Sulfite compound with chirality and isomerism and application thereof

Abstract

The invention relates to a sulfite compound with chirality and isomerism and application thereof. The invention discloses a sulfite compound with chirality and isomerism as well as preparation, separation and application of a chiral structure of the sulfite compound, and belongs to the technical field of agriculture. The invention finds that the chiral and isomeric sulfite compound with a structure of a general formula (A) has excellent inhibitory activity on eggs, particularly has a very strong inhibitory effect on eggs of thrips, mites, lepidoptera moths, aleyrodids and harmonia axyridis, and also has bactericidal activity, and an absolute configuration of the compound is obtained through preparation and separation; the compound with the structure can be used for killing eggs and bacteria, has a very high pesticide research value, and has a wide application prospect in the field of agricultural pharmacology.

Description

Technical Field

[0001] The present invention relates to the field of agricultural technology, and in particular to an insecticidal compound of chiral, isomeric sulfite esters, and chiral preparation, separation and application thereof. Background Art

[0002] The insecticide market is vast and huge, with a market capacity of nearly 10 billion. Typical agricultural insecticides mainly include Orthoptera such as locusts and mole crickets; Hemiptera stink bugs; Homoptera including aphids, leafhoppers, planthoppers, etc.; Thysanoptera thrips; Coleoptera various beetles; Lepidoptera moths and butterflies; Hymenoptera bees and ants; Diptera mosquitoes, flies and horseflies; Acari various red spiders, etc.

[0003] In the existing control concept, most pesticide products focus on contact and stomach poisoning of adults, nymphs or larvae, and control the base number of pests by significantly reducing the number of insects on crops, thereby protecting crops from excessive damage and reducing economic losses after the occurrence of pests. This method can usually control the base number of pests in the environment well, but in the control practice of some pest species with short generation cycles (such as various types of red spiders, thrips, etc.), it often cannot achieve good results.

[0004] Taking red spider mites as an example, there are many types of registered miticides, including ethidium cypermethrin, avermectin, triazolin, fenbutatin, spirocyclofen, etoxazole, Veratrum rhizome extract, matrine and dozens of other plant-based, inorganic mineral or chemical miticides. However, most of these miticides are targeted at adult mites or young mites, and only some have good egg-killing activity. In the field, the breeding speed of harmful mites is extremely fast, and basically one generation is completed every week, so the phenomenon of overlapping generations is very serious. Therefore, if only miticides without egg-killing effect are sprayed, although adult mites are killed, new young mites will soon hatch from the eggs and rapidly expand the population. Although the subsequent hatched harmful mites can be removed by secondary application of pesticides, there will be some problems in actual application. For example, if the pesticide is applied too frequently, the resistance of harmful mites will increase rapidly. At the same time, the cost of pesticide application for farmers will also increase exponentially. In the field, in order to save labor costs, the traditional method of applying pesticides tends to be a mixture of multiple agents, such as acaricides, insecticides, fungicides, regulators, and foliar nutrients. In the actual field pest control application, farmers will choose to use it together with egg-killing agents to extend the effective period. Among the registered acaricides, only etoxazole and spirodiclofen are clearly used as ovicides, and the number is relatively scarce. The scarcity of varieties and the rise of resistance have also led to an increasing demand for new effective mite egg dual-killing acaricides. At the same time, small molecule acaricides with multiple functions are scarce. When farmers apply them in the field, they usually need to mix and apply multiple agents such as regulators, foliar nutrients, fungicides, and ovicides at the same time. The tank-mixed application of multiple chemical agents with different mechanisms of action and different dosage forms is not only easy to cause antagonism between agents, but also easy to destroy the stability of the aqueous solution of the preparation. Precipitation, flocculation, stratification and other phenomena often occur, which seriously affects the field use of the agent. At the same time, the mixing of large amounts of pesticides can easily lead to a further increase in target resistance and adverse effects of pesticide residues on the environment.

[0005] Therefore, the development of new and highly effective insecticides and ovicides with novel structures and unique mechanisms of action is the key to agricultural pest control. Summary of the invention

[0006] The purpose of the present invention is to provide an insecticidal compound of chiral, isomeric sulfite esters, wherein the absolute configuration is obtained by preparation and separation, and one or more compounds of the configuration can solve the problems existing in the above-mentioned prior art and achieve good inhibitory and killing effects on insect eggs.

[0007] When studying the insecticidal activity of sulfite compounds, the inventors accidentally discovered that some of the compounds had low insecticidal activity (insect population reduction rate was less than 75%), but showed excellent inhibitory activity on pest eggs.

[0008] The present invention provides a chiral, isomeric sulfite compound having a structure as shown in formula (A) or its mesomorph, racemate, stereoisomer, and pharmaceutically acceptable salt;

[0009]

[0010] Among them, R 1 , R 2 independently selected from hydrogen, halogen, substituted or unsubstituted C 1 ~C 10 Alkyl, substituted or unsubstituted C 1 ~C 10 Alkoxy, C 2 ~C 10 Alkoxycarbonyl, C 2 ~C 10 Alkylcarbonyl, C 1 ~C 10 Carbonyl;

[0011] R 3 , R 3 '、R 4 , R 4 'are independently selected from hydrogen, C 1 ~C 5 Alkyl, C 1 ~C 5 alkenyl; or, R 3 , R 3 '、R 4 , R 4 'The C connected thereto forms a five-membered heterocycloalkyl group;

[0012] R 5 is selected from halogen, substituted or unsubstituted C 1 ~C 10 alkyl.

[0013] Furthermore, the compound structure is selected from one of the following:

[0014]

[0015] In formula (A), I to VI, further, the C 1 ~C 5 The alkyl group is methyl or ethyl.

[0016] In formula (A), I to VI, further, the C 1 ~C 5 The alkenyl group is selected from vinyl groups.

[0017] In formula (A), I to VI, further, the five-membered heterocycloalkyl group is selected from

[0018] Furthermore, the R 5 is selected from fluoroethyl, bromoethyl, chloroethyl, 2,2-difluoroethyl, 2,2-dichloroethyl; R 1 , R 2 Independently selected from H, F, Cl, Br.

[0019] Furthermore, R 5 -CH 2 CH 2 F; R 1 , R 2 For Cl.

[0020] Furthermore, the compound is selected from the following compounds:

[0021]

[0022]

[0023] In the above, except as already indicated, the term "substituted" means that the group mentioned may be substituted by one or more additional groups, each of which is independently selected from alkyl, cycloalkyl, aryl, carboxyl, heteroaryl, heterocycloalkyl, hydroxy, alkoxy, alkylthio, aryloxy, O=, guanidino, cyano, nitro, acyl, halogen, haloalkyl, amino, etc.

[0024] The compounds of the present invention can be confirmed by conventional methods known to those skilled in the art. If the present invention relates to the absolute configuration of the compound, the absolute configuration can be confirmed by conventional 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 the lone pair of electrons of the group and sulfur are on the same side, the group is shielded, the chemical shift decreases, and the chemical shift moves to the high field. If the group is on the same side as the oxygen atom, the group is deshielded, the chemical shift increases, and moves to the low field. According to the comparison and analysis of the hydrogen spectrum of the chiral separation compound and the test of optical activity, its absolute configuration is obtained.

[0025] The numbers of the above compounds are only for the convenience of subsequent description.

[0026] The invention provides a method for controlling and / or killing pest eggs and / or sterilizing, wherein the above-mentioned compound is applied to pest eggs and / or fungi.

[0027] Further, when used to control and / or kill pest eggs, and / or sterilize, the compound is selected from the following compounds, including mixtures of multiple configurations:

[0028]

[0029]

[0030] The intermediate compounds of the present invention can be prepared by a variety of synthetic methods well known to those skilled in the art, including the specific embodiments listed herein, embodiments formed by combining them with other chemical synthesis methods, and equivalent substitutions well known to those skilled in the art. Preferred embodiments include but are not limited to the embodiments of the present invention.

