Acrylate compound containing biphenyl structure as well as preparation method and application thereof

Abstract

The invention relates to the technical field of pesticides, in particular to an acrylate compound containing a biphenyl structure as well as a preparation method and application of the acrylate compound. The acrylate compound containing the biphenyl structure is a compound as shown in a formula I, or a stereoisomer, a tautomer, an isotope derivative and a pesticide acceptable salt thereof. The acrylate compound containing the biphenyl structure has excellent inhibitory activity on plant pathogenic fungi, especially basidiomycota, ascomycomycota and deuteromycota pathogenic fungi, and can be used for preventing and treating plant diseases generated by the pathogenic fungi in the fields of agriculture or forestry and the like; the bactericidal composition has very good effect and selectivity on prevention and treatment of wheat powdery mildew, soybean rust, corn rust, peach brown rot, wheat sharp eyespot, rice sheath blight disease or apple ring rot, and has outstanding crop safety on crops.

Description

Technical Field

[0001] This application relates to the field of pesticide technology, specifically to an acrylate compound containing a biphenyl structure, its preparation method, and its uses. Background Technology

[0002] For decades, pesticides have played an indelible role in ensuring human food supply and in protecting human safety (preventing and controlling the spread of diseases) and health (killing pathogens and controlling their emergence), greatly reducing property losses. At the same time, pesticides are also indispensable production materials for ensuring stable agricultural production and increased income, and are extremely important strategic resources.

[0003] Fungicides, as pesticides, have held a pivotal position in the pesticide field since their development. With the advent of the 21st century, developing highly effective, low-toxicity, and environmentally friendly fungicides has become a major focus. However, the emergence of pesticide resistance necessitates scientists continuously creating new types of pesticides to address this problem.

[0004] JP2020079269A1 discloses a general formula compound and a specific compound CK1 as shown below, which contains a biphenyl structure and has certain bactericidal activity.

[0005]

[0006] There is still a need to develop novel agricultural fungicides to prevent and control plant diseases caused by pathogens. Summary of the Invention

[0007] To address the technical problems existing in the prior art, this application provides an acrylate compound containing a biphenyl structure. Bioactivity tests show that this type of compound has excellent inhibitory activity against pathogenic fungi, especially plant pathogenic fungi, and can be used for the prevention and control of pathogens in agriculture, forestry, and health fields.

[0008] In a first aspect, this application provides an acrylate compound containing a biphenyl structure, which is a compound represented by Formula I, or a stereoisomer, tautomer, isotopic derivative thereof, or a pesticide-acceptable salt thereof.

[0009]

[0010] R1 and R4 are each independently selected from halogen, amino, hydroxy, nitro, cyano, mercapto, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted alkylthio, or optionally substituted alkylamine.

[0011] R2 and R3 are each independently selected from substituted alkyl groups;

[0012] R5 and R6 each independently represent H, halogen, amino, hydroxyl, nitro, cyano, mercapto, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted alkylthio, or optionally substituted alkylamine.

[0013] "Optional substitution" means that the substance is not substituted, or is substituted by one or more of the following groups: halogen, amino, hydroxyl, nitro, cyano, and mercapto.

[0014] m is selected from 0, 1, 2, or 3;

[0015] n is selected from 0, 1, 2, 3 or 4.

[0016] In one set of embodiments, the alkyl group is a C1-C8 alkyl group.

[0017] In one set of embodiments, the halogen is selected from fluorine, chlorine, and bromine.

[0018] In one set of embodiments, R5 and R6 each independently represent H, halogen, and C1-C8 alkyl. Preferably, R5 and R6 each independently represent halogen. More preferably, R5 and R6 are both fluorine.

[0019] In one set of implementations, m = 0.

[0020] In one set of embodiments, R1 is selected from halogens, C1-8 alkyl groups, and preferably fluorine, chlorine, bromine, or C1-4 alkyl groups.

[0021] In one set of embodiments, n = 1. Preferably, R1 is located at the para position of the phenyl group.

[0022] In one set of embodiments, R2 and R3 are each independently selected from C1-C8 alkyl groups; preferably, R2 and R3 are each independently selected from C1-C4 alkyl groups; more preferably, R2 is selected from methyl or ethyl, and R3 is selected from methyl or ethyl.

