2-cyano-3-amino-3-substituted phenyl acrylate compound and application thereof in prevention and treatment of fungal diseases of crops

Abstract

The invention discloses a 2-cyano-3-amino-3-substituted phenyl acrylate compound and application of the 2-cyano-3-amino-3-substituted phenyl acrylate compound in prevention and treatment of fungal diseases of crops, and belongs to the field of pesticides. The structural formula of the 2-cyano-3-amino-3-substituted phenyl acrylate compound is shown as a formula (I), and the compound has good broad-spectrum bactericidal activity; the compound can be used for preventing and treating plant fungal diseases, especially plant fungal diseases caused by fungi such as pyrethrospora, chlorosclerotium, fusarium, acrocyst, colletotrichum, cercospora, verticillium, black beetle, alternaria, bipolaris, rhizoctonia, bipolaris, botrytis, puccinia, coracosporium and corynespora, and can be used for preventing and treating plant fungal diseases caused by fungi such as pyrethrospora, chlorosclerotium, fusarium, acrocyst, colletotrichum, colletotrichum, colletotrichum, verticillium, black beetle, alternaria. Therefore, the compound can be used for preparing bactericides in the fields of agriculture, horticulture, industry and the like, and has the advantages of broad spectrum, high efficiency, low toxicity, environment friendliness and the like.

Description

Technical Field

[0001] This invention belongs to the field of pesticides, specifically relating to a 2-cyano-3-amino-3-substituted phenyl acrylate compound and its application in the control of fungal diseases in crops. Background Technology

[0002] Acrylic ester compounds have found some application in the pharmaceutical and pesticide fields due to their good biological activity and ecological safety. For example, the 2-cyanoacrylate fungicide cyazofamid can effectively control diseases such as wheat scab and rice bakanae disease. However, cyazofamid is currently the only commercially available cyanoacrylate fungicide, with a very narrow spectrum of activity. It is ineffective against major fungal diseases that severely damage agriculture, such as anthracnose, rice blast, rice false smut, and gray mold, seriously hindering the large-scale application of this type of fungicide in agricultural disease control and significantly impacting its economic value. Research and development of acrylate fungicides has progressed slowly in recent years, with major advancements limited to improving the control efficacy of cyazofamid against wheat scab; there are no reports of expanding its control spectrum. Expanding the control spectrum of acrylate fungicides and enhancing their application value is currently a hot topic in the development of this type of pesticide.

[0003] Patent document CN1160318C discloses a class of 2-cyano-3-substituted phenyl acrylate compounds represented by the following general formula (A), which are effective against a variety of diseases caused by Fusarium wilt, such as wheat scab.

[0004]

[0005] Patent document CN101381326A discloses a class of 2-cyano-3-(substituted)amino-3-phenylacrylate compounds as shown in the following general formula (B), which have a control effect on Fusarium.

[0006]

[0007] Patent document CN109879834A discloses a class of 3-amino-2-cyano-3-amino-3-substituted phenyl acrylate compounds as shown in the following general formula (C), which are Mannich base fungicides with good control effects against Fusarium.

[0008]

[0009] Patent document CN109879841B discloses a class of (Z)-3-imino-1-propenol compounds represented by the following general formula (D). These compounds have a control effect on wheat scab, which causes plant diseases, and can reduce the production of wheat scab toxin (DON).

[0010]

[0011] Patent document CN109867623A discloses a class of 3-pyridyl-3-amino-2-cyanoacrylate compounds as shown in the following general formula (E), which have a preventive effect against wheat scab.

[0012]

[0013] Patent document CN 114790152 A discloses a class of 2-cyanoacrylate compounds as shown in the following general formula (F), which have a control effect on Fusarium fungi.

[0014]

[0015] Patent document CN 119431188 A discloses a class of 2-cyano-3-disubstituted phenyl acrylate compounds represented by the following general formula (G), which are effective against a variety of diseases caused by *Rhizoctonia solani*, *Fusarium*, *Ophiocorium*, *Anthracis*, *Cercospora*, *Verticillium*, and *Ophiocorium*.

[0016] . Summary of the Invention

[0017] The first technical problem to be solved by the present invention is to provide a 2-cyano-3-amino-3-substituted phenyl acrylate compound to solve the problems of narrow spectrum and poor bactericidal effect of existing acrylate bactericides.

[0018] The second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned 2-cyano-3-amino-3-substituted phenyl acrylate compounds.

[0019] The third technical problem to be solved by the present invention is to provide the application of the above-mentioned 2-cyano-3-amino-3-substituted phenyl acrylate compounds in the prevention and control of fungal diseases in crops.

[0020] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0021] This invention discloses a 2-cyano-3-amino-3-substituted phenyl acrylate compound, the structural formula of which is shown in Formula I: ;

[0022] R1 and R2 are independently selected from H, substituted or unsubstituted sulfonate groups or carboxylic acid ester groups;

[0023] Wherein, R1 and R2 are not both H;

[0024] Wherein, the substituents are independently selected from C1–C1. 10 Alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C8 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

[0025] As a preferred embodiment, the 2-cyano-3-amino-3-substituted phenyl acrylate compound is preferably at least one of the following structural formulas (II) to (V): ;

[0026] Among them, R3, R4, R5, and R6 are independently selected from C1–C 10 Alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C8 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

[0027] In some embodiments, the substituents are independently selected from C1–C8 alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C4 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

[0028] In some embodiments, the groups of R1 and R2 include the following two cases:

[0029] Case ①: R2 is H;

[0030] R1 is a sulfonate group or a carboxylic ester group;

[0031] Wherein, the sulfonate group and the carboxylic acid ester group are optionally substituted by one or more substituents, wherein the substituents are independently selected from C1–C8 alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C4 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl;

[0032] Case ②: R1 is H;

[0033] R2 is a sulfonate group or a carboxylic ester group;

[0034] The sulfonate group and carboxylic acid ester group are optionally substituted by one or more substituents, which are independently selected from C1–C8 alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C4 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

[0035] In some embodiments, the groups of R1 and R2 include the following two cases:

[0036] Case ①: R2 is H;

[0037] R1 is a sulfonate group or a carboxylic ester group;

[0038] Wherein, the sulfonate group and carboxylate group are optionally substituted by one or more substituents, wherein the substituents are independently selected from C1–C8 alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C4 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl, or halogenated 6 to 10 aryl; preferably, the substituents are independently selected from C1–C8 alkyl, C3–C4 cycloalkyl, C1–C8 haloalkyl, C1–C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl, or halogenated 6 to 10 aryl; more preferably, the substituents are independently selected from C1–C8 alkyl, C3–C4 cycloalkyl, C1–C3 haloalkyl, C1– C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl;

[0039] The 2-cyano-3-amino-3-substituted phenyl acrylate compounds of general formula (I) of the present invention, when R2 is hydrogen, have the following structural formula (I-1):

[0040] Table 1 lists typical compounds represented by structural formula (I-1), but the typical compounds listed in Table 1 do not limit the scope of the present invention.