[0031] The chemical reactions of the specific embodiments of the present invention are carried out in a suitable solvent, which must be suitable for the chemical changes of the present invention and the reagents and materials required. In order to obtain the compounds of the present invention, it is sometimes necessary for those skilled in the art to modify or select the synthesis steps or reaction processes based on the existing embodiments.

[0032] As used herein, the term "pest" refers to an organism that adversely affects hosts (eg, plants or animals such as mammals) by parasitizing, damaging, attacking, competing with them for nutrients, or infecting them.

[0033] Without particular limitation, pests include arthropods (including insects and arachnids), and include piercing-sucking pests and biting pests (eg, bed bugs, mites, ticks, ants, lice, cockroaches, thrips, etc.).

[0034] Without specific limitation, the pest eggs are produced by insects of the order Thysanoptera, the order Hemiptera, the order Lepidoptera, the order Coleoptera, the order Acarina, the family Tetranychidae, the family Tenebriophoridae, the family Cynocephalae, the family Tarsonematidae, the family Pygeidae, the family Chrysonychidae or the family Carnivorous Mite; the fungi include fungi and bacteria.

[0035] The "Thysanoptera" belongs to the class Insecta. Insects in this order are commonly known as "thrips". They are small insects with a slender body, generally yellow-brown or black; well-developed eyes, piercing-sucking mouthparts, asymmetrical left and right; narrow and long wings with a few or no wing veins, flat and long wing margins, with long or short hairs; there are also wingless species and only vestigial species; lack of cerci; generally suck plant sap, which harms cereals, cotton and tobacco, etc., and some can spread plant viruses, and are pests. Thrips are divided into the suborders Terebrantia and Tubulifera. The suborder Saw-tailed Thrips includes: Aeolothripoidea (Aeolothripidae, Orothripidae, Melanthripidae, Dactuliothripidae, Franklinothripidae), Merothripoidea (Aeolothripoidea), Thripoidea (Heterothripidae, Hemithripidae, Ceratothripidae, Panchaetothripidae, Thripidae); among them, Thripidae is the largest and most important family in this order, with 33 known genera and about 200 species, such as: Frankliniella intonsa, Thripstabaci Lindeman, Taeniothrips distalis Karny, Rice Thrips Stenchaeotothripsbiformis, Yellow-breasted Thrips Thrips hawaiiensis Morgan, Palm Thrips Thrips palmi Karny, Western Flower Thrips Frankliniella occidentalis, Loquat Thrips Thrips japonicus Bagnall, Sugarcane Thrips Thraps serratus Kobus, Grain Thrips Frankliniella tenuicornis Uzel, Scirtothrips dorsalis Hood, Heliothrips haemorrhoidalis Bouche, Scirtothrips dorsalis Hood, Scolothrips sexmaculatus Pergande, etc. are all common species in my country.The suborder of Phlaeothripidae includes: Phlaeothripoidea (Pypothripidae, Ecacanthothripidae, Eupatithripidae, Phlaeothripidae, Chirothripoididae, Hystricothripidae, Idolothripidae, Megathripidae), Urothripoidea (Urothripidae). The brackets after the superfamily are all subfamilies under the superfamily. Similarly, all superfamilies mentioned below are expressed in this way.

[0036] The "Hemiptera" mentioned above belongs to the class Insecta, with a slightly flat and hard body; the mouthparts are piercing-sucking; the antennae are filamentous or rod-shaped; there are two or no ocelli; the pronotum is well developed, and the scutellum is mostly triangular; the forewings are semi-elytra, the hindwings are membranous, and some species have degenerate or no wings; most species have scent glands; there are often claws at the end of the tarsus, and pads under the claws; the abdomen has 9-11 segments, usually 10 segments; there are no cerci; it is named because the forewings are semi-elytra The order Hemiptera is divided into the suborder Auchenorrhyncha and the suborder Sternorrhyncha; the latter includes the superorder Cicadioidea (Cicadidae, Membracidae, Machearotidae, Cercopidae, Cicadellidae) and the superorder Fulgoroidea (Tettigometridae, Delphacidae, Fulgoridae, Eurybrachydidae, Cixiidae, Meenoplidae, Dictyopharidae, Achilidae, Tropiduchidae, Derbidae, Lophoptera) ae, Issidae, Flatidae, Ricaniidae); Sternorhacoidea includes Psylloidea (Psyllidae), Aleyrodoidea (Aleyrodidae), Aphidoidea (Adelgidae, Phylloxeridae, Pemphigidae, Aphididae), and Coccoidea (Margarodidae, Ortheziidae, Kerridae, Kermidae, Dactylopiidae, Pseudococcidae, Asterolecaniidae, Coccidae, Diaspididae).

[0037] The "Lepidoptera" mentioned above belongs to the class Insecta and has a very wide distribution range, with the most abundant species in the tropics. The larvae of most species harm all kinds of cultivated plants. Those with larger bodies often eat all the leaves or bore into the branches. Those with smaller bodies often roll up leaves, attach leaves, form sheaths, spin silk webs, or drill into plant tissues to feed. Adults mostly use nectar as supplementary nutrition, or their mouthparts degenerate and they no longer feed. The order Lepidoptera includes the suborder Zeugloptera (Micropterygidae), the suborder Monotrysia (Eriocraniidea, Hepialoidea, Stigmelloidea, Incurvarioidea) and the suborder Ditrhysia (Tinaeoidea, Cossoidea, Psychoidea, Castnioidea, Tortricoidea, Pyraloidea, Bombycoidea, Calliduloidea, Geometroidea, Sphingoidea, Noctuoidea, Hesperioidea, Papilionoidea).

[0038] The "Coleoptera" is the largest order in the class Insecta and even in the animal kingdom with the most species and the widest distribution. It is divided into the suborder Adephaga, the suborder Polyphaga, and the suborder Rhynchophora; the suborder Caraboidea includes: Caraboidea (Cicindelidae, Carabidae, Amphizoidae, Omophronidae, Hygrobiidae, Haliplidae, Dytiscidae), Gyrinoidea (Gyrinidae), Paussoidea (Paussidae), and the other suborders are the Caraboidea, the Caraboidea, the Omophronidae, the Hygrobiidae, the Haliplidae, and the Dytiscidae. ), Cupesoidea (Cupesidae), Rhysodoidea (Rhysodidae); Polyphagous suborder includes: Hydrophiloidea (Hydrophilidae), Staphylinoidea (Silphidae, Leiodidae, Clambidae, Scydmaenidae, Orthoperidae, Phaenocephalidae, Discolomi dae, Platypsyllidae), Cantharoidea (Lycidae, Lampyridae, Cantharidae, Drilidae, Malachiidae, Phloeophilidae, Prionoceridae, Dasytidae), Lymexyloidea (Lymexylidae, Atractoceridae), Elateroidea (Rhizoceridae), piceridae, Cebrionidae, Elateridae, Eucnemidae, Throscidae), Dryopoidea (Psephenidae, Dryopidae, Helmidae, Georyssidae, Heteroceridae), Dascilloidea (Dascillidae), Tenebrionoidea (Alleculidae,The superfamily Tenebrionidae), the superfamily Ptinidae (Lyctidae, Bostrychidae, Anobiidae, Ptinidae), the superfamily Scarabaeoidea (Scarabaeidae, Aegialiidae, Aphodiidae, Ochodaeidae, Geotrupidae, Trogidae, Melolonthidae, Rutelidae, Dynastidae, Cetoniidae, Trichiidae, Passalidae), the superfamily Cerambycoidea (Saw Prionidae, Cerambycidae, Lamiidae, Sagridae), Brentoidea (Brentidae), Curculionoidea (Anthribidae, Aglycyderidae, Proterhiniidae, Cyladidae, Curculionidae); Suborder Curculionidae includes: Curculionoidea (Anthribidae, Aglycyderidae, Proterhiniidae, Cyladidae, Curculionidae). Common insects (common names): Harmonia axyridis, longhorn beetles, ladybugs, fireflies, dung beetles, blister beetles, rhinoceros beetles, jewel beetles, medlars, scarab beetles, stag beetles, click beetles, water beetles, rice weevils.

