Fungicide compositions and their application in the control of Fusarium diseases in crops

Abstract

The present invention relates to the field of plant disease control technology and discloses five fungicide compositions and their application in the control of Fusarium diseases in crops. The active ingredient of the composition comprises a compound ZJS178 represented by the structural formula (I) and a triazole fungicide, a compound ZJS178 and a succinate dehydrogenase inhibitor fungicide, a compound ZJS178 and a pyrrole fungicide, a compound ZJS178 and an imidazole fungicide, or a compound ZJS178 and a methoxyacrylate fungicide. The composition of the present invention has a compounding effect enhancing action, is free from cross-resistance, can significantly improve fungicide activity and control effect, is advantageous for overcoming and delaying drug resistance of pathogens, has excellent safety for crops, and meets the requirements for reduced pesticide usage and increased effectiveness.

Description

Technology Field

[0001] The present invention relates to the field of plant disease control technology, and specifically to five fungicide compositions and their application in the control of Fusarium diseases in crops. Background Technology

[0002] Fusarium (Fusarium spp.) is a fungus distributed worldwide that causes various diseases in plants, such as root rot, stem rot, flower rot, and ear rot, leading to wilting and death of crops and affecting yield and quality. Common Fusarium crop diseases include rice blast, wheat red mold, corn ear rot, cucurbit wilt, and root rot in various crops.

[0003] Due to recent changes in climate and cultivation practices, wheat red mold caused by the Fusarium graminearum complex is posing a serious threat to the safe production of wheat. Unlike other crop diseases, the red mold pathogen produces mycotoxins such as deoxynivalenol (also known as emetic toxin, DON) and zearalenone (ZEA) in infected wheat, posing a serious threat to human and animal safety. Consequently, this disease has been designated as a "Class 1 crop pest" by the Ministry of Agriculture and Rural Affairs. Furthermore, due to large-scale crop rotation between wheat and corn in China, corn ear rot caused by the Fusarium graminearum complex is showing an worsening trend, drawing significant attention from major productivity agriculture and grain procurement departments.

[0004] In addition to Fusarium graminearum, rice blast caused by the Fusarium fujikuroi complex is also a global fungal disease. In China, with the widespread adoption of intensive seedling cultivation techniques such as mechanical transplanting and broadcast sowing, the occurrence of blast has become increasingly common, with incidence rates reaching 100% in some regions, resulting in severe losses in production.

[0005] Fusarium can also cause wilt diseases in various fruits and vegetables; for example, banana wilt disease caused by Fusarium oxysporum causes large-scale wilting and death of bananas, resulting in massive losses for banana farmers and becoming a "cancer" on the banana industry. In addition, wilt diseases caused by Fusarium oxysporum in cucurbit crops, tomatoes, etc., are seriously hindering the healthy development of the industry.

[0006] Therefore, continuous and effective control of Fusarium diseases in crops is of significant importance for the effective supply of agricultural products and the assurance of quality safety in China.

[0007] Due to the current shortage of highly resistant crop varieties, chemical control still predominates for crop Fusarium disease control.

[0008] Currently, triazole fungicides are widely used to control Fusarium diseases in crops. As sterol biosynthesis inhibitors, triazole fungicides inhibit the synthesis of ergosterol in pathogens, thereby inducing changes in membrane-associated cell functions and exerting fungicidal and fungicidal effects. For example, Tebuconazole (chemical name (RS)-1-p-chlorophenyl-4,4-dimethyl-3-(1H-1,2,4-triazole-1-ylmethyl)pent-3-ol) can be used to control various crop diseases such as rust, red mold, powdery mildew, net blight, and root rot. Metconazole: The chemical name 5-(4-chlorophenyl)-2,2-dimethyl-1-(1H-1,2,4-triazole-1-ylmethyl)cyclopentanol can be used to control various diseases in cereal, barley, and legume crops, and it has excellent protective and curative properties along with a long duration of effect. However, due to the long-term use of the agent, Fusarium diseases develop resistance to this type of agent, which affects the control efficacy of the agent.

[0009] Succinate dehydrogenase inhibitor (SDHI) fungicides, such as pydiflumetofen, can be used to control crop diseases caused by Fusarium, such as Fusarium head blight. Pidiflumetofen, chemical name: 3-(difluoromethyl)-N-methoxy-1-methyl-N-[(RS)-1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide, is a new generation succinate dehydrogenase inhibitor (SDHI) developed by Syngenta. This agent acts on respiratory chain complex II to block ATP synthesis and inhibit the growth of pathogens, thereby inducing their death and ultimately achieving the goal of plant disease control. Penflufen, chemical name: 5-fluoro-1,3-dimethyl-N-[2-(4-methylpent-2-yl)phenyl]-1H-pyrazole-4-carboxamide, is an SDHI-class fungicide developed by Bayer. This agent acts on respiratory chain complex II to inhibit ATP synthesis in pathogens and possesses antiseptic, prophylactic, and curative effects. Currently, it is primarily used as a seed treatment; after application, the agent penetrates the germinating seeds and is delivered to the entire plant through the xylem, thereby providing protection. However, succinate dehydrogenase inhibitor fungicides have a single site of action, and the risk of resistance is continuously increasing due to their widespread use.

[0010] Fludioxonil (chemical name: 4-(2,2-difluoro-1,3-benzodiox-4-yl)pyrrole-3-carbonitrile), a pyrrole fungicide, is a commonly used agent for controlling diseases such as wheat stem rot, rice blast, and tomato wilt. This agent primarily inhibits the growth of fungal mycelia by activating the histidine kinase signaling pathway of pathogens. As a seed treatment agent, it is mainly used to control various seed-borne and soil-borne pathogens such as Alternaria, Fusarium, Cephalosporium, Rhizoctonia, and Penicillium. However, according to current research, pathogenic fungi easily develop resistance to this agent, significantly affecting the control efficacy of the agent (Oiki et al., 2022. Wide distribution of resistance to the fungicides fludioxonil and iprodione in Penicillium species. PLOS ONE 17 (1); Dowling et al., 2021. Characterization of high fludioxonil resistance in Botrytis cinerea isolates from calibrachoa flowers. Phytopathology, 111(3): pp.478-484; Wen et al., 2022. Biological and molecular characterizations of field fludioxonil-resistant isolates of Fusarium graminearum. Pesticide biochemistry and physiology, 184: DOI10.1016 / j.pestbp.2022.105101.).

[0011] Prochloraz (chemical name: N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]-imidazole-1-carboxamide) is a broad-spectrum fungicide that exhibits distinct control effects against diseases caused by Ascomycetes and imperfect fungi in various crops. Carbendazim (chemical name: benzimidazole-2-ylcarbamate) is a broad-spectrum, low-toxicity fungicide that primarily interferes with the process of cell mitosis and is effective against some pathogens of the Ascomycetes and most pathogenic fungi of imperfect fungi. Thiophanate-methyl (chemical name: 1,2-bis(3-methoxycarbonyl-2-thiouredo)benzene) is a broad-spectrum, low-toxicity fungicide that possesses conduction-resistant properties. This agent achieves an inhibitory effect on pathogen growth by acting on the β-tubulin of pathogenic fungi to inhibit cell division.

[0012] Azoxystrobin (chemical name: (E)-2-{2-[6-(2-cyanofenoxy)pyrimidine-4-yloxy]phenyl}-3-methoxyacrylate) is a methoxyacrylate fungicide that kills fungal cells by inhibiting mitochondrial respiration through the inhibition of electron transfer between cytochromes bc1 in fungal cells. This agent has excellent control effects against various crop diseases caused by pathogens of the Ascomycota, Basidiomycota, Flagellates, and Deuteromycota subphyla. It is highly efficient and broad-spectrum, exhibiting excellent activity against powdery mildew, rust, waterlogging disease, net blight, downy mildew, and blast in grains, rice, peanuts, grapes, potatoes, fruit trees, vegetables, coffee, and turfgrass, and can be used for foliar spraying, seed treatment, and soil treatment. Trifloxystrobin (chemical name: (E)-methoxyimino-{(E)-α-[1-(α,α,α-trifluoro-m-tolyl)ethylideneaminoxy]-o-tolyl}acetate is broad-spectrum and long-lasting in efficacy, possessing protective, curative, and eradicative activities against most diseases caused by pathogenic fungi, including Ascomycetes, Basidiomycetes, Oomycetes, and Deuteromycetes. It exhibits no cross-resistance with currently existing fungicides. Fluoxastrobin (chemical name: {2-[6-(2-chlorophenoxy)-5-fluoropyrimidine-4-yloxy]phenyl}(5,6-dihydro-1,4,2-dioxazine-3-yl)methanone O-methyloxime) has broad-spectrum fungicidal activity and exhibits very good activity against diseases of almost all fungi (Ascomycetes, Basidiomycetes, Oomycetes, and Deuteromycetes), such as rust, waterlogged disease, net blight, powdery mildew, and downy mildew. Picoxystrobin (chemical name: (E)-3-methoxy-2-{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}acrylate belongs to broad-spectrum anaerobic fungicides.Pyraclostrobin (chemical name: N-[2-[[1-(4-chlorophenyl)pyrazole-3-yl]oxymethyl]phenyl]-N-methoxycarbamate) possesses protective and therapeutic effects, as well as water absorption conductivity and rain resistance, and has a relatively wide range of applications. Phenaminstrobin (chemical name: (E,E,E)-N-methyl-2-[((((1-methyl-3-(2,6-dichlorophenyl)-2-propenyl)imino)oxy)methyl)phenyl]-2-methoxyiminoacetamide) has a broad fungicidal spectrum, high activity, and possesses preventive and therapeutic effects. It exhibits excellent control efficacy against various plant diseases caused by flagellates, zygomycetes, ascomycetes, basidiomycetes, and imperfect fungi, and shows outstanding control effects against powdery mildew and rust.

[0013] Long-term use of pesticides allows pathogens to easily develop resistance, affecting their control efficacy. Therefore, the research and development of appropriate pesticide combinations for controlling Fusarium diseases in crops is particularly important. The problem to be solved

[0014] The objective of the present invention is to provide a high-efficiency, low-toxicity, and environmentally friendly fungicide composition that is highly effective against crop diseases caused by Fusarium, while simultaneously delaying drug resistance and extending the service life of the drug. means of solving the problem

[0015] It can delay resistance and extend the lifespan of the drug.

[0016] To achieve the above objective, the present invention adopts the following technical solution.

[0017] In a first aspect of the present invention, the present invention provides a sterilizing composition, wherein the active ingredient of the composition comprises a compound ZJS178 represented by the structural formula (I) and a triazole-based sterilizing agent.

[0018] (I)

[0019] The above compound ZJS178 is a new compound previously prepared by the research team of the present invention, and its chemical name is ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate, and its synthesis route is as follows.

[0020]

[0021] The compound is a cyanoacrylate-based fungicide that acts on Fusarium type I myosin (motor protein) to cause the pathogen to lose its growth momentum, thereby killing the pathogen. According to research, ZJS178 has a novel structure and a unique mode of action, exhibits no cross-resistance with triazole-based agents, is effective against diseases caused by Fusariums, and possesses both protective and therapeutic effects.

[0022] Since ZJS178 and triazole fungicides have different mechanisms of action, the present invention combines the two to achieve a significantly higher control effect against Fusarium diseases in crops compared to a single agent, reduces the amount of single agent used, delays the development of drug resistance in pathogens, extends the service life of the fungicide, and helps reduce costs.

[0023] Preferably, the mass ratio of compound ZJS178 to triazole-based disinfectant in the composition is 50:1 to 1:50.

