A pyrazole amide compound and its preparation method and application

Abstract

The present invention provides a compound of formula I and its salt and stereoisomers, wherein R1, R2 and R3 are as defined in the specification. The compound disclosed in the present invention has good fungicidal activity and has good application prospects.

Description

Technical Field

[0001] The present invention belongs to the field of pesticide chemistry, and specifically relates to a pyrazole amide compound, a preparation method and an application thereof. Background Art

[0002] In modern crop production, fungicides play a vital role in controlling plant pathogens, reducing disease losses, and increasing crop yields. However, with the widespread use of fungicides, pathogen resistance is becoming an increasingly serious problem. Currently, fungicides that have been used for a long time and in large quantities in the pesticide market generally exhibit varying degrees of resistance, significantly reducing their inhibitory effectiveness against current pathogens. Therefore, the development of novel structural fungicides with high sensitivity to current pathogens is crucial for modern agricultural production. Summary of the Invention

[0003] The present invention provides a pyrazole amide compound with a novel structure, which has good antibacterial activity against different bacteria.

[0004] Specifically, the present invention provides a compound of formula I, its salt and stereoisomers thereof,

[0005]

[0006] in;

[0007] R1 is selected from one of H, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C1-C6 alkylcarbonyl, -OCOC1-C6 alkyl, halogenated C1-C6 alkylcarbonyl or C1-C6 alkoxycarbonyl;

[0008] R2 and R3 are independently selected from halogen, nitro, cyano, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C3-C6 cycloalkyl, -O-C3-C6 cycloalkyl, C1-C6 alkylamino, halogenated C1-C6 alkylamino, di(C1-C6 alkyl)amino, -NHC3-C6 cycloalkyl, halogenated di(C1-C6 alkyl)amino, di(C1-C6 alkyl)aminocarbonyl, C C1-C6 alkylsulfonyl, -S-C3-C6 cycloalkyl, halogenated C1-C6 alkylthio, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, halogenated C2-C6 alkenyloxy, C2-C6 alkynyloxy, halogenated C2-C6 alkynyloxy, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C1-C6 alkylcarbonyl, -OCOC1-C6 alkyl, halogenated C1-C6 alkylcarbonyl or C1-C6 alkoxycarbonyl.

[0009] The present invention also provides a composition comprising the compound of formula I of the present invention, its salts and stereoisomers thereof, and at least one auxiliary agent.

[0010] The present invention also provides use of compound I, its salts, stereoisomers and the composition of the present invention in preventing and controlling plant diseases.

[0011] Beneficial effects

[0012] The compound of the present invention has excellent bactericidal effect and has broad application prospects in preventing and controlling crop diseases. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 This is the H NMR spectrum of compound I-01 DETAILED DESCRIPTION

[0014] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Unless otherwise expressly stated, throughout the specification and claims, the term "including" or its variations such as "comprising" or "including" will be understood to include the stated components or steps, without excluding other material components or steps.

[0015] Furthermore, in order to better illustrate the present invention, numerous specific details are given in the following detailed description.

[0016] Those skilled in the art will appreciate that the present invention can be practiced without certain specific details. In some embodiments, raw materials, methods, means, etc. well known to those skilled in the art are not described in detail in order to highlight the main purpose of the present invention.

[0017] When the compounds of the present invention are capable of existing in tautomeric forms, the above and below references to

[0018] The compounds described are to be understood as also comprising the corresponding tautomeric forms, even if these are not explicitly mentioned in each case.

[0019] If the compounds of the formula I according to the invention have functional groups which can be ionized, they can also be used in the form of their agriculturally acceptable salts or mixtures thereof.

[0020] The term "C1-C6 alkyl" as used herein refers to, for example, a straight or branched chain alkyl group containing 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl or n-hexyl, but is not limited thereto.

[0021] In the present invention, "C1-C6 alkoxy" refers to, for example, a straight chain or branched alkoxy group containing 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, or n-hexoxy, but is not limited thereto.

[0022] In the present invention, "C 1- The term "C6 alkylthio" refers to, for example, a straight or branched chain alkylthio group containing 1 to 6 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, n-pentylthio, isopentylthio, or n-hexyl, but is not limited thereto.

