A 2-cyanoacrylate compound salt, its preparation method and application

Abstract

This invention provides a 2-cyanoacrylate compound salt, its preparation method, and its application. The general formula of the 2-cyanoacrylate compound salt is shown in Formula (I). Compared with ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate, the 2-cyanoacrylate compound salt of Formula (I) provided by this invention has significantly improved water solubility and still maintains high fungicidal activity against wheat scab.

Description

Technical Field

[0001] This invention belongs to the field of bactericides, specifically relating to a 2-cyanoacrylate compound salt, its preparation method, and its application. Background Technology

[0002] 2-Cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]ethyl acrylate (code name ZJS178) is a cyanoacrylate compound that has protective and curative effects against diseases caused by Fusarium. Its chemical structural formula is as follows:

[0003]

[0004] Chinese patent CN202110105207.5 discloses that ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate exhibits high inhibitory activity against the mycelial growth of Fusarium graminearum, and its activity is superior to that of the control agent cyazofamid at the same concentration. Chinese patents CN202210813382.4, CN202210792944.1, and CN202210805610.3 disclose compositions of ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate with pyrrole, triazole, and succinate dehydrogenase inhibitor fungicides, respectively, demonstrating a synergistic effect after combination, which not only improves fungicidal activity but also delays the development of drug resistance in pathogens.

[0005] However, the existing technology shows that ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate has extremely low solubility in water, which not only affects its efficacy in the field but also limits its application in areas such as the development of water-soluble formulations. Therefore, improving its solubility is of paramount importance. Summary of the Invention

[0006] Purpose of the invention: To address the shortcomings of existing technologies, this invention provides a 2-cyanoacrylate compound salt that can improve water solubility and has high bactericidal activity, as well as a method for its preparation.

[0007] This invention also provides the application of 2-cyanoacrylate compound salts in the prevention and control of fungal diseases.

[0008] Technical solution: To achieve the above objective, the present invention provides a 2-cyanoacrylate compound salt, the general formula of which is shown in formula (I):

[0009]

[0010] in:

[0011] n is selected from any value between 0 and 3;

[0012] X is independently selected from hydroiodic acid, hydrobromic acid, hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, sulfurous acid, carbonic acid, citric acid, malic acid, lactic acid, boric acid, C1-C 20 Alkyl carboxylic acids, C1-C 20 Any one of alkyl sulfonic acids and acids with structures shown in X1 to X2.

[0013]

[0014] in:

[0015] R is independently selected from hydrogen, C1-C 20 Alkyl, halogenated C1-C 20 Alkyl, C3-C 20 cycloalkyl, halogenated C3-C 20 cycloalkyl, C1-C 20 Alkoxy, halogenated C1-C 20 Alkoxy, C1-C 20 Alkylthio, Halogenated C1-C 20 Alkyl thio, halogen, nitro, cyano, hydroxy, or mercapto.

[0016] m is selected from integers from 0 to 5.

[0017] Preferably, n is selected from any value from 0 to 2.

[0018] Preferably, n is selected from any value between 0.2 and 1.

[0019] Preferably, X is independently selected from hydroiodic acid, hydrobromic acid, hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, sulfurous acid, carbonic acid, citric acid, malic acid, lactic acid, boric acid, C1-C 10 Alkyl carboxylic acids, C1-C 10 Alkyl sulfonic acid, or any one of the acids with the structures shown in X1 to X2.

[0020] Preferably, X is independently selected from any one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, sulfurous acid, carbonic acid, citric acid, malic acid, lactic acid, boric acid, C1-C6 alkylcarboxylic acid, C1-C6 alkylsulfonic acid, and acids with structures shown in X1 to X2.

[0021] Preferably, X is independently selected from any one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, sulfurous acid, carbonic acid, citric acid, malic acid, lactic acid, boric acid, C1-C3 alkyl carboxylic acid, C1-C3 alkyl sulfonic acid, and acids with structures shown in X1 to X2.

