Chiral sulfite ester compounds having isomers and their use

Abstract

This invention provides a compound that exhibits excellent inhibitory activity against insect eggs, and in particular, has very strong inhibitory activity against the eggs of thrips, mites, lepidopteran moths, whiteflies, and ladybugs, as well as bactericidal activity. [Solution] A chiral sulfite ester compound having the structure of the following formula (A). (In the formula, R1 and R2 are each independently hydrogen, halogen, substituted or unsubstituted C1-C) 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, C2~C 10 Alkoxycarbonyl, C2~C 10 Alkylcarbonyl, C1~C 10 Selected from carbonyl groups, R3, R3', R4, and R4' are each independently selected from hydrogen, C1-C5 alkyl, and C1-C5 alkenyl groups, or R3, R3', R4, and R4' together with the attached C to form a 5-membered heterocycloalkyl group, and R5 is a halogen, substituted or unsubstituted C1-C5 10 Selected from alkyl groups. JPEG0007891568000053.jpg31170

Description

Technical Field

[0001] The present invention belongs to the field of agricultural technology, and particularly relates to sulfite-based insecticidal compounds that are chiral and have isomers, the preparation and separation of their chirality, and their use.

Background Art

[0002] The pesticide market is vast and huge, and its market scale reaches about 10 billion yuan. Typical agricultural insecticides mainly target orthoptera such as locusts and cicadas, hemiptera such as stink bugs, homoptera such as 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 midges, and various types of spider mites such as eriophyid mites.

[0003] In the existing control concept, most pesticide products focus on the contact and stomach toxicity effects on adults, nymphs, and larvae, and control the pest population base by significantly reducing the number of insects on the crop. Thereby, protecting the crop from excessive damage and reducing the economic losses after pest occurrence. This method can usually very well control the root cause of pests in the environment, but in the control practice of some pests with short generation cycles (such as spider mites, thrips, etc.), good results are often not obtained.

[0004] Taking red mites as an example, there are numerous registered acaricides, including dozens of plant-derived, inorganic mineral, or chemical acaricides such as ethazonil, avermectin, triazoletin, fenbutyltin, spirobiphene, etoxazole, veratrum rhizome extract, and matrin. However, most of these acaricides target adult mites or young nymphs, and only a few possess excellent ovicidal activity. In agricultural fields, pest mites reproduce very quickly, completing a generation basically every week, so the phenomenon of generational overlap is very serious. Therefore, if only acaricides without ovicidal effect are sprayed, adult mites will be killed, but new mites will quickly hatch from eggs, rapidly increasing the population. It is possible to control pest mites that hatch later through secondary spraying, but there are several problems with its practical application. For example, if insecticides are sprayed too frequently, the resistance of pest mites will rapidly increase. Also, the cost of pesticide spraying for farmers will increase dramatically. In agricultural fields, to save on labor costs, conventional insecticide application methods tend to involve mixing multiple insecticides, such as acaricides, insecticides, fungicides, regulators, and foliar nutrients. In actual agricultural mite control applications, farmers use ovicides in combination to extend the duration of effectiveness. Of the registered acaricides, only two, etoxazole and spirodiclofen, are clearly used as ovicides, and this is relatively rare. Due to a shortage of varieties and increasing resistance, there is a growing demand for new, effective acaricides that double-kill mite eggs. Furthermore, there is a shortage of small-molecule acaricides with multiple functions. When farmers apply acaricides to their fields, they usually need to mix and spray multiple chemicals such as regulators, foliar nutrients, fungicides, and ovicides simultaneously. When multiple chemical agents with different mechanisms of action and dosage forms are used together, not only are antagonisms between the agents likely to occur, but the stability of the aqueous solution is also easily compromised. Phenomena such as precipitation, aggregation, and stratification occasionally occur, significantly impacting the use of pesticides in agricultural fields. Furthermore, the combined use of multiple pesticides can further increase target resistance, easily leading to adverse environmental impacts from pesticide residues.

[0005] Therefore, the development of new, highly efficient insecticides and ovicides with novel structures and unique mechanisms of action is key to controlling agricultural pests. [Overview of the Initiative]

[0006] The object of the present invention is to provide a chiral sulfite ester insecticidal compound having isomers. Absolute configurations can be obtained by preparation and separation. One or more of these configurations can solve the problems described above in the prior art and achieve good inhibitory and killing effects against insect eggs.

[0007] When the inventors studied the insecticidal activity of sulfite ester compounds, they discovered that some compounds exhibited low insecticidal activity (less than 75% reduction in insect population) but showed excellent inhibitory activity against pest eggs.

[0008] The present invention provides a chiral sulfite ester compound having a structure represented by formula (A), or a meso compound, racemic compound, stereoisomer, or pharmaceutically acceptable salt thereof. In the formula JPEG0007891568000001.jpg27153, R1 and R2 are independently hydrogen, halogen, substituted or unsubstituted C1-C, respectively. 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, C2~C 10 Alkoxycarbonyl, C2~C 10 Alkylcarbonyl, C1~C 10 Selected from carbonyl, R3, R3', R4, and R4' are each independently selected from hydrogen, C1-C5 alkyl, and C1-C5 alkenyl, or R3, R3', R4, and R4' together with the C bonded to them form a 5-membered heterocycloalkyl group. R5 is C1-C, which is halogen, substituted or unsubstituted. 10 Selected from alkyl groups. Furthermore, the structure of the compound is It is one of the images selected from JPEG0007891568000002.jpg123158.

[0009] In formulas (A), I-VI, furthermore, the C1-C5 alkyls are methyl and ethyl. In formulas (A), I to VI, the C1 to C5 alkenyls are further selected from vinyl. In formulas (A), I to VI, furthermore, the 5-membered heterocycloalkyl is Selected from JPEG0007891568000003.jpg21170.

[0010] Furthermore, R5 is selected from fluoroethyl, bromoethyl, chloroethyl, 2,2-difluoroethyl, and 2,2-dichloroethyl, and R1 and R2 are each independently selected from H, F, Cl, and Br.

[0011] Furthermore, R5 is -CH2CH2F, and R1 and R2 are Cl.

[0012] Furthermore, compound A is Select from JPEG0007891568000004.jpg128170 or JPEG0007891568000005.jpg157170.

[0013] In the foregoing, unless otherwise specified, “substitution” means that the group concerned may be substituted by one or more additional groups. Each of these additional groups is independently selected from alkyl, cycloalkyl, aryl, carboxyl, heteroaryl, heterocycloalkyl, hydroxyl, alkoxy, alkylthio, aryloxy, O=, guanidino, cyano, nitro, acyl, halogen, alkyl halide, amino, and the like.

[0014] The structure of the compounds of the present invention can be confirmed by conventional methods well known to those skilled in the art. If the present invention relates to the absolute configuration of a compound, the absolute configuration can be confirmed by ordinary technical means in the art. According to the literature (Absolute configuration of glycosyl sulfoxides, Tetrahedron: Asymmetry, Volume 21, Issue 15, 2010, Pages 1830-1832), if a group is on the same side as the lone pair of electrons of sulfur, the group is shielded, the chemical shift decreases, and the chemical shift shifts to the high magnetic field side. If the group is on the same side as the oxygen atom, the shielding of the group is released, the chemical shift increases, and it shifts to the low magnetic field side. The absolute configuration can be obtained based on comparison and analysis of the hydrogen spectra of chiralized compounds and testing of optical rotation.

[0015] The compound numbers listed above are merely for convenience in the subsequent explanation.

[0016] The present invention further provides a method for controlling and / or killing insect eggs and / or fungi by applying the above-mentioned compounds to the insect eggs and / or fungi.

[0017] Furthermore, when used for the control and / or killing of pest eggs and / or sterilization, the compound is selected from the following compounds and comprises a mixture of multiple components. JPEG0007891568000006.jpg133170 The intermediate compounds of the present invention can be prepared by various synthetic methods well known to those skilled in the art. These include specific embodiments described herein, embodiments formed in combination with other chemical synthesis methods, and equivalent substitution methods known to those skilled in the art. Preferred embodiments include, but are not limited to, the examples of the present invention.

[0018] The chemical reactions of specific embodiments of the present invention are completed in a suitable solvent. The solvent must be suitable for the chemical changes, required reagents, and materials of the present invention. In some cases, those skilled in the art may need to modify or select synthesis steps or reaction procedures based on existing embodiments to obtain the compounds of the present invention.

[0019] As used in this invention, the term "pest" refers to an organism that adversely affects a host (for example, a plant or an animal such as a mammal) by parasitizing, damaging, attacking, competing for nutrients, or infecting the host.

[0020] Pests include, but are not limited to, arthropods (including insects and spiders), blood-sucking pests, and biting pests (bed bugs, mites, ticks, ants, lice, cockroaches, thrips, etc.).

[0021] There are no special restrictions, but pest eggs originate from thrips, hemipterans, lepidopterans, coleopterans, acari, spider mites, lepidopterans, gall mites, terrestrial mites, lice mites, claw mites, or predatory mites. The aforementioned fungi include fungi and bacteria.