[0039] The “mites” mentioned in this application mainly include agricultural pest mites, most of which belong to the families Tetranychidae, Tenuipalpidae, Eriophyidae, Tarsonemidae, Pyemotidae, Penthaleidae and Cheyetidae of the class Acachnida.

[0040] The Tetranychus family is divided into the genus Oligonychus (such as: Oligonychus baipisongis, Oligonychus karamatus, Oligonychus rubicundus, etc.), the genus Eotetranychus (such as: Eotetranychus albus, Eotetranychus bailae, Eotetranychus camelliae, etc.), the genus Tetranychus (such as: Tetranychus neocaledonicus, Tetranychus phaselus, Tetranychus surticae, Tetranychus cinnabarinus), the genus Schizotetranychus (such as: Schizotetranychus baltazarae, Schizotetranychus bamboo bambusae, Schizotetranychus elongatus, etc.), Mixonychus (such as Mixonychus (Bakerina) aestiva, Mixonychus (Mixonychus) ganjuis, Mixonychus (Bakerina) murrayae, etc.), Panonychus (such as Panonychus citri, Panonychus caglei, Panonychus ulmi, etc.), Allonychus (such as Allonychus bambusae, Allonychus wuyinicus), Stigmaeopsis (such as Stigmaeopsis stigmaeopsis), celarius, Nanjing elk mite Stigmaeopsisnanjingensis), Mononychellus (such as Georgian Mononychellus), Acanthonychus (such as Acanthonychusjiangfengensis), Amphitetranychus (such as Amphitetranychus chinensis),viennensis), Sonotetranychus (e.g. Sonotetranychus neosalix), Xinella (e.g. Xinella huangshanensis), Yunonychus (e.g. Yunonychusdaliensis), 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 xi'an xianensis), 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), chinensis), Petrobia (e.g. Petrobia (Petrobia) xinjiangensis, Petrobia (Tetranychina) zachvatkini), Tetranycopsis (e.g. Tetranycopsis hystriciformis, Tetranycopsis spiraeae), Aplonobia (e.g. Aplonobia spp.alkalisalinae), Mesobryobia (e.g. Mesobryobiaterpoghossiani), Dolichonobia (Dolichonobia altaiensis).

[0041] Further, the insect eggs are produced from Frankliniella intonsa, Thrips tabaci Lindeman, Taeniothrips distalis Karn, Stenchaeotthrips biformis, Thrips hawaiiensis Morgan, Thrips palmi Karny, Frankliniella occidentalis, Thrips japonicus Bagnall, Thrips serratus Kobus, Frankliniella tenuicornis Uzel, Scirtothrips dorsalis Hood, Heliothrips haemorrhoidalis Bouche, Scirtothrips dorsalis Hood, Scolothrips sexmaculatusPergande), Rice Leaf Folder (Cnaphalocrocis medinalis), Beet Armyworm (Spodoptera exigua), Spodoptera litura (Spodoptera litura), Peach Borer (Carposina sasakii), Cotton Bollworm (Helicoverpaarmigera), Diamondback Moth (Plutella xylostella), Melon Silkworm (Diaphania indica),Marucatestulalis Geyer, Bemisia tabaci Gennadius, Trialeurodes vaporariorum, Aleurocanthus spiniferus, Dialeurodes citriashm, Bemisia myricae Kuwana, Aleurocybotus indicus, Aleurodicus dispersus, Oligonychus baipisongis, Oligonychus karamatus, Oligonychus rubicundus, Cerambycidae, Coccinellidae, Lampyridae, Scarabaeidae, Mylabrisphalerata, Allomyrina dichotoma), Buprestidae, Melyridae, Scarabaeidae, Lucanidae, Elateridae, Dytiscidae, Sitophilus oryzae, Harmonia axyridis, Eotetranychus albus, Eotetranychus bailae, Eotetranychus camelliae, Tetranychus neocaledonicus, Tetranychus phaselus, Tetranychus urticae, Tetranychus cinnabarinus, Citrus schizocarpus,

[0042] (Schizotetranychus baltazarae), bamboo split claw mite (Schizotetranychus bambusae), long split claw mite (Schizotetranychus elongatus), fig symphytic mite (Mixonychus (Bakerina) aestiva), citrus symphytic mite (Mixonychus (Mixonychus) ganjuis), citrus panonychus (Panonychus citri), card's panonychus (Panonychus caglei), bamboo heteroonychus (Allonychus bambusae), Wuyi heteroonychus (Allonychuswuyinicus), bamboo elk mite (Stigmaeopsis celarius), Georgia monoonychus (Mononychellusgeorgicus), spiked secondary claw mite (Acanthonychusjiangfengensis), hawthorn double claw mite (Amphitetranychus viennensis).

[0043] Wherein, the fungi are selected from fungi.

[0044] In a specific embodiment of the present invention, the fungus is selected from the rice blast pathogen, which causes rice blast disease and harms rice seedlings, leaves, ears, nodes and the like.

[0045] The "control" mentioned in the present invention includes, but is not limited to, any killing of eggs, hatching regulation, inhibition / interference of egg activity, prevention of hatching, etc.; the "preventing hatching" mentioned herein refers to preventing or delaying the hatching of larvae from eggs.

[0046] The term "killing" as used in the present invention means that the insect eggs permanently lose their ability to grow and hatch.

[0047] The "sterilization" mentioned in the present invention refers to directly killing or inhibiting the growth of plant pathogens, and its pathogenic microorganisms include fungi and bacteria; the sterilization includes: protective sterilization and systemic sterilization. Protective sterilization directly contacts with pathogens outside or on the surface of the plant body to kill or inhibit the pathogens and prevent them from entering the plant, thereby protecting the plant from the harm of pathogens; systemic sterilization can be absorbed by the plant and transmitted to the site of infection by the pathogens in the body to eliminate the pathogens.

[0048] In the present invention, when used, the sulfite compound is made into an agricultural product for use, and the agricultural product also includes one or more of an auxiliary material dispersant, a wetting agent, a binder, a surfactant, a stabilizer, and a solvent.

[0049] Suitable surfactant can be selected by those skilled in the art according to actual use requirements. Examples of surfactants that can be used in some embodiments of the present invention include, but are not limited to, ethoxylated castor oil, sodium lauryl sulfate, saponin, ethoxylated alcohol, ethoxylated fatty esters, alkoxylated glycols, ethoxylated fatty acids, carboxylated alcohols, carboxylic acids, fatty acids, ethoxylated alkylphenols, fatty esters, sodium dodecyl sulfide, other surfactants based on fatty acids, 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 suitable surfactants depends on relevant applications and conditions of use, and suitable surfactants are known to those skilled in the art.

[0050] In the present invention, the dosage forms include but are not limited to emulsifiable concentrates, soluble powders, soluble granules, solutions, dispersible liquids, aqueous emulsions, microemulsions, microcapsule suspensions, seed treatment liquids, aerosols, and the like.

[0051] EC is a type of pesticide formulation. It is a liquid made by dissolving a high concentration of active ingredients in a solvent and adding an emulsifier. It is usually diluted with a large amount of water to form a stable emulsion and then spread with a sprayer. It can also be sprayed in low volume or ultra-low volume. It can be used directly or diluted with water before spraying.

[0052] Wettable powder is a very fine dry preparation obtained by mixing and crushing the original drug, fillers, surfactants and other additives together.

[0053] Suspension concentrate refers to a preparation in which solid technical drugs are evenly dispersed in water as particles below 4 microns. The international code is SC. It has a fine particle size, generally 0.1 to 3 μm, and a high suspension rate. Suspension concentrates are divided into two types: water suspension concentrates and oil suspension concentrates. Water suspension concentrates use water as the suspension medium, while oil suspension concentrates 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 completely eliminate the need for organic solvents and are a good dosage form for processing solid technical drugs. Suspension concentrates are a mixture of solid powder and liquid suspended in water. They need to be shaken before use, then diluted with water and sprayed. Suspension concentrates are easy to carry and dilute, can be sprayed evenly, and have good adhesion and lasting effect.