[0024] The above triazole-based disinfectants include, but are not limited to, tebuconazole, metconazole, micerobutanil, diphenoconazole, triadimefon, epoxyconazole, diniconazole, prothioconazole, propiconazole, etc.

[0025] Preferably, the triazole-based disinfectant is tebuconazole or metconazole.

[0026] Furthermore, preferably, the mass ratio of compound ZJS178 to triazole-based fungicide in the composition is 15:1 to 1:15.

[0027] According to research, compound ZJS178 and triazole fungicides exhibit synergistic effects under specific mixing ratio conditions, thereby enhancing the efficacy of controlling Fusarium diseases. For example, against Fusarium oxysporum, compound ZJS178 and triazole fungicides exhibit enhanced efficacy when mixed in a mass ratio of 8:1 to 1:8. Against Fusarium fujikuroi, compound ZJS178 and triazole fungicides exhibit enhanced efficacy in inhibiting metconazole-susceptible Fusarium fujikuroi when mixed in a mass ratio of 4:1 to 1:5, and the two components exhibit enhanced efficacy in inhibiting metconazole-resistant Fusarium fujikuroi when mixed in a mass ratio of 5:1 to 1:3. Regarding Fusarium graminearum, compound ZJS178 and a triazole fungicide have an enhanced effect on inhibiting tebuconazole-susceptible Fusarium graminearum when combined in a mass ratio of 3:1 to 1:3, and the two components have an enhanced effect on inhibiting tebuconazole-resistant Fusarium graminearum when combined in a mass ratio of 2:1 to 1:3.

[0028] Preferably, the mass ratio of compound ZJS178 to triazole-based disinfectant in the composition is 8:1 to 1:8.

[0029] More preferably, the mass ratio of compound ZJS178 and the triazole fungicide is mixed in a ratio of 2:1 to 1:3.

[0030] Furthermore, the above-mentioned sterilization composition further includes auxiliary components necessary for pesticide formulations, and the mass ratio of the active component in the composition is 1 to 90%. The above-mentioned auxiliary components are carriers and adjuvants commonly used in pesticides.

[0031] Preferably, the mass percentage of the active ingredient in the composition is 15 to 40%.

[0032] In accordance with methods known to those skilled in the art, the sterilizing composition of the present invention may be prepared in various formulations that are agriculturally acceptable for actual application, and includes water-dispersible granules, suspensions, aqueous emulsions, microemulsions, and suspensions for seed treatment.

[0033] In the case of water-dispersible granules, a person skilled in the art can complete the present invention by using the appropriate auxiliary agent. Polycarboxylates, lignin sulfonates, and alkylnaphthalene sulfonates may be selected as dispersants. Alkyl sulfates, alkyl sulfonates, and naphthalene sulfonates may be selected as wetting agents. Ammonium sulfate, urea, sucrose, and glucose may be selected as disintegrants. Diatomaceous earth, corn starch, polyvinyl alcohol, and carboxymethyl(ethyl)cellulose may be selected as binders. Diatomaceous earth, kaolin, white carbon black, hard calcium, talc powder, attapulgite, and clay may be selected as fillers.

[0034] The adjuvants that can be used in suspension formulations are as follows: Polycarboxylates, lignin sulfonates, and alkylnaphthalene sulfonates may be selected as dispersants. Alkylphenol polyoxyethylene polygroup ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate ester, benzylphenol polyoxyethylene ether phosphate ester, alkyl sulfate, alkyl sulfonate, and naphthalene sulfonate may be selected as wetting agents. Xanthan gum, polyvinyl alcohol, and bentonite may be selected as thickeners. Formaldehyde, benzoic acid, and sodium benzoate may be selected as preservatives. Organosilicon-based defoaming agents may be used as defoaming agents. Inorganic salts such as ethylene glycol, propylene glycol, glycerin, urea, and sodium chloride may be selected as antifreeze agents.

[0035] The following are adjuvants that can be used in aqueous emulsion formulations: As emulsifiers, nonylphenol polyoxyethylene ether phosphate ester, tribenzylethylphenol polyoxyethylene ether phosphate ester (pesticide emulsifier 600# phosphate ester), pesticide emulsifier 700#, pesticide emulsifier 2201#, Span-60#, emulsifier T-60, surfactant TX-10, pesticide emulsifier 1601#, pesticide emulsifier 600#, and pesticide emulsifier 400# can be selected. As solvents, xylene, toluene, cyclohexanone, and solvent oils (S-150, S-180, S-200) can be selected. As stabilizers, triphenyl phosphite, epichlorohydrin, and acetic anhydride can be selected. Xanthan gum, polyvinyl alcohol, bentonite, and aluminum magnesium silicate can be selected as thickeners. Methanol, benzoic acid, and sodium benzoate can be selected as preservatives.

[0036] The following are adjuvants that can be used for the microemulsion type: As emulsifiers, calcium dodecylbenzenesulfonate (pesticide emulsifier 500#), pesticide emulsifier 700#, pesticide emulsifier 2201#, Span-60#, Tween-80-60#, TX-10, pesticide emulsifier 1601, pesticide emulsifier 600#, and pesticide emulsifier 400# can be selected. As auxiliary emulsifiers, methanol, isopropanol, n-butanol, and ethanol can be selected. As solvents, cyclohexanone, N-methylpyrrolidone, xylene, toluene, and solvent oils (S-150, S-180, S-200) can be selected. As stabilizers, triphenyl phosphite and epichlorohydrin can be selected.

[0037] The adjuvants that may be used in seed treatment suspensions are as follows: As film-forming agents, polyethylene glycol, polyvinyl alcohol resin, polyvinylpyrrolidone, hydroxyethylcellulose, polyvinyl acetate, sodium carboxymethylcellulose, gum arabic, gelatin, polyvinyl alcohol or polyacrylamide, or mixtures thereof may be used. The technician may adjust the proportion of polyvinyl acetate according to the viscosity required for the product.

[0038] The present invention further provides the application of the above fungicide composition in the control of crop diseases caused by Fusarium.

[0039] Furthermore, the above Fusarium refers to plant pathogenic Fusarium and mainly includes Fusarium graminearum complex, Fusarium fujikuroi complex, Fusarium oxysporum and Fusarium moniliforme, etc.

[0040] Furthermore, the above crop diseases include wheat red mold, rice blast, and strawberry wilt.

[0041] Specifically, in the application for controlling wheat red mold disease, the fungicide composition is used at the early stage of heading and flowering of wheat, and the agent is used again at intervals of 6 to 7 days.

[0042] In a second aspect of the present invention, the present invention provides a high-efficiency sterilization composition, wherein the active ingredient of the composition comprises a compound ZJS178 represented by the structural formula (I) and a succinate dehydrogenase inhibitor-based sterilizer.

[0043] (I)

[0044] The above compound ZJS178 is a new compound previously prepared by the research team of the present invention, and its chemical name is ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate, and its synthesis route is as follows.

[0045]

[0046] The compound in question is a cyanoacrylate-based fungicide that acts on the myosin type I of Fusarium. Myosin type I is a motor protein of pathogens that hydrolyzes ATP to convert biological energy into mechanical energy, thereby providing power for life activities such as growth, infection, and toxin synthesis. ZJS178 specifically acts on the myosin type I of Fusarium to cause the pathogens to lose their growth power, thereby killing the pathogens.

[0047] ZJS178 has a novel structure and a unique mechanism of action. Studies show that ZJS178 does not exhibit cross-resistance with succinate dehydrogenase inhibitors (SDHI), is effective against diseases caused by Fusariums, and possesses both protective and therapeutic effects.

[0048] Although ZJS178 and SDHI-based fungicides have different mechanisms of action, their sites of action are related; therefore, the present invention combines these two to significantly enhance the fungicidal effect, delay the development of drug resistance in pathogens, and reduce control costs. Specifically, SDHI-based fungicides can effectively inhibit ATP synthesis in pathogens, and rationally combining ZJS178 and SDHI agents allows for the simultaneous blocking of ATP synthesis and motor protein activity. This is akin to simultaneously blocking the pathogen's "gasoline" and "engine," thereby achieving the effect of inhibiting pathogen growth with high efficiency and delaying the pathogen from developing resistance to either agent.

[0049] Preferably, the mass ratio of compound ZJS178 to succinate dehydrogenase inhibitor-based disinfectant in the composition is 50:1 to 1:50.

[0050] The above-mentioned succinate dehydrogenase inhibitor-based disinfectants include, but are not limited to, pidiflumetofen, fenflufen, fluxapiroxad, flupiram, carboxyl, etc.

[0051] Preferably, the mass ratio of compound ZJS178 to succinate dehydrogenase inhibitor-based disinfectant in the composition is 9:1 to 1:9.

[0052] According to research, compound ZJS178 and succinate dehydrogenase inhibitor fungicides exhibit a synergistic effect under specific mixing ratio conditions, thereby enhancing the effectiveness of Fusarium disease control. When the mass ratio of compound ZJS178 to succinate dehydrogenase inhibitor fungicides in the composition is 7:1 to 1:5, it enhances the effectiveness of inhibiting Fusarium graminearum and Fusarium fujikuroi.

[0053] Furthermore, the high-efficiency sterilization composition further includes a pesticide-acceptable carrier and an adjuvant. The mass ratio of the active ingredient in the composition is 1 to 90%.

[0054] Preferably, the mass ratio of the active ingredient in the composition is 10-40%.

[0055] In accordance with methods known to those skilled in the art, the sterilizing composition of the present invention may be prepared in various formulations that are agriculturally acceptable for actual application, and commonly used formulations include water-dispersible granules, suspensions, microemulsions, aqueous emulsions, suspensions, and suspensions for seed treatment.

[0056] In the case of water-dispersible granules, a person skilled in the art can complete the present invention by using the appropriate auxiliary agent. Polycarboxylates, lignin sulfonates, and alkylnaphthalene sulfonates may be selected as dispersants. Alkyl sulfates, alkyl sulfonates, and naphthalene sulfonates may be selected as wetting agents. Ammonium sulfate, urea, sucrose, and glucose may be selected as disintegrants. Diatomaceous earth, corn starch, polyvinyl alcohol, and carboxymethyl(ethyl)cellulose may be selected as binders. Diatomaceous earth, kaolin, white carbon black, hard calcium, talc powder, attapulgite, and clay may be selected as fillers.

[0057] The adjuvants that can be used in suspension formulations are as follows: Polycarboxylates, lignin sulfonates, and alkylnaphthalene sulfonates may be selected as dispersants. Alkylphenol polyoxyethylene polygroup ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate ester, benzylphenol polyoxyethylene ether phosphate ester, alkyl sulfate, alkyl sulfonate, and naphthalene sulfonate may be selected as wetting agents. Xanthan gum, polyvinyl alcohol, and bentonite may be selected as thickeners. Formaldehyde, benzoic acid, and sodium benzoate may be selected as preservatives. Organosilicon-based defoaming agents may be used as defoaming agents. Inorganic salts such as ethylene glycol, propylene glycol, glycerin, urea, and sodium chloride may be selected as antifreeze agents.

[0058] The following are auxiliary agents that can be used in aqueous emulsion formulations: As emulsifiers, nonylphenol polyoxyethylene ether phosphate ester, tribenzylethylphenol polyoxyethylene ether phosphate ester (pesticide emulsifier 600# phosphate ester), pesticide emulsifier 700#, pesticide emulsifier 2201#, Span-60#, emulsifier T-60, surfactant TX-10, pesticide emulsifier 1601#, pesticide emulsifier 600#, and pesticide emulsifier 400# can be selected. As solvents, xylene, toluene, cyclohexanone, and solvent oils (S-150, S-180, S-200) can be selected. As stabilizers, triphenyl phosphite, epichlorohydrin, and acetic anhydride can be selected. Xanthan gum, polyvinyl alcohol, bentonite, and aluminum magnesium silicate can be selected as thickeners. Methanol, benzoic acid, and sodium benzoate can be selected as preservatives.