[0022] The aforementioned order "Thysanoptera" belongs to the class Insecta, and insects of this order are called "thrips." They are small insects with somewhat elongated bodies, generally yellowish-brown or black, with well-developed eyes, piercing mouthparts, and a bilaterally asymmetrical body. Their wings are narrow and long, with little or no wing veins, and the wingtips are flat and long, with long or short hairs. Some types are wingless or have only vestigial wings. They lack tail barbels and usually feed on plant sap, damaging grains, cotton, tobacco, etc., spreading plant viruses, and are considered pests. Thrips are divided into the suborders Terebrantia and Tubulifera. The suborder Thripidae includes the superfamilies Aeolothripoidea (Aeolothripidae, Orothripidae, Melanthripidae, Dactuliothripidae, Franklinothripidae), Merothripoidea (Aeolothripoidea), and Thripoidea (Heterothripidae, Hemithripidae, Ceratothripidae, Panchaetothripidae, Thripidae). The family Thripidae is the most important family within this order. This family is known to comprise 33 genera and approximately 200 species.For example, the flat-headed thrips (Frankliniella intonsa), onion thrips (Thrips tabaci Lindeman), bean thrips (Taeniothrips distalis Karny), rice thrips (Stenchaeotothrips biformis), flower thrips (Thrips hawaiiensis Morgan), southern yellow thrips (Thrips palmi Karny), orange thrips (Frankliniella occidentalis), loquat thrips (Thrips japonicus Bagnall), sugarcane thrips (Thrips serratus Kobus), cajonka thrips (Frankliniella tenuicornis Uzel), tea thrips (Scirtothrips dorsalis Hood), and croton thrips (Heliothrips haemorrhoidalis) Species such as Bouche, Scirtothrips dorsalis Hood, and Scolothrips sexmaculatus Pergande are commonly found in China. The suborder Tubulobaceae includes the superfamilies Phlaeothripoidea (Pypothripidae, Ecacanthothripidae, Eupatithripidae, Phlaeothripidae, Chirothripoididae, Hystricothripidae, Idolothripidae, Megathripidae) and Urothripoidea (Urothripidae). All families listed in parentheses after the superfamilies are subfamilies within those superfamilies, and this method will be used in the following explanation.

[0023] The aforementioned "Hemiptera" belong to the class Insecta. Their bodies are nearly flattened and rigid, their mouthparts are piercing, their antennae are oval or rod-shaped, they have two or none of the simple eyes, their pronotum is well-developed, their scutellum is mostly triangular, their forewings are hemicoleoptera (half-coleoptera) and their hindwings are membranous, with some species having reduced wings or no wings at all. Most species have scent glands, and often have claws at the tips of their feet with claw pads beneath them. Their abdomen has 9 to 11 segments, usually 10. They lack caudal palps, and their name comes from the fact that their forewings are hemicoleoptera. The Hemiptera are divided into the suborders Auchenorrhyncha and Sternorrhyncha. The suborder Nerviolus includes the superfamily Cicadiodea (Cicadidae, Membracidae, Macearotidae, Cercopidae, Cicadellidae) and the superfamily Fulgoroidea (Tettigometridae, Delphacidae, Fulgoridae, Eurybra). This includes families such as chydidae, Cixiidae, Meenoplidae, Dictyopharidae, Achilidae, Tropiduchidae, Derbidae, Lopphopidae, Issidae, Flatidae, and Ricaniidae.The suborder Stomachrophidae includes the superfamilies Psylloidea (Psyllidae), Aleyrodoidea (Aleyrodidae), Aphidoidea (Adelgidae, Phylloxeridae, Pemphigidae, Aphididae), and Coccoidea (W) This includes families such as Margarodidae, Ortheziidae, Kerridae, Kermidae, Dactylopiidae, Pseudococcidae, Asterolecaniidae, Coccidae, and Diaspididae.

[0024] The aforementioned order, Lepidoptera, belongs to the class Insecta and is widely distributed, with the largest number of species found in tropical regions. The larvae of most species damage various cultivated plants, and relatively large species can devour leaves or chew through branches and trunks. Smaller species tend to roll or bind leaves, create sheaths, spin webs by spinning silk, or burrow into plant tissue to feed. Adults often obtain nectar from flowers as a supplementary source of nutrition, but some species have vestigial mouthparts and do not feed. The order Lepidoptera includes the suborder Zeugloptera (family Micropterygidae), the suborder Monotrysia (superfamilies Eriocraniidea, Hepialoidea, Stigmelloidea, and Incurvarioidea), and the suborder Ditrhysia (superfamilies Tineoidea, Cossoidea, Psychoidea, Castnioidea, Tortricoidea, Pyraloidea, Bombycoidea, Calliduloidea, Geometroidea, Noctuoidea, Hesperioidea, and Papilionoidea).

[0025] The aforementioned "Coleoptera" is the largest and most widely distributed order in the insect and animal kingdom, and is divided into the suborders Adephaga, Polyphaga, and Rhynchophora. The Adephaga suborder includes the superfamilies Caraboidea (Cicindelidae, Carabidae, Amphizoidae, Omophronidae, Hygrobiidae, Haliplidae, Dytiscidae), Gyrinoidea (Gyrinidae), Paussoidea (Paussidae), Cupesoidea (Cupesidae), and Rhysodoidea (Rhysodidae).Polyphagous suborders include the superfamily Hydrophiloidea (Hydrophilidae), the superfamily Staphylinoidea (Silphidae, Leiodidae, Clambidae, Scydmaenidae, Orthoperidae, Phae nocephalidae, Discolomidae, Platypsyllidae), Pholipidae (Lycidae, Lampyridae, Cantharidae, Drilidae, Malachiidae, Phloeoph) ilidae, Prionoceridae, Dasytidae), Lymexyloidea (Lymexylidae, Atractoceridae), Elateroidea (Rhipiceridae, Cebr ionidae, Elateridae, Eucnemidae, Throscidae), Dryopoidea (Psephenidae, Dryopidae, Helmidae, Georyssidae, Heteroceridae), Nagafuna Superfamilies Dascilloidea (Dascillidae), Tenebrionoidea (Alleculidae, Tenebrionidae), Ptinidae (Lyctidae, Bostrychidae, Anobiidae, Ptinidae), Scarabaeoidea (Scarabaeidae, Aegialiidae, Aphodiidae, Ochodaeidae, Geotrupidae, Trogidae, Melolon This includes the superfamilies thidae, Rutelidae, Dynastidae, Cetoniidae, Trichiidae, and Passalidae, the superfamily Cerambycoidea (Prionidae, Cerambycidae, Lamiidae, and Sagridae), the family Brentoidea (Brentidae), and the superfamily Curculionoidea (Anthribidae, Aglycyderidae, Proterhiniidae, Cyladidae, and Curculionidae).The subfamily Scrophularia includes the superfamily Curculionoidea (Anthribidae, Aglycyderidae, Proterhiniidae, Cyladidae, Curculionidae). Common insects (common names) include the Asian ladybug, longhorn beetle, ladybug, firefly, scarab beetle, Mirabris phallellata, rhinoceros beetle, jewel beetle, soldier beetle, scarab beetle, Lucanidae, click beetle, diving beetle, and granary weevil.

[0026] The term "mites" as used in this invention mainly includes agricultural pest mites, and most belong to the families Tetranychidae, Tenuipalpidae, Eriophyidae, Tarsonemidae, Pyemotidae, Pentaleidae, and Cheytidae within the class Acachnida.

[0027] The family Mites includes the genera Oligonychus (e.g., Oligonychus baipisongis, Oligonychus karamatus, Oligonychus rubicundus, etc.), Eotetranychus (e.g., Eotetranychus albus, Eotetranychus bailae, Eotetranychus camelliae, etc.), and Tetranychus (e.g., Tetranychus neocaledonicus, Tetranychus phaselus, Tetranychus urticae, Tetranychus serrata). cinnabarinus), Schizotetranychus (e.g., Schizotetranychus baltazarae, Schizotetranychus bambusae, 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) bambusae, Allonychus wuyinicus, Stigmaeopsis genus (e.g., Stigmaeopsis celarius, Stigmaeopsis nanjingensis), Mononychellus genus (e.g., Mononychellus georgicus)(Georgicus), Acanthonychus (e.g., Acanthonychus jiangfengensis), Amphitetranychus (e.g., Amphitetranychus viennensis), Sonotetranychus (e.g., Sonotetranychus neosalix), Xinella (e.g., Xinella huangshanensis), Yunoychus (e.g., Yunoychus daliensis), Neotetranychus (e.g., Neotetranychus lek), Eurytetranychus (e.g., Eurytetranychus glycyrrhizae, Eurytetranychus wuyishanensis), Aponychus (e.g., Aponychus aequilibris, Aponychus corpuzae), Eutetranychus (e.g., Eutetranychus orientalis (Eutetranychus xianensis), Stylophoronychus (e.g., Stylophoronychus baghensis), Eurytetranychoides (e.g., Eurytetranychoides), Tenuipalpoides (e.g., Tenuipalpoides hastata, Tenuipalpoides zizyphus), Bryobia (e.g., Bryobia borealis, Bryobia exserta), Sinobryobia (e.g., Sinobryobia chinensis), Petrobia (e.g., Petrobia (Petrobia) xinjiangensis, Petrobia (Tetranychina) zachvatkini, etc.), Tetranycopsis hystriciformis, Tetranycopsis spiraeae, etc.), Aplonobia (e.g., Aplonobia alkalisaline).They are divided into alkalisalinae, Mesobryobia (for example, Mesobryobia terpoghossiani), and Dolichonobia (Dolichonobia altaiensis).