[0023] In the present invention, "C3-C6 cycloalkyl" refers to a cycloalkyl group containing 3-6 carbon atoms, which is a monocyclic group, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., but not limited thereto.

[0024] In the present invention, "C1-C6 alkylsulfonyl" refers to a straight or branched chain alkylsulfonyl group containing 1 to 6 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, secondary butylsulfonyl, and tertiary butylsulfonyl, but are not limited thereto. Examples of halogenated alkylsulfonyl groups include hydrocarbyl- and / or fluoro-halogenated substituents thereof, such as difluoromethylsulfonyl, trifluoromethylsulfonyl, and chlorodifluoromethylsulfonyl, but are not limited thereto.

[0025] In the present invention, "C2-C6 alkenyl" refers to a straight chain or branched alkenyl group containing 2-6 carbon atoms, which contains one or more double bonds, for example, vinyl, 1-propenyl, 1,3-butadienyl, etc., but is not limited thereto.

[0026] In the present invention, "C2-C6 alkynyl" refers to a straight chain or branched chain containing 2 to 6 carbon atoms and may have a triple bond at any position.

[0027] The "C2-C6 alkenyloxy group" of the present invention refers to an alkenyloxy group containing 2 to 6 carbon atoms, for example, vinyloxy group, but is not limited thereto.

[0028] The "C2-C6 alkynyloxy group" of the present invention refers to an alkynyloxy group containing 2 to 6 carbon atoms, for example, ethynyloxy and 1-propynyloxy, but is not limited thereto.

[0029] The "C1-C6 alkylcarbonyl group" of the present invention refers to a straight-chain or branched alkyl acyl group containing 1 to 6 carbon atoms, for example, formyl, acetyl, etc., but is not limited thereto.

[0030] In the present invention, halogenated C1-C6 alkyl, halogenated C1-C6 alkoxy, halogenated C1-C6 alkylamino, halogenated di(C1-C6 alkyl)amino, halogenated C1-C6 alkylthio, halogenated C2-C6 alkenyloxy, halogenated C2-C6 alkynyloxy, halogenated C1-C6 alkylsulfonyl, halogenated C1-C6 alkylcarbonyl, etc., indicate that the relevant groups are substituted by halogen. For example, halogenated C1-C6 alkyl means a group having a chain length of 1 to 6 carbon atoms. The alkyl group is substituted with halogen, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, difluorochloromethyl and dichlorofluoromethyl, etc., but not limited thereto. For example, Examples of the halogenated C1-C6 alkoxy group include monofluoromethoxy, difluoromethoxy, trifluoromethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, 2,2,2-trifluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, pentafluoroethoxy, 1,1-difluoro-2,2,2-trichloroethoxy, 2,2,3,3-tetrafluoroethoxy and 2,2,2-trichloroethoxy; preferably, fluoromethoxy, difluoromethoxy, trifluoromethoxy, trichloromethoxy, difluorochloromethoxy and dichlorofluoromethoxy, etc., but are not limited thereto.

[0031] In the present invention, halogen is usually fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine.

[0032] The compounds of formula I in each case in free form or in salt form, and where appropriate their tautomers, may be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of the asymmetric carbon atoms present in the molecule, and / or on the configuration of the non-aromatic double bonds present in the molecule; the present invention relates to these pure isomers, and also to all possible isomer mixtures and the present invention should be understood in this sense in each case above and below (even if no specific stereochemical details are mentioned in each case). Therefore, the present invention covers all such isomers and tautomers and their mixtures in all proportions, as well as isotopic forms, such as deuterated compounds.

[0033] The present invention also encompasses salts or N-oxides of each compound of Formula I.

[0034] One of ordinary skill in the art will also appreciate that because salts of chemical compounds exist in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions, the salts also possess the biological utility of the non-salt form.

[0035] Therefore, the various salts of the compound of the present invention (and the active ingredient used in combination with the active ingredient of the present invention) can be used for preventing and treating plant diseases and insect pests. The salt among the salts allowed in agriculture and / or physiology includes the acid addition salts formed with the following inorganic acid or organic acid, such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid. The salt among the salts allowed in agriculture and / or physiology can also be those whose cations do not adversely affect the plant disease prevention and treatment effect of the compound of Formula I. Therefore, especially suitable cations are ions of alkali metals (including sodium, potassium and lithium), ions of alkaline earth metals (including calcium and magnesium), and ions of transition metals (including manganese, copper, iron, zinc, cobalt, lead, silver, nickel).