[0059] The following are adjuvants that can be used for the microemulsion type: As emulsifiers, calcium dodecylbenzenesulfonate (pesticide emulsifier 500#), pesticide emulsifier 700#, pesticide emulsifier 2201#, Span-60#, Tween-80-60#, TX-10, pesticide emulsifier 1601, pesticide emulsifier 600#, and pesticide emulsifier 400# can be selected. As auxiliary emulsifiers, methanol, isopropanol, n-butanol, and ethanol can be selected. As solvents, cyclohexanone, N-methylpyrrolidone, xylene, toluene, and solvent oils (S-150, S-180, S-200) can be selected. As stabilizers, triphenyl phosphite and epichlorohydrin can be selected.

[0060] The adjuvants that may be used in seed treatment suspensions are as follows: As film-forming agents, polyethylene glycol, polyvinyl alcohol resin, polyvinylpyrrolidone, hydroxyethylcellulose, polyvinyl acetate, sodium carboxymethylcellulose, gum arabic, gelatin, polyvinyl alcohol or polyacrylamide, or mixtures thereof may be used. The technician may adjust the proportion of polyvinyl acetate according to the viscosity required for the product.

[0061] The present invention further provides an application of the above-described high-efficiency sterilization composition in the control of Fusarium diseases in crops.

[0062] Furthermore, the above Fusarium refers to plant pathogenic Fusarium and mainly includes Fusarium graminearum complex, Fusarium fujikuroi complex, Fusarium oxysporum and Fusarium moniliforme, etc.

[0063] Furthermore, crop diseases caused by Fusarium include, but are not limited to, wheat red mold and rice blast.

[0064] Specifically, the agent combining compound ZJS178 and pidiflumetofen is applied once at the early stages of heading and flowering of wheat to control red mold disease, and then applied again after a 6-day interval. The agent combining compound ZJS178 and fenflufen is used as a seed treatment agent for controlling crop diseases.

[0065] In a third aspect of the present invention, the present invention provides a disinfectant composition, wherein the active ingredient of the composition comprises a compound ZJS178 represented by the structural formula (I) and a pyrrole-based disinfectant.

[0066] (I)

[0067] The above compound ZJS178 is a new compound previously prepared by the research team of the present invention, and its chemical name is ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate, and its synthesis route is as follows.

[0068]

[0069] The compound is a cyanoacrylate-based fungicide that acts on Fusarium's type I myosin (motor protein) to cause the pathogen to lose its growth momentum and kill the pathogen.

[0070] Compound ZJS178 has a novel structure and a unique mode of action, and does not exhibit cross-resistance with pyrrole-based agents such as fludioxonil. Since ZJS178 and pyrrole-based disinfectants have different mechanisms of action, the present invention combines the two to expand the range of bactericidal activity and enhance the bactericidal effect, as well as delay the development of drug resistance in pathogens.

[0071] Preferably, the mass ratio of compound ZJS178 to pyrrole-based disinfectant in the composition is 50:1 to 1:50.

[0072] The above pyrrole-based disinfectants include, but are not limited to, fludioxonil, fenpiclonil, etc.

[0073] Furthermore, preferably, the mass ratio of compound ZJS178 to pyrrole-based fungicide is 11:1 to 1:11.

[0074] According to the study, compound ZJS178 and pyrrole-based fungicides exhibit a synergistic effect under specific mixing ratio conditions, thereby enhancing the efficacy of Fusarium inhibition. Specifically, regarding Fusarium pseudograminearum, compound ZJS178 and pyrrole-based fungicides enhance the efficacy of inhibiting fludioxonil-resistant Fusarium pseudograminearum when mixed in a mass ratio of 3:1 to 1:2, and enhance the efficacy of inhibiting fludioxonil-susceptible Fusarium pseudograminearum when mixed in a mass ratio of 1:2 to 3. Regarding Fusarium fujikuroi, compound ZJS178 and pyrrole-based fungicides enhance the efficacy when mixed in a mass ratio of 1:1 to 2. For Fusarium oxysporum, compound ZJS178 and pyrrole-based fungicides have an enhanced effect when combined in a mass ratio of 1:1 to 3.

[0075] Preferably, the mass ratio of compound ZJS178 to pyrrole-based disinfectant in the disinfectant composition is 1:1 to 3.

[0076] Furthermore, in addition to the active ingredient, the above composition further includes a pesticide-acceptable carrier and an adjuvant. The mass ratio of the active ingredient is 1 to 90%.

[0077] Preferably, the mass ratio of the active ingredient in the composition is 25 to 40%.

[0078] According to methods known to those skilled in the art, the fungicide composition of the present invention can be prepared in various formulations that are agriculturally acceptable for actual application, and preferred formulations are suspensions for seed treatment, water-dispersible granules, microemulsions, and aqueous emulsions.

[0079] In the case of suspensions for seed treatment, those skilled in the art are well accustomed to completing the present invention using the appropriate adjuvants. The adjuvants that can be used for suspensions for seed treatment are as follows: As film-forming agents, polyethylene glycol, polyvinyl alcohol resin, polyvinylpyrrolidone, hydroxyethylcellulose, polyvinyl acetate, sodium carboxymethylcellulose, gum arabic, gelatin, polyvinyl alcohol or polyacrylamide, or mixtures thereof may be used. A person skilled in the art may adjust the proportion of polyvinyl acetate according to the viscosity required for the product.

[0080] For water-dispersible granules, polycarboxylates, lignin sulfonates, and alkylnaphthalene sulfonates may be selected as dispersants. Alkyl sulfates, alkyl sulfonates, and naphthalene sulfonates may be selected as wetting agents. Ammonium sulfate, urea, sucrose, and glucose may be selected as disintegrants. Diatomaceous earth, corn starch, polyvinyl alcohol, and carboxymethyl(ethyl)cellulose may be selected as binders. Diatomaceous earth, kaolin, white carbon black, hard calcium, talc powder, attapulgite, and clay may be selected as fillers.

[0081] The following are auxiliary agents that can be used in aqueous emulsion formulations: As emulsifiers, nonylphenol polyoxyethylene ether phosphate ester, tribenzylethylphenol polyoxyethylene ether phosphate ester (pesticide emulsifier 600# phosphate ester), pesticide emulsifier 700#, pesticide emulsifier 2201#, Span-60#, emulsifier T-60, surfactant TX-10, pesticide emulsifier 1601#, pesticide emulsifier 600#, and pesticide emulsifier 400# can be selected. As solvents, xylene, toluene, cyclohexanone, and solvent oils (S-150, S-180, S-200) can be selected. As stabilizers, triphenyl phosphite, epichlorohydrin, and acetic anhydride can be selected. Xanthan gum, polyvinyl alcohol, bentonite, and aluminum magnesium silicate can be selected as thickeners. Methanol, benzoic acid, and sodium benzoate can be selected as preservatives.

[0082] The adjuvants that can be used for the microemulsion type are as follows: As emulsifiers, calcium dodecylbenzenesulfonate (Pesticide Emulsifier 500#), pesticide emulsifier 700#, pesticide emulsifier 2201#, Span-60#, Tween-80-60#, TX-10, pesticide emulsifier 1601, pesticide emulsifier 600#, and pesticide emulsifier 400# can be selected. As auxiliary emulsifiers, methanol, isopropanol, n-butanol, and ethanol can be selected. As solvents, cyclohexanone, N-methylpyrrolidone, xylene, toluene, and solvent oil (Product No.: S-150, S-180, S-200) can be selected. As stabilizers, triphenyl phosphite and epichlorohydrin can be selected.

[0083] The present invention further provides the application of the fungicide composition in the control of crop diseases caused by Fusarium.

[0084] Furthermore, the above Fusarium refers to plant pathogenic Fusarium, and mainly includes Fusarium pseudograminearum, Fusarium fujikuroi, Fusarium oxysporum, etc.

[0085] The above crop diseases include, but are not limited to, wheat stem rot, rice blast, and tomato wilt.

[0086] Furthermore, the above application includes preparing the fungicide composition as a seed treatment agent to treat crop seeds.

[0087] In a fourth aspect of the present invention, the present invention provides a sterilizing composition, said composition comprising a compound ZJS178 represented by the chemical formula (I) and an imidazole-based sterilizing agent.

[0088] (I)

[0089] The above compound ZJS178 is a new compound previously prepared by the research team of the present invention, and its chemical name is ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate, and its synthesis route is as follows.

[0090]

[0091] This compound is a cyanoacrylate-based fungicide that acts on Fusarium type I myosin (motor protein) to cause the pathogen to lose its growth momentum, thereby killing the pathogen. ZJS178 has a novel structure and a unique mode of action, and it does not exhibit cross-resistance with imidazole-based fungicides.

[0092] Preferably, the mass mixing ratio of ZJS178 and the imidazole-based disinfectant in the above composition is 60:1 to 1:60.

[0093] The above imidazole-based disinfectants include, but are not limited to, prochloraz, carbendazim, prochloraz manganese salt, thiophanate methyl, etc.

[0094] Furthermore, preferably, the mass mixing ratio of ZJS178 to the imidazole-based disinfectant in the above composition is 20:1 to 1:20.

[0095] Furthermore, preferably, the mass mixing ratio of ZJS178 to the imidazole-based disinfectant in the above composition is 12:1 to 1:12.

[0096] Furthermore, preferably, the mass mixing ratio of ZJS178 to the imidazole-based disinfectant in the above composition is 6:1 to 1:6.

[0097] Most preferably, the mass mixing ratio of ZJS178 and the imidazole-based disinfectant in the above composition is 3:1 to 1:3.

[0098] The composition provided by the present invention is suitable for sterilization, and is particularly suitable for agricultural sterilization.

[0099] Preferably, the composition provided by the present invention is suitable for controlling diseases caused by Fusarium.

[0100] Furthermore, preferably, the above Fusarium refers to plant pathogenic Fusarium and mainly includes Fusarium graminearum complex, Fusarium fujikuroi complex, Fusarium oxysporum and Fusarium moniliforme, etc.

[0101] Furthermore, preferably, crop diseases caused by Fusarium include, but are not limited to, cucurbit wilt, tomato wilt, banana wilt, cotton wilt, strawberry wilt, rice blast, and wheat red mold.

[0102] The disinfectant provided by the present invention contains 0.5 to 90% of the above composition by weight.

[0103] Furthermore, preferably, the disinfectant contains 5 to 80% of the composition by weight.

[0104] The fungicide provided by the present invention may further include an agriculturally acceptable carrier and an auxiliary agent in addition to the above composition.

[0105] Since ZJS178 and imidazole fungicides have different mechanisms of action, the present invention combines ZJS178 with them to provide a significantly higher control effect against diseases caused by Fusarium than with a single agent, reduce the amount of single agent used, delay the development of drug resistance in pathogens, and help extend the service life of the fungicide.

[0106] According to research, compound ZJS178 and imidazole fungicides have a synergistic effect on inhibiting the growth of Fusarium under specific mixing ratio conditions. For example, compound ZJS178 and thiophanate-methyl are mixed in a mass ratio of 3:1 to 1:3, which has a significant effect on inhibiting the growth of Fusarium oxysporum.

[0107] Furthermore, the fungicide further includes auxiliary components necessary for a pesticide formulation, and the mass ratio of the active component in the composition is 0.5 to 90%. The auxiliary components are carriers and adjuvants commonly used in pesticides.