[0023] In one set of embodiments, the compound represented by Formula I is represented by Formula II:

[0024] Preferably, R1 is selected from halogens and C1-8 alkyl groups, and R2 and R3 are each independently selected from C1-C8 alkyl groups; more preferably, R1 is selected from fluorine, chlorine, bromine, and C1-4 alkyl groups, and R2 and R3 are each independently selected from C1-C4 alkyl groups; most preferably, R1 is selected from fluorine, chlorine, bromine, and methyl, R2 is selected from methyl and ethyl groups, and R3 is selected from methyl groups.

[0025] In one set of embodiments, the compound represented by Formula I is one of the following compounds 1-6:

[0026]

[0027] Compound numbering <![CDATA[R1]]> <![CDATA[R2]]> 1 Me Me 2 F Me 3 Cl Me 4 Br Me 5 Me Et 6 F Et

[0028] In a second aspect, this application provides a method for preparing the acrylate compound containing the biphenyl structure described in the first aspect, which is prepared according to the following synthetic route:

[0029]

[0030] The groups R1-R6, m, and n are defined as described in the first aspect.

[0031] Furthermore, the reaction can be carried out under normal or high pressure, preferably under atmospheric pressure, and post-processing can be performed according to conventional methods.

[0032] Furthermore, the solvent is selected from one or more of acetonitrile, dichloromethane, toluene, DMF, DMSO, xylene, 1,2-dichloroethane, tetrahydrofuran, methanol, ethanol, and isopropanol.

[0033] Furthermore, the reaction temperature is -50 to 150°C, preferably -10 to 110°C.

[0034] Furthermore, all four reactions are carried out in the presence of a base, which is selected from one or more of sodium methoxide, potassium methoxide, potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, N,N-dimethylformamide, pyridine, triethylamine, DMAP, DIPEA, or sodium hydride; preferably, the base is selected from sodium methoxide, potassium methoxide, potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, or sodium carbonate.

[0035] In one set of embodiments, the reaction for preparing compound III from formula IV is carried out in the presence of dimethyl sulfate.

[0036] In one set of embodiments, the reaction for preparing compound I from formula III is carried out in the presence of a metal catalyst, preferably in the presence of a palladium catalyst, and more preferably in the presence of palladium dichloride bis(triphenylphosphine).

[0037] In a third aspect, this application also provides a bactericidal composition comprising at least one of the biphenyl-containing acrylate compounds described in the first aspect of this application as an active ingredient; and optionally a pesticide-acceptable carrier and / or adjuvant.

[0038] The bactericidal composition of this application can be applied in the form of a formulation, wherein the acrylate compound containing a biphenyl structure is dissolved or dispersed in a carrier as an active component or formulated into a formulation for easier dispersion when used as a bactericidal composition. The bactericidal composition can be formulated into various liquid formulations, such as soluble powders, dispersible liquids, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, water-in-oil emulsions, and water-dispersible granules.

[0039] The bactericidal composition of this application may contain one or more other insecticides, fungicides, herbicides, plant growth regulators, or fertilizers.

[0040] This application also discloses the use of the acrylate compounds containing biphenyl structures described in the first aspect or the bactericidal compositions described in the third aspect for controlling plant diseases caused by pathogenic fungi; preferably for use in agriculture, forestry, horticulture, and sanitation.

[0041] In one set of embodiments, an effective amount of the biphenyl-containing acrylate compound or the fungicide composition as described above is applied to plants, plant propagation materials or subsequently grown plant organs and cultivation media, cultivation materials or cultivation space; or an effective amount of the biphenyl-containing acrylate compound or the fungicide composition as described above is used to prevent or control pathogenic fungi in wood roots.

[0042] Preferably, an effective amount of the acrylate compound containing a biphenyl structure as described above or the bactericidal composition as described above is applied to the leaves, roots, seeds, or soil.

[0043] In one set of embodiments, the pathogenic fungi include, but are not limited to, Plasmodiophoromycota, Oomycota, Chytridiomycota, Zygomycota, Ascomycota, Basidiomycota, and Deuteromycota; preferably, Basidiomycota, Ascomycota, and Deuteromycota pathogenic fungi.

[0044] In one set of embodiments, the plant disease is preferably powdery mildew, rust, brown rot, sheath blight, or ring spot; more preferably, wheat powdery mildew, soybean rust, corn rust, peach brown rot, wheat sheath blight, rice sheath blight, or apple ring spot.