[0054] Powder refers to the powder of the original drug, or the powder prepared by adding a certain diluent. It can be sprayed directly with a simple powder sprayer, with high work efficiency, small adhesion to crops, small residue, and not easy to cause drug damage.

[0055] Granules, also known as granules, are a solid dosage form obtained by mixing the original drug with carriers, adhesives, dispersants, wetting agents, stabilizers and other additives. Its performance requirements mainly include fineness, uniformity, storage stability, hardness, disintegration, etc. Granules are the largest particle size among solid dosage forms, with a diameter of 300 to 1700um. They have the advantages of simple use, small outward diffusion, and long-lasting efficacy.

[0056] Aqueous solution is a solution of the original drug. The drug is evenly dispersed in water in the form of ions or molecules. The concentration of the drug depends on the water solubility of the original drug, which is generally its maximum solubility. It is diluted with water when used.

[0057] In the present invention, the sulfite compound can be used in combination with most commercially available agricultural preparations such as insecticides, miticides, fungicides, etc., and a synergistic effect can be obtained.

[0058] Furthermore, when sulfite compounds are used to control and / or kill pest eggs and / or sterilize, the concentration of sulfite compounds is not less than 0.1 ppm. Furthermore, the concentration of sulfite compounds is not less than 1 ppm.

[0059] Wherein, the concentration of the sulfite compound used is 0.1-10000ppm, or it can be 0.1-500ppm, 0.1-200ppm, 0.1-100ppm, 0.1-50ppm, 1-500ppm, 1-200ppm, 1-100ppm, 1-50ppm, 1-10ppm, 1-5ppm, 2-200ppm, 2-100ppm, 2-50ppm, 2-10ppm, 3-200ppm, 3-100ppm, 3-50ppm, 3-10ppm, 4-200ppm, 4-100ppm, 4-50ppm, 4-10ppm, 10-1000ppm. Specific examples 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 and the like.

[0060] Furthermore, when the sulfite compound is used to control and / or kill insect eggs, the concentration of the sulfite compound is 0.1-500ppm; when the sulfite compound is used for sterilization, the concentration of the sulfite compound is 10-1000ppm.

[0061] The present invention also provides a pesticide composition, which uses the compound of formula (A) as an active substance.

[0062] In the present invention, the pesticide composition may further include a dispersant, a wetting agent, a binder, a surfactant, a stabilizer, a solvent and the like.

[0063] In the present 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, etc., thereby generating additional advantages and effects. For example, other insecticides can be flupyrazone, deltamethrin, ethiprole, tetrazopyrad, imidacloprid, spirotetramat, spirodiclofen, bicyclafen, cypermethrin, bromofenac, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, pymetrozine, thiamethoxam, lufenuron, avermectin, chlorfenapyr, bifenthrin, cyantraniliprole, cyflumetofen, ethyl spinosad, trifluanid, sulfoxaflor, methyl pyrimidine, indoxacarb, dinotefuran, bispyribac, hydrazone, permethrin, hexaflumuron, fluazifop-butyl.

[0064] In one embodiment of the present invention, the pesticide composition further comprises a mixture of ginger rhizome extract and galangal rhizome extract, ginger rhizome extract: galangal rhizome extract = 7:3, wherein the ginger rhizome extract is obtained by extracting the ginger rhizome with ethanol: ethyl acetate = 1-4:1; the galangal rhizome extract is galangal rhizome volatile oil. The proportion of the above ginger, galangal mixture and the compound of formula (A) can be (200-500): (0.1-1). Experimental studies have shown that the combined use of the two will have a certain synergistic effect and can reduce the concentration of the active ingredient.

[0065] As used in this application, “including” or “comprising” are to be interpreted in their open-ended sense, i.e. specifying the presence of mentioned specified features, elements, steps or components, but not excluding the presence or addition of further features, elements, steps or components.

[0066] In some embodiments, any of the above compositions are applied outdoors, or to plants or agricultural areas and / or the interior or exterior of a building. In some embodiments, any of the above compositions are applied to surfaces within a home, 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.

[0067] In some embodiments, any of the above compositions are formulated in a deliverable form suitable for a specific application, including, but 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 mattress cover treatments. Suitable deliverable forms can be selected and formulated by those skilled in the art using methods known in the art. In different use scenarios, the above-mentioned compositions can be used in a variety of ways and can be used directly, diluted, or concentrated. Other uses include: wood or furniture protective oils, laundry detergents, gels or pastes that can be applied to target areas, oil-based lotions, mixtures for dusting, drywall materials, fillers or other sealing materials used to fill cracks or gaps, foams, caulking materials, scented mists or candles, aerosol or spray insecticides, and treatments for mattresses or bedspreads. In some cases, these mixtures can be used in a dispersed form in domestic or commercial settings to combat pest eggs and fungi. In addition, they can also be used in agricultural or other outdoor settings to control pest eggs and fungi.

[0068] The "solvent" used in the above-mentioned products or compositions can be selected from water, ketones, alcohols, aldehydes, ethers, esters or carboxylic acids, and can 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.

[0069] 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.

[0070] The beneficial effects of the present invention are as follows: the present invention provides the application of chiral, isomeric sulfite compounds in inhibiting insect eggs, the chiral, isomeric sulfite compounds have a strong inhibitory effect on insect eggs, especially have a strong inhibitory activity on the eggs of various thrips, mites, and whiteflies of Thysanoptera pests; the compound of this structure can be used as an insecticide or an insecticidal ovum agent, has a high pesticide research value, and has a broad application prospect in the field of pesticide science. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Figure 1 This is a chromatogram showing the separation of a mixture of compound 1 and compound 1' using an IG column;

[0072] Figure 2 This is a chromatogram of separation of the R configuration of compound 1 and compound 1' using an IG column;

[0073] Figure 3 This is a chromatogram showing the separation of compound 1' and the S configuration of compound 1 using an IG column;

[0074] Figure 4 This is the chromatogram of the first peak separated from the R configuration in the IG column;

[0075] Figure 5 Chromatogram of the second peak separated from the R configuration in the IG column

[0076] Figure 6 Chromatogram of the third peak separated from the R configuration in the IG column

[0077] Figure 7 This is the chromatogram of the fourth peak separated from the R configuration in the IG column;

[0078] Figure 8 This is the chromatogram of the first peak separated from the S configuration in the IG column;

[0079] Fig. 9 This is the chromatogram of the second peak separated from the S configuration in the IG column;

[0080] Fig.10 This is the chromatogram of the third peak separated from the S configuration in the IG column;

[0081] Fig.11 This is the chromatographic peak when the first peak of the S-configuration of compound 1 and compound 1' separated on the IG column is separated using an AS column. DETAILED DESCRIPTION

[0082] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiment.It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.In addition, if not clearly stated, all reagents, raw materials and other test supplies used in the following embodiments are all commercially available, or can be synthesized, cultured or cultivated according to this article or known methods, and for experimental conditions not listed, they are also easily available to those skilled in the art.

[0083] When providing a numerical range, it is understood that each intermediate value between the upper and lower limits of the range (to one tenth of the unit of the lower limit, unless the context clearly indicates otherwise) and any other specified or intermediate values ​​within the specified range are included in the embodiments of the present application. The upper and lower limits of these smaller ranges can independently define smaller numerical ranges, and it will be understood that these smaller ranges are intended to be included in the embodiments of the present application, subject to any explicitly excluded limits within the specified range.

[0084] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which this application belongs. Any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of embodiments of this application.

[0085] Example 1 Synthesis of Compounds S-1 and S-1'

[0086]

[0087] Step 1:

[0088]

[0089] 2,4-Dichlorophenol (500 mg, 3.1 mmol), R-propylene oxide (356 mg, 6.1 mmol), DMF (12 mL), cesium carbonate (4.0 g, 12.3 mmol) were added to the reaction flask, heated to 100 degrees Celsius, and refluxed. TLC monitoring. After the reaction was completed, the residue was concentrated and dissolved with water (10 mL) and ethyl acetate (50 mL). The liquid was separated, the aqueous phase was extracted with ethyl acetate (50 mL x 2), the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and column chromatography obtained compounds iii-1 and iii-1' (a total of 511 mg, colorless transparent oil).

