Application of a class of hydrazone compounds in fungicides

Abstract

The present invention discloses a hydrazone compound represented by Formula I and its applications, wherein the definitions of the substituents are as defined in the specification. The compounds of the present invention have good bactericidal activity and broad application prospects.

Description

Technical Field

[0001] The present invention relates to the field of agricultural fungicides, and specifically relates to a class of hydrazone compounds having bactericidal activity, compositions containing these compounds, and their use as fungicides in agriculture. Technical Background

[0002] Hydrazones, as a kind of multifunctional reagent, have various uses in organic synthesis. They not only serve as good ligands in palladium-catalyzed reactions, but also are used as important substrates for the synthesis of heterocyclic compounds and can be used as useful organic carbene precursors. In particular, hydrazone compounds, as an important structural scaffold, have unique physicochemical properties after combining with other functional groups. Studies on the properties and synthesis of hydrazones and their derivatives have shown that such compounds exhibit considerable biological activities and can be used to treat various diseases, especially cancer, malaria, Chagas disease, viral infections, Alzheimer's disease (AD), bacterial and fungal infections, as well as various anti-inflammatory effects. Moreover, due to their unique biological activities, hydrazone compounds also play an important role in the field of pesticides such as antibacterial agents, insecticides, herbicides, and plant growth regulators.

[0003]

[0004] Hydrazone Compounds with Biological Activity

[0005] The diverse variations of hydrazone compounds have made hydrazones with pesticidal activity increasingly abundant. Therefore, developing an effective method to construct this important skeleton is of great value.

[0006] During the research process, the applicant found that a hydrazone compound has excellent bactericidal activity and broad application prospects. Summary of the Invention

[0007] The present invention provides a hydrazone compound having excellent bactericidal activity. Specifically, the present invention discloses a compound of formula I and its agriculturally acceptable salts, stereoisomers, N-oxides, and, if appropriate, their tautomeric forms, and, if appropriate, can also be obtained in the form of hydrates and / or including other solvents for use as agricultural fungicides.

[0008]

[0009] Wherein,

[0010] R is H, optionally substituted aryl, optionally substituted cycloalkyl;

[0011] R1 is H, optionally substituted alkyl, optionally substituted aryl;

[0012] R2 is optionally substituted alkyl, substituted aryl, optionally substituted heteroaryl.

[0013] The present invention also provides a method for controlling or preventing useful plants from being infected by phytopathogenic microorganisms, by applying the compound of the present invention or a composition containing the compound as an active ingredient to the plant, to its parts or its locus.

[0014] The present invention also provides a composition for controlling or combating phytopathogenic microorganisms, comprising the compound of the present invention and an inert carrier.

[0015] Beneficial effects

[0016] The hydrazone compounds of the present invention have more excellent bactericidal activity, especially excellent activity at low application rates, and the plants have good tolerance and excellent environmental safety. Detailed embodiments

[0017] To make the objectives, 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. Apparently, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention. Unless otherwise clearly stated, in the whole specification and claims, the term "comprising" or its variations such as "comprises" or "including" etc. will be understood to include the stated components or steps, without excluding other components or steps.

[0018] In addition, for better illustration of the present invention, numerous specific details are given in the following detailed embodiments.

[0019] Those skilled in the art should understand that the present invention can be implemented without some specific details. In some embodiments, the raw materials, methods, means, etc. well-known to those skilled in the art are not described in detail, so as to highlight the gist of the present invention.

[0020] If the compound of formula I described in the present invention can form geometric isomers, such as E / Z isomers, both the pure isomers and their mixtures can be applied in the composition of the present invention.

[0021] If the compound of formula I described in the present invention has one or more chiral centers and thus exists as enantiomers or diastereomers, pure enantiomers, racemates, diastereomers can be used in the composition of the present invention.

[0022] If the compound of formula I described in the present invention has functional groups that can be ionized, they can also be used in the form of their agricultural salts or their mixtures.

[0023] Suitable are generally salts of those cations whose cations have no adverse effect on the action of the active compound ("agriculturally usable"). Preferred cations are the ions of the alkali metals, preferably lithium, sodium and potassium ions, the ions of the alkaline earth metals, preferably calcium and magnesium ions, and the ions of the transition metals, preferably manganese, copper, zinc and iron ions.