[0045] The acrylate compounds containing biphenyl structures described in the first aspect of this application or the bactericidal compositions described in the third aspect can be used in conjunction with one or more other insecticides, fungicides, herbicides, plant growth regulators, or fertilizers.

[0046] The beneficial effects of this invention are as follows:

[0047] The acrylate compounds containing biphenyl structures described in this application exhibit excellent inhibitory activity against plant pathogenic fungi, especially common basidiomycetes, ascomycetes, and deuteromycetes. They can be used for the prevention and control of plant diseases caused by pathogenic fungi in agriculture or forestry. In particular, they have good efficacy and selectivity in the prevention and control of wheat powdery mildew, soybean rust, corn rust, peach brown rot, wheat sheath blight, rice sheath blight, or apple ring rot, and have outstanding crop safety. Detailed Implementation

[0048] The alkyl group in the term "alkyloxy", the alkyl group in "alkylthio", the alkyl group in "alkylamine", and the alkyl group refer to a monovalent saturated aliphatic hydrocarbon group, preferably containing 1-20, 1-18, 1-16, 1-12, or 1-10 carbon atoms, more preferably 1-8 carbon atoms (C1-8 alkyl) straight-chain or branched group (the number of carbon atoms is between 1 and 8, specifically 1, 2, 3, 4, 5, 6, 7, or 8), more preferably containing 1-6 carbon atoms (i.e., C1-6 alkyl, the number of carbon atoms is between 1 and 6, specifically 1, 2, 3, 4, 5, or 6). Examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, n-heptyl, n-octyl, etc.

[0049] The term "alkyloxy" refers to an alkyl-O- group, "alkylthio" refers to an alkyl-S- group, and "alkylamine" refers to an alkyl-NH- or dialkyl-N- group. The alkyl group in the dialkyl-N- group can be selected from the same group or from different groups.

[0050] The term "halogen" refers to F, Cl, Br, and I.

[0051] The acrylate compounds containing biphenyl structures described in this application are interpreted as including the compound of Formula I and its stereoisomers, tautomers, isotopic derivatives, or pesticide-acceptable salts thereof. The stereoisomers, tautomers, isotopic derivatives, or pesticide-acceptable salts of the compound are obtained through conventional techniques in the art and exert the same or similar effects in vitro and in vivo through substantially the same mechanism of action as the compound.

[0052] The term "stereoisomer" refers to isomers resulting from different spatial arrangements of atoms in a molecule, including configurational isomers and conformational isomers. Configurational isomers include geometric isomers (or cis-trans isomers) and optical isomers (including enantiomers and diastereomers). Geometric isomers may be present in this compound. Optical isomers refer to substances with identical molecular structures and similar physicochemical properties, but different optical rotations. The compounds of this invention may contain asymmetrically substituted carbon atoms in the R or S configuration, wherein the terms "R" and "S" are as defined in IUPAC 1974 Recommendations for Section E, Fundamental Stereochemistry, Pure Appl. Chem. (1976) 45, 13-10. Compounds with asymmetrically substituted carbon atoms (having equal numbers of R and S configurations) are racemic at those carbon atoms. Having an excess of atoms in one configuration (relative to another) results in a higher quantity of that configuration, preferably an excess of about 85%-90%, more preferably an excess of about 95%-99%, and even more preferably an excess greater than about 99%. Accordingly, the present invention includes racemic mixtures, relative and absolute optical isomers, and mixtures of relative and absolute optical isomers.

[0053] The term "tautomer" refers to structural isomers with different energies that can interconvert through a low energy barrier. If tautomerism is possible (e.g., in solution), chemical equilibrium can be achieved for the tautomers. For example, proton tautomers (also called proton transfer tautomers) involve interconversions via proton migration, such as keto-enol isomerization and imine-enamine isomerization. Valence tautomers involve interconversions via the rearrangement of some bonding electrons.

[0054] The term "isotope derivative" refers to compounds of the present invention that can exist in an isotopically traced or enriched form, containing one or more atoms whose atomic weights or mass numbers differ from the atomic weights or mass numbers of the most abundant atoms found in nature. Isotopes can be radioactive or non-radioactive. Isotopes of atoms such as hydrogen, carbon, phosphorus, sulfur, fluorine, chlorine, bromine, and iodine include, but are not limited to: 2 H, 3 H, 13 C, 14 C, 15 N, 18 O, 32 P, 35 S, 18 F, 36 Cl, 80 Br and 125I. Compounds containing these and / or other isotopes are within the scope of this invention. The isotopically labeled compounds of this invention can be prepared using general methods well known to those skilled in the art.