[0041] Table 1

[0042]

[0043] Case ②: R1 is H;

[0044] R2 is a sulfonate group or a carboxylic ester group;

[0045] Wherein, the sulfonate group and carboxylate group are optionally substituted by one or more substituents, wherein the substituents are independently selected from C1–C8 alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C4 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl, or halogenated 6 to 10 aryl; preferably, the substituents are independently selected from C1–C8 alkyl, C3–C4 cycloalkyl, C1–C8 haloalkyl, C1–C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl, or halogenated 6 to 10 aryl; more preferably, the substituents are independently selected from C1–C8 alkyl, C3–C4 cycloalkyl, C1–C3 haloalkyl, C1– C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

[0046] The 2-cyano-3-amino-3-substituted phenyl acrylate compounds represented by general formula (I) of this invention, when R1 is hydrogen, have the following structural formulas (I-2):

[0047] Table 2 lists typical compounds represented by structural formula (I-2), but the typical compounds described in Table 2 do not limit the scope of the present invention.

[0048] Table 2

[0049]

[0050] In some embodiments, the 2-cyano-3-disubstituted phenyl acrylate compound has any one of the following structures: .

[0051] Most preferably, it is selected from compound 2, compound 5, compound 6, compound 7, compound 8, compound 9, compound 10, compound 13, compound 24, compound 25, compound 27 and compound 30.

[0052] Tables 3-1 to 3-4 below show the NMR data of some compounds in Tables 1 and 2. The compound numbers in Tables 3-1 to 3-4 correspond to those in Tables 1 and 2; that is, compound No. 2 in Table 3 is the same as compound No. 2 in Table 1. In Tables 3-1 to 3-4, s represents a singlet, d represents a doublet, dd represents a doublet, t represents a triplet, td represents a triplet-doublet, q represents a quartet, and m represents a multiplet.

[0053] Tables 3-1 to 3-4 NMR data of compounds

[0054] Table 3-1

[0055]

[0056] Table 3-2

[0057]

[0058] Table 3-3

[0059]

[0060] Table 3-4

[0061]

[0062] This invention further discloses a method for preparing the above-mentioned 2-cyano-3-amino-3-substituted phenyl acrylate compounds, comprising the following two methods:

[0063] Method 1: The preparation method of the 2-cyano-3-amino-3-substituted phenyl acrylate compound includes the following steps: 4-hydroxybenzonitrile a-1 undergoes a first alcoholysis reaction with anhydrous ethanol solution of hydrogen chloride to obtain intermediate b-1; intermediate b-1 undergoes a first condensation reaction with ethyl cyanoacetate under the action of a first base to obtain intermediate c-1; intermediate c-1 undergoes a first substitution reaction with a substituted compound under the action of a second base and a first catalyst to obtain 2-cyano-3-amino-3-substituted phenyl acrylate compound I-1;

[0064]

[0065] R1 is a sulfonate group or a carboxylic ester group;

[0066] Wherein, the sulfonate group and carboxylate group are optionally substituted by one or more substituents, wherein the substituents are independently selected from C1–C8 alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C4 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl, or halogenated 6 to 10 aryl; preferably, the substituents are independently selected from C1–C8 alkyl, C3–C4 cycloalkyl, C1–C8 haloalkyl, C1–C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl, or halogenated 6 to 10 aryl; more preferably, the substituents are independently selected from C1–C8 alkyl, C3–C4 cycloalkyl, C1–C3 haloalkyl, C1– C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

[0067] In some embodiments, the molar ratio of 4-hydroxybenzonitrile a-1 to anhydrous ethanol solution of hydrogen chloride is 1:5~20, preferably 1:8~15, and more preferably 1:10; the first alcoholysis reaction is carried out at a temperature of -10~25℃ for 24~96 h; the first base is an organic or inorganic base; the organic base is triethylamine, pyridine, 1,8-diazabicyclo-bicyclo(5,4,0)-7-undecene, diisopropylaminolithium, or N,N-diisopropylethylamine; the inorganic base is sodium carbonate, potassium carbonate, or sodium hydroxide; the molar ratio of intermediate b-1 to ethyl cyanoacetate and the first base is 1:1~5:1~10, preferably 1:1~2:1~5, and more preferably 1:1.1:1.2; the first condensation reaction is carried out at a temperature of 70~150℃ for 5~24 h; the second base is an organic or inorganic base; the organic base is... The reagents are triethylamine, lithium diisopropylaminodimethylamine, or N,N-diisopropylethylamine; the inorganic base is cesium carbonate, potassium carbonate, potassium phosphate, or sodium hydroxide; the first catalyst is DMAP, TATU, TBTU, or COMU; the molar ratio of intermediate c-1 to the substituted compound, the second base, and the first catalyst is 1:1~10:1~10:0.05~5, preferably 1:1~5:1~5:0.05~2, more preferably 1:1~2:1~2:0.1~2, and even more preferably 1:2:2:2; the first substitution reaction is carried out at a temperature of 10~50℃ for 6~24 h.

[0068] In some embodiments, preferably, the molar ratio of 4-hydroxybenzonitrile a-1 to anhydrous ethanol solution of hydrogen chloride is 1:10; the first alcoholysis reaction is carried out at a temperature of -5 to 5°C for 24 to 36 h; the first base is an organic base; the organic base is triethylamine; the molar ratio of intermediate b-1 to ethyl cyanoacetate and the first base is 1:1.1:1.2; the first condensation reaction is carried out at a temperature of 70 to 100°C for 6 to 12 h; the second base is an organic base; the organic base is DIEA; the first catalyst is TATU; the molar ratio of intermediate c-1 to the substituted compound, the second base, and the first catalyst is 1:2:2:2; the first substitution reaction is carried out at a temperature of 10 to 50°C for 10 h.

[0069] The solvent used in the first alcoholysis reaction is any one or a combination of several of the following: anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide, and anhydrous dimethyl sulfoxide, preferably anhydrous 1,2-dichloroethane. The amount of solvent used is sufficient to dissolve the materials in the reaction system and achieve a suitable viscosity.

[0070] The solvent used in the first condensation reaction is any one or a combination of several of the following: anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide, and anhydrous dimethyl sulfoxide, preferably anhydrous ethanol. The amount of solvent used is sufficient to dissolve the materials in the reaction system and achieve a suitable viscosity.

[0071] The solvent used in the first substitution reaction is any one or a combination of several of anhydrous dichloromethane, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide, and anhydrous dimethyl sulfoxide, preferably anhydrous dichloromethane. The amount of solvent used is sufficient to dissolve the materials in the reaction system and achieve a suitable viscosity.