[0028] Furthermore, the eggs of the aforementioned insects include those of the flat-headed thrips (Frankliniella intonsa), onion thrips (Thrips tabaci Lindeman), bean thrips (Taeniothrips distalis Karn), rice thrips (Stenchaeotothrips biformis), flower thrips (Thrips hawaiiensis Morgan), southern yellow thrips (Thrips palmi Karny), orange yellow thrips (Frankliniella occidentalis), loquat thrips (Thrips japonicus Bagnall), sugarcane thrips (Thrips serratus Kobus), cajonka thrips (Frankliniella tenuicornis Uzel), and tea yellow thrips (Scirtothrips dorsalis). Hood), Croton thrips (Heliothrips haemorrhoidalis Bouche), Tea yellow thrips (Scirtothrips dorsalis Hood), Scolothrips sexmaculatus Pergande, Rice leaf borer (Cnaphalocrocis medinalis), White armyworm (Spodoptera exigua), Beet armyworm (Spodoptera litura), Peach fruit moth (Carposina sasakii), Tobacco budworm (Helicoverpa armigera), Diamondback moth (Plutella xylostella), Cotton leaf borer (Diaphania indica), Bean leaf borer (Maruca testulalis Geyer), Tobacco whitefly (Bemisia tabaci Gennadius), Greenhouse whitefly (Trialeurodes) vaporariorum), citrus whitefly (Aleurocanthus spiniferus), citrus whitefly (Dialeurodes citri Ashm), bayberry whitefly (Bemisia myricae Kuwana), Aleurocybotus indicusIndicus), Pyraling whitefly (Aleurodicus dispersus), Oligonychus baipisongis, Larch spider mite (Oligonychus karamatus), Pampyris gracilis mite (Oligonychus rubicundus), Longhorn beetle (Cerambycidae), Ladybug (Coccinellidae), Firefly (Lampyridae), Scarabaeidae, Mylabris phalerata, Rhinoceros beetle (Allomyrina) dichotoma), jewel beetles (Buprestidae), soldier beetles (Melyridae), scarab beetles (Scarabaeidae), Lucanidae, click beetles (Elateridae), diving beetles (Dytiscidae), grain weevils (Sitophilus oryzae), ladybugs (Harmonia axyridis), Eotetranychus albus, Eotetranychus bailae, camelliae mites, Tetranychus neocaledonicus, Tetranychus phaselus, Tetranychus urticae, false spider mites (Tetranychus cinnabarinus), Schizotetranychus baltazarae, Schizotetranychus bambusae, Schizotetranychus elongatus, Mixonychus (Bakerina) aestiva, Mixonychus (Mixonychus) ganjuis, Panonychus citri, Panonychus caglei, Allonychus bambusaeIt is derived from the following mites: bambusae, Allonychus wuyinicus, Stigmaeopsis celarius, Mononychellus georgicus, Acanthonychus jiangfengensis, and Amphitetranychus viennensis.

[0029] The aforementioned fungi are selected from among the fungi.

[0030] In a specific embodiment of the present invention, the fungus is selected from the rice blast fungus. The rice blast fungus causes rice blast disease, damaging seedlings, leaves, ears, nodes, etc.

[0031] The term "control" in this invention includes, but is not limited to, the arbitrary killing of insect eggs, regulation of hatching, suppression / inhibition of insect egg activity, and prevention of hatching. The term "prevention of hatching" refers to preventing or delaying the hatching of larvae from eggs.

[0032] In this invention, "killing" refers to permanently depriving the eggs of their ability to grow and hatch.

[0033] In this invention, "sterilization" refers to directly killing or inhibiting the growth of plant pathogenic microorganisms. These pathogenic microorganisms include fungi and bacteria. The sterilization includes protective sterilization and internal absorption sterilization. Protective sterilization refers to killing pathogenic bacteria or inhibiting their entry into the plant by directly contacting them on the outside or surface of the plant, thereby protecting the plant from the damage caused by pathogenic bacteria. Internal absorption sterilization refers to being absorbed by the plant and transmitted to the site of bacterial infection within the plant to eliminate the bacteria.

[0034] In the present invention, the sulfite ester compound is prepared into an agricultural product for use at the time of use. The agricultural product further contains one or more of the following auxiliary agents: dispersants, wetting agents, adhesives, surfactants, stabilizers, and solvents.

[0035] A suitable surfactant can be selected by those skilled in the art as required by the actual circumstances. Examples of surfactants usable in embodiments of the present invention include, but are not limited to, ethoxylated castor oil, sodium lauryl sulfate, saponins, ethoxylated alcohols, ethoxylated fatty acid esters, alkoxylated glycols, ethoxylated fatty acids, carboxylated alcohols, carboxylic acids, fatty acids, ethoxylated alkylphenols, fatty acid esters, sodium lauryl 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 conditions of use, and suitable surfactants are known to those skilled in the art.

[0036] In the present invention, the dosage form includes, but is not limited to, emulsions, soluble powders, soluble granules, solutions, dispersible liquids, aqueous emulsions, microemulsions, microcapsule suspensions, seed treatment liquids, aerosols, and the like.

[0037] Emulsions are a type of pesticide formulation, made by dissolving a relatively high concentration of active ingredients in a solvent and adding an emulsifier. Generally, they are diluted with a large amount of water to form a stable emulsion, which is then sprayed using a sprayer. Low-volume or very low-volume spraying is also possible. They can be used as is or diluted with water before spraying.

[0038] Wettable powders are very fine drying agents obtained by mixing and grinding active pharmaceutical ingredients, excipients, surfactants, and other additives.

[0039] A suspension is a formulation in which a solid active pharmaceutical ingredient is uniformly dispersed in water as particles smaller than 4 μm. Its international code is SC, and it typically has a particle size of 0.1-3 μm and a high suspension efficiency. Suspensions are divided into two types: aqueous suspensions and oily suspensions. Aqueous suspensions use water as the suspension medium, while oily suspensions use oil as the suspension medium and do not contain water. Commonly used oils include vegetable oils such as corn oil and rapeseed oil. Suspensions completely eliminate the need for organic solvents and are a suitable dosage form for processing solid raw materials. A suspension is a mixture of a solid powder and a liquid suspended in water, and it needs to be shaken and diluted with water before use for spraying. Suspensions are easy to carry and dilute, can be sprayed uniformly, and have excellent adhesion and durability.

[0040] Powdered formulations refer to the powdered form of the active ingredient, or a powder prepared by adding a specific diluent. They can be applied directly with a simple duster, resulting in high work efficiency, low adhesion and residue to crops, and minimal phytotoxicity.

[0041] Granules, or granular formulations, are solid forms produced by mixing an active pharmaceutical ingredient with additives such as carriers, adhesives, dispersants, wetting agents, and stabilizers. Their performance requirements primarily include fineness, uniformity, storage stability, hardness, and disintegration properties. Granules have the largest particle size among solid forms, ranging from 300 to 1700 μm, making them easy to use, with minimal outward diffusion and long-lasting effects.

[0042] Aqueous formulations are solutions of the active pharmaceutical ingredient (API). 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 API, and is generally the maximum solubility; water is added to dilute it before use.

[0043] In the present invention, the sulfite ester compound can be used in combination with most commercially available insecticides, acaricides, fungicides, and other agricultural formulations to obtain a synergistic effect.

[0044] Furthermore, when sulfite compounds are used to control and / or kill and / or sterilize insect eggs, the concentration of the sulfite compound must be 0.1 ppm or higher. Additionally, the concentration of the sulfite compound must be 1 ppm or higher.

[0045] The concentration of the sulfite ester compound used is 0.1 to 10000 ppm, and may 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. Specifically, 0.1 ppm, 0.2 ppm, 0.3 ppm, 0.4 ppm, 0.5 ppm, 0.6 ppm, 0.7 ppm, 0.8 ppm, 0.9 ppm, 1 ppm, 1.1 ppm, 1.2 ppm, 1.3 ppm, 1.4 ppm, 1.5 ppm, 1.6 ppm, 1.7 ppm, 1.8 ppm, 1.9 ppm, 2.0 ppm, 2.5 ppm, 3 ppm, 3.5 ppm, 4 ppm, 4.5 ppm PM, 5 ppm, 5.5 ppm, 6 ppm, 6.5 ppm, 7 ppm, 7.5 ppm, 8 ppm, 8.5 ppm, 9 ppm, 9.5 ppm, 10 ppm, 11 ppm, 12 ppm, 13 ppm, 14 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 100 ppm, etc. may be selected, but are not limited to these.

[0046] Furthermore, when the sulfite ester compound is used for controlling and / or killing insect eggs, the concentration of the sulfite ester compound used is 0.1-500 ppm. When the sulfite ester compound is used for sterilization, the concentration of the sulfite ester compound used is 10-1000 ppm.

[0047] According to the present invention, a pesticide composition comprising the compound of formula (I) as an active substance is further provided.

[0048] In the present invention, the pesticide composition may further contain a dispersant, a wetting agent, an adhesive, a surfactant, a stabilizer, a solvent, and the like.

[0049] In the present invention, the pesticide composition may be combined with other products. This includes, but is not limited to, one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators, fertilizers, and compounds that perform equivalent functions but have not yet been commercialized. This may result in further advantages and effects. For example, other insecticides may include fluopifranone, deltamethrin, ethinyl, tetrazopyramide, imidacloprid, spirotetramato, spirodiclofen, diprocyclap, fenfenthoril, cis-cypermethrin, bromifenamide, etofenyl, beta-cyhalothrin, pymetrozine, thiamethoxam, lufenuron, abamectin, chlorantraniliprole, bifenthrin, cyantraniliprole, fenflufenthrin, spinosad, triflufenacil, sulfoxaflor, pirimiphosmethyl, indoxacarb, dinotefuran, dinotefuran, dimethonate, flufenhydrazone, permethrin, flufurfenuron, and flufendifen.

[0050] In one embodiment of the present invention, the pesticide composition further comprises a mixture of ginger rhizome extract and galangal rhizome extract. The ratio of ginger rhizome extract to galangal rhizome extract is 7:3. Here, the ginger rhizome extract is obtained by extracting ginger rhizome with ethanol:ethyl acetate = 1 to 4:1, and the galangal rhizome extract is the volatile oil of galangal rhizome. The mixing ratio of the ginger / galangal mixture and the compound of formula (A) may be (200 to 500):(0.1 to 1). Experimental studies have shown that using both in combination produces a synergistic effect and can reduce the concentration of the active ingredient.

[0051] As used in this invention, "contains" or "includes" shall be interpreted in their open sense. That is, the presence of any particular feature, element, step, or component mentioned shall not preclude the presence or addition of any further features, elements, steps, or components.

[0052] In some embodiments, the above-mentioned optional compositions are applied outdoors, to plants or farmland, and / or inside or outside structures. In some embodiments, any of the above compositions are applied to surfaces inside a house, residence, or building. 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.

