, 1.2ppm, 1.3ppm, 1.4ppm, 1.5ppm, 1.6ppm, 1.7ppm, 1.8ppm, 1.9ppm, 2.0ppm, 2.5ppm, 3ppm, 3.5ppm, 4ppm, 4.5ppm, 5ppm, 5.5ppm, 6ppm, 6.5ppm, 7ppm, 7.5ppm, 8ppm, 8.5ppm, 9ppm, 9.5ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm, 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm, 50ppm, 100ppm, etc.

[0042] Furthermore, when the compound is used to control and / or kill insect eggs, the concentration of the compound applied is 0.1-500 ppm; when the compound is used for sterilization, the concentration of the compound applied is 10-1000 ppm.

[0043] The present invention also provides a pesticide composition, wherein the active substance is a compound of formula (A).

[0044] In this invention, the pesticide composition may further include dispersants, wetting agents, binders, surfactants, stabilizers, solvents, etc.

[0045] In this invention, the pesticide composition can also be compounded with other products, including but not limited to one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers, and compounds with equivalent functions but not yet commercialized, thereby producing additional advantages and effects. For example, other insecticides may be flupyradifurone, deltamethrin, acetamiprid, tetrazole, imidacloprid, spirotetramat, spirodiclofen, difenoconazole, chlorfenapyr, cis-cypermethrin, brofenoxam, acetamiprid, lambda-cyhalothrin, pymetrozine, thiamethoxam, lufenuron, abamectin, chlorantraniliprole, bifenthrin, brofenoxam, diflubenzuron, spinosad, trifluralin, flonicamid, methyl pyrimiphos, indoxacarb, dinotefuran, dithion, flufenoxuron, permethrin, flufenoxuron, and flufenoxuron diethyl.

[0046] In one embodiment of the present invention, the pesticide composition further includes a mixture of ginger rhizome extract and galangal rhizome extract, wherein the ratio of ginger rhizome extract to galangal rhizome extract is 7:3. The ginger rhizome extract is obtained by extracting ginger rhizomes with ethanol and ethyl acetate at a ratio of 1-4:1; the galangal rhizome extract is volatile oil from galangal rhizomes. The ratio of the above-mentioned ginger and galangal mixture to the above-mentioned compound can be (200-500):(0.1-1). Experimental studies have shown that the combined use of the two has a certain synergistic effect and can reduce the concentration of the active ingredient.

[0047] As used in this application, “comprising” or “including” is interpreted in their open sense, meaning that the specified feature, element, step or component mentioned is present, but does not exclude the presence or addition of further features, elements, steps or components.

[0048] In some embodiments, any of the above compositions are applied outdoors, or to the interior or exterior of vegetation or agricultural areas and / or buildings. In some embodiments, any of the above compositions are applied to surfaces within homes, residences, or buildings. In some embodiments, any of the above compositions are applied to mattresses, sheets, fabrics, travel bags / suitcases, carpets, painted or unpainted hard surfaces, wood, flooring, furniture, and / or buildings.

[0049] In some embodiments, any of the above-described compositions are formulated in a deliverable form suitable for a particular application. These deliverable forms include, but are not limited to, liquids, emulsions, solids, waxes, dusts, fumigants, aqueous suspensions, oil dispersions, pastes, powders, dusts, emulsifiable concentrates, aerosol sprays, wood fillers, varnishes, wood treatments or furniture oils, cleaners, drywall mixtures, scented candles, caulking compositions, crack and fissure fillers, sealants, and mattress and bedding treatments. Suitable deliverable forms can be selected and formulated by those skilled in the art using methods known in the art. In different application scenarios, the above-mentioned compositions can be used in various ways, including directly, after dilution, or in concentrated form. In addition, these can be used as: a protective oil for wood or furniture; a laundry detergent; a gel or paste that can be applied to a target area; an oily emulsion; a component of dry wall materials for dust mixtures; a filler or other sealant for filling cracks or gaps; foam; a component of grout; incense mist or candles; an aerosol or spray insecticide; and a treatment for mattresses or bedspreads. In some cases, these mixtures can be used in domestic or commercial environments to combat pest eggs and fungi in a dispersed form. Furthermore, they can also be used in agricultural or other outdoor environments to control pest eggs and fungi.