[0072] Method 2: The preparation method of the 2-cyano-3-amino-3-substituted phenyl acrylate compounds includes the following steps: benzonitrile compound a-2 undergoes a second alcoholysis reaction with anhydrous ethanol solution of hydrogen chloride to obtain intermediate b-2; intermediate b-2 undergoes a second condensation reaction with ethyl cyanoacetate under the action of a third base to obtain intermediate c-2; intermediate c-2 undergoes a second substitution reaction with a substituted compound under the action of a fourth base and a second catalyst to obtain 2-cyano-3-amino-3-substituted phenyl acrylate compound I-2;

[0073]

[0074] Where X = -Br, -I;

[0075] R2 is a sulfonate group or a carboxylic ester group;

[0076] Wherein, the sulfonate group and carboxylate group are optionally substituted by one or more substituents, wherein the substituents are independently selected from C1–C8 alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C4 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl, or halogenated 6 to 10 aryl; preferably, the substituents are independently selected from C1–C8 alkyl, C3–C4 cycloalkyl, C1–C8 haloalkyl, C1–C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl, or halogenated 6 to 10 aryl; more preferably, the substituents are independently selected from C1–C8 alkyl, C3–C4 cycloalkyl, C1–C3 haloalkyl, C1– C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

[0077] In some embodiments, the molar ratio of the benzonitrile compound a-2 to the anhydrous ethanol solution of hydrogen chloride is 1:5~20, preferably 1:8~15, and more preferably 1:10; the second alcoholysis reaction is carried out at a temperature of -10~25℃ for 24~96 h; the third base is an organic or inorganic base; the organic base is triethylamine, pyridine, 1,8-diazabicyclo-bicyclo(5,4,0)-7-undecene, diisopropylaminolithium, or N,N-diisopropylethylamine; the inorganic base is sodium carbonate, potassium carbonate, or sodium hydroxide; the molar ratio of the intermediate b-2 to ethyl cyanoacetate and the third base is 1:1~5:1~10, preferably 1:1~2:1~5, and more preferably 1:1.1:1.2; the second condensation reaction is carried out at a temperature of 70~150℃ for 5~24 h. h; the fourth base is an organic or inorganic base; the organic base is triethylamine, lithium diisopropylamino, or N,N-diisopropylethylamine; the inorganic base is cesium carbonate, potassium carbonate, potassium phosphate, or sodium hydroxide; the second catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the second catalyst is 1:1~10, preferably 1:1~5, more preferably 1:2; the molar ratio of intermediate c-2 to the substituted compound, the fourth base, and the second catalyst is 1:1~10:1~10:1~20, preferably 1:1~5:1~5:1~10, more preferably 1:1~2:1~2:1~5, and even more preferably 1:2:2:3; the second substitution reaction is carried out at a temperature of 100~180℃ for 6~24 h.

[0078] In some embodiments, preferably, the molar ratio of the benzonitrile compound a-2 to the anhydrous ethanol solution of hydrogen chloride is 1:10; the second alcoholysis reaction is carried out at a temperature of -5 to 5°C for 24 to 36 h; the third base is an organic base; the organic base is triethylamine; the molar ratio of intermediate b-2 to ethyl cyanoacetate and the third base is 1:1.1:1.2; the second condensation reaction is carried out at a temperature of 70 to 100°C for 6 to 12 h; the fourth base is an inorganic base; the inorganic base is cesium carbonate; the second catalyst is L-proline and cuprous iodide; the molar ratio of L-proline to cuprous iodide in the second catalyst is 1:2; the molar ratio of intermediate c-2 to the substituted compound, the fourth base, and the second catalyst is 1:2:2:3; the second substitution reaction is carried out at a temperature of 100 to 140°C for 24 h.

[0079] The solvent used in the second alcoholysis reaction is any one or a combination of several of the following: anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide, and anhydrous dimethyl sulfoxide, preferably anhydrous 1,2-dichloroethane. The amount of solvent used is sufficient to dissolve the materials in the reaction system and achieve a suitable viscosity.

[0080] The solvent used in the second condensation reaction is any one or a combination of several of the following: anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide, and anhydrous dimethyl sulfoxide, preferably anhydrous ethanol. The amount of solvent used is sufficient to dissolve the materials in the reaction system and achieve a suitable viscosity.

[0081] The solvent used in the second substitution reaction is any one or a combination of several of the following: anhydrous ethanol, anhydrous toluene, anhydrous 1,2-dichloroethane, anhydrous acetonitrile, anhydrous acetone, anhydrous tetrahydrofuran, anhydrous dioxane, anhydrous N,N-dimethylformamide, and anhydrous dimethyl sulfoxide, preferably anhydrous dimethyl sulfoxide. The amount of solvent used is sufficient to dissolve the materials in the reaction system and achieve a suitable viscosity.

[0082] Furthermore, the present invention discloses a pesticide formulation containing 0.001%-99.99% by weight of the above-mentioned 2-cyano-3-amino-3-substituted phenyl acrylate compound.

[0083] Specifically, the pesticide formulation contains an agriculturally acceptable carrier and / or excipient.

[0084] The carrier can be liquid or solid; the liquid carrier can be water or an organic solvent. When water is used as a solvent or diluent, the organic solvent can also be used as an auxiliary agent or antifreeze additive. The organic solvent includes aromatic hydrocarbons, such as benzene, toluene, xylene, etc.; aliphatic hydrocarbons, such as cyclohexane, petroleum fractions, light mineral oil; chlorinated hydrocarbons, such as chlorobenzene, chloroform, vinyl chloride, dichloromethane, etc.; ketones, such as cyclohexanone, acetone, dimethylformamide, and N-methylpyrrolidone, or their ethers and esters; alcohols, such as isopropanol, ethylene glycol, butanol, glycerol, or cyclohexanol; the solid carrier includes natural or synthetic clays and silicates, such as diatomaceous earth and natural silica; magnesium aluminum silicate, such as kaolin, kaolinite, montmorillonite, and mica; magnesium silicate, such as talc; limestone; calcium carbonate, white carbon black, light calcium carbonate; sodium sulfate; calcium sulfate; amine salts such as hexamethylethylenediamine and ammonium sulfate.

[0085] The carrier can also be a surfactant, which is an ionic or nonionic emulsifier, dispersant, or wetting agent; the nonionic emulsifier is a polyoxyethylene fatty alcohol ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty amine, or a commercially available emulsifier, including: Agricultural Emulsion 100#, Agricultural Emulsion 500#, Agricultural Emulsion 600#, Agricultural Emulsion 600-2#, Agricultural Emulsion 2201B, Agricultural Emulsion NP-10, Ningru 36#, Agricultural Emulsion 0203B, Agricultural Emulsion 1601, Agricultural Emulsion OX-667, Agricultural Emulsion 2201, Agricultural Emulsion NP-15, Agricultural Emulsion 507#, Agricultural Emulsion OX-635, Agricultural Emulsion OX-622, and Agricultural Emulsion OX-653; the dispersant is a methylnaphthalene sulfonate formaldehyde condensate, sodium lignosulfonate, calcium lignosulfonate, or a separating agent; the wetting agent is sodium alkylnaphthalene sulfonate, sodium lauryl sulfate, or sodium dodecylbenzene sulfonate.

[0086] Specifically, the pesticide formulation is any one of the following: suspension concentrate, dispersible oil suspension concentrate, dispersible liquid concentrate, suspension seed coating agent, tablet, microemulsion, aqueous solution, emulsion, emulsifiable concentrate, water suspension concentrate, powder, wettable powder, soluble powder, soluble liquid, granules, soluble granules, water-dispersible granules, capsules, microcapsules, microcapsule suspension concentrate, or nano-formulation.