[0055] The term "pesticide-acceptable salt" refers to a salt obtained by reacting the biphenyl-containing acrylate compound of this application with a chemically acceptable acid. The chemically acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid, or hydrobromic acid) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, or benzoic acid). The pesticide-acceptable salt can also be a salt obtained by reacting the biphenyl-containing acrylate compound of this application with a chemically acceptable base. The chemically acceptable base can be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate) or an organic base (such as trimethylamine, triethylamine, etc.). Further, the pesticide-acceptable salt can be a potassium salt, sodium salt, ammonium salt, calcium salt, pyridine salt, choline salt, hydrochloride salt, phosphate salt, acetate salt, benzenesulfonate salt, or oxalate salt.

[0056] The term "pesticide-acceptable carrier" includes, but is not limited to, surfactants, including ionic and nonionic surfactants. The surfactants include emulsifiers, dispersants, or wetting agents. Specifically, the emulsifiers may be polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amines, and commercially available emulsifiers; the dispersants include sodium lignosulfonate, dispersing agents, calcium lignosulfonate, or methylnaphthalenesulfonate formaldehyde condensate, etc.; the wetting agents include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, or alkylnaphthalenesulfonate, etc. The pesticide-acceptable carrier includes solid carriers and / or liquid carriers. Preferably, the solid carrier includes natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicate, such as talc; magnesium aluminum silicate, such as kaolinite, montmorillonite, and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; and amine salts such as ammonium sulfate and hexamethylenediamine. Preferably, the liquid carrier comprises water and an organic solvent; when water is used as a solvent or diluent, the organic solvent can be used as an auxiliary agent or antifreeze additive. Preferably, the organic solvent includes aromatic hydrocarbons (e.g., benzene, xylene, or toluene), chlorinated hydrocarbons (e.g., chlorobenzene, vinyl chloride, chloroform, or dichloromethane), aliphatic hydrocarbons (e.g., petroleum fractions, cyclohexane, or light mineral oil), alcohol solvents (e.g., isopropanol, butanol, ethylene glycol, glycerol, or cyclohexanol), ether solvents, ester solvents, ketone solvents (e.g., acetone, cyclohexanone, or N-methylpyrrolidone), or dimethylformamide, etc.

[0057] The bactericide composition can be formulated by mixing the active component with a liquid carrier and / or a solid carrier, and by adding surfactants (such as emulsifiers, dispersants, stabilizers, and wetting agents), as well as other additives (such as adhesives, defoamers, and oxidants).

[0058] According to this application, the acrylate compound containing the biphenyl structure can be used together with one or more other insecticides, fungicides, herbicides, plant growth regulators or fertilizers, etc., and the components can be applied simultaneously, sequentially or separately.

[0059] The present invention will be further illustrated below with reference to embodiments; however, these embodiments do not limit the scope of the invention. Unless otherwise stated, all reactants used in the embodiments are commercially available or can be prepared by methods known in the literature or as detailed in the description; the instruments and equipment used in the synthesis experiments and product analysis are all conventional instruments and equipment commonly used in organic synthesis.

[0060] Those skilled in the art will understand that the compounds of this invention can also be synthesized using other synthetic routes. Although the specific raw materials and conditions in the synthetic routes have been described below, they can be readily replaced with other similar raw materials and conditions. Variations or modifications to the preparation methods of this invention, such as various isomers of the compounds, are all included within the scope of this invention. Furthermore, the preparation methods described below can be further modified according to the disclosure of this invention using conventional chemical methods well known to those skilled in the art. For example, appropriate groups may be protected during the reaction process.

[0061] Example 1: Preparation method of compound 1

[0062]

[0063] Weigh 9.3 g (50 mmol) of 2-methyl-5-bromophenol into a 250 ml reaction flask, add 100 ml of acetonitrile and 9.12 g (60 mmol) of methyl bromoacetate into the reaction solution, and add potassium carbonate (13.8 g (100 mmol) in portions into the reaction flask at room temperature. After the addition is complete, transfer the reaction to an oil bath, slowly heat to 70 °C, and maintain the temperature for 2 hours. Monitor the reaction for complete reaction by TLC. Cool to room temperature, filter, and concentrate the filtrate to obtain 11.6 g of oily product, with a yield of 90%. This product can be used directly in the next step without further purification.