[0050] The "solvent" used in the above products or compositions may be water, ketone, alcohol, aldehyde, ether, ester or carboxylic acid, and may include non-aryl ketones, non-aryl alcohols, non-aryl aldehydes, non-aryl esters, non-aryl carboxylic acids, aryl alcohols, aryl-alkyl alcohols, aryl aldehydes, aryl-alkyl ketones, aryl-aryl ketones, aryl carboxylic acids, aryl-alkyl esters, aryl-aryl esters, aryl-alkyl ethers, aryl-aryl ethers and / or combinations thereof.

[0051] In some embodiments, the solvent includes ethanol, isopropanol, benzyl alcohol, acetone, acetophenone, water, citric acid, lactic acid, glycerol, castor oil, benzoic acid, carbonic acid, ethoxylated alcohols, ethoxylated amides, glycerides, butanol, 1-propanol, hexanol, other alcohols, dimethyl ether, polyethylene glycol, etc.

[0052] The beneficial effects of this invention are: this invention provides the application of a class of compounds in inhibiting insect eggs. The compounds have a strong inhibitory effect on insect eggs, especially on the eggs of various thrips, mites, and whiteflies, which are pests of the order Thysanoptera. The compounds with this structure can be used as insecticides or ovicidal agents, have high value in pesticide research, and have broad application prospects in the field of pesticide science. Detailed Implementation

[0053] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Furthermore, unless otherwise specified, all reagents, raw materials, and other experimental materials used in the following embodiments are commercially available or can be synthesized, cultured, or cultivated according to methods described herein or known to the public. Experimental conditions not listed are also readily available to those skilled in the art.

[0054] When numerical ranges are provided, it is understood that the intermediate values ​​between the upper and lower limits of the range (to one-tenth of the unit of the lower limit, unless the context explicitly indicates otherwise) and any other provisions or intermediate values ​​within the specified range are covered in the embodiments of this application. The upper and lower limits of these smaller ranges may independently define smaller numerical ranges, and it will be understood that these smaller ranges are intended to be covered in the embodiments of this application, subject to any explicitly excluded limits within the specified range.

[0055] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. Any methods and materials similar to or equivalent to those described herein may also be used in the practice or testing of embodiments of this application.

[0056] Example 1: Synthesis of Compound 19

[0057]

[0058] Step 1:

[0059]

[0060] 2,4-Dichlorophenol was added to a reaction flask and dissolved in 20 mL of DMF. 1,2-Epoxybutane and cesium carbonate were added, and the mixture was heated in an oil bath at 100 °C. After 6 h, the reaction was monitored by TLC until complete. 100 mL of water was added, and the mixture was extracted with ethyl acetate (30 mL × 3). The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then purified by separation and chiral preparation (instrument: Shimadzu preparative high-performance liquid chromatography, LC20AR; chiral column: CHIRALPAK® normal phase IG column, 4.6 mm I.D. × 250 mm, diameter: 5 μm; mobile phase: n-hexane:isopropanol = 90:10) to obtain compound iii-19.

[0061] Step 2:

[0062]

[0063] Thionyl chloride was added to a reaction flask and dissolved in 15 mL of dichloromethane. The mixture was then stirred in an ice bath at 0°C, and compound iii-19 was slowly added dropwise. After the addition was complete, the mixture was allowed to react at room temperature for 10 h. Once the reaction was complete as monitored by TLC, the reaction solution was concentrated under reduced pressure to obtain the crude product of compound v-19, which was then set aside for use.

[0064] Step 3:

[0065]

[0066] Compound vi-1 was added to a reaction flask, followed by the addition of triethylamine. The flask was then moved to an ice bath at 0°C with stirring, and compound v-19 was slowly added dropwise. After the addition was complete, the mixture was moved to room temperature and reacted for 6 h. Once the reaction was complete as monitored by TLC, 100 mL of water was added to the reaction solution, and the mixture was extracted with dichloromethane (30 mL × 3). The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography to obtain the target compound 19 (692 mg, colorless transparent liquid).

[0067] 1 H NMR (400 MHz, CDCl3) δ 7.32 – 7.29 (m, 1H), 7.14 – 7.09 (m, 1H), 6.85 –6.81 (m, 1H), 4.75 – 3.96 (m, 7H), 1.86-1.66 (m, 2H), 0.98 (t, J = 6.7Hz, 3H) ppm.

[0068] HRMS (ESI) Calculation. For C 12 H 15 O4Cl2FS + [M+H] + 344.0052; Found: 344.0026.