[0087] The application of the above-mentioned pesticide formulations in the prevention and control of fungal diseases in crops is also within the scope of protection of this invention.

[0088] Specifically, the crop fungal diseases are caused by any one or more of the genera *Pyrrosia*, *Rhizoctonia*, *Fusarium*, *Ophiocorium*, *Anthracnose*, *Cercospora*, *Verticillium*, *Heliophyta*, *Alternaria*, *Heliophyta*, *Heliophyta*, *Heliophyta*, *Botrytis*, *Russula*, *Rhizoctonia*, *Rhizoctonia*, *Heliophyta*, *Botrytis*, *Russula*, *Rhizoctonia*, *Rhizoctonia*, *Heliophyta*, *Botrytis*, *Rhizoctonia*, *Rhizoctonia*, *Rhizoctonia*, or *Russula*. Most preferably, they are caused by any one or more of the genera *Pyrrosia*, *Alternaria*, *Rhizoctonia*, *Heliophyta*, *Botrytis*, *Rhizoctonia*, or *Russula*.

[0089] And / or, the disease mentioned is any one or more of the following: rice blast, rice false smut, wheat scab, rice bakanae disease, banana wilt, wheat stem base rot, wheat take-all disease, strawberry anthracnose, apple anthracnose, grape anthracnose, osmanthus anthracnose, citrus anthracnose, rubber tree anthracnose, corn anthracnose, soybean anthracnose, onion anthracnose, pepper anthracnose, wolfberry anthracnose, mango anthracnose, camellia anthracnose, yam anthracnose, peanut brown spot, cotton verticillium wilt, apple tree rot, tomato early blight, summer leaf spot, wheat sheath blight, corn large leaf spot, gray mold, and cucumber target spot, preferably any one or more of the following: rice blast, tomato early blight, wheat sheath blight, corn large leaf spot, gray mold, soybean rust, corn rust, wheat stripe rust, wheat leaf rust, or cucumber target spot.

[0090] In some embodiments, the application rate of the 2-cyano-3-amino-3-substituted phenyl acrylate compound is 1-1000 g per hectare.

[0091] Beneficial effects:

[0092] (1) The present invention provides a novel acrylate compound that exhibits good bactericidal activity and has a significant inhibitory effect on a variety of pathogens, including Pyrrosia spp., Rhizoctonia spp., Fusarium spp., Capillaria spp., Anthrax spp., Cercospora spp., Verticillium spp., Corynebacterium spp., Alternaria spp., Helicobacter spp., Rhizoctonia spp., Helicobacter spp., Botrytis spp., Styloides spp., and Corynebacterium spp.

[0093] (2) Compared with Chinese Patent CN 119431188 A, the novel compounds provided by this invention not only maintain good inhibitory activity against Rhizoctonia solani, Fusarium, Rhizoctonia solani, Anthrax, Cercospora, Verticillium and Cordyceps, but also extend to Rhizoctonia solani, Alternaria, Rhizoctonia solani, Helicobacter convexum, Botrytis, Styloides and Cordyceps, showing broad-spectrum antibacterial properties. Therefore, this invention broadens the antibacterial spectrum of acrylate compounds and can be used in the preparation of bactericides in agriculture, horticulture and industry, with the advantages of broad spectrum, high efficiency, low toxicity and environmental friendliness. Detailed Implementation

[0095] The present invention will be further described in detail below with reference to embodiments and data, but the invention is not limited to these specific embodiments. Those skilled in the art should recognize that the present invention covers all alternatives, improvements, and equivalents that may be included within the scope of the claims. In the present invention, unless otherwise specified, all parts and percentages are in units of weight, and the equipment and raw materials used are commercially available or commonly used in the art. Unless otherwise specified, the methods in the following embodiments are conventional methods in the art.

[0096] (I) Compound Preparation

[0097] 1. The synthesis of No.1

[0098]

[0099] Compound a-1-1 (10.00 mmol, 2.00 g) was weighed and placed in a 50 mL round-bottom flask. Anhydrous ethanol-hydrogen chloride solution (100.0 mmol, 8.50 g, 8.00 mol / L) and 10 mL of anhydrous 1,2-dichloroethane were added at 2 °C. The mixture was stirred at 2 °C for 30 h to carry out alcoholysis. After the reaction, the reaction solution was concentrated and dried under vacuum to obtain intermediate b-1-1, which was used directly in the next reaction without purification. Intermediate b-1-1 (10.00 mmol, 2.40 g) was weighed and placed in a three-necked flask. 20 mL of anhydrous ethanol was added to dissolve it. The mixture was placed at 0 °C, and triethylamine (Et3N, 12.00 mmol, 1.20 g) was slowly added dropwise, controlling the reaction temperature to not exceed 5 °C. The mixture was stirred for 30 min. Subsequently, the temperature was slowly raised to 80 °C and refluxed. Ethyl cyanoacetate (11.00 mmol, 1.24 g) was slowly added dropwise. After the addition of g), the mixture was refluxed to carry out the condensation reaction. The reaction degree was observed every 2 h until the reaction was complete. The reaction time was 8 h. After the reaction, the reaction solution was concentrated and separated by column chromatography to obtain intermediate c-1-1. Intermediate c-1-1 (1.00 mmol, 0.31 g), acetic acid (2.00 mmol, 0.12 g), TATU (2.00 mmol, 0.64 g) and DIEA (2.00 mmol, 0.26 g) were weighed and placed in a 25 mL round-bottom flask. Then 5 mL of anhydrous DCM was added, and the substitution reaction was carried out at 25 °C for 10 h. The reaction was monitored by TLC. After the reaction, the reaction solution was concentrated and separated by column chromatography (DCM) to obtain product I-1-1, which was designated as No.1.

[0100] 2. The preparation methods for compounds No. 2 to No. 38 (i.e., the compounds recorded in Table 1) are the same as those in "1. Synthesis of No. 1" in Example 1. The preparation methods for compounds No. 2, No. 3, No. 4, No. 5, and No. 6 are as follows:

[0101] Synthesis of compound No.2: The preparation method is the same as that of "1 and No.1" in Example 1, except that acetic acid is replaced with 2-pyridinecarboxylic acid, that is, product I-1-2 is prepared, which is denoted as No.2.

[0102] Synthesis of Compound No. 3: The preparation method is the same as that in Example 1, "Synthesis of No. 1", except that acetic acid is replaced with 3-(difluoromethyl)-1-methyl-1-methyl. H -Pyrazole-4-carboxylic acid, i.e., product I-1-3, is prepared and designated as No.3.

[0103] Synthesis of compound No.4: The preparation method is the same as that in “Synthesis of No.1” in Example 1, except that acetic acid is replaced with pimelic acid, that is, product I-1-4 is prepared, which is denoted as No.4.

[0104] Synthesis of compound No.5: The preparation method is the same as that of "1. Synthesis of No.1" in Example 1, except that acetic acid is replaced with 2,4,6-trichlorophenoxyacetic acid, that is, product I-1-5 is prepared, which is denoted as No.5.