[0036] Specifically, the present invention first provides a compound of formula I, a salt thereof and a stereoisomer thereof,

[0037]

[0038] in,

[0039] R1 is selected from one of H, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C1-C6 alkylcarbonyl, -OCOC1-C6 alkyl, halogenated C1-C6 alkylcarbonyl or C1-C6 alkoxycarbonyl;

[0040] R2 and R3 are independently selected from halogen, nitro, cyano, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C3-C6 cycloalkyl, -O-C3-C6 cycloalkyl, C1-C6 alkylamino, halogenated C1-C6 alkylamino, di(C1-C6 alkyl)amino, -NHC3-C6 cycloalkyl, halogenated di(C1-C6 alkyl)amino, di(C1-C6 alkyl)aminocarbonyl, C C1-C6 alkylsulfonyl, -S-C3-C6 cycloalkyl, halogenated C1-C6 alkylthio, C2-C6 alkenyl, C2-C6 alkynyl, C2-C6 alkenyloxy, halogenated C2-C6 alkenyloxy, C2-C6 alkynyloxy, halogenated C2-C6 alkynyloxy, C1-C6 alkylsulfonyl, halogenated C1-C6 alkylsulfonyl, C1-C6 alkylcarbonyl, -OCOC1-C6 alkyl, halogenated C1-C6 alkylcarbonyl or C1-C6 alkoxycarbonyl.

[0041] In some technical solutions, R1 is selected from one of H, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methoxycarbonyl or methylcarbonyloxy; preferably H and methyl.

[0042] In some technical solutions, R2 is selected from one of H, fluorine, chlorine, bromine, methyl, difluoromethyl, trifluoromethyl, methoxy and trifluoromethoxy; preferably H, fluorine, chlorine, bromine, methyl, difluoromethyl and trifluoromethyl.

[0043] In some technical solutions, R3 is selected from one of H, fluorine, chlorine, bromine, methyl, difluoromethyl, trifluoromethyl, methoxy and trifluoromethoxy; preferably one of H, fluorine, methyl, difluoromethyl and trifluoromethyl.

[0044] Particularly preferred compounds of formula I according to the present invention are selected from the following compounds:

[0045]

[0046] The present invention also provides a composition comprising the compound of formula I, its salt and stereoisomer thereof and at least one auxiliary agent.

[0047] The present invention also provides use of the compound I, its salts and stereoisomers, and the composition of the present invention in preventing and controlling plant diseases.

[0048] General synthesis process

[0049] In this specification, if there is any difference between the chemical name and the chemical structure, the structure is the preferred one. Generally, the compounds of the present invention can be prepared by the methods described herein, unless otherwise specified. The following synthetic schemes and examples are provided to further illustrate the present invention.

[0050] Those skilled in the art will recognize that the chemical reactions described herein can be used to appropriately prepare many other compounds of the present invention, and other methods for preparing the compounds of the present invention are considered to be within the scope of the present invention. For example, the synthesis of non-exemplified compounds according to the present invention can be successfully accomplished by those skilled in the art through modification methods, such as appropriate protection of interfering groups, by utilizing other known reagents (in addition to those described herein), or by making some conventional modifications to the reaction conditions. In addition, the reactions disclosed herein or known reaction conditions are also generally applicable to the preparation of other compounds of the present invention.

[0051] The compounds of the present invention can be prepared by the following synthetic routes:

[0052]

[0053] Wherein, R1, R2 and R3 are defined as above in Formula I.

[0054] A specific synthesis process is to react 2,4,6-trichloroaniline with a compound of formula II in the presence of an acylation agent and a base to synthesize compound I. Preferably, the reaction is carried out in an organic solvent, the acylation agent is methanesulfonyl chloride, the organic solvent is dichloroethane, dichloromethane, toluene, chloroform, chlorobenzene, and acetonitrile, etc., but not limited thereto, the base is triethylamine, pyridine, potassium carbonate, sodium carbonate, 3-methylpyridine, etc., but not limited thereto, and the reaction temperature is 0-100°C.