[0108] In accordance with methods known to those skilled in the art, the fungicide composition of the present invention can be prepared in various formulations acceptable for agricultural application and includes water-dispersible granules, suspensions, and suspensions for seed treatment.

[0109] For water-dispersible granules, polycarboxylates, lignin sulfonates, and alkylnaphthalene sulfonates can be selected as dispersants. Alkyl sulfates, alkyl sulfonates, and naphthalene sulfonates can be selected as wetting agents. Ammonium sulfate, urea, sucrose, and glucose can be selected as disintegrants. Diatomaceous earth, corn starch, polyvinyl alcohol, and carboxymethylcellulose can be selected as binders. Diatomaceous earth, kaolin, white carbon black, hard calcium, talc powder, attapulgite, clay, etc. can be selected as fillers.

[0110] For suspension formulations, the adjuvants that can be used are as follows: Polycarboxylates, lignin sulfonates, and alkylnaphthalene sulfonates may be selected as dispersants. Alkylphenol polyoxyethylene polygroup ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate ester, benzylphenol polyoxyethylene ether phosphate ester, alkyl sulfate, alkyl sulfonate, and naphthalene sulfonate may be selected as wetting agents. Xanthan gum, polyvinyl alcohol, and bentonite may be selected as thickeners. Formaldehyde, benzoic acid, and sodium benzoate may be selected as preservatives. Organosilicon-based defoaming agents may be used. Inorganic salts such as ethylene glycol, propylene glycol, glycerin, urea, and sodium chloride may be selected as antifreeze agents.

[0111] For seed treatment suspensions, the adjuvants that may be used are as follows: As film-forming agents, polyethylene glycol, polyvinyl alcohol resin, polyvinylpyrrolidone, hydroxyethylcellulose, polyvinyl acetate, sodium carboxymethylcellulose, gum arabic, gelatin, polyvinyl alcohol or polyacrylamide, or mixtures thereof may be used. The technician may adjust the proportion of polyvinyl acetate according to the viscosity required for the product.

[0112] In the fifth aspect of the present invention,

[0113] The present invention provides a sterilization composition, said composition comprising a compound ZJS178 represented by chemical formula (I) and a methoxyacrylate-based sterilizer.

[0114] (I)

[0115] The above compound ZJS178 is a new compound previously prepared by the research team of the present invention, and its chemical name is ethyl 2-cyano-3-amino-3-[4-(N-ethyl-N-methylamino)phenyl]acrylate, and its synthesis route is as follows.

[0116]

[0117] This compound is a cyanoacrylate-based fungicide that acts on Fusarium type I myosin (motor protein) to cause the pathogen to lose its growth momentum, thereby killing the pathogen. ZJS178 has a novel structure and a unique mode of action, and it does not exhibit cross-resistance with methoxyacrylate-based fungicides.

[0118] Preferably, the mass mixing ratio of the ZJS178 and the methoxyacrylate-based disinfectant is 60:1 to 1:60.

[0119] The above methoxyacrylate-based disinfectants include, but are not limited to, azoxystrobin, trifloxystrobin, fluoxastrobin, picoxystrobin, pyraclostrobin, benzene cresoxim methyl and phenaminestrobin.

[0120] Furthermore, preferably, the mass mixing ratio of the above ZJS178 and the methoxyacrylate-based disinfectant is 20:1 to 1:20.

[0121] Furthermore, preferably, the mass mixing ratio of the above ZJS178 and the methoxyacrylate-based disinfectant is 12:1 to 1:12.

[0122] Furthermore, preferably, the mass mixing ratio of the above ZJS178 and the methoxyacrylate-based disinfectant is 6:1 to 1:6.

[0123] Most preferably, the mass mixing ratio of the above ZJS178 and the methoxyacrylate-based disinfectant is 3:1 to 1:3.

[0124] The composition provided by the present invention is suitable for sterilization, and is particularly suitable for agricultural sterilization.

[0125] Preferably, the composition provided by the present invention is suitable for controlling diseases caused by Fusarium.

[0126] Furthermore, preferably, the above Fusarium refers to plant pathogenic Fusarium and mainly includes Fusarium graminearum complex, Fusarium fujikuroi complex, Fusarium oxysporum and Fusarium moniliforme, etc.

[0127] Furthermore, preferably, the composition provided by the present invention is used for controlling diseases such as cucurbit wilt disease, tomato wilt disease, banana wilt disease, cotton wilt disease, strawberry wilt disease, rice blast disease, and wheat red mold disease.

[0128] In the sterilization composition provided by the present invention, the sterilizer contains 0.5 to 90% of the composition by weight.

[0129] Furthermore, preferably, the disinfectant contains 5 to 80% of the composition by weight.

[0130] The fungicide provided by the present invention may further include an agriculturally acceptable carrier and an auxiliary agent in addition to the above composition.

[0131] Since ZJS178 and methoxyacrylate-based fungicides have different mechanisms of action, the present invention combines ZJS178 with them to provide a significantly higher control effect against diseases caused by Fusarium than with a single agent, reduce the amount of single agent used, delay the development of drug resistance in pathogens, and help extend the service life of the fungicide.

[0132] According to research, compound ZJS178 and methoxyacrylate fungicides have a synergistic effect on inhibiting the growth of Fusarium under specific mixing ratio conditions. For example, when compound ZJS178 and azoxystrobin are mixed in a mass ratio of 3:1 to 1:1, there is a significant increase in the effect on inhibiting the growth of Fusarium oxysporum.

[0133] Furthermore, the above-mentioned sterilization composition further includes auxiliary components necessary for pesticide formulations, and the mass ratio of the active component in the composition is 0.5 to 90%. The above-mentioned auxiliary components are carriers and adjuvants commonly used in pesticides.

[0134] In accordance with methods known to those skilled in the art, the sterilizing composition of the present invention may be prepared in various formulations acceptable for agricultural use in actual application, and includes water-dispersible granules, suspensions, and suspensions for seed treatment.

[0135] For water-dispersible granules, polycarboxylates, lignin sulfonates, and alkylnaphthalene sulfonates can be selected as dispersants. Alkyl sulfates, alkyl sulfonates, and naphthalene sulfonates can be selected as wetting agents. Ammonium sulfate, urea, sucrose, and glucose can be selected as disintegrants. Diatomaceous earth, corn starch, polyvinyl alcohol, and carboxymethylcellulose can be selected as binders. Diatomaceous earth, kaolin, white carbon black, hard calcium, talc powder, attapulgite, clay, etc. can be selected as fillers.

[0136] For suspension formulations, the adjuvants that can be used are as follows: Polycarboxylates, lignin sulfonates, and alkylnaphthalene sulfonates may be selected as dispersants. Alkylphenol polyoxyethylene polygroup ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate ester, benzylphenol polyoxyethylene ether phosphate ester, alkyl sulfate, alkyl sulfonate, and naphthalene sulfonate may be selected as wetting agents. Xanthan gum, polyvinyl alcohol, and bentonite may be selected as thickeners. Formaldehyde, benzoic acid, and sodium benzoate may be selected as preservatives. Organosilicon-based defoaming agents may be used. Inorganic salts such as ethylene glycol, propylene glycol, glycerin, urea, and sodium chloride may be selected as antifreeze agents.

[0137] For seed treatment suspensions, the adjuvants that may be used are as follows: As film-forming agents, polyethylene glycol, polyvinyl alcohol resin, polyvinylpyrrolidone, hydroxyethylcellulose, polyvinyl acetate, sodium carboxymethylcellulose, gum arabic, gelatin, polyvinyl alcohol or polyacrylamide, or mixtures thereof may be used. The technician may adjust the proportion of polyvinyl acetate according to the viscosity required for the product. Effects of the invention

[0138] Compared to conventional technology, the present invention has the following beneficial effects.

[0139] (1) The fungicidal composition provided by the present invention has an excellent control effect against crop diseases caused by Fusarium, and the combination of compound ZJS178 and a triazole fungicide has an effect-enhancing effect, which can significantly improve fungicidal activity and control effect. The combination of compound ZJS178 and a succinate dehydrogenase inhibitor fungicide has two components that inhibit the mechanical energy (motor protein) and biological energy (ATP synthesis) of the pathogen, respectively; although the mechanisms of action of the two components are different, they are interrelated, so the combination of the two components has a significant effect-enhancing effect and significantly enhances the fungicidal effect. The combination of compound ZJS178 and a pyrrole fungicide has an effect-enhancing effect, significantly improves fungicidal activity against Fusarium, and provides a significant control effect against seed-borne and soil-borne crop diseases caused by Fusarium. The combination of compound ZJS178 and thiophanate-methyl or prochloraz has an effect-enhancing effect and can significantly improve fungicidal activity and control effect. The combination of compound ZJS178 and methoxyacrylate-based fungicides has a significant effect-enhancing action and can significantly improve fungicidal activity and control effects.

[0140] (2) The composition provided by the present invention is composed of active ingredients with different mechanisms of action, so there is no cross-resistance, which is advantageous for overcoming and delaying drug resistance of pathogens, has excellent safety for crops, and meets the requirements for reducing pesticide usage and increasing effectiveness. Specific details for implementing the invention

[0141] The present invention is described in more detail through the following specific examples. The following examples are for illustrative purposes only and are not intended to limit the scope of application of the present invention. Any modification or substitution of the methods, steps, or conditions of the present invention falls within the scope of the present invention, provided that such modification or substitution does not depart from the spirit and essence of the invention.

[0142] The test methods used in the examples below are all conventional methods unless otherwise specified. Unless otherwise specified, the materials and reagents used are those available through commercial channels.

[0143] Example 1: Synthesis of Compound ZJS178

[0144] Step 1: Synthesis of intermediate b

[0145]

[0146] 7.0 g of raw material a (CAS number: 67710-36-5) and 150 mL of dichloromethane were placed in a reaction flask. Under an ice bath, 11.7 g of Boc acid anhydride was added, followed by the slow addition of 6.0 g of triethylamine and 3.3 g of DMAP. The mixture was stirred continuously under an ice bath for 0.5 hours, then heated to room temperature and stirred for another 5 hours. After the reaction was complete, 1 M hydrochloric acid was added to the reaction mixture, and the organic layer was separated and washed once each with distilled water and saturated saline solution. The organic layer was dried with anhydrous Na2SO4 and concentrated to obtain 9.6 g of intermediate b, which was used directly in the next step of the reaction without further purification.

[0147] Step 2: Synthesis of intermediate c

[0148]

[0149] 9.6 g of intermediate b, 120 mL of ethanol, and 24 mL of water were added to a reaction flask and heated to 90°C. Then, 3.7 g of iron and 12 mL of saturated ammonium chloride solution were added, and the reaction was continued for 4 hours. After the reaction was finished, diatomite was added and the mixture was filtered. The filtrate was concentrated, water was added, and the mixture was extracted three times with ethyl acetate. The organic layers were combined and concentrated, then separated by column chromatography (the eluent consisted of ethyl acetate and petroleum ether, in a volume ratio of 1:2). 4.5 g of intermediate c was obtained, with a yield of 51.1%.

[0150] Step 3: Synthesis of intermediate d

[0151]

[0152] 0.19 g of sodium hydride was added to 20 mL of tetrahydrofuran under an ice bath, followed by the addition of 1.0 g of intermediate c. The mixture was then heated to room temperature and stirred for 30 minutes. Then, 0.74 g of ethyl iodide was added and stirred overnight at room temperature. After the reaction was complete, water was added to terminate the reaction, and the mixture was extracted three times with ethyl acetate. The organic layers were combined and concentrated, then separated by column chromatography (the eluent consisted of ethyl acetate and petroleum ether, in a volume ratio of 1:5). 0.52 g of intermediate d was obtained, with a yield of 48.0%.