[0090] Step 2:

[0091]

[0092] Add thionyl chloride (415 mg, 3.5 mmol) to the reaction flask, dissolve it with 15 mL of dichloromethane, move to 0°C ice bath and stir, slowly dropwise add the mixture of compound iii-1 and iii-1' (511 mg, 2.3 mmol). After the dropwise addition is complete, move to room temperature to react for 10 hours. After the reaction is complete as monitored by TLC, concentrate the reaction solution under reduced pressure to obtain a light yellow oily substance, which is the crude product of compound v-1 and v-1', and set aside.

[0093] Step 3:

[0094]

[0095] Compound vi-1 (224 mg, 3.5 mmol) was added to the reaction flask, triethylamine (349 mg, 3.5 mmol) was added, and the mixture was moved to 0°C in an ice bath and stirred, and a mixture of compounds v-1 and v-1' (690 mg, 2.3 mmol) was slowly added dropwise. After the addition was completed, the mixture was moved to room temperature for 6 hours. After 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 collected after washing with saturated brine, 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).

[0096] Example 2 Synthesis of Compounds R-1 and R-1'

[0097]

[0098] The R-propylene oxide in step 1 of Example 1 was replaced by S-propylene oxide, and the synthesis was performed according to the synthesis method of Example 1 to obtain a mixture of compounds R-1 and R-1' (515 mg, colorless transparent liquid).

[0099] Example 3 Chiral Separation of Compounds S-1, S-1', R-1, R-1'

[0100] 1 Experimental methods

[0101] 1.1 Isolation of compounds

[0102] It was preliminarily determined that the sulfite compounds had two chiral centers. After using chiral raw materials for synthesis and then separation, 8 components were obtained; Instrument: Shimadzu high pressure liquid chromatography, LC20AR; Chiral column: Normal phase IG column, Normal phase AS column, 4.6mm ID×250mm, diameter: 5μm; mobile phase: n-hexane: isopropanol = 95:5. The S mixture of compound 1 and compound 1' was separated into 3 components by IG column, and the R mixture of compound 1 and compound 1' was separated into 4 components by IG column; when the 7 components separated were separated again by AS column, it was found that the first peak in the S configuration of compound 1 and compound 1' contained 2 components, and after further separation, a total of 8 components were obtained.

[0103] In the synthesis of compound 1, the first step of the reaction has two products, iii-1 and iii-1', due to the different positions of the ring opening, which can be separated by chiral preparation. Instrument: Shimadzu high pressure liquid chromatography, LC20AR; Chiral column: Normal phase IG column, 4.6mm ID×250mm, diameter: 5μm; mobile phase: n-hexane: isopropanol = 90:10. (The same conditions are used for separation of iii-4, iii-4', etc.)

[0104] 1.2 Determination of the absolute configuration of compounds

[0105] 1.2.1 Compound hydrogen spectrum test

[0106] 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.), if the group and the lone pair of electrons of sulfur are on the same side, the group is shielded, the chemical position decreases, and the chemical shift moves to the high field. If the group is on the same side as the oxygen atom, the group is deshielded, the chemical shift increases, and moves to the low field. Based on this result, by analyzing the NMR data of the isolated compound, its absolute configuration is inferred as follows:

[0107]

[0108] 1-(R,R): 1 H NMR (400 MHz, CDCl 3)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.

[0109] 1-(R,S): 1 H NMR(400MHz,CDCl 3 )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.

[0110] 1-(S,R): 1 H NMR(400MHz,CDCl 3 )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.

[0111] 1-(S,S): 1 H NMR(400MHz,CDCl 3 )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..

[0112] 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.

[0113] 1’-(S,S): 1 H NMR(400MHz,CDCl 3 )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

[0114] 1’-(R,R): 1 H NMR(400MHz,CDCl 3 )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.

[0115] 1’-(R,S): 1 H NMR(400MHz,CDCl 3)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.

[0116] 1.2.2 Determination of specific rotation of compounds

[0117] Using chloroform as solvent, the concentration is 1 mg / mL, and the specific rotation is measured at 25 degrees. The specific data are as follows:

[0118] 1-(S,R):[α] 25 D=-10.00

[0119] 1-(S,S): [α] 25 D=-9.00

[0120] 1-(R,R):[α] 25 D=+10.00

[0121] 1-(R,S):[α] 25 D=+10.00

[0122] 1'-(R,S): [α] 25 D=-8.00

[0123] 1'-(R,R):[α] 25 D=+41.00

[0124] 1'-(S,R): [α] 25 D=+7.00

[0125] 1'-(S,S): [α] 25 D=-38.00

[0126] The results of specific rotation are consistent with the absolute configuration inferred by NMR analysis, so the configuration of the product should be correct.

[0127] Example 4 Synthesis of Compound 1

[0128]

[0129] Step 1:

[0130]

[0131] 2,4-Dichlorophenol (1g, 6.2mmol) was added to the reaction bottle, dissolved with 20mL DMF, propylene oxide (722mg, 7.6mmol) and cesium carbonate (8g, 24.8mmol) were added, and the mixture was heated in a 100℃ oil bath for reaction. After 6h, the reaction was complete as monitored by TLC, 100mL of water was added, and the mixture was extracted with ethyl acetate (30mL×3), washed with saturated brine, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then separated and purified, and chiral prepared (instrument: Shimadzu high pressure liquid chromatography, LC20AR; chiral column: 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-1 (356 mg, colorless transparent liquid).

[0132] Step 2:

[0133]

[0134] Add thionyl chloride (293 mg, 2.5 mmol) to the reaction flask, dissolve it with 20 mL of dichloromethane, move to 0°C ice bath and stir, slowly add compound iii-1 (356 mg, 1.6 mmol) dropwise. After the addition is complete, move to room temperature to react for 10 hours. After the reaction is complete as monitored by TLC, concentrate the reaction solution under reduced pressure to obtain a light yellow oily substance, which is the crude product of compound v-1, for later use.

[0135] Step 3:

[0136]

[0137] Compound vi-1 (123 mg, 1.9 mmol) was added to the reaction flask, triethylamine (243 mg, 2.4 mmol) was added, and the mixture was moved to 0°C ice bath for stirring, and compound v-1 (480 mg, 1.6 mmol) was slowly added dropwise. After the addition was completed, the mixture was moved to room temperature for reaction for 6 h. After 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 collected after washing with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Compound 1 (423 mg, oily substance) was obtained by column chromatography purification.

[0138] 1 H NMR (400 MHz, CDCl 3)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.

[0139] HRMS(ESI)Calcd.For C 11 H 14 Cl 2 FO 4 SNa + [M+Na] + 352.9768; Found:352.9789,354.9773

[0140] Example 5 Synthesis of Compound 1'

[0141]

[0142] Step 1:

[0143]

[0144] The target compound iii-1' was synthesized by referring to step 1 of Example 4 through chiral preparation.

[0145] Step 2: Same as step 2 of Example 1

[0146] Step 3: Same as step 3 of Example 1

[0147] The target compound 1' (674 mg, colorless transparent liquid) was obtained through synthesis.

[0148] 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.

[0149] HRMS(ESI)Calcd.For C 11 H 14 Cl 2 FO 4 SNa + [M+Na] + 352.9768; Found:352.9786,354.9758.

[0150] Example 6 Synthesis of Compound 10

[0151]

[0152] Step 1:

[0153]

[0154] The target compound iii-10 was synthesized by referring to step 1 of Example 4 via chiral preparation.

[0155] Step 2: Same as step 2 of Example 1

[0156] Step 3: Same as step 3 of Example 1

[0157] The target compound 10 (685 mg, colorless transparent liquid) was obtained through synthesis.