[0053] In some embodiments, the above-mentioned optional compositions are prepared in transport forms suitable for specific applications. These transport forms include, but are not limited to, liquids, emulsions, solids, waxes, dusts, fumigants, aqueous suspensions, oil dispersions, pastes, powders, emulsifying concentrates, aerosol sprays, wood pore fillers, varnishes, wood treatment agents or furniture oils, cleaners, drywall mixtures, scented candles, caulking compositions, crack and gap fillers, sealants, and treatment agents for mattresses and bed covers. Suitable deliverable forms can be selected and prepared by those skilled in the art using methods known in the art. In various use scenarios, the above compositions can be applied in various ways, and can be used directly, diluted, or concentrated. Furthermore, they can also be used in applications such as wood and furniture protective oils, laundry detergents, gels and pastes that can be applied to the target area, oily lotions, dust mixtures, parts of drywall materials, fillers or other sealants used to fill cracks and gaps, foams, parts of caulking agents, incense or candles, aerosol or spray insecticides, and treatment agents used for mattresses or bed covers. In some cases, these mixtures can be used in household or commercial settings to combat pest eggs and fungi in a dispersed form. Furthermore, they can also be used to control pest eggs and fungi in agriculture and other outdoor environments.

[0054] The "solvent" used in the above products or compositions may be water, ketones, alcohols, aldehydes, ethers, esters, carboxylic acids, and may also 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, arylaryl ketones, aryl carboxylic acids, aryl alkyl esters, aryl aryl esters, aryl alkyl ethers, aryl aryl ethers, and / or combinations thereof.

[0055] In some embodiments, the solvent includes ethanol, isopropyl alcohol, benzyl alcohol, acetone, acetophenone, water, citric acid, lactic acid, glycerin, castor oil, benzoic acid, carbonic acid, ethoxylated alcohol, ethoxylated amide, glycerides, butanol, 1-propanol, hexanol, other alcohols, dimethyl ether, polyethylene glycol, and the like.

[0056] The beneficial effects of the present invention are as follows: This invention provides the use of chiral and isomerized sulfite compounds in the suppression of insect eggs. These chiral and isomerized sulfite compounds have a strong inhibitory effect on insect eggs, particularly on the eggs of thrips, mites, and mealybugs. Compounds with this structure can be applied to insecticides or oocyte-killing agents, have high value in agricultural research, and have broad potential applications in the field of agrochemicals. [Brief explanation of the drawing]

[0057] [Figure 1] This is a chromatogram showing the separation of a mixture of compound 1 and compound 1' using an IG column. [Figure 2] This is a chromatogram showing the separation of the R configurations of compound 1 and compound 1' using an IG column. [Figure 3] This is a chromatogram showing the separation of compound 1' and the S configuration of compound 1 using an IG column. [Figure 4] This is the chromatogram in the IG column of the first peak separated from the R configuration. [Figure 5] This is the chromatogram in the IG column of the second peak separated from the R configuration. [Figure 6] This is the chromatogram in the IG column of the third peak separated from the R configuration. [Figure 7] This is the chromatogram in the IG column of the fourth peak separated from the R configuration. [Figure 8] This is the chromatogram in the IG column of the first peak separated from the S configuration. [Figure 9] This is the chromatogram in the IG column of the second peak separated from the S configuration. [Figure 10] This is the chromatogram in the IG column of the third peak separated from the S configuration. [Figure 11] This is the chromatogram peak obtained when the first peak in the IG column is separated using an AS column after separating compound 1' and the S configuration of compound 1. [Modes for carrying out the invention]

[0058] To more clearly explain the object, technical means, and advantages of the present invention, the present invention will be described in more detail below with reference to examples. The following specific examples are merely interpretive and not limiting of the present invention. Furthermore, unless expressly stated otherwise, all reagents, raw materials, and other test supplies used in the following examples are commercially available or can be synthesized, cultured, or incubated according to the methods specified herein or known methods, and conditions not listed are readily available to those skilled in the art.

[0059] When a numerical range is provided, it is understood that each intermediate value between the upper and lower limits of that range (one-tenth to the unit of the lower limit, unless the context otherwise explicitly indicates), and other predetermined or intermediate values ​​within that given range are included in embodiments of the Application. The upper and lower limits of these smaller ranges can independently define smaller numerical ranges, and these smaller ranges are intended to cover limits that are arbitrarily and explicitly excluded within the given range in embodiments of the Application.

[0060] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Any methods and materials similar or analogous to those described herein may be used in the practical or experimental applications of the embodiments of this application.

[0061] A method for synthesizing chiral and isomerized sulfite ester compounds includes the following steps. Step 1: React compound (i) with compound (ii) to obtain compound (iii). JPEG0007891568000007.jpg29170 Step 2: React compound (iii) with compound (iv) to obtain compound (v). JPEG0007891568000008.jpg29170 Step 3: React compound (v) with compound (vi) to obtain compound (I). JPEG0007891568000009.jpg33170

[0062] Example 1: Synthesis of compounds S-1 and S-1' JPEG0007891568000010.jpg791702,4-Dichlorophenol (500 mg, 3.1 mmol), R-Propylene Oxide (356 mg, 6.1 mmol), DMF (12 mL), and Cesium Carbonate (4.0 g, 12.3 mmol) were added to a reaction bottle and heated to 100°C under reflux. The reaction was monitored by TLC. After the reaction was complete, the mixture was concentrated, and the residue was dissolved in water (10 mL) and ethyl acetate (50 mL). The mixture was separated, the aqueous phase was extracted with ethyl acetate (50 mL x 2), the organic phase was combined, washed with saturated saline solution, dried over anhydrous sodium sulfate, filtered, concentrated, and obtained compounds iii-1 and iii-1' (total 511 mg, colorless transparent oil) by column chromatography.

[0063] JPEG0007891568000011.jpg53170 Thionyl chloride (415 mg, 3.5 mmol) was placed in a reaction bottle, dissolved in 15 mL of dichloromethane, and stirred under an ice bath at 0°C. A mixture of compounds iii-1 and iii-1' (511 mg, 2.3 mmol) was slowly added dropwise. After the addition was complete, the reaction was allowed to proceed at room temperature for 10 hours. After confirming that the reaction was complete by TLC monitoring, the reaction solution was concentrated under reduced pressure to obtain crude compounds v-1 and v-1', which were pale yellow oily substances.

[0064] Step 3: Compound vi-1 (224 mg, 3.5 mmol) was placed in a reaction bottle, triethylamine (349 mg, 3.5 mmol) was added, and the mixture was stirred under an ice bath at 0°C. A mixture of compounds v-1 and v-1' (690 mg, 2.3 mmol) was slowly added dropwise. After the addition was complete, the mixture was allowed to react at room temperature for 6 hours. After confirming that the reaction was complete by TLC monitoring, 100 mL of water was added to the reaction solution, and it was extracted with dichloromethane (30 mL x 3). After washing with saturated brine, the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography to obtain a mixture of compounds S-1 and S-1' (501 mg, colorless transparent liquid).

[0065] Example 2: Synthesis of compounds R-1 and R-1' In step 1 of Example 1, R-propylene oxide was replaced with S-propylene oxide, and a mixture of compounds R-1 and R-1' (515 mg, colorless transparent liquid) was obtained by synthesis using the synthesis method of Example 1.

[0066] Example 3: Synthesis of compounds S-19 and S-19' Referring to Step 1 synthesis of Example 1, R-propylene oxide was replaced with R-1,2-butylene oxide to obtain a mixture of target compounds iii-19 and iii-19'. Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compounds S-19 and S-19' (523 mg, colorless, transparent liquid) were obtained through synthesis.

[0067] Example 4: Synthesis of compounds R-19 and R-19' In step 1 of Example 1, R-propylene oxide was replaced with S-1,2-butylene oxide, and the compound R-19' was synthesized using the synthesis method of Example 1 to obtain a mixture of compounds R-19 and R-19' (507 mg, colorless transparent liquid).

[0068] Example 5: Chiral separation of compounds S-1, S-1', R-1, R-1', compound 10, compound 10', S-19, S-19', R-19, and R-19'. 1. Experimental Method 1.1 Separation of Compounds Based on the analysis, sulfite ester compounds 1-9, 1'-9', 19-24, and 19'-24' were determined to have two chiral centers. Eight components were obtained by synthesizing them using chiral starting materials and then separating them. Equipment: Shimadzu Corporation high-pressure liquid preparative chromatography, LC20AR; Chiral columns: CHIRALPAK® normal-phase IG column, CHIRALPAK® normal-phase AS column, 4.6 mm I.D. × 250 mm, diameter: 5 μm; Mobile phase: n-hexane:isopropyl alcohol = 95:5. Three components were obtained by separating the S mixture of compound 1 and compound 1' using the IG column, four components were obtained by separating the R mixture of compound 1 and compound 1' using the IG column, and after further separation of the seven components separated using the AS column, two components were found in the first peak in the S configuration of compound 1 and compound 1'. After separating these, eight components were obtained.

[0069] In the synthesis of compound 1, the reaction in step 1 resulted in two products, iii-1 and iii-1', due to the different ring-opening positions and thus different methyl positions. These can be separated by asymmetric synthesis. Equipment: Shimadzu Corporation high-pressure liquid preparative chromatography, LC20AR; Chiral column: CHIRALPAK® normal-phase IG column, 4.6 mm I.D. × 250 mm, diameter: 5 μm; Mobile phase: n-hexane:isopropyl alcohol = 90:10 (separation of iii-4, iii-4', etc. is under the same conditions).