[0069] Example 2 Synthesis of Compound 19'

[0070]

[0071] Step 1:

[0072]

[0073] Following step 1 of Example 1, the target compound iii-19' was prepared chirally.

[0074] Step 2: Same as step 2 in Example 1

[0075] Step 3: Same as step 3 in Example 1

[0076] The target compound 19' (309 mg, colorless and transparent liquid) was obtained by synthesis.

[0077] 1 H NMR (400 MHz, CDCl3) δ 7.32 – 7.29 (m, 1H), 7.14 – 7.09 (m, 1H), 6.85 –6.81 (m, 1H), 4.75 – 3.96 (m, 7H), 1.86-1.66 (m, 2H), 0.95 (t, J = 6.8Hz, 3H) ppm.

[0078] HRMS (ESI) Calculation. For C 12 H 13 O4Cl2FS + [M+H] + 341.9896; Found: 341.9903.

[0079] Example 3 Synthesis of Compound 28

[0080]

[0081] Step 1:

[0082]

[0083] Following step 1 of Example 1, propylene oxide was replaced with ethylene carbonate to obtain the target compound iii-28.

[0084] Step 2: Same as step 2 in Example 1

[0085] Step 3: Same as step 3 in Example 1

[0086] The target compound 28 (671 mg, colorless and transparent liquid) was obtained by synthesis.

[0087] 1 H NMR (400 MHz, CDCl3) δ 7.31 (d, J = 2.5 Hz, 1H), 7.12 (dd, J = 8.8,2.5 Hz, 1H), 6.78 (d, J = 8.8 Hz, 1H), 4.65 – 4.62 (m, 1H), 4.53 – 4.49 (m,1H), 4.34 – 4.30 (m, 2H), 4.25 – 4.18 (m, 3H) ppm.

[0088] HRMS (ESI) Calculation. For C 10H 11 O4Cl2FS + [M+H] + 316.9739; Found: 316.09658.

[0089] Experimental Example 1: Effect of Compound on Hatching of Tetranychus cinnabarinus Eggs

[0090] 1 Experimental Methods

[0091] (1) Preparation of leaf discs containing eggs: 20 adult female Tetranychus carmineus were transferred to broad bean leaf discs with a diameter of 2.0 cm (with moistened filter paper at the bottom). The discs were then covered with covered culture dishes and kept moist. The adult mites were removed within 36 hours, and the leaf discs containing eggs were examined and counted under a microscope.

[0092] (2) Egg count survey: Before soaking in the drug, the egg count of each leaf disc was investigated by microscopic examination, and each treatment was repeated twice.

[0093] (3) Immersion treatment: The leaf discs carrying mite eggs were immersed in water and the compound of the present invention (concentration of 100 ppm) for 10 seconds respectively, and then removed and kept moist for incubation. Each treatment was repeated no less than 3 times.

[0094] (4) Cultivation and observation: The treated mite eggs and leaf discs were cultured under normal conditions. Five days after the treatment, the hatching of the spider mite eggs was investigated.

[0095] Note: After treatment, the temperature and humidity conditions of the constant temperature and humidity incubator should be carefully controlled to avoid excessive temperature differences, which may cause condensation to form in the dish and drip down, leading to abnormal death of the eggs due to water immersion; it is also necessary to ensure sufficient strong light in the environment, but not direct sunlight on the leaf surface.

[0096] (5) Results Investigation: The experimental materials of each treatment group were regularly moisturized and the hatching of eggs was observed. The number of hatched eggs in each treatment was recorded on the 7th day after the drug was applied, and the investigation results were recorded in the original record book. The investigation time may be shortened or extended according to the experimental requirements and the characteristics of the drug.

[0097] Survey indicators:

[0098] ① Investigate and record the number of hatched eggs for each treatment.

[0099] ② Take photos to record whether the broad bean leaves have suffered pesticide damage.

[0100] ③ Record the developmental status of the test mite eggs and the behavior of the nymphs, such as delayed or stopped development of the mite eggs, difficulty in hatching the nymphs, or painful struggles after hatching.

[0101] (6) Calculation method: Based on the survey data, calculate the prevention effect of each treatment according to the following formula, and keep the calculation results to two decimal places.

[0102] Egg hatching rate (%) = (Number of hatched eggs / Total number of eggs processed) * 100

[0103] Control effect (%) = (hatching rate of eggs in control area - hatching rate of eggs in treatment area) / hatching rate of eggs in control area) * 100.