[0153] Step 4: Synthesis of intermediate e

[0154]

[0155] 0.11 g of sodium hydride was added to 10 mL of tetrahydrofuran under an ice bath, followed by the addition of 0.5 g of intermediate d, and the mixture was heated to room temperature and stirred for 30 minutes. Then, 0.40 g of methyl iodide was added and the mixture was stirred overnight at room temperature. After the reaction was complete, water was added to terminate the reaction, and the mixture was extracted three times with ethyl acetate. The organic layers were combined and concentrated, then separated by column chromatography (the eluent consisted of ethyl acetate and petroleum ether, in a volume ratio of 1:5), yielding 0.34 g of intermediate e, with a yield of 65.5%.

[0156] Step 5: Synthesis of Compound ZJS178

[0157]

[0158] 0.34 g of intermediate e and 10 mL of tetrahydrofuran were added to a reaction flask, hydrogen chloride gas was produced by adding concentrated sulfuric acid dropwise to sodium chloride and slowly introduced into the reaction mixture, and after 1 hour, aeration was stopped and the mixture was stirred overnight at room temperature. After the reaction was finished, an aqueous solution of saturated sodium bicarbonate was added and extracted twice with ethyl acetate. The organic layers were combined and concentrated, then separated by column chromatography (the eluent consisted of ethyl acetate and petroleum ether, in a volume ratio of 1:2), yielding 0.22 g of compound ZJS178, with a yield of 93.2%.

[0159] Example 2: Measurement of indoor toxicity of ZJS178 and tebuconazole combination against wheat red mold pathogen

[0160] Test subjects: Tebuconazole-susceptible (TS) and TR-resistant (TR) wheat red mold fungi (*Fusarium graminearum*) isolated from packaging. After identifying morphology, pathogenicity, and drug resistance, the test strains were preserved in this laboratory for use.

[0161] Test agent: ZJS178 was synthesized in Example 1; tebuconazole (provided by Zhejiang Chemical Research Institute).

[0162] Test Method: The mycelial growth rate method of the <Agricultural Industry Standard of the People's Republic of China NY / T 1156.2-2006> was referenced. For each agent, five dose treatments were established based on the content of the active ingredient, and the pathogen growth inhibition rate was set to be between 10% and 90%. The above-mentioned wheat red mold pathogen was inoculated onto PDA medium, and after waiting until the colony filled 2 / 3 of the culture dish, a mycelial disc was created from the edge of the colony using a 5 mm diameter punch. The mycelial disc was then transferred to the center of a pre-prepared agent-containing medium plate using an inoculation needle, and after incubation in a 25°C incubator for 3 days, the colony diameter of each treatment was measured using calipers with the cross-cross method, and the corrected inhibition percentage was calculated. Subsequently, the EC50 value of each agent was calculated through linear regression analysis between the probability value of the inhibition rate and the logarithm of the continuous concentration, and each treatment was repeated 4 times. ZJS178 is set as the standard drug, and the contingent toxicity factor (CTC) is calculated according to the following formula.

[0163] Actual Toxicity Index (ATI) = (EC50 of Standard Agent / EC50 of Test Agent) × 100;

[0164] Theoretical Toxicity Index (TTI) = Standard Drug Toxicity Index × Percentage of Standard Drug in Mixed Composition + Test Drug Toxicity Index × Percentage of Test Drug in Mixed Composition;

[0165] Co-toxicity Factor (CTC) = (ATI / TTI) × 100%;

[0166] If the CTC value is less than 80, the drug combination exhibits an antagonistic effect; if it is between 80 and 120, it exhibits an additive effect; and if it is greater than 120, it exhibits an effect-enhancing effect.

[0167] The test results are shown in Table 1 and Table 2.

[0168] Table 1: Results of indoor toxicity measurements of the ZJS178 and tebuconazole combination against tebuconazole-susceptible wheat red mold (TS).

[0169]

[0170] Table 2: Results of indoor toxicity measurements of ZJS178 and tebuconazole combinations against tebuconazole-resistant wheat red mold (TR) disease

[0171]

[0172] As shown in Tables 1 and 2, ZJS178 has a very strong antimicrobial effect against tebuconazole-resistant (TR) and susceptible (TS) wheat red mold pathogens. The 2:1, 1:1, and 1:2 combinations of ZJS178 and tebuconazole exhibit an potent effect against both resistant and susceptible strains.

[0173] Example 3: Measurement of indoor toxicity of ZJS178 and metconazole combination against rice blast disease

[0174] Test subjects: Metconazole-susceptible (MS) and resistant (MR) rice blast pathogens (Fusarium fujikuroi) isolated from the field. Test strains were preserved in this laboratory after identification of morphology, pathogenicity, and drug resistance.

[0175] Test agent: ZJS178 was synthesized in Example 1; metconazole (provided by Zhejiang Chemical Research Institute).

[0176] The bioassay method was referenced in Example 2.

[0177] The test results are shown in Tables 3 and 4.

[0178] Table 3: Results of indoor toxicity measurements of ZJS178 and metconazole combinations against metconazole-susceptible rice blast pathogens (MS).

[0179]

[0180] Table 4: Results of indoor toxicity measurements of ZJS178 and metconazole combinations against metconazole-resistant rice blast pathogens (MR).

[0181]

[0182] As shown in Tables 3 and 4, ZJS178 has a very strong inhibitory effect on the mycelial growth of metconazole (MR) and susceptible (MS) rice blast pathogens. The 3:1, 2:1, 1:1, 1:2, and 1:3 combinations of ZJS178 and metconazole exhibit an amplifying effect against both resistant and susceptible strains.

[0183] Example 4: Measurement of indoor toxicity of ZJS178 and tebuconazole combination against strawberry wilt pathogens

[0184] Test subjects: Strawberry wilt pathogen (Fusarium oxysporum) isolated from diseased strawberries in the field. The test strains were preserved in this laboratory after morphological and pathogenic identification.

[0185] Test agent: ZJS178 was synthesized in Example 1; tebuconazole (provided by Zhejiang Chemical Research Institute).

[0186] The bioassay method was referenced in Example 2.

[0187] The test results are shown in Table 5.

[0188] Table 5: Results of indoor toxicity measurements of the ZJS178 and tebuconazole mixture against strawberry wilt pathogens

[0189]

[0190] As can be seen from the results in Table 5, the combination of ZJS178 and tebuconazole has an effect-enhancing effect and can significantly improve the antibacterial effect of the drug against strawberry wilt pathogens.

[0191] Example 5: Packaging efficacy test

[0192] I. Formulation of the Formulation

[0193] The percentage of the formulation ratio for all formulations is a mass percentage.

[0194] (1) 40% ZJS178 Tebuconazole water-dispersible granules

[0195] 10% ZJS178, 30% tebuconazole, 3% TERSPERSE 2700, 2% spreading agent NNO (alkylnaphthalenesulfonate formaldehyde condensate), 3% release agent BX (sodium dibutylnaphthalenesulfonate), 4% K-12 (sodium dodecyl sulfate), 3% diatomite, 5% glucose, and kaolin are added up to 100%.

[0196] According to the mixing ratio, the active ingredient, dispersant, wetting agent, binder, etc. are fed into a granulator equipped with a sieve of a certain size and granulated using a conventional method for manufacturing water-dispersible granules, namely mixing, ultrafine airflow grinding, and granulation. Afterward, the granular product is obtained by drying and sieving.

[0197] (2) 30% ZJS178 Tebuconazole suspension

[0198] 15% ZJS178, 15% tebuconazole, 2% TERSPERSE 2500, 3% TERSPERSE 2425, 0.2% xanthan gum, 3% white carbon black, 5% ethylene glycol, 0.3% benzoic acid, 0.5% organosilicon antifoaming agent, and deionized water are added up to 100% by mass.

[0199] According to the mixing ratio, the raw material, dispersant, suspension aid, and antifreeze agent are placed in a mixing tank with water as the medium and uniformly mixed, then dispersed for 30 minutes using a ball mill or high-speed shear disperser, and then ground with a sand mill to produce a suspension agent.

[0200] (3) 25% ZJS178 Metconazole suspension

[0201] 15% ZJS178, 10% metconazole, 2% NNO, 2% TERSPERSE 2500, 1% emulsifier T-60, 3% pesticide emulsifier 700#, 0.1% xanthan gum, 3% white carbon black, 5% propylene glycol, 0.5% formaldehyde, 0.5% organosilicon defoamer, and deionized water are added up to 100% by mass.

[0202] According to the mixing ratio, the raw material, dispersant, suspension aid, and antifreeze agent are placed in a mixing tank with water as the medium and uniformly mixed, then dispersed for 30 minutes using a ball mill or high-speed shear disperser, and then ground with a sand mill to produce a suspension agent.

[0203] (4) 40% ZJS178 Tebuconazole microemulsion

[0204] 25% ZJS178, 15% tebuconazole, 4% TX-10, 6% pesticide emulsifier 500#, 4% pesticide emulsifier 1601#, 15% cyclohexanone, 5% N-methylpyrrolidone, 5% n-butanol, and 1% epichlorohydrin are completely dissolved and uniformly mixed, and deionized water is added up to 100% by mass and stirred to prepare a microemulsion.

[0205] The active ingredient, solvent, and emulsifier are added together and dissolved into a uniform oil phase; the water-soluble component is mixed with water to form an aqueous phase; and the oil phase and aqueous phase are mixed under high-speed stirring to prepare a microemulsion.

[0206] (5) 15% ZJS178 Tebuconazole aqueous emulsion

[0207] 10% ZJS178, 5% tebuconazole, 1.5% nonylphenol polyoxyethylene (EO=10) ether phosphate ester, 2.5% tribenzylethylphenol polyoxyethylene ether phosphate ester (pesticide emulsifier 600# phosphate ester), 1% epichlorohydrin, 5% ethylene glycol, 20% xylene, 10% cyclohexanone, 0.3% xanthan gum, 0.5% benzoic acid, and deionized water are added up to 100% by mass.

[0208] The above raw materials are mixed and manufactured by high-speed shear emulsification.

[0209] II. Packaging Efficacy Test for Wheat Red Mold Disease

[0210] Control of wheat red mold is carried out in accordance with the regulations of "NY / T1464.15-2007 Pesticide Field Efficacy Test Guidelines - Control of Wheat Red Mold by Fungicides." The pesticide is applied once during the early heading and flowering stages, followed by a second application after a 6-day interval, and results are obtained during the milk ripening stage. In each test area, a diagonal 5-point sampling method is employed, with 100 to 200 ears surveyed at each point. The disease is graded based on the percentage of withered ear area relative to the total ear area, and the number of diseased ears for each grade and the total number of ears are recorded. The disease grading criteria are as follows:

[0211] Grade 0: No disease on the entire ear;

[0212] Grade 1: Withered ear area is 1 / 4 or less of the total ear area;

[0213] Grade 2: Withered ear area is 1 / 4 to 1 / 2 of the total ear area;

[0214] Grade 3: Withered ear area is 1 / 2 to 3 / 4 of the total ear area;

[0215] Grade 5: Withered ear area is 3 / 4 or more of the total ear area.

[0216] Method for Calculating Efficacy: Based on the survey results, the disease index and the chemical control value are calculated using the formula below.

[0217] Incidence =

[0218] Chemical control (%) = ×100%

[0219] The test results are shown in Table 6.

[0220] Table 6: Field efficacy test results of ZJS178 and triazole pesticide combination for wheat red mold disease

[0221]

[0222] Different lowercase letters following the data in the same column indicate a significant difference at the P < 0.05 level.