[0105] Synthesis of compound No.6: The preparation method is the same as that of "Synthesis of No.1" in Example 1, except that acetic acid is replaced with 3-indolebutyric acid, thus obtaining product I-1-6, denoted as No.6.

[0106] Example 2

[0107] 1. Synthesis of No. 39

[0108]

[0109] Compound a-2-39 (10.00 mmol, 2.00 g) was weighed and placed in a 50 mL round-bottom flask. Anhydrous ethanol-hydrogen chloride solution (100.0 mmol, 8.50 g, 8.00 mol / L) and 10 mL of anhydrous 1,2-dichloroethane were added at 2 °C. The mixture was stirred at 2 °C for 30 h to carry out alcoholysis. After the reaction was completed, the reaction solution was concentrated and dried under vacuum to obtain intermediate b-2-39, which was used directly in the next reaction without purification. Intermediate b-2-39 (10.00 mmol, 2.40 g) was weighed and placed in a three-necked flask. 20 mL of anhydrous ethanol was added to dissolve it. The mixture was placed at 0 °C, and triethylamine (Et3N, 12.00 mmol, 1.20 g) was slowly added dropwise, controlling the reaction temperature not to exceed 5 °C. The mixture was stirred for 30 min. Subsequently, the temperature was slowly raised to 80 °C and refluxed, and ethyl cyanoacetate (11.00 mmol, 1.24 g) was slowly added dropwise. After the addition of g), the mixture was refluxed to carry out the condensation reaction. The reaction degree was observed every 2 h until the reaction was complete. The reaction time was 8 h. After the reaction, the reaction solution was concentrated and separated by column chromatography to obtain intermediate c-2-39. Intermediate c-2-39 (1.00 mmol, 0.31 g), acetic acid (2.00 mmol, 0.12 g), TATU (2.00 mmol, 0.64 g), and DIEA (2.00 mmol, 0.26 g) were weighed and placed in a 25 mL round-bottom flask. Then, 5 mL of anhydrous DCM was added, and the substitution reaction was carried out at 25 °C for 10 h. The reaction was monitored by TLC. After the reaction, the reaction solution was concentrated and separated by column chromatography (DCM) to obtain product I-2-39, which was designated as No. 39.

[0110] 2. The preparation methods of compounds No. 40 to No. 72 (i.e., the compounds recorded in Table 2) are the same as those in "2. Synthesis of No. 39" in Example 1, and the preparation method of compound No. 63 is as follows;

[0111] Synthesis of compound No. 63: The preparation method is the same as that of "1. Synthesis of No. 39" in Example 2, except that acetic acid is replaced with ethyl sulfonic acid, that is, product I-2-63 is prepared, which is denoted as No. 63.

[0112] (II) Formulation Preparation

[0113] Examples 3 to 8 below provide practical examples of the preparation of several bactericide formulations using the compound (I) of the present invention as the active ingredient. It should be noted that the present invention is not limited to the scope of the following examples. In these formulation examples, all "%" refers to weight percentage.

[0114] Example 3 Suspension Formulation

[0115] The suspending agent is obtained by uniformly mixing 25% of compound (I), 5% of lignin sulfonate, 1% of lauryl alcohol polyoxyethylene ether (JFC), 30% of diatomaceous earth and 39% of light calcium carbonate, and then pulverizing it.

[0116] Example 4 Wettable Powder Formulation

[0117] Mix 20% of compound (I), 5% of lignin sulfonate, 1% of lauryl alcohol polyoxyethylene ether (JFC), 36% of diatomaceous earth and 10% of light calcium carbonate evenly, and pulverize to obtain a wettable powder.

[0118] Example 5: Emulsifiable Concentrate Formulation

[0119] The emulsifiable concentrate is prepared by heating and stirring 15% of compound (I), 5% of agricultural emulsion No. 500 (calcium salt), 5% of agricultural emulsion No. 602, 5% of N-methyl-2-pyrrolidone, and 70% of xylene until homogeneous.

[0120] Example 6: Formulation of water-dispersible granules

[0121] 30% of compound (I), 4% of naphthalene sulfonate formaldehyde condensate, 1% naphthalene sulfonate, 2% silica, and 63% kaolin are mixed and pulverized. Water is then added and kneaded, followed by granulation in a granulator equipped with a sieve of a specific size. The granules are then dried and sieved (according to the sieve size) to obtain the final granular product.

[0122] Example 7 Granule Formulation

[0123] Mix 10% of compound (I), 1% of polyvinyl alcohol (PVA), 4% of sodium naphthalene sulfonate formaldehyde condensate (NMO) and 85% of clay evenly, crush them, then add 20 parts of water to this 100 parts mixture, knead, and use an extruder to make 14-32 mesh granules, dry them, and you will get the granules.

[0124] Example 8: Water Suspension Formulation

[0125] 30% of compound (I), 1% of fatty alcohol polyoxyethylene ether, 3% of rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, 1% of magnesium aluminum silicate, 0.4% of organosilicon defoamer, 5% of propylene glycol and deionized water (59.5%) are premixed evenly, then added to a sand mill for sand milling, filtered to obtain a suspension mother liquor, and then added to a prepared xanthan gum (0.1%) aqueous solution and sheared and mixed evenly.

[0126] (III) Activity Test

[0127] Examples of bioactivity assays using compounds of the present invention are given below. It should be noted that the present invention is not limited to the examples described below.

[0128] Example 9 Activity Assay

[0129] Experiments on the inhibition of pathogenic fungal hyphal growth by compounds

[0130] (1) PDA plates containing an equal volume of DMSO were used as the solvent control, and cyazofamid at an equal concentration was used as the control agent. The test pathogens were inoculated onto PDA plates and cultured in a 25°C biochemical incubator to the logarithmic phase. Using a punch, 5 mm diameter bacterial discs were made at the edge of fresh colonies and inoculated onto PDA plates containing a certain concentration of the test drug. At the same time, bacterial blocks were inoculated onto PDA medium without the test drug and containing cyazofamid as controls. The plates were cultured in the dark in a 25°C biochemical incubator until the control without the test drug nearly covered the plate. The colony diameter was measured using the cross-sectional method (subtracting the diameter of the 5 mm bacterial disc).

[0131] Mycelial growth inhibition rate (MGIR) was calculated using the following formula: MGIR% = [(CN) / C] × 100%, where C is the colony diameter of the control group and N is the colony diameter of the treatment group. Each treatment was replicated three times, and the experiment was repeated twice.