[0024] The anions of the useful acid addition salts are mainly chloride, bromide, fluoride, iodide, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate.

[0025] In the present invention, C n -C m The subscripts n and m in all cases represent the number of carbon atoms in the group. For example, C1-C6 means containing 1 to 6 carbon atoms. The alkyl groups appearing in the definition of substituents can be straight-chain or branched-chain and are, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, sec-butyl, isobutyl or tert-butyl. The alkoxy groups are derived from the alkyl groups mentioned. Alkoxy groups are, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy. Halogenated alkoxy groups are, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, trifluoromethoxy and 2-chloroethoxy.

[0026] In the present invention, halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine. Correspondingly, this also applies to halogen in combination with other structures, such as halogenated alkyl groups. The halogenated alkyl groups preferably have a chain length of 1 to 6 carbon atoms, more preferably a chain length of 1 to 4 carbon atoms. Examples of halogenated alkyl groups are, 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. "C3-C6 cycloalkyl" means cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, etc., but is not limited thereto.

[0027] In the present invention, "aryl" means a monovalent monocyclic or bicyclic aromatic hydrocarbon group having 6 to 10 ring atoms, such as, for example, phenyl or naphthyl, but is not limited thereto.

[0028] In the present invention, "heteroaryl" refers to an aromatic group preferably having 5 to 10 members, including one or more, especially one or two fused rings, wherein the atoms of the ring are composed of one or more, advantageously 1 to 4, more advantageously 1 or 2 heteroatoms selected from nitrogen, oxygen and sulfur atoms, and the rest are carbon atoms. Heteroaryl can especially be pyridyl, pyrimidinyl, thienyl, furyl, pyrrolyl, indolyl, etc.

[0029] The term "optionally substituted" means that the relevant group can be substituted by a substituent or can be unsubstituted.

[0030] When the relevant group (such as an alkyl group) is substituted by a substituent, the substituents can include hydroxyl, cyano, nitro, halogen, alkyl, alkoxy, haloalkyl and haloalkoxy, etc., but are not limited thereto.

[0031] The term "ambient temperature" or "room temperature" in the present invention means 25 ± 2 °C.

[0032] The present invention discloses the use of a compound of formula I and its agriculturally acceptable salts, stereoisomers, N-oxides, and, if appropriate, its tautomers, and, if appropriate, also in the form of hydrates and / or including other solvents, as agricultural fungicides.

[0033]

[0034] Wherein,

[0035] R is H, optionally substituted aryl, optionally substituted cycloalkyl;

[0036] R1 is H, G-CO2-, wherein G is optionally substituted alkyl, optionally substituted aryl;

[0037] R2 is optionally substituted alkyl, substituted aryl, optionally substituted heteroaryl.

[0038] In some embodiments, R is H, optionally substituted phenyl, optionally substituted cycloalkyl; preferably H, phenyl substituted by halogen, halo C1-C6 alkyl, nitro, cyano, C1-C6 alkyl and C1-C6 alkoxy, cyclohexyl.

[0039] In some embodiments, R1 is H, G-CO2-, wherein G is C1-C6 alkyl, phenyl.

[0040] In some embodiments, R2 is C1-C6 alkyl, optionally substituted aryl, heteroaryl; preferably C1-C6 alkyl, phenyl substituted by halogen, halo C1-C6 alkyl, nitro, cyano, C1-C6 alkyl and C1-C6 alkoxy, naphthyl, pyridyl and pyrimidinyl.