[0223] As can be seen from the results of the packaging efficacy test (Table 6) above, ZJS178 The triazole fungicide formulation can effectively control wheat red mold, and the mixture is significantly superior to a single control agent at the same dosage. It is safe for test crops within the tested agent's usage range.

[0224] In summary, the results of indoor bioassays and field efficacy tests demonstrate the following: The composition of the present invention possesses an effect-enhancing action and exhibits excellent antimicrobial and control effects against Fusarium diseases in various crops. The composition consists of active ingredients with different mechanisms of action, which is advantageous for overcoming and delaying the development of drug resistance in pathogens, and is safe for test crops.

[0225] Example 6: Measurement of indoor toxicity of ZJS178 and pidiflumethofene combination against wheat red mold

[0226] Test Subject: Wheat red mold pathogen (Fusarium graminearum). It was isolated from the field and identified as Fusarium graminearum using biological methods such as morphology and pathogenicity. It was preserved in this laboratory for use.

[0227] Test agent: ZJS178 is the synthetic of Example 1, pidiflumetofen (Syngenta Nantong Crop Protection Co., Ltd., commercial product).

[0228] Test method: The mycelial growth rate method of the <Agricultural Industry Standard of the People's Republic of China NY / T 1156.2-2006> was referenced. For each agent, five dose treatments were established according to the content of the active ingredient, and the pathogen growth inhibition rate was set to be between 10% and 90%. The above wheat red mold pathogen was inoculated onto a PDA medium, and after waiting until the colony filled 2 / 3 of the culture dish, a mycelial disc was made from the edge of the colony using a 5 mm diameter punch, and the mycelial disc was transferred to the center of a pre-prepared agent-containing medium using an inoculation needle. After incubation in a 25°C incubator for 3 days, the colony diameter (cm) of each treatment group was measured using calipers with the cross-cross method, and the corrected inhibition percentage was calculated. Then, the EC50 value of each agent was calculated through linear regression analysis between the probability value of the inhibition rate and the logarithm of the continuous concentration, and each treatment was repeated 4 times. ZJS178 is set as the standard drug, and the contingent toxicity factor (CTC) is calculated according to the following formula.

[0229] Actual Toxicity Index (ATI) = (EC50 of Standard Agent / EC50 of Test Agent) × 100;

[0230] Theoretical Toxicity Index (TTI) = Standard Drug Toxicity Index × Percentage of Standard Drug in Mixed Composition + Test Drug Toxicity Index × Percentage of Test Drug in Mixed Composition;

[0231] Co-toxicity Factor (CTC) = (ATI / TTI) × 100%;

[0232] If the CTC value is less than 80, the drug combination exhibits an antagonistic effect; if it is between 80 and 120, it exhibits an additive effect; and if it is greater than 120, it exhibits an effect-enhancing effect.

[0233] The test results are shown in Table 7.

[0234] Table 7. Results of indoor toxicity measurements of the ZJS178 and pidiflumetofen combination against wheat red mold disease

[0235]

[0236] As can be seen from the results in Table 7, both ZJS178 and pidiflumetofen have excellent antibacterial effects against wheat red mold, and combinations of the two ingredients within the range of 5:1 to 1:5 all show an effect-enhancing action.

[0237] Example 7: Measurement of indoor toxicity of ZJS178 and fenflufen combination against rice blast disease

[0238] Test subject: Rice blast pathogen (Fusarium fujikuroi), isolated from the field, identified as Fusarium fujikuroi by biological methods such as morphology and pathogenicity, and preserved in this laboratory.

[0239] Test agent: ZJS178 is synthesized in Example 1, fenflufen (Bayer Corp., commercial product).

[0240] Refer to Example 6 for the bioassay method.

[0241] The test results are shown in Table 8.

[0242] Table 8: Results of indoor toxicity measurements of the ZJS178 and fenflufen combination against rice blast disease

[0243]

[0244] As can be seen from the results in Table 8, both ZJS178 and pidiflumetofen have very good antibacterial effects against rice blast fungi, and the combination of ZJS178 and fenflufen in the range of 5:1 to 1:5 has a significant increase in effect.

[0245] Example 8: Packaging efficacy test

[0246] I. Formulation of the Formulation

[0247] The percentage of the formulation ratio for all formulations is a mass percentage.

[0248] (1) 40% ZJS178 Pidiflumetofen water-dispersible granules

[0249] 20% ZJS178, 20% pidiflumethofen, 3% TERSPERSE 2700, 2% spreading agent NNO (alkylnaphthalenesulfonate formaldehyde condensate), 3% release agent BX (sodium dibutylnaphthalenesulfonate), 4% K-12 (sodium dodecyl sulfate), 3% diatomite, 5% glucose, and kaolin are added up to 100%.

[0250] According to the mixing ratio, the active ingredient, dispersant, wetting agent, binder, etc. are fed into a granulator equipped with a sieve of a certain size and granulated using a conventional method for manufacturing water-dispersible granules, namely mixing, ultrafine airflow grinding, and granulation. Afterward, the granular product is obtained by drying and sieving.

[0251] (2) 10% ZJS178 Fenflufen suspension

[0252] 5% ZJS178, 5% fenflufen, 2% TERSPERSE 2500, 3% TERSPERSE 2425, 0.2% xanthan gum, 3% white carbon black, 5% ethylene glycol, 0.5% formaldehyde, 0.3% benzoic acid, 0.5% organosilicon defoamer (product name: s-29 Nanjing Sixin Applied Chemicals Co., Ltd.), and deionized water are added up to 100% by mass.

[0253] According to the mixing ratio, the raw material, dispersant, suspension aid, and antifreeze agent are placed in a mixing tank with water as the medium and uniformly mixed, then dispersed for 30 minutes using a ball mill or high-speed shear disperser, and then ground with a sand mill to produce a suspension agent.

[0254] II. Packaging Test

[0255] 2.1 Packaging Efficacy Test for Wheat Red Mold Disease

[0256] Control of wheat red mold is carried out in accordance with the regulations of "NY / T1464.15-2007 Field Efficacy Test Guidelines for Agrochemicals - Control of Wheat Red Mold by Fungicides." The fungicide is applied once during the early heading and flowering stages of wheat, followed by a second application after a 6-day interval. Surveys are conducted two weeks after application. In each test area, a diagonal 5-point sampling method is employed, with 100 to 200 ears surveyed at each point. The disease is graded based on the percentage of withered ear area relative to the total ear area, and the number of diseased ears for each grade and the total number of ears are recorded. The disease grading criteria are as follows:

[0257] Grade 0: No disease on the entire ear;

[0258] Grade 1: Withered ear area is 1 / 4 or less of the total ear area;

[0259] Grade 2: Withered ear area is 1 / 4 to 1 / 2 of the total ear area;

[0260] Grade 3: Withered ear area is 1 / 2 to 3 / 4 of the total ear area;

[0261] Grade 4: Withered ear area is 3 / 4 or more of the total ear area.

[0262] Incidence =

[0263] Chemical control (%) = ×100%

[0264] The test results are shown in Table 9.

[0265] Table 9. ZJS178 Efficacy results of the pidiflumetofen formulation for wheat red mold disease packaging

[0266]

[0267] Different lowercase letters following the data in the same column indicate a significant difference at the P < 0.05 level.

[0268] The results in Table 9 are ZJS178 The pyribencarb combination agent shows excellent control effect against rice blast. Compared with the single agent, the combination of the two components has a significant effect enhancement at the same dosage.

[0269] 2.2 Pesticide efficacy test for controlling rice false smut

[0270] The control of rice false smut is carried out according to the provisions of <GB-T 17980.104-2004 Guidelines for pesticide efficacy test of packaged pesticides (Part 2) - Control of rice false smut by fungicides>. The test site is Dongpuzhen, Shaoxing City ( ), and the rice variety is Zhongzao 39 (susceptible variety). The medicament solution is diluted to a certain concentration and sown at the earliest after soaking the seeds for 72 hours. Raise seedlings using loam soil, and the seedling raising process is strictly carried out according to the mechanical transplanting seedling raising process. The seed amount, soil fertility, etc. of each treatment are all the same. Use 20 seedling trays for each treatment, and the amount of seeds used per tray is 150 g. Investigate the incidence of false smut before transplanting rice for 1 day and before heading, and calculate the diseased plant rate and control efficacy according to the following formulas.

[0271] Diseased plant rate (%) = × 100

[0272] Control efficacy of medicament (%) = × 100

[0273] The test results are shown in Table 10.

[0274] Table 10: ZJS178 Results of pesticide efficacy test for controlling rice false smut by penflufen combination agent

[0275]

[0276] * Different lowercase letters behind the data in the same row indicate significant differences at the P < 0.05 level.

[0277] The results of the packaging efficacy test in Table 10 show that the combination of ZJS178 and fenflufen has excellent control efficacy against rice blast disease. Under the same effective dose conditions, the control efficacy of the combination is significantly superior to that of the single agent. It is safe for test crops within the usage range of the test agents.

[0278] In summary, the results of indoor bioassays and field efficacy tests show the following: The fungicide composition of the present invention exhibits a significant effect-enhancing action, and furthermore, the composition is composed of active ingredients with different mechanisms of action, which can delay the development of resistance by pathogens to a single agent. The formulation shows no distinct side effects on test crops, and leaf color, growth status, etc., are all normal.

[0279] Example 9: Indoor toxicity measurement of ZJS178 and fludioxonil combination against Mild Fusarium pseudogramminiarum

[0280] Test subjects: Fludioxonil resistant (FR) and susceptible (FS) Fusarium pseudograminearum, isolated, identified, and preserved in this laboratory.

[0281] Test agent: ZJS178 was synthesized in Example 1; fludioxonil (provided by Zhejiang Chemical Research Institute).

[0282] Test method: Refer to the mycelial growth rate method of the <Agricultural Industry Standard of the People's Republic of China NY / T 1156.2-2006>. For each drug, five dose treatments were established according to the content of the active ingredient. The above-mentioned *Fusarium pseudograminia* was inoculated onto a PDA medium, and after waiting until the colony filled 2 / 3 of the culture dish, a mycelial disc was made from the edge of the colony using a 5 mm diameter punch. The mycelial disc was then transferred to the center of the pre-prepared drug-containing PDA medium using an inoculation needle, and after incubation in a 25°C incubator for 3 days, the colony diameter (cm) of each treatment group was measured using calipers with the cross-cross method, and the corrected inhibition percentage was calculated. Then, the EC50 value of each drug was calculated through linear regression analysis between the probability value of the inhibition rate and the logarithm of the continuous concentration, and each treatment was repeated 4 times. ZJS178 is set as the standard drug, and the contingent toxicity factor (CTC) is calculated according to the following formula.

[0283] Actual Toxicity Index (ATI) = (EC50 of Standard Agent / EC50 of Test Agent) × 100;

[0284] Theoretical Toxicity Index (TTI) = Standard Drug Toxicity Index × Percentage of Standard Drug in Mixed Composition + Test Drug Toxicity Index × Percentage of Test Drug in Mixed Composition;

[0285] Co-toxicity Factor (CTC) = (ATI / TTI) × 100%;

[0286] If the CTC value is less than 80, the drug combination exhibits an antagonistic effect; if it is between 80 and 120, it exhibits an additive effect; and if it is greater than 120, it exhibits an effect-enhancing effect.

[0287] The test results are shown in Tables 11 and 12.

[0288] Table 11: Indoor toxicity test results of ZJS178 and fludioxonil combination against fludioxonil-resistant Fusarium pseudogramminiarum (FR)

[0289]

[0290] Table 12: Indoor toxicity test results of ZJS178 and fludioxonil formulations on fludioxonil-sensitive Fusarium pseudogramminiarum (FS).