[0070] 1.2 Determination of the absolute configuration of the compound 1.2.1 Hydrogen Spectral Testing of Compounds According to the literature (Absolute configuration of glycosyl sulfoxides, Tetrahedron: Asymmetry, Volume 21, Issue 15, 2010, Pages 180 - 1832, https: / / doi.org / 10.1016 / j.tetasy.2010.06.019.), when the group is on the same side as the non - bonding electron pair of sulfur, the group is shielded, the chemical shift decreases, and the chemical shift moves to the high - magnetic - field side. When the group is on the same side as the oxygen atom, the shielding of the group is released, the chemical shift increases and moves to the low - magnetic - field side. Based on this result, the absolute configuration of the separated compound was inferred as follows by performing NMR data analysis on it. JPEG0007891568000016.jpg130170

[0071] 1-(R,R): 1 H NMR(400MHz,CDCl3)δ7.31(d,J = 2.5Hz,1H),7.11(dd,J = 8.8,2.5Hz,1H),6.76(d,J = 8.8Hz,1H),4.90(td,J = 6.6,4.1Hz,1H),4.62(dd,J = 5.1,3.1Hz,1H),4.53 - 4.45(m,1H),4.37 - 4.10(m,2H),3.98(qd,J = 10.0,5.4Hz,2H),1.39(d,J = 6.5Hz,3H)ppm. 1-(R,S): 1 H NMR(400MHz,CDCl3)δ7.31(d,J = 2.5Hz,1H),7.11(dd,J = 8.8,2.6Hz,1H),6.85(d,J = 8.8Hz,1H),4.64 - 4.55(m,1H),4.55 - 4.38(m,2H),4.22 - 4.11(m,3H),4.04(dd,J = 11.2,4.1Hz,1H),1.32(d,J = 6.3Hz,3H)ppm. 1-(S,R): 1H NMR(400MHz,CDCl3)δ7.31(d,J=2.5Hz,1H),7.11(dd,J=8.8,2.6Hz,1H),6.85(d,J=8.8Hz,1H),4.6463-4.55(m,1H),4.55-4.38(m,2H),4.24-4.11(m,3H),4.04(dd,J=11.2,4.1Hz,1H),1.32(d,J=6.3Hz,3H)ppm. 1-(S,S): 1 H NMR(400MHz,CDCl3)δ7.31(d,J=2.5Hz,1H),7.11(dd,J=8.8,2.5Hz,1H),6.76(d,J=8.8Hz,1H),4.90(td,J=6.6,4.1Hz,1H),4.62(dd,J=5.1,3.1Hz,1H),4.56-4.45(m,2H),4.37-4.10(m,2H),3.98(qd,J=10.0,5.4Hz,2H),1.39(d,J=6.5Hz,3H)ppm.. 1’-(S,R): 1 H NMR(400MHz,CDCl3)δ7.30(d,J=2.5Hz,1H),7.11(dd,J=8.8,2.5Hz,1H),6.76(d,J=8.8Hz,1H),4.88(pd,J=6.4,4.4Hz,1H),4.68-4.56(m,1H),4.55-4.45(m,1H),4.34-4.11(m,2H),4.01(dd,J=10.0,6.3Hz,1H),3.93(dd,J=10.0,4.3Hz,1H),1.43(d,J=6.5Hz,3H)ppm. 1’-(S,S): 1 H NMR(400MHz,CDCl3)δ7.31(d,J=2.5Hz,1H),7.11(dd,J=8.8,2.5Hz,1H),6.76(d,J=8.8Hz,1H),4.90(td,J=6.6,4.1Hz,1H),4.62(dd,J=5.1,3.1Hz,1H),4.53-4.45(m,1H),4.37-4.10(m,2H),3.98(qd,J=10.0,5.4Hz,2H),1.39(d,J=6.5Hz,3H)ppm. 1 1’-(R,R): 1H NMR(400MHz,CDCl3)δ7.31(d,J=2.5Hz,1H),7.11(dd,J=8.8,2.5Hz,1H),6.76(d,J=8.8Hz,1H),4.90(td,J=6.6,4.1Hz,1H),4.69-4.57(m,1H),4.57-4.46(m,1H),4.36-4.09(m,2H),3.98(qd,J=10.0,5.4Hz,2H),1.39(d,J=6.5Hz,3H)ppm. 1’-(R,S): 1 H NMR(400MHz,CDCl3)δ7.30(d,J=2.5Hz,1H),7.11(dd,J=8.8,2.5Hz,1H),6.76(d,J=8.8Hz,1H),4.88(td,J=6.4,4.3Hz,1H),4.65-4.57(m,1H),4.50(td,J=3.9,3.3,1.5Hz,1H),4.32-4.12(m,2H),4.01(dd,J=10.0,6.3Hz,1H),3.93(dd,J=10.0,4.3Hz,1H),1.43(s,3H)ppm. S-10: 1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 1.4 Hz, 1H), 7.27 ‐ 7.25 (m, 1H), 7.10 (d, J = 7.5 Hz, 1H), 4.87 (t, J = 2.9 Hz, 1H), 4.75 (t, J = 2.9 Hz, 1H), 4.42 (s, 2H), 3.97 (t, J = 2.9 Hz, 1H), 3.90 (t, J = 2.9 Hz, 1H), 1.51 (s, 6H) ppm. R-10: 1 H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 1.4 Hz, 1H), 7.31 ‐ 7.27 (m, 1H), 7.18 (d, J = 7.5 Hz, 1H), 4.87 (t, J = 7.2 Hz, 1H), 4.75 (t, J = 7.3 Hz, 1H), 4.30 (s, 2H), 4.01 ‐ 3.03 (m, 2H), 1.47 (s, 6H) ppm. S-10’: 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 1.4 Hz, 1H), 7.32 (dd, J = 7.5, 1.4 Hz, 1H), 7.17 (d, J = 7.5 Hz, 1H), 4.87 (t, J = 3.2 Hz, 1H), 4.75 (t, J = 3.2 Hz, 1H), 4.14 (s, 2H), 4.10 (t, J = 3.2 Hz, 1H), 4.04 (t, J = 3.2 Hz, 1H), 1.47 (s, 6H) ppm. R-10’: 1 H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 1.4 Hz, 1H),7.34 ‐ 7.30 (m, 1H), 7.19 (d, J = 7.5 Hz, 1H), 4.91 (t, J = 2.9 Hz, 1H), 4.78 (t, J = 2.9 Hz, 1H), 4.13 (s, 2H), 3.95 ‐ 3.88 (m, 2H), 1.45 (s, 6H) ppm. 19‐(R,R): 1 H NMR (400 MHz, CDCl3) δ 7.47‐7.43 (m, 1H), 7.29 (dd, J = 7.5, 1.4 Hz, 1H), 7.16 (d, J = 7.5 Hz, 1H), 4.94‐4.88 (m, 2H), 4.75 (t, J = 3.0 Hz, 1H), 4.40‐4.36 (m, 1H), 3.96‐3.93 (m, 1H) 3.86‐3.82 (m, 2H),1.55‐1.48 (m, 2H), 0.99 (t, J = 6.8 Hz, 3H) ppm. 19‐(R,S): 1H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 1.4 Hz, 1H), 7.26‐7.22 (m, 1H), 7.06 (d, J = 7.5 Hz, 1H), 5.12‐5.08 (m, 1H), 4.87 (t, J = 2.8 Hz, 1H), 4.75 (t, J = 2.8 Hz, 1H), 4.24‐4.20 (m, 1H), 4.06 ‐ 3.90 (m, 2H), 3.86 (t, J = 2.8 Hz, 1H), 1.83 ‐ 1.61 (m, 1H), 1.50‐1.46 (m, 1H), 0.99 (t, J = 6.7 Hz, 3H) ppm. 19‐(S,R): 1 H NMR (400 MHz, CDCl3) δ 7.41 (d, J = 1.4 Hz, 1H), 7.29‐7.25 (m, 1H), 7.07 (d, J = 7.4 Hz, 1H), 5.11‐5.05 (m, 1H), 4.87 (t, J = 2.9 Hz, 1H), 4.75 (t, J = 2.9 Hz, 1H), 4.56‐4.48 (m, 1H), 4.00 ‐ 3.69 (m, 3H), 1.55‐1.47 (m, 2H), 0.98 (t, J = 6.7 Hz, 3H) ppm. 19‐(S,S): 1 H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 1.4 Hz, 1H), 7.33‐7.27 (m, 2H), 5.11‐5.06 (m, 1H), 4.87 (t, J = 3.5 Hz, 1H), 4.75 (t, J = 3.5 Hz, 1H), 4.33‐4.30 (m, 1H), 4.10 ‐ 3.82 (m, 3H), 1.67 ‐ 1.41 (m, 2H), 0.98 (t, J = 6.7 Hz, 3H) ppm. 19’ ‐(S,S): 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 1.4 Hz, 1H), 7.35‐7.32 (m, 1H), 7.16 (d, J = 7.5 Hz, 1H), 4.87 (t, J = 2.8 Hz, 1H), 4.75 (t, J = 2.9 Hz, 1H), 4.24 ‐ 3.97 (m, 2H), 3.88 ‐ 3.39 (m, 3H), 1.96 ‐ 1.51 (m, 2H), 0.99 (t, J = 6.7 Hz, 3H) ppm. 19’‐(S,R): 1 H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 1.4 Hz, 1H), 7.32 (dd, J = 7.5, 1.4 Hz, 1H), 7.18 (d, J = 7.5 Hz, 1H), 4.87 (t, J = 2.9 Hz, 1H), 4.75 (t, J = 2.9 Hz, 1H), 4.27 ‐ 4.04 (m, 2H), 4.03 ‐ 3.79 (m, 3H), 1.91 ‐ 1.58 (m, 2H), 0.98 (t, J = 6.7 Hz, 3H) ppm. 19’‐(R,R): 1 H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 1.5 Hz, 1H), 7.34‐7.31 (m, 1H), 7.19 (d, J = 7.5 Hz, 1H), 4.87 (t, J = 3.1 Hz, 1H), 4.75 (t, J = 3.1 Hz, 1H), 4.31‐4.27(m, 1H), 4.20 ‐ 3.95 (m, 3H), 3.85‐3.81 (m, 1H), 1.89 ‐ 1.72 (m, 1H), 1.71 ‐ 1.54 (m, 1H), 0.99 (t, J = 6.7 Hz, 3H) ppm. 19’‐(R,S): 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 1.4 Hz, 1H), 7.32 (dd, J = 7.5, 1.4 Hz, 1H), 7.18‐7.16 (m, 1H), 4.87 (t, J = 2.9 Hz, 1H), 4.75 (t, J = 2.9 Hz, 1H), 4.12-4.00 (m, 2H), 3.99 (t, J = 2.9 Hz, 1H), 3.92 (t, J = 2.8 Hz, 1H),3.86-3.83 (m, 1H), 1.73-1.71 (m, 2H), 0.97 (t, J = 6.7 Hz, 3H) ppm.