[0022] More preferably, X is independently selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, carbonic acid, citric acid, malic acid, lactic acid, formic acid, acetic acid, propionic acid, methanesulfonic acid, benzoic acid, and p-toluenesulfonic acid.

[0023] Preferably, the substituent R is independently selected from hydrogen, C1-C64 ... 10 Alkyl, halogenated C1-C 10 Alkyl, C3-C 10 cycloalkyl, halogenated C3-C 10 cycloalkyl, C1-C 10 Alkoxy, halogenated C1-C 10 Alkoxy, C1-C 10 Alkylthio, Halogenated C1-C 10 Alkyl thio, halogen, nitro, cyano, hydroxy, or mercapto.

[0024] Preferably, the substituent R is independently selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkyl, halogenated C3-C6 cycloalkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio, halogenated C1-C6 alkylthio, halogen, nitro, cyano, hydroxyl or mercapto.

[0025] Preferably, the substituent R is independently selected from hydrogen, C1-C3 alkyl, halogenated C1-C3 alkyl, C1-C3 alkoxy, halogenated C1-C3 alkoxy, C1-C3 alkylthio, halogenated C1-C3 alkylthio, halogen, nitro, cyano, hydroxyl or mercapto.

[0026] Preferably, m is selected from integers from 0 to 4.

[0027] Preferably, m is selected from integers from 0 to 3.

[0028] More preferably, m is selected from integers from 0 to 2.

[0029] The preparation method of the 2-cyanoacrylate compound salt of the present invention is as follows: It is prepared by reacting ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate and an acid in a solvent at a certain temperature. The reaction equation is as follows:

[0030]

[0031] The definitions of substituents X and n are as described above.

[0032] The solvent is selected from water, toluene, dichloromethane, dichloroethane, chloroform, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, methyltetrahydrofuran, 1,3-dioxane, 1,4-dioxane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, acetonitrile, propionitrile, methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, methanol, ethanol, isopropyl... The following is a list of alcohols, benzyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0033] Preferably, the solvent is selected from at least one of toluene, dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, acetonitrile, ethyl acetate, methanol, ethanol, isopropanol, acetone, N,N-dimethylformamide, and dimethyl sulfoxide.

[0034] Further, the molar ratio of the ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate to the acid is 1:0.1 to 10.

[0035] Preferably, the molar ratio of ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate to acid is 1:0.1-5; the reaction temperature of ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate with acid is -20 to 100°C, and the reaction time is 0.1 to 10 hours.

[0036] Preferably, ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate reacts with acid at a temperature of 0–100°C for a reaction time of 0.1–5 hours.

[0037] The present invention provides 2-cyanoacrylate ester compound salts represented by general formula (I). Table 1 lists relevant typical compounds, but the typical compounds in Table 1 do not limit the scope of the present invention.

[0038] Table 1

[0039]

[0040]

[0041] Compound 9 is one of X1, and compound 4 is one of X2.

[0042] The application of the 2-cyanoacrylate compound salts described in this invention in the prevention and control of fungal diseases.

[0043] The application of the 2-cyanoacrylate compound salt prepared by the method described in this invention in the prevention and control of fungal diseases.

[0044] The present invention relates to the application of 2-cyanoacrylate compound salts in the prevention and control of fungal diseases. The application process is as follows: applying 2-cyanoacrylate compound salts to the pathogens that need to be controlled or their growth medium.

[0045] Furthermore, the application of the 2-cyanoacrylate compound salts represented by general formula (I) in the prevention and control of fungal diseases, wherein the 2-cyanoacrylate compound salts are used to prevent and control diseases caused by any one or more fungi selected from the genera Fusarium, Erythromyces bryony, Erythromyces spp., Pterygium, Phytophthora, Alternaria, Cladosporium, Leptotrichum, Atopicula, Ustilago maydis, Ustilago maydis, Aspergillus, Diplosporium, Botrytis, Rhizoctonia, and Xanthomonas.