[0041] Particularly preferred compounds of the present invention are the following compounds:

[0042] 1. Ethyl (E)-4-(hydroxy(phenyl)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3aa)

[0043] 2. Ethyl (E)-4-((4-fluorophenyl)(hydroxy)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3ba)

[0044] 3. Ethyl (E)-4-((4-chlorophenyl)(hydroxy)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3ca)

[0045] 4. Ethyl (E)-4-((2-bromophenyl)(hydroxy)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3da)

[0046] 5. Ethyl (E)-4-((3-bromophenyl)(hydroxy)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3ea)

[0047] 6. Ethyl (E)-4-((4-bromophenyl)(hydroxy)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3fa)

[0048] 7. Ethyl (E)-4-(hydroxy(o-tolyl)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3ga)

[0049] 8. Ethyl (E)-4-(hydroxy(m-tolyl)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3ha)

[0050] 9. Ethyl (E)-4-(hydroxy(p-tolyl)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3ia)

[0051] 10. Ethyl (E)-4-(hydroxy(4-methoxyphenyl)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3ja)

[0052] 11. Ethyl (E)-4-(hydroxy(4-nitrophenyl)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3ka)

[0053] 12. Ethyl (E)-4-((4-cyanophenyl)(hydroxy)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3la)

[0054] 13. Ethyl (E)-4-(hydroxy(4-(trifluoromethyl)phenyl)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3ma)

[0055] 14. Ethyl (E)-4-([1,1'-biphenyl]-4-yl(hydroxy)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3na)

[0056] 15. Ethyl (E)-4-(cyclohexyl(hydroxy)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3qa)

[0057] 16. Ethyl (E)-2-(2-(2-fluorophenyl)hydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate (3-3ab)

[0058] 17. Ethyl (E)-2-(2-(3-fluorophenyl)hydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate (3-3ac)

[0059] 19. Ethyl (E)-2-(2-(4-fluorophenyl)hydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate (3-3ad)

[0060] 20. Ethyl (E)-2-(2-(3-chlorophenyl)hydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate (3-3ae)

[0061] 21. Ethyl (E)-2-(2-(3-bromophenyl)hydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate (3-3ag)

[0062] 22. Ethyl (E)-2-(2-(4-bromophenyl)hydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate (3-3ah)

[0063] 23. Ethyl (E)-4-(hydroxy(phenyl)methyl)-2-(2-(p-tolyl)hydrazono)pent-4-enoate (3-3ai)

[0064] 24. Ethyl (E)-2-(2-(4-ethylphenyl)hydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate (3-3aj)

[0065] 25. Ethyl (E)-4-(hydroxy(phenyl)methyl)-2-(2-(2-methoxyphenyl)hydrazono)pent-4-enoate (3-3ak)

[0066] 26. Ethyl (E)-4-(hydroxy(phenyl)methyl)-2-(2-(3-methoxyphenyl)hydrazono)pent-4-enoate (3-3al)

[0067] 27. Ethyl (E)-4-(hydroxy(phenyl)methyl)-2-(2-(4-methoxyphenyl)hydrazono)pent-4-enoate (3-3am)

[0068] 28. Ethyl (E)-4-(hydroxy(phenyl)methyl)-2-(2-(4-(trifluoromethyl)phenyl)hydrazono)pent-4-enoate (3-3an)

[0069] 29. Ethyl (E)-4-(hydroxy(phenyl)methyl)-2-(2-(naphthalen-2-yl)hydrazono)pent-4-enoate (3-3ao)

[0070] 30. Ethyl (E)-2-(2-benzylhydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate (3-3ap)

[0071] 31. Ethyl (E)-2-(2-(tert-butyl)hydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate (3-3aq)

[0072] 32. Ethyl (E)-4-(hydroxy(phenyl)methyl)-2-(2-(pyridin-2-yl)hydrazono)pent-4-enoate (3-3ar)

[0073] 33. Ethyl (E)-4-(hydroxymethyl)-2-(2-phenylhydrazono)pent-4-enoate (3-8)

[0074] 34. Butyl (E)-2-methylene-1,4-diphenyl-4-(2-toluenesulfonylhydrazono)benzoate (3-5)

[0075] Some intermediate compounds of the present invention can be synthesized by the following schemes:

[0076] 1. Synthesis of allyl carbonates containing hydroxyl groups

[0077] 1.1. Synthesis of MBH alcohol

[0078]

[0079] The corresponding substituted benzaldehyde (10.0 mmol), methyl acrylate (15.0 mmol), and triethylenediamine (DABCO) (10.0 mmol) were added to a 25.0 mL reaction flask and stirred at room temperature for 24 h. After the reaction was completed, the reaction solution was diluted with 50.0 mL of ethyl acetate, washed with water (50 mL × 3), the organic phase was separated, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The MBH allyl alcohol product was separated and purified by silica gel column chromatography (ethyl acetate / petroleum ether = 1:10).