[0072] 1.2.2 Measurement of the specific rotation of compounds The specific rotation was measured at 25°C using chloroform as the solvent at a concentration of 1 mg / mL. The specific data is as follows. 1-(S,R):[α] 25 D = -10.00 1-(S,S):[α] 25 D = -9.00 1-(R,R):[α] 25 D = +10.00 1-(R,S):[α] 25 D = +10.00 1'‐(R,S):[α] 25 D = -8.00 1'‐(R,R):[α] 25 D = +41.00 1'‐(S,R):[α] 25 D = +7.00 1'‐(S,S):[α] 25 D = -38.00 S-10:[α] 25 D = -12.00 R-10:[α] 25 D = +11.00 S-10':[α] 25 D = -7.00 R-10':[α] 25 D = +6.00 19-(R,R):[α] 25 D = +37.00 19-(R,S):[α] 25 D = -10.00 19-(S,R):[α] 25 D = +11.00 19-(S,S):[α] 25 D = -38.00 19'-(R,R):[α] 25 D = +9.00 19'-(R,S):[α] 25 D = +11.00 19'-(S,R):[α] 25 D = -12.00 19'-(S,S):[α] 25 D = -8.00 As can be seen from the specific rotation results, the product's configuration should be correct, as it matches the absolute configuration predicted by NMR analysis.

[0073] Example 6: Synthesis of Compound 1 JPEG0007891568000017.jpg41170

[0074] Step 1: JPEG0007891568000018.jpg401702,4-Dichlorophenol (1 g, 6.2 mmol) was placed in a reaction bottle, dissolved in 20 mL of DMF, and propylene oxide (722 mg, 7.6 mmol) and cesium carbonate (8 g, 24.8 mmol) were added. The mixture was then heated in an oil bath at 100°C to allow the reaction to proceed. After 6 hours, TLC monitoring confirmed that the reaction was complete. Then, 100 mL of water was added, and the mixture was extracted with ethyl acetate (30 mL x 3). After washing with saturated saline solution, the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, separated, purified, and asymmetrically synthesized (instrument: Shimadzu Corporation high-pressure liquid preparative chromatography, LC20AR; chiral column: CHIRALPAK® normal-phase IG column, 4.6 mm I.D. x 250 mm, diameter: 5 μm; mobile phase: n-hexane:isopropyl alcohol = 90:10) to obtain compound iii-1 (781 mg, colorless transparent liquid).

[0075] JPEG0007891568000019.jpg39170 Thionyl chloride (293 mg, 2.5 mmol) was placed in a reaction bottle, dissolved in 20 mL of dichloromethane, stirred in an ice bath at 0°C, and compound iii-1 (356 mg, 1.6 mmol) was slowly added dropwise. After the addition was complete, the reaction was allowed to proceed at room temperature for 10 hours, and after confirming that the reaction was complete by TLC monitoring, the reaction solution was concentrated under reduced pressure to obtain the crude compound v-1, which was a pale yellow oily substance.

[0076] Compound vi-1 (123 mg, 1.9 mmol) was placed in a reaction bottle, triethylamine (243 mg, 2.4 mmol) was added, and the mixture was stirred in an ice bath at 0°C. Compound v-1 (480 mg, 1.6 mmol) was slowly added dropwise. After the addition was complete, the mixture was allowed to react at room temperature for 6 hours. After confirming that the reaction was complete by TLC monitoring, 100 mL of water was added to the reaction solution, and the mixture was extracted with dichloromethane (30 mL x 3). After washing with saturated brine, the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography to obtain compound 1 (423 mg, oily substance).

[0077] 1 H NMR(400MHz,CDCl3)δ7.50(d,J=1.4Hz,1H),7.30-7.27(m,1H),7.08(d,J=7.5Hz,1H),4.87(t,J=2.9Hz,1H),4.75(t,J=2.9Hz,1H) ,4.64-4.54(m,1H),4.51-4.46(m,1H),4.14-4.10(m,1H),3.95(t,J=2.8Hz,1H),3.88(t,J=2.9Hz,1H),1.40(d,J=5.7Hz,3H)ppm. HRMS(ESI)Calcd.For C 11 H 14 Cl2FO4SNa +[ M+Na] + 352.9768;Found:352.9789,354.9773

[0078] Example 7: Synthesis of Compound 1' Referring to Step 1 of Example 1, the target compound iii-1' was obtained by asymmetric synthesis.

[0079] Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compound 1' (423 mg, colorless, transparent liquid) was obtained through synthesis.

[0080] 1 H NMR(400MHz,CDCl3)δ7.39(d,J=2.5Hz,1H),7.20(dd,J=8.8,2.5Hz,1H),6.85(d,J=8.8Hz,1H),5.01-4.93(m,1H),4.74-4.66(m,1H),4.63 -4.55(m,1H),4.40-4.31(m,1H),4.31-4.22(m,1H),4.10(dd,J=10.0,6.3Hz,1H),4.02(dd,J=10.0,4.3Hz,1H),1.52(d,J=6.5Hz,3H)ppm. HRMS(ESI)Calcd.For C 11 H 14 Cl2FO4SNa + [M+Na] + 352.9768;Found:352.9786,354.9758.

[0081] Example 8: Synthesis of Compound 10 The target compound iii-10 was obtained by synthesizing it according to step 1 of Example 6 and then performing chiral preparation. Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compound 10 (685 mg, colorless transparent liquid) was obtained by synthesis. 1H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 1.4 Hz, 1H), 7.29 (dd, J = 7.5, 1.4 Hz, 1H), 7.18 (d, J = 7.5 Hz, 1H), 4.87 (t, J = 7.2 Hz, 1H), 4.75 (t, J = 7.3 Hz, 1H), 4.30 (s, 2H), 4.03 - 3.03 (m, 2H), 1.47 (s, 6H) ppm. HRMS (ESI) Calcd. For C 12 H 16 Cl2FO4S + [M+H] + 345.0125; Found:345.0143.

[0082] Example 9: Synthesis of Compound 10' Referring to Step 1 synthesis of Example 6, the target compound iii-10' was obtained by chiral preparation. Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compound 10' (311 mg, colorless transparent liquid) was obtained through synthesis. 1 H NMR (400 MHz, CDCl3) δ 7.62 (d, J = 1.4 Hz, 1H), 7.29 - 7.27 (m, 1H), 7.16 (d, J = 7.5 Hz, 1H), 4.87 (t, J = 2.9 Hz, 1H), 4.75 (t, J = 2.9 Hz, 1H), 4.13 (s, 2H), 4.04 (t, J = 2.9 Hz, 1H), 3.97 (t, J = 2.9 Hz, 1H), 1.37 (s, 6H). HRMS (ESI) Calcd. For C 12 H 16 Cl2FO4S + [M+H] + 345.0125; Found:345.0126.

[0083] Example 10: Synthesis of Compound 19 JPEG0007891568000024.jpg28170 Step 1:

[0084] Referring to Step 1 synthesis of Example 6, the target compound iii-19 was obtained by chiral preparation. Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compound 19 (692 mg, colorless, transparent liquid) was obtained by synthesis. 1 H NMR (400 MHz, CDCl3)δ7.45 (d, J = 1.6 Hz, 1H), 7.31‐7.27 (m, 1H), 7.16 (d, J = 7.5 Hz, 1H), 4.97‐4.84 (m, 2H), 4.75 (t, J = 3.0 Hz, 1H), 4.39-4.34 (m, 1H), 3.99-3.77 (m, 3H), 1.56-1.43 (m, 2H), 0.99 (t, J = 6.8 Hz, 3H) ppm. HRMS (ESI) Calcd. For C 12 H 15 O4Cl2FS + [M+H] + 344.0052; Found:344.0026.

[0085] Example 11: Synthesis of Compound 19' JPEG0007891568000026.jpg21170JPEG0007891568000027.jpg29170 Referring to the synthesis in Step 1 of Example 6, the target compound iii-19' was obtained by chiral preparation. Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compound 19' (309 mg, colorless, transparent liquid) was obtained through synthesis. 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 1.4 Hz, 1H), 7.32 (dd, J = 7.5, 1.4 Hz, 1H), 7.21‐7.17 (m, 1H), 4.87 (t, J = 3.1 Hz, 1H), 4.75 (t, J = ppm. HRMS (ESI) Calcd. For C 12 H 15 O4Cl2FS + [M+H] + 344.0052; Found:344.0071.

[0086] Example 14: Synthesis of Compound 22 Referring to Step 1 synthesis of Example 6, the target compound iii-22 was obtained by chiral preparation. Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compound 22 (671 mg, colorless, transparent liquid) was obtained by synthesis. 1 H NMR (400 MHz, CDCl3) δ 7.44 (d, J = 1.4 Hz, 1H), 7.30 (dd, J = 7.5, 1.6 Hz, 1H), 7.20 (d, J = 7.5 Hz, 1H), 6.04 - 5.93 (m, 1H), 5.51 - 5.34 (m, 1H), 5.25 - 5.12 (m, 2H), 4.87 (t, J = 3.0 Hz, 1H), 4.75 (t, J = 3.0 Hz, 1H), 4.39 (dd, J = 12.5, 2.4 Hz, 1H), 4.13 - 4.02 (m, 2H), 3.99 (t, J = 3.0 Hz, 1H) ppm. HRMS (ESI) Calcd. For C12 H 13 O4Cl2FS + [M+H] + 341.9896; Found:341.9857.

[0087] Example 15: Synthesis of Compound 22' Referring to Step 1 synthesis of Example 6, the target compound iii-22' was obtained by chiral preparation. Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compound 22' (297 mg, colorless, transparent liquid) was obtained through synthesis. 1 H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 1.4 Hz, 1H), 7.25 (dd, J = 7.5, 1.4 Hz, 1H), 7.18 (d, J = 7.5 Hz, 1H), 5.95 - 5.80 (m, 1H), 5.31 - 5.15 (m, 2H), 4.87 (t, J = 3.0 Hz, 1H), 4.75 (t, J = 3.0 Hz, 1H), 4.54 - 4.50 (m, 1H), 4.14 (dd, J = 12.5, 5.1 Hz, 1H), 3.75 (dd, J = 12.4, 5.0 Hz, 1H), 3.65 (t, J = 3.0 Hz, 1H), 3.59 (t, J = 3.0 Hz, 1H) ppm. HRMS (ESI) Calcd. For C 12 H 13 O4Cl2FS + [M+H] + 341.9896; Found:341.9903.