[0158] 1 H NMR (400 MHz, CDCl 3 )δ7.31(d,J=2.5Hz,1H),7.11(dd,J=8.8,2.6Hz,1H),6.75(d,J=8.8Hz,1H),4.61–4.57(m,1H),4. 49–4.45(m,1H),4.30–2.34(m,1H),4.21–4.18(m,1H),3.92(s,2H),1.58(s,3H),1.57(s,3H)ppm.

[0159] HRMS(ESI)Calcd.For C 12 H 16 Cl 2 FO 4 S + [M+H] + 345.0125;Found:345.0143.

[0160] Example 7 Synthesis of Compound 10'

[0161]

[0162] Step 1:

[0163]

[0164] The target compound iii-10' was prepared by chiral reaction according to step 1 of Example 6.

[0165] Step 2: Same as step 2 of Example 1

[0166] Step 3: Same as step 3 of Example 1

[0167] The target compound 10' (311 mg, colorless transparent liquid) was obtained through synthesis.

[0168] 1 H NMR (400 MHz, CDCl 3 )δ7.31(d,J=2.5Hz,1H),7.11(dd,J=8.8,2.6Hz,1H),6.75(d,J=8.8Hz,1H),4.61–4.57(m,1H),4. 49–4.45(m,1H),4.30–2.34(m,1H),4.21–4.18(m,1H),3.92(s,2H),1.58(s,3H),1.57(s,3H)ppm.

[0169] HRMS(ESI)Calcd.For C 12 H 16 Cl 2 FO 4 S + [M+H] + 345.0125; Found:345.0126.

[0170] Example 8 Synthesis of Compound 19

[0171]

[0172] Step 1:

[0174]

[0175] Synthesize according to step 1 of Example 4, replace propylene oxide with 1,2-butylene oxide, and obtain the target compound iii-19 by chiral preparation.

[0176] Step 2: Same as step 2 of Example 1

[0177] Step 3: Same as step 3 of Example 1

[0178] The target compound 19 (692 mg, colorless transparent liquid) was obtained through synthesis.

[0179] 1 H NMR (400 MHz, CDCl 3 )δ7.32–7.29(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.

[0180] HRMS(ESI)Calcd.For C 12 H 15 O 4 Cl 2 FS + [M+H] + 344.0052;Found:344.0026.

[0181] Example 9 Synthesis of Compound 19'

[0182]

[0183] Step 1:

[0184]

[0185] The target compound iii-19' was synthesized by referring to step 1 of Example 8 via chiral preparation.

[0186] Step 2: Same as step 2 of Example 1

[0187] Step 3: Same as step 3 of Example 1

[0188] The target compound 19' (309 mg, colorless transparent liquid) was obtained through synthesis.

[0189] 1 H NMR (400 MHz, CDCl 3 )δ7.32–7.29(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.

[0190] HRMS(ESI)Calcd.For C 12 H 13 O 4 Cl 2 FS + [M+H] + 341.9896; Found:341.9903.

[0191] Example 10 Synthesis of Compound 22

[0192]

[0193] Step 1:

[0194]

[0195] Synthesize according to step 1 of Example 4, replace propylene oxide with epoxybutene, and obtain the target compound iii-22 by chiral preparation.

[0196] Step 2: Same as step 2 of Example 1

[0197] Step 3: Same as step 3 of Example 1

[0198] The target compound 22 (671 mg, colorless transparent liquid) was obtained through synthesis.

[0199] 1 H NMR (400 MHz, CDCl 3 )δ7.31(dd,J=2.6,1.4Hz,1H),7.11(dd,J=8.8,2.5Hz,1H),6.77(dd,J=8.8,1.2Hz,1H),5.95–5.87(m,1H),5.48(d,J=17.2,H z,1H),5.39-5.33(m,1H),5.17–5.10(m,1H),4.65-4.56(m,1H),4.54-4.45(m,1H),4.40-4.12(m,2H),4.06-3.97(m,2H)ppm.

[0200] HRMS(ESI)Calcd.For C 12 H 13 O 4 Cl 2 FS + [M+H] + 341.9896; Found:341.9857.

[0201] Example 11 Synthesis of Compound 22'

[0202]

[0203] Step 1:

[0204]

[0205] The target compound iii-22' was synthesized by referring to step 1 of Example 6 via chiral preparation.

[0206] Step 2: Same as step 2 of Example 1

[0207] Step 3: Same as step 3 of Example 1

[0208] The target compound 22' (297 mg, colorless transparent liquid) was obtained through synthesis.

[0209] 1 H NMR (400 MHz, CDCl 3 )δ7.31(dd,J=2.6,1.4Hz,1H),7.11(dd,J=8.8,2.5Hz,1H),6.77(dd,J=8.8,1.2Hz,1H),5.95–5.87(m,1H),5.48(d,J=17.2,H z,1H),5.39-5.33(m,1H),5.17–5.10(m,1H),4.65-4.56(m,1H),4.54-4.45(m,1H),4.40-4.12(m,2H),4.06-3.97(m,2H)ppm.

[0210] HRMS(ESI)Calcd.For C 12 H 13 O 4 Cl 2 FS + [M+H] + 341.9896; Found:341.9903.

[0211] Example 12 Synthesis of Compound 25

[0212]

[0213] Step 1:

[0214]

[0215] Synthesize by referring to step 1 of Example 4, replacing propylene oxide with 3,4-epoxytetrahydrofuran to obtain the target compound iii-25.

[0216] Step 2: Same as step 2 of Example 1

[0217] Step 3: Same as step 3 of Example 1

[0218] The target compound 25 (703 mg, colorless transparent liquid) was obtained through synthesis.

[0219] 1 H NMR (400 MHz, CDCl 3)δ7.34–7.31(m,1H),7.15(d,J=8.8,Hz,1H),6.86(d,J=8.8Hz,1H),5.09(dd,J=4.0Hz,1H),4.8 2(d,J=4.4Hz,1H),4.65–4.61(m,1H),4.52–4.57(m,1H),4.25-14(m,4H),4.01-3.87(m,2H)ppm.

[0220] HRMS(ESI)Calcd.ForC 13 H 13 O 5 Cl 2 F + [M+H] + 339.0124; Found:339.0150.

[0221] Example 13 Synthesis of Compound 28

[0222]

[0223] Step 1:

[0224]

[0225] Synthesize by referring to step 1 of Example 6, replacing propylene oxide with ethylene carbonate to obtain the target compound iii-28.

[0226] Step 2: Same as step 2 of Example 1

[0227] Step 3: Same as step 3 of Example 1

[0228] The target compound 22 (671 mg, colorless transparent liquid) was obtained through synthesis.

[0229] 1 H NMR (400 MHz, CDCl 3 )δ7.31(d,J=2.5Hz,1H),7.12(dd,J=8.8,2.5Hz,1H),6.78(d,J=8.8Hz,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.

[0230] HRMS(ESI)Calcd.For C 10 H 11 O 4 Cl 2 FS + [M+H] +316.9739; Found:316.09658.

[0231] The remaining compounds were synthesized according to the above-mentioned synthesis method.

[0232] Experimental 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), Compound 1 and Compound 1' on the Hatching of Tetranychus cinnabarinus Eggs

[0233] 1 Experimental methods

[0234] (1) Preparation of leaf discs containing eggs: 20 adult female Tetranychus cinnabarinus mites were transferred to a broad bean leaf disc with a diameter of 2.0 cm (with a soaked filter paper at the bottom), and then covered with a petri dish to keep the moisture. The adult mites were removed within 36 hours and the leaf discs containing eggs were counted under a microscope.

[0235] (2) Investigation of the number of egg openings: The number of egg openings on each leaf disc was investigated under a microscope before immersion, with two replicates for each treatment.

[0236] (3) Immersion treatment: Immerse the leaf discs carrying mite eggs in clean water and sulfite compounds for 10 seconds respectively, take them out and keep them moisturized. Repeat each treatment for no less than 3 times.

[0237] (4) Cultivation and observation: The treated mite eggs and leaf discs were cultured under normal conditions. Five days after the drug application, the hatching of spider mite eggs was investigated.