[0080] 1.2. Reduction to form a diol product

[0081]

[0082] Dissolve the obtained MBH allyl alcohol product (10.0 mmol) above in 40.0 mL of ultradry dichloromethane. Under argon protection, slowly add diisobutylaluminum hydride (DIBAL) (3.0 equivalents, 30.0 mmol) dropwise at -78 °C. After the addition is complete, stir for 1 hour. After the reaction is completed, slowly add 1.0 M aqueous HCl dropwise to quench the reaction. Separate the organic phase, extract the aqueous phase with dichloromethane (50.0 mL × 3), combine the organic phases, dry over anhydrous sodium sulfate, and concentrate under reduced pressure. The diol product is obtained by separation and purification through column chromatography (ethyl acetate / petroleum ether = 1:15 - 1:3).

[0083] 1.3 Selective protection of hydroxyl groups to form allyl carbonates containing hydroxyl groups 1

[0084]

[0085] Dissolve di-tert-butyl dicarbonate (1.1 equivalents, 5.5 mmol) and triethylamine (20.0 mol%, 1.0 mmol) in 5.0 mL of dichloromethane, and slowly add it dropwise to a solution of the diol product (5.0 mmol) dissolved in 10.0 mL of dichloromethane. React overnight. After the reaction is completed, concentrate under reduced pressure, and separate and purify through a silica gel column (ethyl acetate / petroleum ether = 1:15 - 1:10) to obtain allyl carbonate 1 containing hydroxyl groups.

[0086] 1.4 Synthesis of aldehyde hydrazone 3-2

[0087]

[0088] In a 100 mL reaction flask, add 20.0 mmol of the corresponding R2NH2NH2HCl hydrazine, dissolve it in 40.0 mL of anhydrous tetrahydrofuran, and add 20 mmol of ethyl glyoxylate dropwise at 0 °C. Stir the mixture at 0 °C for 30 min, and let it react overnight at room temperature. After the reaction is completed, concentrate under reduced pressure, quickly separate the crude product through a column (ethyl acetate / petroleum ether = 1:10), and then recrystallize from petroleum ether / ethyl acetate to purify the desired aldehyde hydrazone 3-2. (If hydrazine hydrochloride is used as the raw material, after dissolving it in anhydrous tetrahydrofuran, first treat it with triethylamine (12.0 mmol), and after the reaction is completed, filter to remove triethylamine hydrochloride.)

[0089] 2 General procedure for palladium-catalyzed allylic alkylation reaction

[0090] Add aldehyde hydrazone 3-2 (0.1 mmol), palladium catalyst Pd2(dba)3·CHCl3 (2.5 mol%, 0.0025 mmol) and DpePhos (10.0 mol%, 0.01 mmol) to a 10 mL Schlenk tube equipped with a magnetic stir bar. Evacuate and refill with argon three times. Under argon protection, add a solution of hydroxy-containing allyl carbonate 1 (0.15 mmol) in ultradry 1,4-dioxane (2.0 mL) to the Schlenk tube. Stir at 25 °C for 48 h. After the reaction is complete, rotary evaporate the solvent under reduced pressure and separate by column chromatography (ethyl acetate / petroleum ether = 1:15–1:10) to obtain the final C(sp 2 )-H allyl alkylation product 3-3.