[0064] 1 H NMR (400MHz, Chloroform-d) δ2.25(s,3H)3.84(s,3H)4.66(s,2H)6.84(d,1H)7.05(m,2H).

[0065]

[0066] Weigh 10.3 g (40 mmol) of methyl 2-(5-bromo-2-methylphenoxy)acetate and dissolve it in tetrahydrofuran (120 ml, ultra-dry). Add methyl formate (24 g, 24.8 ml, 400 mmol). Under an ice-water bath and nitrogen protection, add sodium methoxide (4.32 g, 80 mmol) in portions. Keep the system temperature below 30°C throughout the reaction. After the addition is complete, slowly raise the temperature to room temperature and continue stirring for 1 h. Monitor the reaction for completeness by TLC. Quench the reaction with sodium bicarbonate aqueous solution, concentrate to remove solvent, extract with ethyl acetate (200 ml × 3), wash with saturated brine, dry with anhydrous sodium sulfate, filter, and concentrate to obtain the product. This product can be used directly in the next step without further purification.

[0067]

[0068] 12.72 g (40 mmol) of methyl 2-(5-bromo-2-methylphenoxy)-3-hydroxy-3-methoxypropionate was weighed and dissolved in DMF (50 ml). Potassium carbonate (8.28 g, 60 mmol) was added at room temperature, followed by the slow addition of dimethyl sulfate (6.05 g, 48 mmol). After the addition was complete, the reaction was allowed to proceed at room temperature for 2 hours. The reaction was monitored by TLC, and the reaction was quenched by adding water (20 ml). The product was extracted with ethyl acetate (200 ml × 3), washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 9.0 g of the product (75% yield).

[0069] 1 H NMR (400MHz, Chloroform-d) δ2.31(s,3H)3.74(s,3H)3.91(s,3H)6.86(d,1H)7.05(m,2H)7.35(s,1H).

[0070]

[0071] 2-(5-bromo-2-methylphenoxy)-3-methoxyacrylate (9.0 g, 30 mmol), (2,2-difluorobenzo[d][1,3]dioxolane-5-yl)boronic acid (7.3 g, 36 mmol), and bis(triphenylphosphine)palladium dichloride (0.42 g, 0.6 mmol, 0.02 eq) were dissolved in a toluene (50 ml) / water (20 ml) mixture. Potassium carbonate (8.28 g, 60 mmol) was added. The reaction mixture was heated to 110 °C and refluxed for 2 h. Liquid chromatography-mass spectrometry was used to monitor the complete reaction of the starting materials. The mixture was cooled to room temperature, extracted with ethyl acetate (200 ml × 3), washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 7.7 g of product, with a yield of 68%.

[0072] 1 H NMR(400MHz,Chloroform-d)δ7.57(d,J=1.7Hz,1H),7.22(m,2H),7.16(d,J=2.1Hz,1H),7.05 (m,1H),6.98(s,1H),6.87(q,J=1.3Hz,1H),3.78(s,3H),3.66(d,J=1.1Hz,3H),2.17(s,3H).

[0073] Example 2: Preparation method of compound 2

[0074]

[0075] Weigh 9.5 g (50 mmol) of 2-fluoro-5-bromophenol into a 250 ml reaction flask, add 100 ml of acetonitrile and 9.12 g (60 mmol) of methyl bromoacetate into the reaction solution, and add potassium carbonate (13.8 g (100 mmol) in portions into the reaction flask at room temperature. After the addition is complete, transfer the reaction to an oil bath, slowly heat to 70 °C, and maintain the temperature for 2 hours. Monitor the reaction for complete reaction by TLC. Cool to room temperature, filter, and concentrate the filtrate to obtain 10.5 g of oily product with a yield of 80%. This product can be used directly in the next step without further purification.

[0076] 1 H NMR (400MHz, Chloroform-d) δ7.27 (d, J - 8.4Hz, 1H), 7.11 (d, J = 8.4Hz, 1H), 6.99 (d, J = 2.1Hz, 1H), 4.73 (s, 2H), 3.85 (s, 3H).