[0046] The application of the 2-cyanoacrylate compound salt represented by the general formula (I) in the prevention and control of fungal diseases, wherein the 2-cyanoacrylate compound salt is used to prevent and control any one of the following diseases: Fusarium head blight, rice blast, gray mold, anthracnose, bakanae disease, downy mildew and powdery mildew.

[0047] As a preferred application, the 2-cyanoacrylate compound salts represented by general formula (I) are used in the prevention and control of wheat scab.

[0048] The application of the 2-cyanoacrylate compound salt of the present invention in the preparation of pesticide formulations for controlling the above-mentioned fungal diseases, wherein the pesticide formulation contains 0.001%-99.99% by weight of the 2-cyanoacrylate compound salt represented by general formula (I).

[0049] Furthermore, when the pesticide formulation is used for sterilization, the application rate of the 2-cyanoacrylate compound salt in the pesticide formulation is 10 to 1000 grams per hectare.

[0050] Furthermore, the pesticide formulation can be formulated into emulsifiable concentrates, suspension concentrates, aqueous suspensions, microemulsions, (aqueous) emulsions, powders, wettable powders, soluble powders, (water-dispersible) granules, or capsules, etc.

[0051] The pesticide formulation provided by the present invention, in addition to containing 0.001%-99.99% by weight of 2-cyanoacrylate compound salts represented by general formula (I), may further contain an agriculturally acceptable carrier.

[0052] Furthermore, the carrier can be solid or liquid. Suitable solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as kaolinite, montmorillonite, and mica; white carbon black, calcium carbonate, and light calcium carbonate; calcium sulfate; limestone; sodium sulfate; and amine salts such as ammonium sulfate and hexamethylethylenediamine. Liquid carriers include water and organic solvents, which can also be used as auxiliaries or antifreeze additives when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, and toluene; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, and dichloromethane; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, and light mineral oils; alcohols such as isopropanol, butanol, ethylene glycol, glycerol, and cyclohexanol; their ethers and esters; and ketones such as acetone, cyclohexanone, dimethylformamide, and N-methylpyrrolidone.

[0053] Alternatively, the carrier can also be a surfactant. Suitable surfactants can be emulsifiers, dispersants, or wetting agents; they can be ionic or nonionic. Examples of nonionic emulsifiers include polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amines, and commercially available emulsifiers such as Agricultural Emulsion 2201B, Agricultural Emulsion 0203B, and Agricultural Emulsion 100. # 500g of agricultural dairy products # 600g of agricultural dairy products # 600-2 Agricultural Milk # Agricultural Milk 1601, Agricultural Milk 2201, Agricultural Milk NP-10, Agricultural Milk NP-15, Agricultural Milk 507 # Agricultural Milk OX-635, Agricultural Milk OX-622, Agricultural Milk OX-653, Agricultural Milk OX-667, Ningru 36 # Dispersants include sodium lignosulfonate, dispersing agents, calcium lignosulfonate, and methylnaphthalenesulfonic acid formaldehyde condensate. Wetting agents include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium alkylnaphthalenesulfonate.

[0054] The present invention also provides a sterilization method, the method comprising: applying a 2-cyanoacrylate compound salt of general formula (I) to a pathogen that needs to be controlled or its growth medium, wherein when the 2-cyanoacrylate compound salt of general formula (I) is applied to the pathogen that needs to be controlled or its growth medium, the application amount is 10 to 1000 grams per hectare.

[0055] This invention provides a novel 2-cyanoacrylate compound salt, wherein the novel bactericide candidate compound ZJS178 is modified to prepare various salts of ZJS178 with novel structures, and these salts are characterized and their activity is determined. The specific salts prepared by this invention can significantly improve the solubility while maintaining the original high activity of ZJS178, and can even enhance the high activity of ZJS178, which has very good and unexpected technical effects.

[0056] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0057] The 2-cyanoacrylate compound salts of general formula (I) provided by this invention have significantly improved water solubility compared to ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate, while still maintaining high fungicidal activity against wheat scab. Detailed Implementation

[0058] The present invention will be further described below with reference to specific embodiments, 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.