[0055] The present invention also provides a composition comprising the compound of formula II of the present invention and at least one adjuvant selected from the group consisting of surfactants, solid diluents and liquid diluents.

[0056] The present invention relates to the use of the compound or a composition containing the compound as a fungicide in agriculture or gardening, for controlling or preventing useful plants from being damaged by diseases.

[0057] The diseases described in the present invention include, but are not limited to, the following:

[0058] Oomycetes, such as Pythium, Pseudoperonospora, Phytophthora, Peronospora, Peronophythora, and other genera; Deuteromycetes, such as Fusarium, Rhizoctonia, Colletotrichum, Curyularia, and other genera; Ascomycetes, such as Cochliobolus, Gibberella, Erysiphe, Valsa, Claviceps, Taphrina, Venturia, Mycosphaerella, Neovossia, and other genera; and other pathogens that cause plant diseases, such as bacteria. Examples of related diseases caused by related pathogens include but are not limited to: wheat stem rot, wheat root rot, wheat eyebrow blight, wheat fusarium wilt, wheat rot, wheat take-all disease, corn bacterial wilt, corn seedling blight, corn stem rot, corn rot and other soil-borne diseases.

[0059] The plant objects to which the compounds of the present invention can be applied are not particularly limited; for example, cereals (e.g., rice, barley, wheat, rye, oats, corn, sorghum, etc.), legumes (soybeans, adzuki beans, broad beans, peas, peanuts, etc.), fruit trees / fruits (apples, citrus, pears, grapes, peaches, Japanese apricots, cherries, walnuts, apricots, bananas, strawberries, etc.), vegetables (cabbage, tomatoes, spinach, broccoli, lettuce, onions, green onions, green peppers, etc.), root vegetables (carrots, potatoes, sweet potatoes, radishes, etc.), The main crops include: radish, lotus root, turnip, etc.), industrial crops (cotton, hemp, paper mulberry, jasmine, rapeseed, sugar beet, hops, sugarcane, sugar beet, olives, rubber, coffee, tobacco, tea, etc.), berries (pumpkin, cucumber, watermelon, melon, etc.), forage grasses (orchard grass, milo, timothy, alfalfa, lucerne, etc.), lawn grasses (Korean zoysia, bentgrass, etc.), spices and other crops (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), and flowers (chrysanthemum, rose, orchid, etc.).

[0060] The compounds of the present invention can generally be used as active ingredients of pesticides in compositions or formulations, which usually also include pesticide-acceptable surfactants and carriers. The carriers can be solid carriers or liquid carriers.

[0061] Suitable solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as kaolinite, kaolin, montmorillonite and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; ammonium salts, such as ammonium sulfate, hexamethylenediamine and urea, etc.

[0062] Liquid carriers include water and organic solvents. When water is used as the solvent or diluent, organic solvents can also be used as adjuvants or antifreeze additives. Useful liquefied gaseous fillers or carriers are those liquids that are gaseous at standard temperature and standard pressure, such as aerosol propellants, such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide, etc.

[0063] Suitable organic solvents include aromatic hydrocarbons, such as benzene, xylene, toluene, etc.; chlorinated hydrocarbons, such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, etc.; aliphatic hydrocarbons, such as petroleum fractions, cyclohexane, light mineral oil; alcohols, such as isopropyl alcohol, butanol, ethylene glycol, glycerol and cyclohexanol, etc.; and their ethers and esters; ketones, such as acetone, cyclohexanone, dimethylformamide and N-methyl-pyrrolidone, vegetable oils, such as soybean oil, rapeseed oil and cottonseed oil, etc.