[0077]

[0078] Weigh 10.5 g (40 mmol) of methyl 2-(5-bromo-2-fluorophenoxy)acetate and dissolve it in tetrahydrofuran (120 ml, ultra-dry). Add methyl formate (24 g, 24.8 ml, 400 mmol). Under an ice-water bath and nitrogen protection, add sodium methoxide (4.32 g, 80 mmol) in portions. Keep the system temperature below 30°C throughout the reaction. After the addition is complete, slowly raise the temperature to room temperature and continue stirring for 1 h. Monitor the reaction for completeness by TLC. Quench the reaction with sodium bicarbonate aqueous solution, concentrate to remove solvent, extract with ethyl acetate (200 ml × 3), wash with saturated brine, dry with anhydrous sodium sulfate, filter, and concentrate to obtain the product. This product can be used directly in the next step without further purification.

[0079]

[0080] 12.88 g (40 mmol) of methyl 2-(5-bromo-2-fluorophenoxy)-3-hydroxy-3-methoxypropionate was weighed and dissolved in DMF (50 mL). Potassium carbonate (8.28 g, 60 mmol) was added at room temperature, followed by the slow addition of dimethyl sulfate (6.05 g, 48 mmol). After the addition was complete, the reaction was allowed to proceed at room temperature for 2 hours. The reaction was monitored by TLC, and the reaction was quenched by adding water (20 mL). The product was extracted with ethyl acetate (200 mL × 3), washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give 7.9 g of the product (65% yield).

[0081] 1 H NMR (400MHz, Chloroform-d) δ7.38-7.37(m,1H),7.36(s,2H),7.19-7.17(m,1H),3.88(3H,s),3.72(3H,s).

[0082]

[0083] 2-(5-bromo-2-fluorophenoxy)-3-methoxymethyl acrylate (9.12 g, 30 mmol), (2,2-difluorobenzo[d][1,3]dioxolane-5-yl)boronic acid (7.3 g, 36 mmol), and bis(triphenylphosphine)-palladium dichloride (0.42 g, 0.6 mmol, 0.02 eq) were dissolved in a toluene (50 ml) / water (20 ml) mixture. Potassium carbonate (8.28 g, 60 mmol) was added. The reaction mixture was heated to 110 °C and refluxed for 2 h. Liquid chromatography-mass spectrometry was used to monitor the complete reaction of the starting materials. The mixture was cooled to room temperature, extracted with ethyl acetate (200 ml × 3), washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain 6.2 g of the product, with a yield of 54%.

[0084] 1 H NMR(500MHz,Chloroform-d)δ7.55(d,J=1.8Hz,1H),7.34(m,1H),7.26(m,3H),7 .06(d,J=7.8Hz,1H), 6.77(q,J=1.2Hz,1H), 3.84(s,3H), 3.65(d,J=1.1Hz,3H).

[0085] Compounds 3 to 6 were synthesized using the methods described above. The specific compound structures and 1H NMR spectral data are shown in Table 1.

[0086]

[0087] Table 1. Structures and 1H NMR spectral data of specific compounds.

[0088]

[0089] Example of activity test (wheat powdery mildew Erysiphe graminis)

[0090] Weigh out a certain mass of samples 1 to 6 of compounds and the control compound, dissolve them in acetone, and prepare a stock solution for later use. During the experiment, prepare a series of concentration gradient solutions of the compound samples and the control compound with 0.1% Tween 80 water for activity screening.

[0091] When the first leaf of the wheat seedlings was fully unfolded, wheat seedlings with uniform growth were selected as experimental host plants for wheat powdery mildew. A bioassay spray tower was used, spraying 30 ml of the solution per treatment and allowing it to air dry. After 24 hours, the seedlings were inoculated with the pathogen, with a blank control included. Mature wheat powdery mildew spores were gently shaken off and evenly inoculated onto the wheat seedlings, which were then cultured in a greenhouse. After 7–10 days, the disease incidence was assessed based on the results from the blank control. Results were analyzed according to "A Manual of Assessment Keys for Plant Diseases" compiled by the American Plant Pathology Association, using a scale of 100 to 0, with "100" representing no disease and "0" representing the most severe disease severity.

[0092] The structure of the control compound CK1 is as follows:

[0093] The test results are shown in Table 2.

[0094] Table 2. Control efficacy of the compound of this application against wheat powdery mildew.