[0132] (2) The experimental pathogens were rice blast fungus, rice false smut fungus, wheat scab fungus (Fusarium graminearum), rice seedling blight fungus, banana wilt fungus (Fusarium oxysporum), wheat stem base rot fungus (Fusarium pseudograminearum), wheat take-all fungus, strawberry anthracnose fungus, apple anthracnose fungus, grape anthracnose fungus, osmanthus anthracnose fungus, citrus anthracnose fungus, rubber anthracnose fungus, corn anthracnose fungus, soybean anthracnose fungus, onion anthracnose fungus, pepper anthracnose fungus, wolfberry anthracnose fungus, mango anthracnose fungus, camellia anthracnose fungus, apple anthracnose fungus, peanut brown spot fungus, cotton verticillium wilt fungus, apple tree rot fungus, tomato early blight fungus, Kentucky blue summer spot blight fungus, wheat sheath blight, corn large leaf spot fungus, gray mold fungus, and cucumber target spot fungus. Except for the pesticides used for rice blast fungus and wheat scab, which were tested at a concentration of 1 μg / mL, the pesticides used for other pathogens were tested at a concentration of 10 μg / mL. "μg / mL" refers to micrograms of active ingredient per milliliter. Cyazofamid was used as a control pesticide.

[0133] (3) Evaluation results of mycelial growth inhibition activity showed that the series of compounds prepared in this invention (see Tables 1-2) exhibited broad-spectrum and highly effective mycelial growth inhibition characteristics. As shown in Tables 4-1 to 7, they all showed good inhibitory activity against the mycelial growth of various pathogenic fungi, including *Pyrrosia*, *Rhizoctonia*, *Fusarium*, *Helicobacter*, *Anthracis*, *Cercospora*, *Verticillium*, *Helicobacter*, *Alternaria*, *Gastropoda*, *Rhizoctonia*, *Helicobacter*, *Botrytis*, and *Corynebacterium*. In contrast, cyazofamid, used as a control, showed no significant inhibitory effect on the mycelial growth of the above pathogens. This stark contrast confirms that the compounds of this invention have successfully overcome the limitations of existing agents and significantly broadened the control spectrum of acrylate fungicides.

[0134] Table 4-1

[0135]

[0136] Table 4-2

[0137]

[0138] Table 5

[0139]

[0140] Table 6

[0141]

[0142] Table 7

[0143]

[0144] Tests on the inhibition of rust by compounds

[0145] (1) Indoor toxicity determination was performed using the detached leaf segment method. The test agent and 6-benzylaminopurine (60 mg / L) were added to a 0.6% water agar culture dish, and a concentration of 10 mg / L was set. The medium containing 6-benzylaminopurine without the agent was used as a blank control. A urediniospore suspension (300 urediniospores / μL) was prepared using Novec 7100 electronic fluoride solution. 1 μL was taken and inoculated onto wheat leaves. After incubation under suitable conditions for 7 days, leaf segments of 4 cm inoculation site were cut and placed on the water agar with the back of the leaf pressed against the blank control and water agar with different agent contents. Five leaf segments were placed in each dish. The dish was placed in an artificial climate chamber with 16 ℃ light for 16 h and 13 ℃ darkness for 8 h. After 10 days, the size of the uredinia of rust fungus on the leaf surface was measured and the inhibition rate was calculated.

[0146] Inhibition rate = (Length of uredinia of control rust on leaf surface - Length of uredinia of treated rust on leaf surface) / Length of uredinia of control rust on leaf surface × 100%;

[0147] (2) The test pathogens were soybean rust, corn rust, wheat stripe rust and wheat leaf rust. The test concentration of the agent used was 10 mg / L. “mg / L” refers to milligrams of active ingredient per liter. A control agent of equal concentration of cyazofamid was used.

[0148] (3) The results of the inhibitory activity evaluation show that the series of compounds prepared in this invention (see Tables 1-2) exhibit broad-spectrum and highly efficient inhibitory properties against mycelial growth. As shown in Tables 8-1 and 8-2, they all showed good inhibitory activity against the growth of *Stemona* species, while the control compound, cyazofamid, had no significant inhibitory effect on the above pathogens. This stark contrast confirms that the compounds of this invention have successfully overcome the limitations of existing agents and significantly broadened the control spectrum of acrylate fungicides.

[0149] Table 8-1

[0150]

[0151] Table 8-2

[0152]

[0153] Example 10: Indoor activity determination of 25% Compound No. 4 suspension against soybean rust.

[0154] In this embodiment, all percentages in the suspending agent formulation are by mass percentage. The preparation method is the same as in Example 3: Weigh 25% of Compound No. 4 (prepared in Example 1), 2% of TERSPERSE 2500, 3% of TERSPERSE 2425, 0.25% of xanthan gum, 2.95% of silica, 4.5% of ethylene glycol, 0.3% of benzoic acid, and 0.5% of silicone defoamer (trade name: S-29, produced by Nanjing Sixin Applied Chemicals Co., Ltd.), and add deionized water to 100% by mass. According to the above formulation ratio, using water as the medium, add the active ingredient, dispersant, suspending agent, and antifreeze to the mixing tank and mix evenly. Disperse the mixture for 35 minutes using a ball mill or high-speed shear mill, and then grind it using a sand mill to prepare the final product.

[0155] The soybean used in the experiment was Liaoning Soybean 15. Seedlings were selected when they reached the two true leaf stage for testing. The pesticide was evenly sprayed onto the leaves using a throat sprayer, with each treatment repeated three times. After spraying, the plants were allowed to air dry indoors. 24 hours after spraying, 2*10... 5 Soybean rust spores at a concentration of 1 spore / mL were inoculated onto the plant leaves. After inoculation, an investigation was conducted after the control group had fully developed disease. The incidence of soybean rust was investigated, and the control efficacy was calculated using the formula below.

[0156] ;

[0157] .

[0158] The survey was conducted using the following grading method:

[0159] Level 0: No disease;

[0160] Grade 1: The area of ​​lesions accounts for less than 5% of the total leaf area;

[0161] Grade 3: Lesions cover 6% to 25% of the entire leaf area;

[0162] Level 5: Lesions cover 26% to 50% of the entire leaf area;

[0163] Level 7: Lesions cover 51% to 75% of the entire leaf area;

[0164] Level 9: The lesion area accounts for more than 75% of the total leaf area.

[0165] Table 9. Indoor activity assay (protective activity) of 25% compound No. 4 suspension against soybean rust.

[0166]

[0167] The results in Table 9 show that, in the indoor activity test, 25% cyazofamid suspension had no inhibitory effect on soybean rust, while 25% compound No.4 suspension showed certain protective activity against soybean rust, with a control efficacy of over 95% at doses of 10 mg / L and above. Its activity was comparable to that of the control agent prothioconazole. However, due to its different mechanism of action, this compound can be used in combination with prothioconazole to delay the development of drug resistance in soybean rust.

[0168] Example 11: Indoor activity determination of 25% Compound No. 4 suspension against wheat stripe rust.

[0169] In this embodiment, all percentages in the suspending agent formulation are by mass percentage. The preparation method is the same as in Example 3: Weigh 25% of Compound No. 4 (prepared in Example 1), 2% of TERSPERSE 2500, 3% of TERSPERSE 2425, 0.25% of xanthan gum, 2.95% of silica, 4.5% of ethylene glycol, 0.3% of benzoic acid, and 0.5% of silicone defoamer (trade name: S-29, produced by Nanjing Sixin Applied Chemicals Co., Ltd.), and add deionized water to 100% by mass. According to the above formulation ratio, using water as the medium, add the active ingredient, dispersant, suspending agent, and antifreeze to the mixing tank and mix evenly. Disperse the mixture for 35 minutes using a ball mill or high-speed shear mill, and then grind it using a sand mill to prepare the final product.