[0059] Unless otherwise specified, the experimental methods described in the examples are conventional methods; the materials and reagents used in the examples are commercially available unless otherwise specified.

[0060] All pathogenic bacteria used in this invention are wild-type strains, which are common pathogens affecting various vegetables and fruits. They can be isolated or purchased. All pathogenic bacteria used in this invention were provided by Jiangsu Provincial Pesticide Research Institute Co., Ltd.

[0061] Example 1

[0062] Preparation of 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate hydrochloride (compound 1)

[0063]

[0064] Ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate (2 g, 7.32 mmol) was dissolved in 20 mL of ethanol, and concentrated hydrochloric acid (0.73 mL, 8.78 mmol) with a concentration of 12 mol / L was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 0.5 h. The resulting solid was washed with ethyl acetate, filtered, and dried to give 2.15 g of pure product, with a yield of 94.7%.

[0065] 1H NMR (MeOD, 400MHz) δ: 7.75 (d, J=7.6Hz, 2H, Ph-H), 7.66-7.61 (m, 2H, Ph-H), 4.20 (q, J=7.2Hz, 2H, -CH2), 3.63(q,J=7.2Hz,2H,-CH2), 3.25(s,3H,-CH3), 1.26(t,J=7.2Hz,3H,-CH3), 1.14(t,J=7.2Hz,3H,-CH3).

[0066] Example 2

[0067] Preparation of 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]ethyl acrylate sulfate (compound 2)

[0068]

[0069] Ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate (2 g, 7.32 mmol) was dissolved in 20 mL of methanol, and concentrated sulfuric acid (0.60 mL, 11.00 mmol) with a concentration of 18.4 mol / L was slowly added dropwise. After the addition was complete, the mixture was stirred at room temperature for 0.5 h. Most of the solvent was removed by vacuum distillation, and the mixture was filtered. The filter cake was washed with ethyl acetate and dried to give 2.62 g of pure product, with a yield of 96.5%.

[0070] 1 H NMR (D2O, 400MHz) δ: 7.81 (d, J=8.8Hz, 2H, Ph-H), 7.69 (d, J=8.8Hz, 2H, Ph-H), 4.24 (q, J=7.2Hz, 2H, -CH2) ,3.65(q,J=7.2Hz,2H,-CH2),3.27(s,3H,-CH3),1.27(t,J=7.2Hz,3H,-CH3),1.15(t,J=7.2Hz,3H,-CH3).

[0071] Example 3

[0072] Preparation of 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate methylsulfonate (compound 3)

[0073]

[0074] Ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate (2 g, 7.32 mmol) was dissolved in 20 mL of ethanol, and methanesulfonic acid (0.77 g, 8.05 mmol) was slowly added dropwise. After the addition was complete, the mixture was heated to 50 °C and stirred for 1 h. The resulting solid was washed with ethyl acetate, filtered, and dried to give 2.66 g of pure product, with a yield of 98.7%.

[0075] 1 H NMR (MeOD, 400MHz) δ: 7.78-7.74 (m, 2H, Ph-H), 7.65-7.58 (m, 2H, Ph-H), 4.20 (q, J=7.2Hz, 2H, -CH2), 3.64 (q, J=7 .2Hz,2H,-CH2),3.25(s,3H,-CH3),2.65(s,3H,-CH3),1.26(t,J=7.2Hz,3H,-CH3),1.14(t,J=7.2Hz,3H,-CH3).

[0076] Example 4

[0077] Preparation of 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate p-toluenesulfonate (compound 4)

[0078]

[0079] Ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate (2 g, 7.32 mmol) was dissolved in 20 mL of dichloromethane, and p-toluenesulfonic acid (1.26 g, 7.32 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 h. The resulting solid was washed with ethyl acetate, filtered, and dried to give 3.20 g of pure product, with a yield of 99.8%.