[0095] Compound numbering Concentration (ppm) Protection level 1 1.56 100 2 1.56 80 3 1.56 90 4 1.56 85 5 1.56 80 6 1.56 85 CK1 1.56 75

[0096] Based on the above bioactivity test results, the acrylate compounds containing biphenyl structures described in this application have highly efficient antibacterial activity, especially at low concentrations, which can inhibit wheat powdery mildew fungus and can be used for the prevention and control of plant diseases, especially wheat powdery mildew.

[0097] Furthermore, various embodiments of the present invention can be combined arbitrarily, as long as they do not violate the spirit of the present invention, and should also be considered as part of the content disclosed in the present invention. The above-described embodiments only illustrate one implementation of this application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application.

Claims

1. An acrylate compound containing a biphenyl structure, characterized in that, It is a compound represented by Formula I, or its stereoisomers, tautomers, isotopic derivatives, and pesticide-acceptable salts; R1 and R4 are each independently selected from halogen, amino, hydroxy, nitro, cyano, mercapto, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted alkylthio, or optionally substituted alkylamine. R2 and R3 are each independently selected from substituted alkyl groups; R5 and R6 each independently represent H, halogen, amino, hydroxyl, nitro, cyano, mercapto, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted alkylthio, or optionally substituted alkylamine. "Optional substitution" means that it is not substituted, or is substituted by one or more of the following groups: halogen, amino, hydroxyl, nitro, cyano, and mercapto. m is selected from 0, 1, 2, or 3; n is selected from 0, 1, 2, 3 or 4.

2. The compound according to claim 1, characterized in that, R5 and R6 each independently represent H, halogen, and C1-C8 alkyl; preferably, R5 and R6 each independently represent halogen; more preferably, R5 and R6 are both fluorine.

3. The compound according to any one of claims 1-2, characterized in that, m＝0。 4. The compound according to any one of claims 1-3, characterized in that, R1 is selected from halogens, C1-8 alkyl groups, and preferably fluorine, chlorine, bromine, or C1-4 alkyl groups.

5. The compound according to any one of claims 1-4, characterized in that, n＝1。 6. The compound according to any one of claims 1-5, characterized in that, R2 and R3 are each independently selected from C1-C8 alkyl groups; preferably, R2 and R3 are each independently selected from C1-C4 alkyl groups; more preferably, R2 is selected from methyl or ethyl, and R3 is selected from methyl or ethyl.

7. The compound according to any one of claims 1, 4, and 6, characterized in that, The compound represented by Formula I is the same as that represented by Formula II:

8. The compound according to claim 7, characterized in that, The compound represented by Formula I is one of the following compounds 1-6: 。 9. The method for preparing the compound according to any one of claims 1-8, characterized in that, The following synthetic route was followed: The groups R1-R6, m, and n are defined as described in any one of claims 1-8.

10. A bactericidal composition, characterized in that, The active ingredient comprises at least one of the acrylate compounds with a biphenyl structure as described in any one of claims 1-8, and optionally a pesticide-acceptable carrier and / or adjuvant.

11. The use of the acrylate compound containing a biphenyl structure according to any one of claims 1-8 or the bactericidal composition according to claim 10, characterized in that, Used to control plant diseases caused by pathogenic fungi.

12. The use according to claim 11, characterized in that, Apply an effective amount of the acrylate compound containing a biphenyl structure as described in any one of claims 1-8 or the fungicidal composition as described in claim 10 to plants, plant propagation materials or subsequently grown plant organs and cultivation media, cultivation materials or cultivation space; or to prevent or control pathogenic fungi in the roots of wood.

13. The use according to claim 11, characterized in that, Apply an effective amount of the acrylate compound containing a biphenyl structure as described in any one of claims 1-8 or the fungicide composition as described in claim 10 to the leaves, roots, seeds, or soil.

14. The use according to any one of claims 11-13, characterized in that, The pathogenic fungi are selected from the phyla Plasmodiophoromycota, Oomycota, Chytridiomycota, Zygomycota, Ascomycota, Basidiomycota, and Deuteromycota; preferably, they are pathogenic fungi from the phyla Basidiomycota, Ascomycota, and Deuteromycota.

15. The use according to any one of claims 11-14, characterized in that, The plant diseases mentioned are powdery mildew, rust, brown rot, sheath blight, or ring spot; preferably, wheat powdery mildew, soybean rust, corn rust, peach brown rot, wheat sheath blight, rice sheath blight, or apple ring spot.

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