[0088] Example 16: Synthesis of Compound 25 Referring to Step 1 synthesis of Example 6, propylene oxide was replaced with 3,4-tetrahydrofuran to obtain the target compound iii-25. Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compound 25 (703 mg, colorless, transparent liquid) was obtained by synthesis.

[0089] Example 17: Synthesis of Compound 28 Referring to Step 1 synthesis of Example 6, propylene oxide was replaced with ethylene carbonate to obtain the target compound iii-28. Step 2: Same as Step 2 of Example 1. Step 3: Same as Step 3 of Example 1. The target compound 22 (671 mg, colorless, transparent liquid) was obtained by synthesis.

[0090] The remaining compounds were synthesized according to the synthesis method described above. The structures of all compounds are shown in Table 1. JPEG0007891568000032.jpg151170JPEG0007891568000033.jpg131170

[0091] Test Example 1: Effects of Compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S), Compounds 1 and 1', Compounds S-10, R-10, S-10', R-10', Compounds 10 and 10', Compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), Compounds 19 and 19' on the hatching of false spider mite eggs. 1. Experimental Method (1) Preparation of leaf discs containing eggs: Twenty adult female false spider mites were transferred to a 2.0 cm diameter broad bean leaf disc (with a wet filter paper at the bottom), then covered with a lidded culture dish and incubated in a humid environment. Adult mites were removed within 36 hours, and the leaf discs containing eggs were counted under a microscope.

[0092] (2) Investigation of the number of egg ovipositors: Before immersion in the chemical solution, the number of egg ovipositors on each leaf disc was examined under a microscope, and each treatment was repeated twice.

[0093] (3) Immersion treatment: Leaf discs containing mite eggs were immersed in clean water and sulfite ester compound for 10 seconds each, then removed and incubated in a humid environment. Each treatment was repeated at least three times.

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

[0095] Note: After processing, pay attention to the temperature and humidity conditions of the constant humidity incubator. Excessive temperature fluctuations can cause condensation inside the dish, potentially submerging the eggs and causing them to die. It is also necessary to ensure that there is sufficient strong light in the environment. However, care must be taken to avoid direct sunlight on the leaves.

[0096] (5) Results Investigation: The test materials for each treatment group were regularly moistened with water, and the hatching status of the eggs was observed. On the fourth day after application, the number of hatched eggs for each treatment was recorded, and the results were recorded in a logbook. The investigation time may be shortened or extended depending on the test requirements and the characteristics of the drug.

[0097] Survey Indicators (a) The number of hatched eggs in each treatment was investigated and recorded.

[0098] (b) The broad bean leaf discs were photographed to record whether pesticide damage had occurred.

[0099] (c) The developmental status of test mite eggs and the behavior of nymph mites were recorded (for example, abnormal phenomena such as delayed or stopped development of mite eggs, difficulty for nymph mites to break out of their shells, or suffering after hatching).

[0100] (6) Calculation method: Based on the survey data, the control for each treatment was calculated using the following formula. The calculation results were rounded to two decimal places.

[0101] Egg hatching rate (%) = Number of hatched eggs / Total number of processed eggs * 100 Control effectiveness (%) = (Egg hatching rate in control group - Egg hatching rate in treated group) / Egg hatching rate in control group) * 100.

[0102] The experimental design is shown in Table 2.

[0103] JPEG0007891568000034.jpg102170JPEG0007891568000035.jpg255159JPEG0007891568000036.jpg77170

[0104] 2. Experimental Results The results are shown in Table 3. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S), and compounds 1, 1', S-10, S-10', and compounds 10, 10', 19-(S,R), 19-(R,S), 19'-(S,S), 19'-(R,R), and compounds 19 and 19' all showed excellent inhibitory effects on the hatching of false spider mite eggs at 1 ppm.

[0105] JPEG0007891568000037.jpg132170JPEG0007891568000038.jpg255155JPEG0007891568000039.jpg106170

[0106] Test Example 2: Effects of compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S) and compounds 1, 1', S-10, R-10, S-10', R-10' and compounds 10, 10', compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compounds 19 and 19' on thrips egg hatching. In this study, the method of Test Example 1 was used, and the inhibitory effect of 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S), and compounds 1, 1', S-10, R-10, S-10', R-10', and compounds 10, 10', 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compounds 19 and 19' on thrips egg hatching was investigated mainly using the leaf disk method. The concentration of all compounds was 100 ppm.

[0107] The experimental results are shown in Table 4. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S), and compounds 1, 1', S-10, S-10', and compounds 10, 10', 19-(S,R), 19-(R,S), 19'-(S,S), 19'-(R,R), and compounds 19 and 19' all showed high inhibitory activity against thrips egg hatching at 100 ppm.

[0108] JPEG0007891568000040.jpg200170

[0109] Test Example 3: Effects of Compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S) and Compounds 1, 1', S-10, R-10, S-10', R-10' and Compounds 10, 10', Compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), Compounds 19 and 19' on the hatching of spider mite eggs. In this study, the method of Test Example 1 was used, and the inhibitory effect of compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S), and compounds 1, 1', S-10, R-10, S-10', R-10' and compounds 10, 10', compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compounds 19 and 19' on the hatching of spider mite eggs was investigated mainly using the leaf disk method. The concentration of all compounds was 5 ppm.

[0110] The experimental results are shown in Table 5. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S), and compounds 1, 1', S-10, S-10', and compounds 10, 10', 19-(S,R), 19-(R,S), 19'-(S,S), 19'-(R,R), and compounds 19 and 19' all showed high inhibitory activity against the hatching of spider mite eggs at 5 ppm.

[0111] JPEG0007891568000041.jpg189170

[0112] Test Example 4: Effects of compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S) and compounds 1, 1', S-10, R-10, S-10', R-10' and compounds 10, 10', compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compounds 19 and 19' on the hatching of citrus red mite eggs. In this study, the method of Test Example 1 was used, and the effects of compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S), and compounds 1, 1', S-10, R-10, S-10', R-10' and compounds 10, 10', compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compounds 19 and 19' on the hatching of citrus red mite eggs were investigated mainly using the leaf disk method. The concentration of all compounds was 1 ppm.

[0113] The experimental results are shown in Table 6. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S), and compounds 1, 1', S-10, S-10', and compounds 10, 10', 19-(S,R), 19-(R,S), 19'-(S,S), 19'-(R,R), and compounds 19 and 19' all showed a high inhibitory effect on the hatching of citrus red mite eggs at 1 ppm.

[0114] JPEG0007891568000042.jpg138170JPEG0007891568000043.jpg66170

[0115] Test Example 5: Effects of compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S) and compounds 1, 1', S-10, R-10, S-10', R-10' and compounds 10, 10', compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compounds 19 and 19' on the hatching of whitefly eggs In this study, the method of Test Example 1 was used, and the effect of compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S), and compounds 1, 1', S-10, R-10, S-10', R-10' and compounds 10, 10', compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compounds 19 and 19' on the inhibition of whitefly egg hatching was investigated mainly using the leaf disk method. The concentration of all compounds was 10 ppm.

[0116] The experimental results are shown in Table 7. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S), and compounds 1, 1', S-10, S-10', and compounds 10, 10', 19-(S,R), 19-(R,S), 19'-(S,S), 19'-(R,R), and compounds 19 and 19' all show strong inhibitory activity against the hatching of whitefly eggs at 10 ppm.

[0117] JPEG0007891568000044.jpg200170

[0118] Test Example 6: Effects of compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S), and compounds 1, 1', S-10, R-10, S-10', R-10' and compounds 10, 10', compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compounds 19 and 19' on the hatching of beet armyworm eggs. 1. Experimental Plan (1) Preparation of egg-containing paper: Egg masses were cut into small pieces, with approximately 60 egg grains per mass. The egg-laying paper was immersed in the test reagents (all compounds at a concentration of 500 ppm) for 10 minutes. After removal, excess solution adhering to the egg-laying paper and egg mass was absorbed and removed using absorbent paper. (2) Cultivation: Each egg mass was placed in a glass test tube (5.0 cm high, 2.5 cm in diameter, the same applies below), sealed with plastic paper punctured with an insect pin, and cultured in an artificial climate box at (24±1)℃, relative humidity (80±10)%, and light-dark cycle L:D=12:12. When the eggs had developed to the point of almost hatching, castor leaves approximately 3 cm in diameter were added and fed to the hatched larvae. (3) Observation: The number of hatched and unhatched eggs in each egg was inspected and recorded, and the egg hatching rate was calculated using a formula. Each treatment was repeated three times. (4) Results Investigation: The test materials for each treatment group were regularly moistened with water, and the hatching status of the eggs was observed. On the fourth day after application, the number of hatched eggs for each treatment was recorded, and the results were recorded in a logbook. The investigation time may be shortened or extended depending on the test requirements and the characteristics of the drug.

[0119] Survey Indicators (a) The number of hatched eggs in each treatment was investigated and recorded.

[0120] (b) The developmental status of the test beet armyworm eggs and the behavior of the nymphs (for example, abnormal phenomena such as delay or cessation of the beet armyworm egg development process) were recorded.

[0121] (5) Calculation method: Based on the survey data, the control effect of each treatment was calculated using the following formula. The calculation results were rounded to two decimal places.

[0122] Egg hatching rate (%) = Number of hatched eggs / Total number of processed eggs * 100 Control effectiveness (%) = (Egg hatching rate in control group - Egg hatching rate in treated group) / Egg hatching rate in control group) * 100

[0123] 2. Experimental Results The experimental results are shown in Table 8. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S), S-10, S-10, 19-(S,R), 19-(R,S), 19'-(S,S), and 19'-(R,R) showed high inhibitory activity against the hatching of beet armyworm eggs at 500 ppm.