[0064] Suitable surfactants (adjuvants, emulsifiers, dispersants, protective colloids, wetting agents and binders) include all common ionic and nonionic substances, for example ethoxylated nonylphenols, polyalkylene glycol ethers of linear or branched alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, reaction products of fatty acid amines with ethylene oxide and / or propylene oxide, and also fatty acid esters, alkylsulfonates, alkyl sulfates, alkyl ether sulfates, alkyl ether phosphates, aryl sulfates, ethoxylated arylalkylphenols (such as tristyrylphenol ethoxylate), and ethoxylated and propoxylated arylalkylphenols, such as sulfated and phosphated arylalkylphenol ethoxylates and -ethoxylates and -propoxylates. Other examples are natural and synthetic water-soluble polymers, such as ligninsulfonates, gelatin, gum arabic, phospholipids, starch, hydrophobically modified starch and cellulose derivatives, in particular cellulose esters and cellulose ethers, as well as polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid and copolymers of (meth)acrylic acid and (meth)acrylic esters, as well as copolymers of methacrylic acid and methacrylic esters neutralized with alkali metal hydroxides, and condensates of optionally substituted naphthalenesulfonates with formaldehyde. If one of the active ingredients and / or one of the inert carriers is insoluble in water and application is carried out in water, the presence of a surfactant is essential.

[0065] The pesticide of the present invention can be prepared by a common method. For example, the active substance is mixed with a liquid solvent and / or a solid carrier, and a surfactant such as an emulsifier, dispersant, stabilizer, or wetting agent is added. Other adjuvants such as adhesives, defoamers, foaming agents, antioxidants, crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet regulators, pigments, neutralizers and buffers, corrosion inhibitors, dyes, flavoring agents, spreading agents, penetration aids, micronutrients, dispersants, thickeners, freezing point depressants, and antimicrobial agents may also be added.

[0066] The fungicidal pesticide of the present invention can be applied in the form of its formulation or in a use form prepared therefrom, such as capsule suspensions, fine granules, foams, pastes, suspension concentrates, suspoemulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granules, water-soluble and water-dispersible granules or tablets, etc., but are not limited thereto.

[0067] The formulation of the present invention may also contain other components, such as other fungicides, insecticides, herbicides, plant growth regulators, attractants, acaricides, nematicides, fertilizers, safeners, etc., which can be formulated with liquid fertilizers or solid, granular fertilizer carriers such as ammonium nitrate, urea, etc., or mixed with fine sand or soil.

[0068] When a pesticide composition containing a compound of Formula I of the present invention is used to control plant diseases in the form of an emulsifiable concentrate, wettable powder, or microemulsion, these formulations are typically diluted with water to a concentration of the active ingredient (i.e., the compound of Formula I) within a range of 0.01 to 5000 ppm for application. Granules or powders have been investigated for application without dilution. Research results indicate that the compound of Formula I of the present invention exhibits an inhibition rate or lethality of at least 50% against certain diseases at a concentration of 0.01 to 100 ppm (0.01 mg / L to 100 mg / L), preferably 0.01 ppm to 10 ppm.

[0069] 1) Preparation Example

[0070] Generally, the compounds of the present invention can be prepared by the methods described herein, unless otherwise specified. The raw materials, reagents, etc. used to prepare the compounds of the present invention are commercially available or can be prepared by conventional methods in the art.

[0071] Preparation of Example 1I-01

[0072]

[0073] At 25°C, a thermometer-equipped, mechanically stirred three-necked flask (250 ml) was charged with 2,4,6-trichloroaniline (0.1 mol, 19.6 g, 1.0 eq.), 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (0.1 mol, 17.6 g, 1.0 eq.), and 100 ml of acetonitrile. Stirring was initiated, and 3-methylpyridine (0.12 mol, 11.2 g, 1.2 eq.) was added dropwise. The mixture was stirred for 30 minutes. Methanesulfonyl chloride (0.11 mol, 12.5 g, 1.1 eq.) was added dropwise, maintaining the temperature at 25°C. Stirring was continued for 3 hours after the addition was complete. The temperature was raised to 50°C. The reaction was complete, as monitored by TLC. The solvent was removed under reduced pressure, and an appropriate amount of water was added dropwise. The mixture was stirred and filtered. The filter cake was washed with a small amount of methanol and dried to yield 32.9 g of a white solid (93.0% yield).

[0074] NMR data

[0075] 1 H NMR (400MHz, DMSO-d6) δ8.49 (s, 1H), 7.82 (d, J = 1.6 Hz, 2H), 7.28 (t, J = 54.0 Hz, 1H), 3.99 (s, 3H). 13 C NMR (100MHz, DMSO-d6) δ160.25, 135.39, 133.43 (d, J = 48.9Hz), 132.41, 128.83, 115.18, 109.94.