[0104] 2. Experimental Results

[0105] The experimental results are shown in Table 1. The hatching rate of all compounds was less than 15%, and they all showed good activity in killing acaricide eggs.

[0106] Table 1

[0107]

[0108] Experimental Example 2

[0109] A mixture of ginger extract and galangal volatile oil was prepared in a ratio of 7:3. This mixture was then compounded with compound 19. Based on the experimental method of Example 1, the leaf disc method was used to investigate the control effect on Tetranychus cinnabarinus eggs.

[0110] Ginger extract is prepared by extracting ginger rhizomes using a mixed solvent of ethyl acetate and ethanol in a ratio of 1:4.

[0111] Bliss, based on his concept of independent synergistic effects, believes that the theoretical mortality rate P when insecticides and acaricides are mixed can be calculated using the following formula:

[0112] P = Pm + Pn(1 - Pm)

[0113] Pm represents the target mortality rate (%) of the first active component at a concentration of m; Pn represents the target mortality rate (%) of the second active component at a concentration of n.

[0114] If the actual mortality rate of the target is greater than the theoretical mortality rate P after the two active components are mixed at a certain concentration, it is determined that the two active components have a synergistic effect when used together at the set concentration; otherwise, they have an antagonistic effect.

[0115] The experimental results are shown in Table 2. Compound 19, when combined with a mixture of ginger and sand ginger, has a synergistic effect on the control of spider mite eggs.

[0116] Table 2

[0117]

[0118] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A compound, characterized in that, The compound is selected from one of the following compounds: 。 2. A method for controlling and / or killing insect eggs, or for sterilization, characterized in that, The compound of claim 1 or a mixture of two or more of them is applied to insect eggs and / or fungi.

3. The method according to claim 2, characterized in that, The insect eggs are produced by insects of the orders Thysanoptera, Hemiptera, Lepidoptera, Coleoptera, Tetranychidae, Avesidae, Eriophyridae, Tardiidae, Pyromitidae, Lepidoptera, or Carnivorous mites; the fungi include fungi and bacteria.

4. The method according to claim 2, characterized in that, The eggs are laid by various insect species, including flower thrips, tobacco thrips, bean thrips, rice thrips, yellow-breasted thrips, palm thrips, western flower thrips, melon thrips, loquat thrips, sugarcane thrips, rice thrips, tea yellow thrips, greenhouse thrips, tea yellow thrips, six-spotted thrips, rice leaf roller, tobacco whitefly, greenhouse whitefly, black spiny whitefly, citrus whitefly, mulberry whitefly, rice whitefly, spiral whitefly, white pine small claw mite, larch small claw mite, carmine small claw mite, ladybug, longhorn beetle, ladybug, and firefly. Insects, dung beetles, blister beetles, rhinoceros beetles, jewel beetles, blister beetles, scarab beetles, stag beetles, click beetles, water beetles, rice weevils, white spider mites, white wax spider mites, camellia spider mites, cabbage spider mites, bean spider mites, two-spotted spider mites, cinnabar spider mites, citrus split spider mites, bamboo split spider mites, long split spider mites, fig split spider mites, citrus split spider mites, citrus whole spider mites, Carrion whole spider mites, bamboo heterocarya, Wuyi heterocarya, bamboo-eating mites, Georgian single spider mite, sharp-peaked second spider mite, hawthorn double spider mite.

5. The method according to claim 2, characterized in that, The concentration of the compound used is not less than 0.1 ppm.

6. The method according to claim 2, characterized in that, When used, the compound is formulated into an agricultural product, which further includes one or more of the following: excipient dispersant, wetting agent, binder, emulsifier, stabilizer, and solvent.

7. The method according to claim 6, characterized in that, The formulations of the agricultural products are emulsifiable concentrates, suspension concentrates, wettable powders, powders, granules, aqueous solutions, mother liquors, or mother powders.

8. A pesticide composition, characterized in that, The compound of claim 1 is used as the active substance.

9. The pesticide composition according to claim 8, characterized in that, It also includes a mixture of ginger rhizome extract and sand ginger rhizome extract, with a ginger rhizome extract: sand ginger rhizome extract ratio of 7:

3. The ginger rhizome extract is obtained by extracting ginger rhizomes with ethanol: ethyl acetate in a ratio of 1 to 4:

1. The sand ginger rhizome extract is the volatile oil of sand ginger rhizomes.

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