[0124] JPEG0007891568000045.jpg189170

[0125] Test Example 7: Effects of compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S), and compounds 1, 1', S-10, R-10, S-10', R-10' and compounds 10, 10', compounds 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compounds 19 and 19' on the hatching of ladybug eggs. 1. Test Plan The ladybug egg cards (each card containing approximately 20 eggs) were purchased from Henan Jiyuan Baiyun Industrial Co., Ltd. The number of eggs on each egg card was statistically counted and used as the base number before treatment. Five egg cards constituted one treatment, and each treatment was repeated three times. The egg cards were immersed in a 100 ppm solution for 30 seconds, then removed, dried, and cultured under humid conditions. The treated mite eggs and leaf discs were cultured at 27°C. Four days after treatment, the hatching status of the ladybug eggs was investigated. The control effect was calculated using the following formula.

[0126] Egg hatching rate (%) = Number of hatched eggs / Total number of processed eggs * 100 Control effectiveness (%) = (Egg hatching rate in control group - Egg hatching rate in treated group) / Egg hatching rate in control group) * 100

[0127] 2. Test Results The experimental results are shown in Table 9. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S), and compounds 1, 1', S-10, S-10', and compounds 10, 10', 19-(S,R), 19-(R,S), 19'-(S,S), 19'-(R,R), and compounds 19 and 19' all showed high inhibitory activity against the hatching of ladybug eggs at 100 ppm.

[0128] JPEG0007891568000046.jpg197170

[0129] Test Example 8: Primary screening of fungicidal activity (against rice blast fungus) of compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S) and compound 1, compound 1', S-10, R-10, S-10', R-10' and compound 10, compound 10', compound 19-(S,S), 19-(S,R), 19-(R,R), 19-(R,S), 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compound 19 and compound 19'. 1. Experimental Design Test materials: culture medium, activated bacteria, sterile water, 96-well plate, multichannel pipette.

[0130] Rapid screening system (200 μL): culture medium (150 μL) + drug (40 μL) + bacteria (10 μL).

[0131] Test steps: Preparation, culture medium addition, drug addition, bacterial addition, detection (1) Preparation: The drug was prepared at a final concentration of 100 ppm, and the prepared drug was transferred to a 1.5 mL centrifuge tube for storage. (2) The culture medium and drug were added to a 96-well plate using a multichannel pipette. (3) Preparation of inoculum: The cultured culture dish (rice blast fungus) was taken, 15 mL of sterile water was added to the culture dish, and the hyphae were broken by sliding the pipette head across the surface of the hyphae and dispersed in the sterile water. A 10 μL bacterial suspension was examined under a microscope on a glass slide. There were more than 10 hyphae in the field of view. The bacteria were cultured to OD600 = 1.0 and diluted 1000 times to prepare the inoculum. The oomycozoans were 1 * 10 5 The number was greater than or equal to / mL.

[0132] (4) Detection: Fungal measurements were recorded at OD=450nm and bacterial measurements at OD=600nm, with data recorded at 0 hours. After incubation for the corresponding time, growth data was recorded, and the bacterial inhibition rate was calculated using the following formula.

[0133] Bacterial suppression rate (%) = ((Blank control OD (72h) - Blank control OD (0h)) - (Treatment OD (72h) - Treatment OD (0h)) / Blank control OD (72h) - Blank control OD (0h)) * 100

[0134] 2. Experimental Results The experimental results are shown in Table 10. Compounds 1-(S,S), 1-(S,R), 1-(R,R), 1-(R,S), 1'-(S,S), 1'-(S,R), 1'-(R,R), 1'-(R,S) and compound 1, compound 1', S-10, R-10, S-10', R-10' and compound 10, compound 10', compound 19-(S,S), 19-(S,R), 19-(R,R), 19-(R, Compounds S, 19'-(S,S), 19'-(S,R), 19'-(R,R), 19'-(R,S), compound 19 and compound 19' showed high inhibition rates against rice blast fungus at 100 ppm, and in particular, the inhibition rates against compounds 1-(S,S), 1-(R,R), 1'-(R,S), 1'-(S,R), compound 1 and compound 1' were high at over 90%.

[0135] JPEG0007891568000047.jpg173170

[0136] Experimental Example 9: Effect of sulfite ester compounds on the hatching of false spider mite eggs 1. Experimental Method In this study, the method described in Test Example 1 was used, and the effects of compound 1-compound 30 and compound 1'-compound 30' on the hatching of citrus red mite eggs were investigated mainly using the leaf disk method. The concentration of each compound was 100 ppm.

[0137] 2. Experimental Results The experimental results are shown in Table 11. The hatching rates for compound 1, compound 2, compound 3, compound 4, compound 5, compound 6, compound 7, compound 8, compound 9, compound 1', compound 2', compound 3', compound 4', compound 5', compound 6', compound 7', compound 8', and compound 9' were all 15% or less, indicating high mite egg killing activity.

[0138] JPEG0007891568000048.jpg255166JPEG0007891568000049.jpg87170

[0139] Example 10 A ginger-ginger mixture was obtained by mixing ginger extract and ginger volatile oil in a ratio of 7:3. This mixture was combined with compounds 1, 10, and 19, and its control effect against false spider mite eggs was investigated by the leaf disk method based on the test method of Example 1. The ginger extract is obtained by extracting ginger rhizomes with a mixed solvent of ethyl acetate and ethanol in a ratio of 1:4. Bliss believes that, based on the concept of independent combined action, the theoretical mortality rate P when insecticides and acaricides are used in combination can be calculated using the following formula. P = Pm + Pn(1 - Pm) Pm is the target mortality rate (%) when the concentration of the first active ingredient is m, and Pn is the target mortality rate (%) when the concentration of the second active ingredient is n. If, after mixing two active ingredients at predetermined concentrations, the actual mortality rate of the target exceeds the theoretical mortality rate P, then it can be determined that the combined use of the two active ingredients at predetermined concentrations has a synergistic effect, while the reverse effect has an antagonistic effect. The experimental results are shown in Table 12. Compounds 1, 10, and 19, when combined with a mixture of ginger and ginger, exhibit a synergistic effect in controlling false spider mite eggs. JPEG0007891568000050.jpg163170

[0140] The above embodiments are merely illustrative examples illustrating the principles and effects of the present invention and do not limit it. Those 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 within the scope of the spirit and technical content of the present invention should still be included within the claims of the present invention.

Claims

1. A chiral sulfite ester compound having the structure represented by formula (A), a meso compound, a racemic compound, a stereoisomer, or a pharmaceutically acceptable salt thereof, used for controlling and / or killing insect eggs or for sterilization. (In the formula, R1 and R2 are Cl, R3, R3', R4, and R4' are combinations of three hydrogen atoms and one C2-C5 alkenyl atom, or R3' and R4' are hydrogen atoms, R3 and R4 together with the C bonded to them form a five-membered heterocycloalkyl group, and R5 is -CH2CH2F.)

2. A method for controlling and / or killing or sterilizing insect eggs, characterized by applying the sulfite ester compound described in claim 1 to the insect eggs and / or fungi.

3. The sulfite ester compound is The method according to claim 2, characterized in that it is one or a mixture of two or more selected from.

4. The method according to claim 2, characterized in that the aforementioned pest eggs originate from thrombi, hemipterans, lepidopterans, coleopterans, spider mites, pygmy mites, gall mites, terrestrial mites, lice mites, claw mites, or predatory mites, and the aforementioned fungi include fungi and bacteria.

5. The aforementioned pest eggs include those of the flat-headed thrips, onion thrips, bean thrips, rice thrips, flower thrips, southern yellow thrips, citrus yellow thrips, southern yellow thrips, loquat thrips, sugarcane thrips, cajonka thrips, tea yellow thrips, croton thrips, tea yellow thrips, Scolotripsy sexmaculatus, leaf borer, tobacco whitefly, greenhouse whitefly, citrus whitefly, bayberry whitefly, Areurosibotus indica, pyraling whitefly, Oligonyx bipysongis, and larch whitefly.

2. Spider mites, ladybugs, longhorn beetles, ladybugs, fireflies, scarab beetles, Mirabris phallellata, rhinoceros beetles, jewel beetles, soldier beetles, scarab beetles, Lucanidae, click beetles, diving beetles, corn weevils, Eotetranic The method according to claim 2, characterized in that it is derived from *Eotetranicus albus*, *Eotetranicus bailae*, *Camellia sasanqua*, *Tetranychus nassensis*, *Tetranychus sagamiensis*, *Tetranychus spp.*, *Tetranychus purpurea*, *Tetranychus leucocarpus*, *Schizotetranicus elongatas*, *Mixonyx (Bacherina) aesteva*, *Mixonyx ganjuis*, *Lycoperdon citrina*, *Pannonius cagleyi*, *Aronicus bambusae*, *Aronicus winicus*, *Tetranychus spp.*, *Mononicerus georgicus*, *Acanthonius jampengensis*, and *Tetranychus chernifolia*, and the fungus is a rice blast fungus.

6. The concentration of the sulfite ester compound used is 0.1 ppm or higher. The method according to claim 2, characterized by the features described herein.

7. The method according to claim 2, characterized in that, when used, the sulfite ester compound is prepared into an agricultural product and used, and the agricultural product further contains one or more of the following auxiliary agents: a dispersant, a wetting agent, an adhesive, an emulsifier, a stabilizer, and a solvent.

8. The method according to claim 7, characterized in that the dosage form of the product is an emulsion, a suspension, a wettable powder, a powder, granules, a liquid, a mother liquor, or a mother powder.

9. A pesticide composition characterized in that the compound of formula (A) described in claim 1 is used as the active substance.

10. The pesticide composition according to claim 9, further comprising a mixture of ginger rhizome extract and galangal rhizome extract, wherein the ratio of ginger rhizome extract to galangal rhizome extract is 7:3, where the ginger rhizome extract is obtained by extracting ginger rhizome with ethanol:ethyl acetate in a ratio of 1 to 4:1, and the galangal rhizome extract is characterized by being a volatile oil of galangal rhizome.

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