[0170] The tested wheat variety was Mingxian 169. Wheat plants at the "two-leaf-one-heart-leaf" stage with similar growth were marked on the upper part of their second leaf and coated with different concentrations of the aforementioned pesticide solution, with six replicates for each concentration. Twenty-four hours after application, the treated areas were inoculated with rust spores of *Striga styracifolium* using the powdering method. The wheat was first cultured in darkness for 24 hours, then at 15°C, with a 16-hour photoperiod and 90% relative humidity. After 12-15 days, the incidence of wheat stripe rust was investigated, and the control efficacy was calculated using the formula below.

[0171] ;

[0172] .

[0173] The survey was conducted using the following grading method:

[0174] Level 0: No disease;

[0175] Grade 1: The area of ​​lesions accounts for less than 5% of the total leaf area;

[0176] Grade 3: Lesions cover 6% to 25% of the entire leaf area;

[0177] Level 5: Lesions cover 26% to 50% of the entire leaf area;

[0178] Level 7: Lesions cover 51% to 75% of the entire leaf area;

[0179] Level 9: The lesion area accounts for more than 75% of the total leaf area.

[0180] Table 10. Indoor activity determination (protective activity) of 25% compound No. 4 suspension against wheat stripe rust.

[0181]

[0182] The results in Table 10 show that, in the indoor activity test, 25% cyazofamid suspension had no inhibitory effect on wheat stripe rust, while 25% compound No.4 suspension showed good protective activity against wheat stripe rust, with a control efficacy of 100% at doses of 25 mg / L and above. Its activity was higher than that of the control agent prothioconazole. At the same time, due to its different mechanism of action, this compound can be used in combination with prothioconazole to delay the development of resistance in wheat stripe rust.

[0183] Example 12: Field efficacy trial of 25% Compound No. 4 suspension for controlling rice blast.

[0184] In this embodiment, all percentages in the suspending agent formulation are by mass percentage. The preparation method is the same as in Example 3: Weigh 25% of Compound No. 4 (prepared in Example 1), 2% of TERSPERSE 2500, 3% of TERSPERSE 2425, 0.25% of xanthan gum, 2.95% of silica, 4.5% of ethylene glycol, 0.3% of benzoic acid, and 0.5% of silicone defoamer (trade name: S-29, produced by Nanjing Sixin Applied Chemicals Co., Ltd.), and add deionized water to 100% by mass. According to the above formulation ratio, using water as the medium, add the active ingredient, dispersant, suspending agent, and antifreeze to the mixing tank and mix evenly. Disperse the mixture for 35 minutes using a ball mill or high-speed shear mill, and then grind it using a sand mill to prepare the final product.

[0185] The tested rice variety was Taihu Nuo 2, which is susceptible to rice blast. Before application of the pesticide, the rice was growing well, and the main type of rice blast in the field was level 2 neck blast. Field management practices were consistent across all experimental plots. A second application was given 7 days after the first, for a total of two applications. Twenty-five days after the second application, the incidence of rice blast was investigated according to the "GB / T 15790-2009 Rice Blast Monitoring and Survey Specification," and the control efficacy was calculated using the following formula.

[0186] ;

[0187] .

[0188] The results in Table 11 show that, in the field, 25% cyazofamid suspension had almost no control effect on rice blast, while the compound of this invention showed excellent control effect on rice blast, comparable to the efficacy of the commercially available fungicide tricyclazole. However, tricyclazole only inhibits the infection process of *Pyroxburghii*, i.e., it only has a preventive effect, and its inhibitory effect on mycelial growth is very poor, i.e., it has no curative effect. The compound of this invention not only has a preventive effect, but also has a good inhibitory effect on mycelial growth, i.e., it also has a certain curative effect.

[0189] Table 11 Field efficacy of 25% compound No. 4 suspension against rice blast.

[0190]

[0191] Example 13: Field efficacy trial of 25% Compound No. 4 suspension for controlling strawberry root rot.

[0192] In this embodiment, all percentages in the suspending agent formulation are by mass percentage. The preparation method is the same as in Example 3: Weigh 25% of Compound No. 4 (prepared in Example 1), 2% of TERSPERSE 2500, 3% of TERSPERSE 2425, 0.25% of xanthan gum, 2.95% of silica, 4.5% of ethylene glycol, 0.3% of benzoic acid, and 0.5% of silicone defoamer (trade name: S-29, produced by Nanjing Sixin Applied Chemicals Co., Ltd.), and add deionized water to 100% by mass. According to the above formulation ratio, using water as the medium, add the active ingredient, dispersant, suspending agent, and antifreeze to the mixing tank and mix evenly. Disperse the mixture for 35 minutes using a ball mill or high-speed shear mill, and then grind it using a sand mill to prepare the final product.

[0193] The strawberry variety used in the experiment was "Hongyan," which is susceptible to root rot. Field planting and management practices were consistent across all experimental plots. The first application was a root drench with water at transplanting, 150 ml per plant. After the seedlings had established themselves, two more applications of 100 ml per plant were given, for a total of three applications. Thirty days after the third application, the incidence of strawberry anthracnose was assessed, and the control efficacy was calculated using the formula below.

[0194] .

[0195] The survey was conducted using the following grading method:

[0196] Grade 0: Healthy roots, no symptoms in the above-ground parts.

[0197] Grade 1: Slight browning of the roots and slight loss of green color in the above-ground leaves.

[0198] Grade 2: Root browning area ≤50%, aboveground parts slightly wilted.

[0199] Grade 3: Root browning area > 50%, aboveground parts severely wilted.

[0200] Level 4: Plant dead.

[0201] The results in Table 12 show that, in the field, the compounds of this invention have excellent control effects against strawberry anthracnose.

[0202] Table 12 Field efficacy of 25% Compound No. 4 suspension against strawberry root rot

[0203]

[0204] The strawberry seedlings used were purchased from plug seedlings, and it was uncertain whether they were free of pathogens. Both seedlings appeared healthy at the time of transplanting.

[0205] The main pathogens causing strawberry root rot include anthracnose fungi and Fusarium, and No. 4 exhibits significant inhibitory activity against both mycelial growth and spore germination. Field experiments showed that, 30 days after transplanting, 25% cyazofamid suspension was ineffective against strawberry root rot fungi. Except for the water control, the survival rate of strawberry seedlings treated with the other agents was above 90%. The tested agent, 25% No. 4 SC, showed some control efficacy against strawberry leaf anthracnose and transplanting-related seedling death, comparable to commonly used agents. However, current agents are ternary compound formulations, which have already developed resistance. The compound reported in this patent has a novel mechanism of action and exhibits resistance to these agents. Furthermore, no adverse effects on strawberries were observed during the experiments, indicating its safety for strawberries.