[0080] 1 ¹H NMR (MeOD, 400MHz) δ: 7.75-7.73 (m, 2H, Ph-H), 7.66-7.63 (m, 2H, Ph-H), 7.60-7.56 (m, 2H, Ph-H), 7.19-7.17 (m, 2H, Ph-H), 4.20 (q, J = 7.2Hz, 2H, -CH₂), 3.62 (q, J = 7.2Hz, 2H, -CH₂), 3.25 (s, 3H, -CH₃), 2.31 (s, 3H, -CH₃), 1.26 (t, J = 7.2Hz, 3H, -CH₃), 1.13 (t, J = 7.2Hz, 3H, -CH₃). Solubility test.

[0081] Examples of water solubility determination using the compounds of the present invention are given below. It should be noted that the present invention is not limited to the examples described below.

[0082] Example 5

[0083] Water solubility test

[0084] The 2-cyanoacrylate salts prepared in Examples 1, 2, 3, and 4 were added in excess to distilled water (until saturation was achieved). The mixtures were stirred at room temperature for 12 hours under sealed conditions, then allowed to stand. The supernatant was collected, and the concentration of the solution was determined by HPLC. The HPLC instrument was a Shimadzu LC-20A system; the column was a Cosmosil 250mm C18 column; the detector was a diode array detector (DAD); the column temperature was 35.0℃; the mobile phase was acetonitrile (60%) + pure water (40%); and the flow rate was 1.00 mL / min.

[0085] The solubility of the compounds listed in Table 1 (compounds 1, 2, 3, and 4 are salts of 2-cyanoacrylate compounds prepared in Examples 1, 2, 3, and 4, respectively) in water was determined. The results showed that the compounds of this invention have good water solubility, and their solubility in water is significantly higher than that of ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate. "mg / L" refers to milligrams of compound per liter, as detailed in Table 1 below.

[0086] Table 1

[0087]

[0088] The 2-cyanoacrylate salts, such as hydrochloride or sulfate, prepared from the present invention can significantly improve the solubility of ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate.

[0089] Formulation preparation

[0090] Examples 6 to 10 below provide practical examples of the formulation of several bactericide formulations using 2-cyanoacrylate compounds of general formula (I) as active ingredients. It should be noted that the present invention is not limited to the scope of the examples below. In these formulation examples, all "%" refer to weight percentage.

[0091] Example 6

[0092] Wettable powder formulation

[0093] By mass percentage, 10% of the 2-cyanoacrylate compound salt represented by general formula (I) and 5% of the lignin sulfonate (M q 1%, 1% lauryl alcohol polyoxyethylene ether (JFC), 40% diatomaceous earth and 44% light calcium carbonate are uniformly mixed and pulverized to obtain a wettable powder.

[0094] Example 7

[0095] emulsion formula

[0096] The emulsifiable concentrate is prepared by heating and stirring 10% of any 2-cyanoacrylate salt of general formula (I), 5% of agricultural emulsion No. 500 (calcium salt), 5% of agricultural emulsion No. 602, 5% of N-methyl-2-pyrrolidone and 75% of xylene by mass percentage.

[0097] Example 8

[0098] Granule formulation

[0099] By mass percentage, 5% of 2-cyanoacrylate salt of any formula (I), 1% polyvinyl alcohol (PVA), 4% sodium naphthalene sulfonate formaldehyde condensate (NMO) and 90% clay are uniformly mixed, pulverized, and then 20 parts of water are added to 100 parts of this mixture by weight. The mixture is kneaded, granulated using an extruder to form granules of 14-32 mesh, and dried to obtain granules.

[0100] Example 9

[0101] Water-dispersible granule formulation

[0102] By mass percentage, 20% of any 2-cyanoacrylate salt of general formula (I), 4% of naphthalene sulfonate formaldehyde condensate, 1% of naphthalene sulfonate, 2% of silica, and 73% of kaolin are mixed and pulverized, then water is added and kneaded. The mixture is then fed into a granulator equipped with a sieve of a specific size for granulation. After drying and sieving (according to the sieve size range), granular product is obtained.

[0103] Example 10

[0104] Water suspension formulation

[0105] By mass percentage, 25% of any 2-cyanoacrylate compound salt of general formula (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 69.5% of deionized water 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.