[0091] The inventors have found that the compounds of formula I according to the invention have a very advantageous broad spectrum of activity, protecting useful plants against diseases caused by phytopathogenic microorganisms such as fungi, bacteria or viruses. The invention relates to a method for controlling or preventing the infestation of useful plants by phytopathogenic microorganisms, in which the compounds of formula I are applied as active ingredients to the plants, to their parts or to their sites. The compounds of formula I according to the invention are characterized by excellent activity at low application rates, good tolerance by plants and environmental safety. They have very useful therapeutic, prophylactic and systemic properties and are used to protect a large number of useful plants. The compounds of formula I can be used to inhibit or eliminate diseases occurring on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while also protecting those plant parts growing later, for example from phytopathogenic microorganisms. The compounds of formula I can also be used as seed dressing agents to treat plant propagation material, in particular seeds (fruits, tubers, grains), to protect against fungal infestation and against phytopathogenic fungi present in the soil. The compounds of formula I are, for example, effective against phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). In addition, they are effective against Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and other Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara). A significant activity against powdery mildew (Erysiphe spp.) has been observed. Furthermore, the compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp., Pseudomonas spp., Erwinia amylovora and tobacco mosaic virus). Good activity against Asian soybean rust (Phakopsora pachyrhizi) has been observed.

[0092] Within the scope of the present invention, useful plants which can be protected generally include plants of the following categories: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); sugar beets (sugar beet and fodder beet); pomaceous, stone and berry fruits (apple, pear, plum, peach, almond, cherry, strawberry, raspberry and blackberry); leguminous plants (kidney bean, lentil, pea, soybean); oil plants (rape, mustard, poppy, olive, sunflower, coconut, castor oil plants, cocoa bean, soybean plants); cucurbitaceous plants (pumpkin, cucumber, melon); fiber plants (cotton, flax, jute); citrus fruits (orange, lemon, grapefruit, tangerine); vegetables (spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, pepper); Lauraceae (avocado, cinnamon, camphor) or plants such as tobacco, nut, coffee, eggplant, sugar cane, tea, pepper, vine, hops, banana and natural rubber plants, as well as ornamental plants.

[0093] The compounds of formula I according to the invention can be used in unchanged form or preferably in combination with carriers and auxiliaries customary in the art of formulation.

[0094] The present invention also relates to a fungicidal composition for controlling or combating phytopathogenic microorganisms, which comprises a compound of formula I according to the invention and an inert carrier, and to a method for controlling or preventing useful plants from being infested by phytopathogenic microorganisms, wherein a composition comprising a compound of formula I as active ingredient and an inert carrier is applied to the plants, to parts thereof or to their habitat. The compounds of formula I according to the invention and the inert carrier are conveniently formulated in a known manner as emulsifiable concentrates, coatable seed dressings, aqueous emulsion concentrates, microemulsions, wettable powders, granules, etc. The composition may also comprise other auxiliaries such as stabilizers, defoamers, viscosity regulators, binders or tackifiers and fertilizers, micronutrient donors or other formulations for obtaining special effects.

[0095] Suitable carriers and auxiliaries in the compositions according to the invention can be solid or liquid and are conventional in the art of formulation, for example natural or regenerated minerals, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.

[0096] A preferred method of applying the compounds of formula I according to the invention or a composition comprising a compound of formula I as active ingredient and an inert carrier is foliar application. The frequency and rate of application will depend on the risk of infestation by the corresponding pathogens. However, the compounds of formula I can penetrate into the plants via the roots through the soil (systemic action) by perfusion of the plant habitat with a liquid formulation or by applying the compound in solid form, for example in the form of granules, to the soil (soil application). In rice crops, such granules can be applied to flooded rice fields. The compounds of formula I can also be applied to seeds (coating) by impregnating the seeds or tubers with a fungicidal liquid formulation or by coating them with a solid formulation.

[0097] Pesticide formulations generally include 0.1 to 99% weight, preferably 0.1 to 95% weight of formula I compound of the present invention. Favorable rate of application is normally 0.05g to 1kg of active ingredient (ai) every hectare (ha), and suitable rate of application is 10mg to 1g of active ingredient every kg seed. When pest control agent of the present invention is mixed with emulsifiable concentrate, wettable powder etc., usually they are diluted with water so that the concentration of active ingredient is in the range of 0.0001 to 10,000ppm, and spray them subsequently, use these preparations. Can determine by experiment the rate of application that produces the effect of hope. Rate of application depends on the developmental stage of for example action type, useful plant and uses (place, opportunity, application method), and changes in a wide range with these parameters.

[0098] The present invention also discloses a fungicide composition comprising the compound of formula I. Furthermore, the fungicide composition further comprises additional active ingredients, including insecticides, fungicides and herbicides.