[0291]

[0292] The results in Tables 11 and 12 show that ZJS178 has very good antimicrobial effects against both fludioxonil-resistant (FR) and susceptible (FS) Fusarium pseudograminiarum. The reasonable combination of ZJS178 and fludioxonil has additive or enhancing effects against resistant and susceptible strains, and there is no antagonistic effect.

[0293] Example 10: Measurement of indoor toxicity of ZJS178 and fludioxonil combination against rice blast pathogens

[0294] Test subject: Rice blast pathogen (Fusarium fujikuroi), preserved in the strain room of this laboratory.

[0295] Test agent: ZJS178 was synthesized in Example 1; fludioxonil (provided by Zhejiang Chemical Research Institute).

[0296] Refer to Example 9 for the bioassay method.

[0297] The test results are shown in Table 13.

[0298] Table 13: Results of indoor toxicity measurements of ZJS178 and fludioxonil combination against rice blast pathogens

[0299]

[0300] The results in Table 13 show that both ZJS178 and fludioxonil have excellent antibacterial effects against rice blast disease, and that the combination of the two components exhibits additive or enhanced effects.

[0301] Example 11: Measurement of indoor toxicity of ZJS178 and fludioxonil combination against tomato wilt pathogens

[0302] Test subject: The tomato wilt pathogen (Fusarium oxysporum) is preserved in the strain room of this laboratory.

[0303] Test agent: ZJS178 was synthesized in Example 1; fludioxonil (provided by Zhejiang Chemical Research Institute).

[0304] Refer to Example 9 for the bioassay method.

[0305] The test results are shown in Table 14.

[0306] Table 14. Results of indoor toxicity measurements of the ZJS178 and fludioxonil mixture against tomato wilt pathogens

[0307]

[0308] The results in Table 14 show that both ZJS178 and fludioxonil have significant antibacterial activity against tomato wilt pathogens, and that a reasonable combination of the two components has an additive or enhanced effect.

[0309] Example 12: Packaging efficacy test

[0310] 1. 25% ZJS178 Manufacture of fludioxonil suspension

[0311] The percentages of the formulation ratios for the seed treatment suspension are all mass percentages. According to the following formulation ratios, the stock agent, dispersant, suspension aid, antifreeze agent, etc. are placed in a mixing tank with water as the medium and uniformly mixed, then dispersed for 30 minutes using a ball mill or high-speed shear disperser, and then ground with a sand mill to produce the product.

[0312] 15% ZJS178, 10% fludioxonyl, 2% TERSPERSE 2500, 3% TERSPERSE 2425, 0.2% xanthan gum, 3% white carbon black, 5% ethylene glycol, 0.3% benzoic acid, 0.5% organosilicon defoamer (product name: s-29 Nanjing Sixin Applied Chemicals Co., Ltd.), and deionized water are added up to 100% by mass.

[0313] II. Packaging Test

[0314] Packaging Application Example 1: Packaging Pharmacodynamic Test for Controlling Rice Sheath Blight

[0315] The control of rice sheath blight is carried out according to the provisions of <GB-T 17980.104-2004 Pesticide Packaging Pharmacodynamic Test Guidelines (Part 2) - Control of Rice Sheath Blight by Fungicides>. The test site is Dongpu Town, Shaoxing City, and the rice variety is Zhongzao 39 (susceptible variety). The medicament solution is diluted to a certain dilution ratio and sown at the earliest after soaking the seeds for 72 hours. Seedlings are raised using loam soil, and the seedling raising process is strictly carried out according to the mechanical transplanting seedling raising process. The seed amount, soil fertility, etc. of each treatment are all made the same. 20 seedling trays are used for each treatment, and the seed usage per tray is 150 g. Investigate the incidence of sheath blight 1 day before rice transplanting and before heading, and calculate the disease incidence rate and control efficacy according to the following formula.

[0316] Disease incidence rate (%) = × 100

[0317] Medicament control efficacy (%) = × 100

[0318] The test results are shown in Table 15.

[0319] Table 15. ZJS178 Results of the Packaging Pharmacodynamic Test for Controlling Rice Sheath Blight with Fluoxastrobin Formulation

[0320]

[0321] * Different lowercase letters behind the data in the same column indicate significant differences at the P < 0.05 level.

[0322] The results in Table 15 show that under the same effective dose soaking and seeding conditions, the control efficacy of ZJS178 against rice sheath blight with the fluoxastrobin formulation is significantly better than that of the single agent control efficacy.

[0323] Packaging Application Example 2: Packaging Pharmacodynamic Test for Controlling Wheat Stem Rot

[0324] The test site was established in Dongfu Town, Shaoxing City. The soil type was loam, with moderate fertility and a neutral pH. The wheat variety used was Jimai 22. The seed quantity and soil fertility were kept identical for all treatments. The chemical solution was diluted to a specific ratio and the seeds were dispersed; water usage during dispersion was set at 2% of the seed weight. After dispersion, the seeds were dried and stored in a well-ventilated area protected from light. For each treatment, three zones were established. Prior to heading, samples were taken from five points within each zone, and 100 plants were surveyed at each point. The total number of plants and the number of diseased plants were recorded. Based on the survey results, the disease incidence rate and control efficacy were calculated using the following formulas. The test data were statistically analyzed using Duncan's New Multiple Range Test (DMRT).

[0325] Lee Byeong-ju Rate (%) = ×100

[0326] Chemical control (%) = ×100

[0327] The test results are shown in Table 16.

[0328] Table 16. ZJS178 Results of packaging efficacy test of fludioxonil formulation for wheat stem rot

[0329]

[0330] Different lowercase letters following the data in the same column indicate a significant difference at the P < 0.05 level.

[0331] The results in Table 16 are for ZJS178 under the same effective dose condition. It shows that the control efficacy of fludioxonil combination agent against wheat stem rot is significantly superior to that of the single agent.

[0332] In summary, the results of indoor bioassays and field efficacy tests show the following: the composition combination of the present invention has a significant effect-enhancing effect, and the composition is composed of active ingredients with different mechanisms of action, which is advantageous for overcoming and delaying the development of drug resistance in pathogens, and there are no distinct side effects on the test crops, and the leaf color, growth status, etc. are all normal, and the safety is excellent.

[0333] Example 13: Measurement of indoor toxicity of ZJS178 and thiophanate-methyl combination against watermelon wilt pathogens

[0334] Test subjects: Watermelon wilt pathogen (F. oxysporum f.sp. niveum) isolated from the field. After identifying the morphology and pathogenicity of the test strains, they were preserved in this laboratory for use.

[0335] Test agents: ZJS178 was synthesized in Example 1, and thiophanate-methyl was provided by the Zhejiang Chemical Research Institute.

[0336] Test Method: The mycelial growth rate method of the <Agricultural Industry Standard of the People's Republic of China NY / T 1156.2-2006> was referenced. For each agent, five dose treatments were established based on the content of the active ingredient, and the pathogen growth inhibition rate was set to be between 10% and 90%. The above watermelon wilt pathogen was inoculated onto PDA medium, and after waiting until the colony filled 2 / 3 of the culture dish, a mycelial disc was created from the edge of the colony using a 5 mm diameter punch. The mycelial disc was then transferred to the center of a pre-prepared agent-containing medium plate using an inoculation needle, and after incubation in a 25°C incubator for 3 days, the colony diameter of each treatment was measured using calipers with the cross-sectional method, and the corrected inhibition percentage was calculated. Subsequently, the EC50 value of each agent was calculated through linear regression analysis between the probability value of the inhibition rate and the logarithm of the continuous concentration, and each treatment was repeated 4 times. ZJS178 is set as the standard drug, and the contingent toxicity factor (CTC) is calculated according to the following formula.

[0337] Actual Toxicity Index (ATI) = (EC50 of Standard Agent / EC50 of Test Agent) × 100;

[0338] Theoretical Toxicity Index (TTI) = Standard Drug Toxicity Index × Percentage of Standard Drug in Mixed Composition + Test Drug Toxicity Index × Percentage of Test Drug in Mixed Composition;

[0339] Co-toxicity Factor (CTC) = (ATI / TTI) × 100%;

[0340] If the CTC value is less than 80, the drug combination exhibits an antagonistic effect; if it is between 80 and 120, it exhibits an additive effect; and if it is greater than 120, it exhibits an effect-enhancing effect.

[0341] The test results are shown in Table 17.

[0342] Table 17: Results of indoor toxicity measurements of ZJS178 and thiophanate-methyl mixture against watermelon wilt disease

[0343]

[0344] As shown in Table 17, when the mass ratio of ZJS178 to thiophanate-methyl is 6:1 to 1:3, there is a significant enhancement in the antibacterial effect against the growth of watermelon wilt pathogens. Other mixing ratios have an additive effect.

[0345] Example 14: Measurement of indoor toxicity of ZJS178 and prochloraz mixture against wheat red mold

[0346] Test Subject: Wheat red mold (Fusarium graminearum) is preserved in the strain room of this laboratory.

[0347] Test Method: The mycelial growth rate method of the <Agricultural Industry Standard of the People's Republic of China NY / T 1156.2-2006> was referenced. For each drug, five dose treatments were established according to the content of the active ingredient. The aforementioned wheat red mold pathogen was cultured on PDA medium. After waiting until the colony filled two-thirds of the culture dish, a mycelial disc was created from the edge of the colony using a 5 mm diameter punch. The mycelial disc was then transferred to the center of the pre-prepared drug-containing PDA medium using an inoculation needle and incubated in a 25°C incubator. Each treatment was repeated four times. The colony growth status of the control group was observed, and the colony diameter (cm) of each treatment group was measured using calipers via the cross-cross method to determine the corrected inhibition percentage. The EC50 value of each drug was calculated through linear regression analysis between the probability value of the inhibition rate and the logarithm of the continuous concentration, and the Co-Target Toxicity (CTC) was calculated according to the Sun Yunfei method.

[0348] Calculation of Efficacy: The size of the colony is represented by the average of the two cross-sectional diameters of each colony. The colony growth inhibition rate is calculated using the following formula: Colony Growth Inhibition Rate % = (Blank Control Colony Growth Diameter - Pharmacological Treatment Colony Growth Diameter) × 100 / Blank Control Colony Growth Diameter.

[0349] Table 18: Results of indoor toxicity measurements of ZJS178 and prochloraz mixtures against wheat red mold

[0350]

[0351] As shown in Table 18, when the mass ratio of ZJS178 to prochloraz is 1:15 to 12:1, it exhibits a significant enhancement effect on the antibacterial effect against the growth of wheat red mold. Other mixing ratios exhibit an additive effect.

[0352] Example 15: Measurement of indoor toxicity of ZJS178 and prochloraz manganese mixture against strawberry wilt disease

[0353] Test Subject: Strawberry wilt disease (Fusarium oxysporum) is preserved in the strain room of this laboratory. The bioassay method was referenced in Bioassay Example 14.

[0354] Table 19: Results of indoor toxicity measurements of ZJS178 and prochloraz manganese mixture against strawberry wilt disease

[0355]

[0356] As shown in Table 19, when the mass ratio of ZJS178 to prochloraz manganese salt is 1:12 to 15:1, it exhibits a significant enhancement effect on the antibacterial effect against the growth of strawberry wilt pathogens. Other mixing ratios exhibit an additive effect.

[0357] Example 16: Packaging efficacy test

[0358] I. Formulation of the Formulation

[0359] The percentage of the formulation ratio for all formulations is a mass percentage.