[0238] Note: After treatment, pay attention to the control of the temperature and humidity conditions in the constant temperature and humidity incubator to avoid excessive temperature differences, which may cause condensation to form and drip in the dish, resulting in abnormal death of eggs due to being soaked in water; it is also necessary to ensure that the environment has sufficient strong light, but not directly on the leaves.

[0239] (5) Result investigation: Regularly replenish water and moisturize the test materials of each treatment group and observe the hatching of eggs. On the 7th day after drug administration, record the number of hatched eggs of each treatment and record the investigation results in the original record book. The investigation time can be shortened or extended according to the test requirements and the characteristics of the drug.

[0240] Survey indicators:

[0241] ①Investigate and record the number of hatched eggs in each treatment.

[0242] ② Take photos to record whether the broad bean leaf discs have been damaged by pesticides.

[0243] ③Record the development status of the test mite eggs and the behavior of the nymphs, such as abnormal phenomena such as delayed or stopped development of the mite eggs, difficulty for the nymphs to hatch, or painful struggles after hatching.

[0244] (6) Calculation method: Calculate the control effect of each treatment based on the survey data using the following formula, with the results rounded to two decimal places.

[0245] Egg hatching rate (%) = number of hatched eggs / total number of processed eggs * 100

[0246] Control effect (%) = (egg hatching rate in the control area - egg hatching rate in the treatment area) / egg hatching rate in the control area) * 100.

[0247] The experimental design is shown in Table 1.

[0248] Table 1 Experimental design

[0249]

[0250]

[0251] 2 Experimental results

[0252] The results are shown in Table 2. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S) and compound 1 and compound 1' all showed excellent inhibitory effects on the hatching of Tetranychus cinnabarinus eggs at 1 ppm.

[0253] Table 2

[0254]

[0255]

[0256] 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 Compound 1 and Compound 1' on Hatching of Thrips Eggs

[0257] This test adopts the method of Test Example 1 in the technical part, and mainly uses the leaf disc method to explore the effects 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 compound 1 and compound 1' on the inhibition of thrips egg hatching. The concentration of the compounds is 100 ppm.

[0258] The experimental results are shown in Table 3. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S) and compound 1 and compound 1' showed strong inhibitory activity against the hatching of thrips eggs at 100 ppm.

[0259] Table 3

[0260]

[0261] 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 Compound 1 and Compound 1' on the Hatching of Eggs of Tetranychus urticae

[0262] This experiment adopted the method of Experimental Example 1 in the technical part, and mainly used the leaf disc method to explore 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 compound 1 and compound 1' on the hatching inhibition of two-spotted spider mite eggs. The concentration of the compounds was 5 ppm.

[0263] The experimental results are shown in Table 4. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S) and compound 1 and compound 1' showed strong inhibitory activity against the hatching of two-spotted spider mite eggs at 5 ppm.

[0264] Table 4

[0265]

[0266] 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 Compound 1 and Compound 1' on the Hatching of Eggs of Panonychus citri

[0267] This experiment adopted the method of Experimental Example 1 in the technical part, and mainly used the leaf disc method to explore 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 compound 1 and compound 1' on the hatching of citrus Panonychus mites eggs. The concentration of the compounds was 1 ppm.

[0268] The experimental results are shown in Table 5. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S) and compound 1 and compound 1' all showed good inhibitory effects on the hatching of citrus mite eggs at 1 ppm.

[0269] Table 5

[0270]

[0271]

[0272] 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 Compound 1 and Compound 1' on Whitefly Egg Hatching

[0273] This experiment adopted the method of Experimental Example 1 in the technical part, and mainly used the leaf disc method to explore 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 compound 1 and compound 1' on the inhibition of whitefly egg hatching. The concentration of the compounds was 10 ppm.

[0274] The experimental results are shown in Table 6. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S) and compound 1 and compound 1' showed strong inhibitory activity against the hatching of whitefly eggs at 10 ppm.

[0275] Table 6

[0276]

[0277] 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 Compound 1 and Compound 1' on the Hatching of Eggs of Spodoptera litura

[0278] 1 Experimental plan

[0279] (1) Preparation of egg-containing paper: Cut the egg mass into small pieces, each containing about 60 eggs, and soak them together with the egg-laying paper in the pre-prepared test agent for 10 min (the compound concentration is 500 ppm). After taking them out, use absorbent paper to absorb the excess solution adhering to the egg-laying paper and the egg mass.

[0280] (2) Cultivation: Each egg mass was placed in a glass test tube (5.0 cm in height and 2.5 cm in diameter, the same below), sealed with plastic paper with fine holes punched with insect pins, and placed in an artificial climate box at (24±1)°C, relative humidity (80±10)%, and a photoperiod of L:D=12:12 for cultivation. When the eggs developed to the point of hatching, castor leaves with a diameter of about 3 cm were added for the hatched larvae to feed on;

[0281] (3) Observation: Check and record the number of hatched and unhatched eggs in each egg block, and calculate the egg hatching rate according to the formula. Each treatment was repeated 3 times.

[0282] (4) Result investigation: Regularly replenish water and moisturize the test materials of each treatment group and observe the hatching of eggs. On the 4th day after drug administration, record the number of hatched eggs of each treatment and record the investigation results in the original record book. The investigation time can be shortened or extended according to the test requirements and the characteristics of the drug.

[0283] Survey indicators:

[0284] ①Investigate and record the number of hatched eggs in each treatment.

[0285] ②Record the developmental status of the Spodoptera litura eggs and the behavior of the nymphs, such as any abnormal phenomena such as the delay or cessation of the development process of the Spodoptera litura eggs.

[0286] (5) Calculation method: Calculate the control effect of each treatment based on the survey data using the following formula, with the results rounded to two decimal places.

[0287] Egg hatching rate (%) = number of hatched eggs / total number of processed eggs * 100

[0288] Control effect (%) = (egg hatching rate in the control area - egg hatching rate in the treatment area) / egg hatching rate in the control area) * 100

[0289] 2 Experimental results

[0290] The experimental results are shown in Table 7. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), and 1'-(R,S) showed good inhibitory activity against the hatching of Spodoptera litura eggs at 500 ppm.

[0291] Table 7

[0292]

[0293] 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 Compound 1 and Compound 1' on the Hatching of Harmonia axyridis Eggs

[0294] 1 Experimental plan

[0295] Harmonia axyridis egg cards (each egg card has about 20 eggs) were purchased from Jiyuan Baiyun Industrial Co., Ltd. in Henan Province. The number of eggs on the egg cards was counted as the pre-drug base number. Five egg cards were used as a treatment, and one treatment was repeated three times. After the egg cards were immersed in 100ppm of the drug solution for 30 seconds, they were taken out and dried and cultured in a moisturizing manner. The treated mite eggs and leaf discs were cultured at 27°C. Four days after the drug was applied, the hatching of Harmonia axyridis eggs was investigated. The protective effect was calculated according to the following formula.

[0296] Egg hatching rate (%) = number of hatched eggs / total number of processed eggs * 100

[0297] Control effect (%) = (egg hatching rate in the control area - egg hatching rate in the treatment area) / egg hatching rate in the control area) * 100

[0298] 2 Test results

[0299] The experimental results are shown in Table 8. Compounds 1-(S,S), 1-(R,R), 1'-(S,R), 1'-(R,S), compound 1 and compound 1' showed strong inhibitory activity against the hatching of Harmonia axyridis eggs at 100 ppm.

[0300] Table 8

[0301]

[0302]

[0303] Test Example 8 Preliminary screening of fungicidal activity (rice blast pathogen) 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 and compound 1'

[0304] 1 Experimental plan

[0305] Test materials: culture medium, activated bacteria, sterile water, 96-well plate, and swab gun.

[0306] Rapid screening system (200 μL): culture medium (150 μL) + drug (40 μL) + bacteria (10 μL).

[0307] Test steps: preparation, adding culture medium, adding medicine, adding bacteria, testing

[0308] (1) Preparation: Prepare the drug at a final concentration of 100 ppm and transfer the prepared drug into a 1.5 mL centrifuge tube for later use.