[0206] This invention provides a 2-cyano-3-amino-3-substituted phenyl acrylate compound and its application in the control of fungal diseases in crops, along with a method. Many methods and approaches exist for implementing this technical solution; the above description is merely a preferred embodiment of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention. All components not explicitly stated in this embodiment can be implemented using existing technologies.

Claims

1. A 2-cyano-3-amino-3-substituted phenyl acrylate compound, characterized in that, The structural formula of the 2-cyano-3-amino-3-substituted phenyl acrylate compounds is shown in Formula I: R1 and R2 are independently selected from H, substituted or unsubstituted sulfonate groups or carboxylic acid ester groups; Wherein, R1 and R2 are not both H; Wherein, the substituents are independently selected from C1 – C1. 10 Alkyl, C3–C8 cycloalkyl, C1–C8 haloalkyl, C1–C8 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

2. The 2-cyano-3-amino-3-substituted phenyl acrylate compound according to claim 1, characterized in that, The substituents are independently selected from C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C1-C4 alkylamino, 5- to 14-membered heteroaryl, halogenated 5- to 14-membered heteroaryl, 6- to 10-membered aryl or halogenated 6- to 10-membered aryl.

3. The 2-cyano-3-amino-3-substituted phenyl acrylate compound according to claim 1, characterized in that, The groups of R1 and R2 include the following two cases: Case ①: R2 is H; R1 is a sulfonate group or a carboxylic ester group; Wherein, the sulfonate group and the carboxylic acid ester group are optionally substituted by one or more substituents, wherein the substituents are independently selected from C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C1-C4 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl; Case ②: R1 is H; R2 is a sulfonate group or a carboxylic ester group; The sulfonate group and carboxylic acid ester group are optionally substituted by one or more substituents, which are independently selected from C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C1-C4 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

4. The 2-cyano-3-amino-3-substituted phenyl acrylate compound according to claim 1, characterized in that, The groups of R1 and R2 include the following two cases: Case ①: R2 is H; R1 is a sulfonate group or a carboxylic ester group; Wherein, the sulfonate group and carboxylate group are optionally substituted by one or more substituents, wherein the substituents are independently selected from C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C1-C4 alkylamino, 5- to 14-membered heteroaryl, halogenated 5- to 14-membered heteroaryl, 6- to 10-membered aryl, or halogenated 6- to 10-membered aryl; preferably, the substituents are independently selected from C1-C8 alkyl, C3-C4 cycloalkyl, C1-C8 haloalkyl, C1-C2 alkylamino, 5- to 14-membered heteroaryl, halogenated 5- to 14-membered heteroaryl, 6- to 10-membered aryl, or halogenated 6- to 10-membered aryl; more preferably, the substituents are independently selected from C1-C8 alkyl, C3-C4 cycloalkyl, C1-C3 haloalkyl, C1- C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl; Case ②: R1 is H; R2 is a sulfonate group or a carboxylic ester group; Wherein, the sulfonate group and carboxylate group are optionally substituted by one or more substituents, wherein the substituents are independently selected from C1-C8 alkyl, C3-C8 cycloalkyl, C1-C8 haloalkyl, C1-C4 alkylamino, 5- to 14-membered heteroaryl, halogenated 5- to 14-membered heteroaryl, 6- to 10-membered aryl, or halogenated 6- to 10-membered aryl; preferably, the substituents are independently selected from C1-C8 alkyl, C3-C4 cycloalkyl, C1-C8 haloalkyl, C1-C2 alkylamino, 5- to 14-membered heteroaryl, halogenated 5- to 14-membered heteroaryl, 6- to 10-membered aryl, or halogenated 6- to 10-membered aryl; more preferably, the substituents are independently selected from C1-C8 alkyl, C3-C4 cycloalkyl, C1-C3 haloalkyl, C1- C2 alkylamino, 5 to 14 heteroaryl, halogenated 5 to 14 heteroaryl, 6 to 10 aryl or halogenated 6 to 10 aryl.

5. The 2-cyano-3-amino-3-substituted phenyl acrylate compound according to claim 1, characterized in that, The 2-cyano-3-amino-3-substituted phenyl acrylate compounds are selected from at least one of the following structural formulas: 。 6. A pesticide formulation, characterized in that, The pesticide formulation contains 0.001%-99.99% by weight of the 2-cyano-3-amino-3-substituted phenyl acrylate compound as described in claim 1.

7. The pesticide formulation according to claim 6, characterized in that, The pesticide formulation is any one of the following: suspension concentrate, dispersible oil suspension concentrate, dispersible liquid concentrate, suspension seed coating agent, tablet, microemulsion, aqueous solution, emulsion, emulsifiable concentrate, water suspension concentrate, powder, wettable powder, soluble powder, soluble liquid, granules, soluble granules, water-dispersible granules, capsules, microcapsules, microcapsule suspension concentrate, or nano-formulation.

8. The use of the 2-cyano-3-amino-3-substituted phenyl acrylate compound according to any one of claims 1 to 5 or the pesticide formulation according to claim 6 in the control of fungal diseases of crops.

9. The application according to claim 8, characterized in that, The crop fungal diseases mentioned are caused by any one or more of the genera *Pyrrosia*, *Rhizoctonia*, *Fusarium*, *Cercospora*, *Verticillium*, *Heliophyta*, *Alternaria*, *Heliophyta*, *Heliophyta*, *Botrytis*, *Stenocystis*, *Russula*, *Rhizoctonia*, *Heliophyta*, *Botrytis*, *Russula*, *Rhizoctonia*, *Rhizoctonia*, *Heliophyta*, *Botrytis*, *Rhizoctonia*, *Rhizoctonia*, *Rhizoctonia*, *Rhizoctonia*, *Botrytis*, *Rhizoctonia*, or *Rhizoctonia*. The most preferred are diseases caused by any one or more of the genera *Pyrrosia*, *Alternaria*, *Cercospora*, *Verticillium*, *Heliophyta*, *Heliophyta*, *Alternaria*, *Heliophyta*, *Botrytis*, *Rhizoctonia*, or *Rhizoctonia*. And / or, The diseases mentioned are any one or more of the following: rice blast, rice false smut, wheat scab, rice bakanae disease, banana wilt, wheat stem base rot, wheat take-all disease, strawberry anthracnose, apple anthracnose, grape anthracnose, osmanthus anthracnose, citrus anthracnose, rubber tree anthracnose, corn anthracnose, soybean anthracnose, onion anthracnose, pepper anthracnose, wolfberry anthracnose, mango anthracnose, camellia anthracnose, yam anthracnose, peanut brown spot, cotton verticillium wilt, apple tree rot, tomato early blight, summer leaf spot, wheat sheath blight, corn large leaf spot, gray mold, or cucumber target spot disease. Preferably, they are any one or more of the following: rice blast, tomato early blight, wheat sheath blight, corn large leaf spot, gray mold, soybean rust, corn rust, wheat stripe rust, wheat leaf rust, or cucumber target spot disease.

10. The application according to claim 8, characterized in that, The application rate of 2-cyano-3-amino-3-substituted phenyl acrylate compounds is 1-1000 g per hectare.

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