[0076] Preparation of Example 2I-02

[0077]

[0078] At 25°C, add 2,4,6-trichloroaniline (0.1 mol, 19.6 g, 1.0 eq.), 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid (0.1 mol, 15.8 g, 1.0 eq.), and 100 ml of acetonitrile to a three-necked flask (250 ml) equipped with a thermometer and mechanical stirring. Stirring is initiated, and 3-methylpyridine (0.12 mol, 11.2 g, 1.2 eq.) is added dropwise. Stir for 30 minutes. Maintaining the system at 25°C, methanesulfonyl chloride (0.11 mol, 12.5 g, 1.1 eq.) is added dropwise. Stirring is continued for 3 hours. The temperature is raised to 50°C and the reaction is complete, as monitored by TLC. The solvent is removed under reduced pressure, an appropriate amount of water is added dropwise, and the mixture is stirred. Filter with suction, wash the filter cake with a small amount of methanol, and dry to obtain 31.9 g of a white solid (95.0% yield).

[0079] NMR data

[0080] 1H NMR (400MHz, DMSO-d6) δ7.73(s,2H),3.89(s,3H),2.61(s,3H). 13 C NMR (100MHz, DMSO-d6) δ14.88,35.16,95.40,129.75,129.76,137.20,146.16,154.44,156.94,162.60.

[0081] Preparation of Example 3I-03

[0082]

[0083] To a 250ml three-necked flask equipped with a thermometer and mechanical stirring at 25°C was added 2,4,6-trichloroaniline (0.1mol, 19.6g, 1.0eq.), 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (0.1mol, 19.4g, 1.0eq.), and 100ml of acetonitrile. Stirring was initiated, and 3-methylpyridine (0.12mol, 11.2g, 1.2eq.) was added dropwise. Stirring was continued for 30 minutes. Methanesulfonyl chloride (0.11mol, 12.5g, 1.1eq.) was added dropwise, maintaining the system at 25°C. Stirring was continued for 3 hours after addition was complete. The reaction was monitored by TLC to confirm completion. The solvent was removed under reduced pressure, and an appropriate amount of water was added dropwise. The mixture was stirred and filtered. The filter cake was washed with a small amount of methanol and dried to yield 35.7g of an off-white solid (96.0% yield).

[0084] NMR data

[0085] 1 H NMR (400MHz, DMSO-d6) δ8.50 (s, 1H), 7.84 (d, J = 1.6Hz, 2H), 4.01 (s, 3H). 13 CNMR (100MHz, DMSO-d6) δ160.26, 135.40, 133.44 (d, J = 49.0Hz), 132.42, 128.86, 115.20, 109.88.

[0086] The compounds of the present invention and reference compounds were synthesized according to the above method, see Table 1.

[0087] Table 1 Compounds of the present invention

[0088]

[0089] 2) Biological activity assay

[0090] 1. Isolation of fungi

[0091] 1.1 Test Target

[0092] Fusarium graminearum (FG), Pseudomonas graminearum (FP), Colletotrichum solani (CG), Phytophthora capsici (PC), Rhizoctonia solani (RC), and Apricot brown rot (MF).

[0093] 1.2 Test Method

[0094] The mycelial growth method (NY / T 1156.2-2006) was used to prepare compounds I-01 to I-06 of the present invention at concentrations of 100, 50, 25, 12.5, 6.25, 3.125, and 1.5625 (ppm), respectively. The in vitro inhibitory concentration (EC) of each compound on fungi such as Fusarium graminearum (FG), Pseudomonas graminearum (FP), Colletotrichum spp. (CG), Bletillaria spp. (BS), Phytophthora capsici (PC), Rhizoctonia solani (RC), Apricot brown rot (MF), and Alternaria truncatula (AKT) was calculated based on the experimental data. 50 ).

[0095] 1.3 Test Results

[0096] Table 2 Effects of the compounds of the present invention on relevant test targets

[0097]

[0098] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. Compounds:

2. A composition, characterized in that The invention comprises the compound according to claim 1, a salt thereof and at least one auxiliary agent.

3. Use of the compound according to claim 1, its salt and the composition according to claim 2 in preventing and controlling plant diseases.

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