[0106] Activity test

[0107] 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.

[0108] Example 11

[0109] Indoor activity assay

[0110] The inhibitory activity of the test compounds against the test pathogens was determined using the mycelial growth rate method. The test pathogens were inoculated onto 90 mm diameter PDA plates. When the colonies approached the edge of the plate, a 5 mm diameter punch was used to create a small 1 / 3 hole at the outer edge of the fresh colonies. These small filaments were then transferred using an inoculation needle to the center of a pre-prepared PDA plate containing a series of concentration gradients of the test compounds (1-4). Simultaneously, a control PDA plate containing only an equal volume of solvent was inoculated. The plates were incubated at 25°C for 2-3 days. When the pathogen colonies in the control group approached the edge of the 90 mm plate, photographs were taken, and the colony diameter was measured using the cross-sectional method. The mycelial growth inhibition rate (MGIR) was calculated using the following formula: MGIR% = [(CN) / (C-5)] × 100%, where C is the colony diameter of the blank control group, N is the colony diameter of the positive control or treatment group, and 5 is the diameter of the small filament. This experiment was repeated twice, with three plates per replicate. The experimental pathogen was *Fusarium graminearum*, the pathogen of wheat scab (strain number 2021). EC was calculated using the inhibition rate MGIR. 90 The test results are shown in Table 2 below:

[0111] Table 2

[0112]

[0113] The active ingredient is the content of ZJS178 in the compound or salt.

[0114] This invention evaluated the in vitro bactericidal activity of some of the compounds listed in Table 1. The results showed that the compounds of this invention have good bactericidal activity and a good inhibitory effect on Fusarium graminearum pathogen. "μg / mL" refers to micrograms of active ingredient per milliliter. After ZJS178 is prepared as a salt, EC... 90 The value is even lower than that of ZJS178 original drug, and the activity is significantly improved. The above experiments prove that the specific salt prepared by the present invention can significantly improve the solubility and maintain or even improve the activity of ZJS178.

Claims

1. A 2-cyanoacrylate salt, characterized in that, The general formula of the 2-cyanoacrylate salt is shown in formula (I): ， in: n is selected from 1; X is selected from hydrochloric acid or sulfuric acid.

2. A method for preparing the 2-cyanoacrylate salt of claim 1, characterized in that, The specific method is as follows: It is prepared by reacting ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate with an acid in a solvent. The reaction equation is: , Wherein, the substituents X and n are as described in claim 1, and the acid is sulfuric acid or hydrochloric acid.

3. The method for preparing the 2-cyanoacrylate compound salt according to claim 2, characterized in that: The solvent is selected from water, toluene, dichloromethane, dichloroethane, chloroform, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, methyltetrahydrofuran, 1,3-dioxane, 1,4-dioxane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, acetonitrile, propionitrile, methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, methanol, ethanol, isopropanol. At least one of benzyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

4. The method for preparing 2-cyanoacrylate compound salts according to claim 2, characterized in that, The molar ratio of ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate to acid is 1:0.1~10, the reaction temperature is -20~120℃, and the reaction time is 0.1~10 hours.

5. The use of the 2-cyanoacrylate compound salt of claim 1 in the preparation of pesticide formulations for controlling fungal diseases, wherein the diseases are caused by fungi of the genus Fusarium.

6. The application according to claim 5, characterized in that, The application process involves applying 2-cyanoacrylate compound salts to the fungi that need to be controlled or their growth medium.

7. The application according to claim 5, characterized in that, The 2-cyanoacrylate compound salts are used to control either Fusarium head blight or Bakanae disease.

8. The application according to claim 5, characterized in that, The pesticide formulation contains 0.001%-99.99% by weight of 2-cyanoacrylate compound salts.

9. The application according to claim 5, characterized in that, The pesticide formulation according to claim 8 is used for sterilization, wherein the application rate of the 2-cyanoacrylate compound salt in the pesticide formulation is 10 to 1000 grams per hectare.

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