[0099] The compound of formula I of the present invention or the fungicidal composition containing the compound of formula I of the present invention is preferably used to prevent and control plant diseases, and the plant diseases are preferably one or more of aphanidermatus, wheat fusarium, tomato gray mold, watermelon wilt, wheat sheath blight, tobacco red star, pepper black spot, cucumber target spot, pepper anthrax and cabbage black spot.

[0100] Preparation Example

[0101] In this specification, if there is any difference between the chemical name and the chemical structure, the structure is preferred. 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 all commercially available or can be prepared by methods conventional in the art.

[0102] All reactions under inert gas protection were carried out under argon protection (gas replacement was performed three times through a double-row tube, with each evacuation lasting ten minutes).

[0103] All glassware were dried in an oven at 110°C for two hours before use and were sourced from Shuniu Glass Instrument Co., Ltd. and Xinweier Glass Instrument Co., Ltd.

[0104] Unless otherwise specified, all reagents used in the experiments were purchased directly from reagent companies without further purification.

[0105] All conventional solvents used were directly purchased anhydrous solvents from Hines, J.B. & K. or Anergy. Some anhydrous solvents that could not be purchased, such as anhydrous chloroform and toluene, were used after being dried by reflux with calcium hydride.

[0106] Deuterated solvents used are deuterated chloroform, heavy water, and deuterated dimethyl sulfoxide from CIL, Anyij, and Leyan companies.

[0107] The solvents were removed using a rotary evaporator (Tokyo Rika EYELA-N type) under reduced pressure by a water circulation vacuum pump (Hengyan Instrument Co., Ltd.) or directly using a rotary vane oil pump (Hengyan Instrument Co., Ltd.).

[0108] The reaction results were monitored by TLC (thin layer chromatography) method, developed by irradiating with ultraviolet light of wavelengths (365 nm or 254 nm), combined with potassium permanganate and iodine fuming methods for color development.

[0109] The silica gel column used silica gel of 200 - 300 mesh (Qingdao Ocean Company).

[0110] The nuclear magnetic resonance spectra (proton, carbon, and fluorine spectra) were obtained using a 500M instrument produced by Bruker Corporation, with tetramethylsilane as the internal standard.

[0111] The infrared data was measured using a NICOLET IS10 instrument (Thermo Fisher Company).

[0112] The high-resolution mass spectrometry data was obtained from tests by companies such as Renren Experiment and Fengpu Technology Co., Ltd.

[0113] The X-ray single crystal diffraction data was obtained from tests by Science Compass Company.

[0114] Synthesis of Ethyl (E)-4-(hydroxy(phenyl)methyl)-2-(2-phenylhydrazono)pent-4-enoate (3-3aa) in Example 1

[0115]

[0116] Add aldehyde hydrazone 3-2a (1.0 mmol), palladium catalyst Pd2(dba)3·CHCl3 (2.5 mol%, 0.02 mmol), and DpePhos (bis(2-diphenylphosphinophenyl)ether) (10.0 mol%, 0.1 mmol) to a 50 mL Schlenk tube. Evacuate and refill with gas three times. Under argon protection, add a solution of hydroxy-containing allyl carbonate 1a (1.5 mmol) in ultradry 1,4-dioxane (20.0 mL) to the Schlenk tube and react at 25 °C. After the reaction, concentrate under reduced pressure and purify by column chromatography (ethyl acetate / petroleum ether = 1:15) to obtain the final allyl alkylation product 3-3aa. Colorless oil (93% yield, 31.4 mg), and the eluent ratio is (6.7 - 10.0% ethyl acetate / petroleum ether); 11H NMR (500 MHz, CDCl3) δ 8.57 (s, 1H), 7.45–7.40 (m, 2H), 7.39 (t, J = 7.6 Hz, 3H), 7.37–7.30 (m, 1H), 7.27 (d, J = 9.9 Hz, 3H), 7.09 (d, J = 7.2 Hz, 2H), 6.94 (t, J = 7.4 Hz, 1H), 5.34 (d, J = 3.3 Hz, 1H), 5.16 (s, 1H), 4.99 (s, 1H), 4.29 (q, J = 7.1 Hz, 2H), 3.28 (q, J = 16.6 Hz, 2H), 2.82 (d, J = 3.3 Hz, 1H), 1.35 (t, J = 7.1 Hz, 3H).