[0309] (2) Use a spray gun to add culture medium and reagents into the prepared 96-well plate.

[0310] (3) Preparation of inoculation solution: Take a culture dish (Pyricularia oryzae), add 15 mL of sterile water to the dish, slide the tip of a gun on the surface of the mycelium to break the mycelium and dissolve it in the sterile water, take 10 μL of the bacterial suspension on a glass slide for microscopic examination, and ensure that there are at least 10 mycelium in the field of vision. The bacteria are cultured to OD600 = 1.0, diluted 1000 times, and the inoculation solution is obtained; the number of zoospores of oomycetes is not less than 1*10 5 / mL.

[0311] (4) Detection: OD = 450 nm for fungal assay and OD = 600 nm for bacterial assay, recorded as 0 hour data. After the corresponding incubation time, the growth data was recorded and the inhibition rate was calculated according to the formula.

[0312] Inhibition rate (%) = ((blank control OD (72h) - blank control OD (0h)) - (treatment OD (72h) - treatment OD (0h)) / blank control OD (72h) - blank control OD (0h)) * 100

[0313] 2 Experimental results

[0314] The experimental results are shown in Table 9. 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 and compound 1' have strong inhibition rates against rice blast pathogen at 100 ppm, especially compounds 1-(S,S), 1-(R,R), 1'-(R,S), 1'-(S,R), compound 1 and compound 1', whose inhibition rates are as high as over 90%.

[0315] Table 9

[0316]

[0317] Experimental Example 9 Effects of sulfite compounds on the hatching of Tetranychus cinnabarinus eggs

[0318] 1 Experimental methods

[0319] This experiment adopted the method of Experimental Example 1 in the technical part, mainly using the leaf disc method to explore the effects of Compounds 1-Compound 30 and Compounds 1'-Compound 24' on the hatching of eggs of Panonychus citri. The concentration of the compounds was 100 ppm.

[0320] 2 Experimental results

[0321] The experimental results are shown in Table 10. The hatching rates of all compounds were below 15%, and all compounds showed good activity in killing acarid eggs.

[0322] Table 10

[0323]

[0324]

[0325] Example 10

[0326] A ginger and galangal mixture was prepared by mixing ginger extract and galangal volatile oil in a ratio of 7:3, and compounded with compound 1, compound 10 and compound 19. Based on the test method of Example 1, the leaf disc method was used to investigate the control effect on Tetranychus cinnabarinus eggs.

[0327] The ginger extract is prepared by extracting ginger rhizomes with a mixed solvent of ethyl acetate:ethanol=1:4.

[0328] Among them, Bliss, based on the concept of independent combined action proposed by him, believes that the theoretical mortality rate P of mixed insecticides and acaricides can be calculated by the following formula:

[0329] P=Pm+Pn(1-Pm)

[0330] Pm is the target mortality rate (%) when the concentration of the first active component is m; Pn is the target mortality rate (%) when the concentration of the second active component is n.

[0331] If the actual mortality rate of the target after the two active components are mixed at a certain concentration is greater than the theoretical mortality rate P, it is determined that the two active components have a synergistic effect when mixed at the set concentration, otherwise it is an antagonistic effect.

[0332] The experimental results are shown in Table 11. After compound 1, compound 10 and compound 19 were compounded with the mixture of ginger and galangal, they had a synergistic effect on the prevention and treatment of Tetranychus cinnabarinus eggs.

[0333] Table 11

[0334]

[0335]

[0336]

[0337] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may 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 a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A sulfite compound having a structure as shown in formula (A) or its meso-, racemic-, stereoisomer-, or pharmaceutically acceptable salt: in, R1 and R2 are independently selected from 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 Carbonyl; R3, R3', R4, R4' are independently selected from hydrogen, C1-C5 alkyl, C1-C5 alkenyl; or, R3, R3', R4, R4' and the C to which they are connected form a five-membered heterocyclic alkyl group; R5 is selected from halogen, substituted or unsubstituted C1-C 10 alkyl.

2. The sulfite compound or its meso-form, racemate, stereoisomer, or pharmaceutically acceptable salt according to claim 1, characterized in that: The C1-C5 alkyl group is selected from methyl and ethyl; the C1-C5 alkenyl group is selected from vinyl; the five-membered heterocyclic alkyl group is selected from 3. The sulfite compound or its meso-form, racemic form, stereoisomer, or pharmaceutically acceptable salt according to claim 1, characterized in that: The compound structure is selected from one of the following:

4. The sulfite compound or its meso-form, racemate, stereoisomer, or pharmaceutically acceptable salt according to claim 1, characterized in that: The R5 is selected from fluoroethyl, bromoethyl, chloroethyl, 2,2-difluoroethyl, 2,2-dichloroethyl; R1 and R2 are independently selected from H, F, Cl, and Br.

5. The sulfite compound or its meso-form, racemic form, stereoisomer, or pharmaceutically acceptable salt according to claim 1, characterized in that: R5 is -CH2CH2F; R1 and R2 are Cl.

6. The sulfite compound or its meso-body, racemate, stereoisomer, or pharmaceutically acceptable salt according to claim 1, characterized in that: The compound is selected from the following compounds:

7. A method for controlling and / or killing insect eggs, or sterilizing, characterized in that: The compound according to any one of claims 1 to 6 is applied to pest eggs and / or fungi.

8. The method according to claim 7, characterized in that When used for controlling and / or killing pest eggs, and / or sterilizing, the compound is selected from one or a mixture of two or more of the following compounds:

9. The method according to claim 7, characterized in that: The pest eggs are produced from insects of the order Thysanoptera, Hemiptera, Lepidoptera, Coleoptera, Tetranychus, Tenuipalpidae, Pseudocomycetes, Tarsonemae, Pygeidae, Chrysonychidae or Carnivorous Mite; the fungi include fungi and bacteria.

10. The method according to claim 7, characterized in that The eggs are produced by flower thrips, tobacco thrips, bean thrips, rice thrips, yellow-breasted thrips, palm thrips, western flower thrips, melon thrips, loquat thrips, sugarcane thrips, grass thrips, tea yellow hard thrips, greenhouse thrips, tea yellow thrips, six-spotted thrips, rice leaf roller, Bemisia tabaci, greenhouse whitefly, black thorn whitefly, citrus whitefly, mulberry whitefly, rice whitefly, spiral whitefly, whitefly, white bark pine claw mite, larch claw mite, carmine claw mite, axyridis, longhorn beetle, ladybug, firefly, dung beetle , blister beetles, rhinoceros beetles, jewel beetles, merlins, beetles, stag beetles, click beetles, water lice, 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-nailed mites, bamboo split-nailed mites, long-nailed mites, fig synonychus mites, citrus synonychus mites, citrus panonychus mites, carlesiomyces mites, bamboo heteroonychus mites, wuyi heteroonychus mites, bamboo-eating elk mites, Georgia monoonychus mites, spiked secondary claw mites, and hawthorn double spider mites; the fungus is the rice blast pathogen.

11. The method according to claim 7, characterized in that The concentration of the sulfite compound used is not less than 0.1 ppm.

12. The method according to claim 7, characterized in that: When in use, the sulfite compound is made into an agricultural product for use, and the agricultural product also includes one or more of an auxiliary material dispersant, a wetting agent, a binder, an emulsifier, a stabilizer, and a solvent.

13. The method according to claim 12, characterized in that: The dosage form of the product is emulsifiable concentrate, suspension, wettable powder, dust, granule, aqueous solution, mother liquid or mother powder.

14. A pesticide composition, characterized in that: The compound of formula (A) is the active substance.

15. The pesticide composition according to claim 14, characterized in that It also includes a mixture of ginger rhizome extract and galangal rhizome extract, with the ratio of ginger rhizome extract to galangal rhizome extract being 7:3, wherein the ginger rhizome extract is obtained by extracting the ginger rhizome with ethanol:ethyl acetate=1-4:1; and the galangal rhizome extract is volatile oil from the galangal rhizome.

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