[0117] Synthesize the following compounds by referring to the preparation method of Example 1:

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125] Biological Example: Fungicidal Activity Assay

[0126] In this experiment, PDA medium was used, and the test strains were Pythium aphanidermatum, Gibberella zeae, Botrytis cinerea, Fusarium oxysporum f. sp. niveum, Rhizoctonia cerealis, Alternaria alternata, Alternaria brassicae, Corynespora cassiicola, Colletotrichum capsici, and Alternaria brassicae. The antibacterial activities of 4 new compounds against the above 10 strains were determined by the growth rate method.

[0127] The specific operation steps are as follows:

[0128] 1. Preparation of the medium. PDA medium: 20% potato, 2% glucose, 2% agar.

[0129] 2. Preparation of the liquid medicine. First dissolve it in acetone, and then prepare the liquid medicine with distilled water.

[0130] 3. Preparation of the plate. After mixing the liquid medicine and PDA medium in a ratio of 1:9, pour it into a petri dish and let it stand flat until it solidifies.

[0131] 4. Inoculation operation: In a laminar flow hood, use a punch to prepare a 5-mm mycelial disc, inoculate it in the center of the petri dish, seal the film, and then place it in an incubator at 26 °C for cultivation and observation.

[0132] 5. After culturing for a period of time, use the cross method to measure the growth diameter of each colony. The culturing time varies for different strains: Pythium aphanidermatum (2 days), Gibberella zeae (4 days), Botrytis cinerea (4 days), Fusarium oxysporum f. sp. niveum (5 days), Rhizoctonia cerealis (6 days), Alternaria alternata (6 days), Alternaria brassicae (7 days), Corynespora cassiicola (7 days), Colletotrichum capsici (8 days), and Alternaria brassicae (9 days).

[0133] 6. Calculation of inhibition rate:

[0134]

[0135] Table 1 Control effects of compounds against Pythium aphanidermatum, Gibberella zeae, Botrytis cinerea, Fusarium oxysporum f. sp. niveum, and Rhizoctonia cerealis

[0136]

[0137] Table 2 Control effects of compounds against Alternaria alternata, Alternaria brassicae, Corynespora cassiicola, Colletotrichum capsici, and Alternaria brassicae

[0138]

[0139]

Claims

1. Use of a compound and its agriculturally acceptable salts in agricultural fungicides, characterized in that, the compound is selected from the following compounds: (E)-Ethyl 4-((4-fluorophenyl)(hydroxy)methyl)-2-(2-phenylhydrazono)pent-4-enoate; (E)-Ethyl 2-(2-(4-fluorophenyl)hydrazono)-4-(hydroxy(phenyl)methyl)pent-4-enoate; (E)-Ethyl 4-(hydroxy(phenyl)methyl)-2-(2-(4-(trifluoromethyl)phenyl)hydrazono)pent-4-enoate.

2. Use of the compound according to claim 1 and its agriculturally acceptable salts as agricultural fungicides, characterized in that, Controlling plant diseases, said plant diseases being one or more of Pythium aphanidermatum, Gibberella zeae, Botrytis cinerea, Fusarium oxysporum f. sp. niveum, Rhizoctonia cerealis, Alternaria alternata, Alternaria brassicae, Corynespora cassiicola, Colletotrichum capsici and Alternaria brassicae var. nigra.

3. A bactericidal composition, characterized in that, Comprising the compound according to claim 1.

4. The bactericidal composition according to claim 3, wherein Further comprising an additional active ingredient, said additional active ingredient including insecticides, fungicides and herbicides.

5. Use of the fungicidal composition according to claim 3 in controlling plant diseases.

6. The application according to claim 5, characterized in that, The diseases are one or more of Pythium aphanidermatum, Gibberella zeae, Botrytis cinerea, Fusarium oxysporum f. sp. niveum, Rhizoctonia cerealis, Alternaria alternata, Alternaria brassicae, Corynespora cassiicola, Colletotrichum capsici and Alternaria brassicae var. nigra.

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