[0360] (1) 20% ZJS178 thiophanate-methyl suspension

[0361] 10% ZJS178, 10% thiophanate methyl, 2% TERSPERSE 2500, 3% TERSPERSE 2425, 0.2% xanthan gum, 3% white carbon black, 5% ethylene glycol, 0.3% benzoic acid, 0.5% organosilicon defoamer, and deionized water are added up to 100% by mass.

[0362] According to the mixing ratio, the raw material, dispersant, suspension aid, and antifreeze agent are placed in a mixing tank with water as the medium and uniformly mixed, then dispersed for 30 minutes using a ball mill or high-speed shear disperser, and then ground with a sand mill to produce a suspension agent.

[0363] (2) 46% ZJS178 Prochloraz suspension

[0364] 23% ZJS178, 23% prochloraz, 2% NNO, 2% TERSPERSE 2500, 1% emulsifier T-60, 3% pesticide emulsifier 700#, 0.1% xanthan gum, 3% white carbon black, 5% propylene glycol, 0.5% formaldehyde, 0.5% organosilicon defoamer, and deionized water are added up to 100% by mass.

[0365] According to the mixing ratio, the raw material, dispersant, suspension aid, and antifreeze agent are placed in a mixing tank with water as the medium and uniformly mixed, then dispersed for 30 minutes using a ball mill or high-speed shear disperser, and then ground with a sand mill to produce a suspension agent.

[0366] II. Packaging Test

[0367] 2.1 Field Efficacy Test for Control of Wheat Red Mold Disease

[0368] Control of wheat red mold is carried out in accordance with the regulations of "NY / T1464.15-2007 Pesticide Field Efficacy Test Guidelines - Control of Wheat Red Mold by Fungicides." A single application is performed during the early heading and flowering stages of wheat, and results are obtained during the milk ripening stage. In each test area, a diagonal 5-point sampling method is employed, with 100 to 200 ears surveyed at each point. The disease is graded based on the percentage of withered ear area relative to the total ear area, and the number of diseased ears for each grade and the total number of ears are recorded. The disease grading criteria are as follows.

[0369] Grade 0: No disease on the entire ear;

[0370] Grade 1: Withered ear area is 1 / 4 or less of the total ear area;

[0371] Grade 3: Withered ear area is 1 / 4 to 1 / 2 of the total ear area;

[0372] Grade 5: Withered ear area is 1 / 2 to 3 / 4 of the total ear area;

[0373] Grade 7: Withered ear area is 3 / 4 or more of the total ear area.

[0374] Method for calculating efficacy: Based on the results of the investigation, the incidence and control values ​​are calculated using the formulas (1) and (2) below. The test data are statistically analyzed using Duncan’s new multiple range test (DMRT).

[0375] Incidence = ×100 (1)

[0376] Pest Control (%) = (2)

[0377] Here, CK1 is the incidence after treatment of the blank control group, and PT1 is the incidence after treatment of the drug group.

[0378] Table 20: Results of field efficacy test for wheat red mold control

[0379]

[0380] Different lowercase letters following the data in the same column indicate a significant difference at the P < 0.05 level.

[0381] The results in Table 20 show the following: 46% ZJS178 Prochloraz suspension contains 5g of active ingredient / free ( It has an excellent control rate against wheat red mold at a dose of ) to 15 g / mu, and the control rate reaches 91.31% to 97.88%, which is superior to the control rate of the control agent. The test agent is safe for the test crop.

[0382] 2.2 Field Efficacy Test for Tomato Wilt Disease Control

[0383] The test site was established in Dongfu Town, Shaoxing City. The soil type was loam, fertility was moderate, and pH was neutral. The variety used was Zhefen 202. After transplanting the tomatoes, liquid pesticides were applied via drenching; the types and amounts of pesticides are shown in Table 5. Drenching was performed once more one week after the first treatment. The incidence of tomato wilt disease was assessed 21 days after treatment. Five random sampling points were selected from each treatment plot, and an area of ​​5 square meters was surveyed at each point. The total number of tomato plants and the number of diseased plants were recorded at each point. The disease incidence rate and control rate were calculated.

[0384] Control Rate (%) = {(Control Disease Rate - Treatment Disease Rate) / Control Disease Rate} × 100

[0385] The test results are shown in Table 21.

[0386] Table 21: Results of packaging efficacy test of ZJS178 and thiophane-methyl combination for tomato wilt disease

[0387]

[0388] Different lowercase letters following the data in the same column indicate a significant difference at the P < 0.05 level.

[0389] The results in Table 21 are for ZJS178 under the same effective dose conditions The thiophanate-methyl combination effectively controls tomato wilt disease and demonstrates significantly superior control efficacy compared to single agents. The test agent is safe for the test crop.

[0390] In summary, the results of indoor bioassays and field efficacy tests demonstrate the following: The composition of the present invention has reasonable components, combines therapeutic and protective effects, exhibits excellent fungicidal effects, reduces the frequency of drug treatments, and has low drug costs. Furthermore, its activity and fungicidal effects are not merely superpositions of the activities of each component but exhibit a significant enhancement of efficacy. The composition consists of active ingredients with different mechanisms of action, which increases the site of action and is advantageous for overcoming and delaying the development of drug resistance in pathogens. Additionally, there are no distinct side effects on any of the test crops, and leaf color and growth conditions are all normal. Its excellent safety meets the safety requirements of pesticide formulations. The present invention has an excellent control effect against diseases caused by Fusarium.

[0391] Example 17: Measurement of indoor toxicity of ZJS178 and azoxystrobin combination against tomato wilt pathogens

[0392] Test subjects: Tomato wilt pathogen (F. oxysporum f. sp. lycopersici) isolated from diseased tomatoes. After identifying the morphology and pathogenicity of the test strains, they were preserved in this laboratory for use.

[0393] Test agent: ZJS178 was synthesized in Example 1; azoxystrobin was provided by the Zhejiang Research Institute of Chemical Engineering.

[0394] Test method: The mycelial growth rate method of the <Agricultural Industry Standard of the People's Republic of China NY / T 1156.2-2006> was referenced. For each agent, five dose treatments were established according to the content of the active ingredient, and the pathogen growth inhibition rate was set to be between 10% and 90%. The above tomato wilt pathogen was inoculated onto a PDA medium, and 50 μg / ml salicyl hydroxyloxamic acid (SHAM) was added to the medium to inhibit the alternative respiration of the pathogen. After waiting until the colony filled 2 / 3 of the culture dish, a mycelial disc was made from the edge of the colony using a 5 mm diameter punch, and the mycelial disc was transferred to the center of a pre-prepared agent-containing medium plate using an inoculation needle. After incubation in a 25°C incubator for 3 days, the colony diameter of each treatment was measured using calipers with the cross-cross method, and the corrected inhibition percentage was calculated. Next, the EC50 value of each drug is calculated through linear regression analysis between the probability value of the inhibition rate and the logarithm of the continuous concentration, and each treatment is repeated 4 times. ZJS178 is set as the standard drug, and the co-toxicity coefficient (CTC) is calculated according to the following formula.

[0395] Actual Toxicity Index (ATI) = (EC50 of Standard Agent / EC50 of Test Agent) × 100;

[0396] Theoretical Toxicity Index (TTI) = Standard Drug Toxicity Index × Percentage of Standard Drug in Mixed Composition + Test Drug Toxicity Index × Percentage of Test Drug in Mixed Composition;

[0397] Co-toxicity Factor (CTC) = (ATI / TTI) × 100%;

[0398] If the CTC value is less than 80, the drug combination exhibits an antagonistic effect; if it is between 80 and 120, it exhibits an additive effect; and if it is greater than 120, it exhibits an effect-enhancing effect.

[0399] The test results are shown in Table 22.

[0400] Table 22: Results of indoor toxicity measurements of ZJS178 and azoxystrobin combinations against tomato wilt pathogens

[0401]

[0402] As shown in Table 22, when the mass ratio of ZJS178 to azoxystrobin is 4:1 to 1:6, there is a significant enhancement in the antibacterial effect against the growth of tomato wilt pathogens. Other mixing ratios have an additive effect.

[0403] Example 18: Measurement of indoor toxicity of ZJS178 and pyraclostrobin combination against rice blast disease

[0404] Test subject: Rice blast (Fusarium moniliforme) is preserved in the strain room of this laboratory. Refer to Example 17 for the bioassay method.

[0405] Table 23: Results of indoor toxicity measurements of ZJS178 and pyraclostrobin combination against rice blast disease

[0406]

[0407] As shown in Table 23, when the mass ratio of ZJS178 to pyraclostrobin is 1:12 to 8:1, there is a significant enhancement in the antibacterial effect against the growth of rice blast pathogens. Other mixing ratios have an additive effect.

[0408] Example 19: Packaging efficacy test

[0409] I. Formulation of the Formulation

[0410] The percentage of the formulation ratio for all formulations is a mass percentage.

[0411] (1) 40% ZJS178 Azoxystrobin suspension

[0412] 30% ZJS178, 10% azoxystrobin, 2% NNO, 2% TERSPERSE 2500, 1% emulsifier T-60, 3% pesticide emulsifier 700#, 0.1% xanthan gum, 3% white carbon black, 5% propylene glycol, 0.5% formaldehyde, 0.5% organosilicon defoamer, and deionized water are added up to 100% by mass.

[0413] According to the mixing ratio, the raw material, dispersant, suspension aid, and antifreeze agent are placed in a mixing tank with water as the medium and uniformly mixed, then dispersed for 30 minutes using a ball mill or high-speed shear disperser, and then ground with a sand mill to produce a suspension agent.

[0414] (2) 24% ZJS178 Pyraclostrobin suspension

[0415] 16% ZJS178, 8% pyraclostrobin, 2% TERSPERSE 2500, 3% TERSPERSE 2425, 0.2% xanthan gum, 3% white carbon black, 5% ethylene glycol, 0.3% benzoic acid, 0.5% organosilicon defoamer (product name: s-29 Nanjing Sixin Applied Chemicals Co., Ltd.), and deionized water are added up to 100% by mass.

[0416] According to the mixing ratio, the raw material, dispersant, suspension aid, and antifreeze agent are placed in a mixing tank with water as the medium and uniformly mixed, then dispersed for 30 minutes using a ball mill or high-speed shear disperser, and then ground with a sand mill to produce a suspension agent.

[0417] II. Packaging Test

[0418] Field efficacy test for watermelon wilt disease control

[0419] The control of watermelon wilt disease is carried out according to the regulations of <GB-T 17980.113-2004 Pesticide Package Potency Test Guidelines (II) - Control of Cucurbit Crop Wilt Disease by Fungicides>. The test site was set up in Dongfuzhen, Shaoxing City. The soil type of the test plot is loam, the fertility is medium, and the pH is neutral. The variety is Jiami No. 8. After transplanting and regular planting of watermelon, it is watered with the medicated solution, and the control agent is sprayed. The types and dosages of the agents are shown in Table 3. Water it again one week after the first agent treatment. 14 days after the agent treatment, check whether there are typical symptoms of wilt disease in all plants in the area, and record the number of diseased plants and the total number of surveyed plants of wilt disease. According to the survey results, calculate the disease incidence and control efficacy according to the following formulas (1) and (2). The test data is statistically analyzed by Duncan's new multiple range test method (DMRT).

[0420] Disease incidence (%) = × 100 (1)

[0421] Control efficacy (%) = × 100 (2)

[0422] The test results are shown in Table 24.

[0423] Table 24: Results of Potted Fungicidal Efficacy Test of Watermelon Wilt Disease with ZJS178 and Azoxystrobin Mixture

[0424]

[0425] * Different lowercase letters behind the data in the same column indicate significant differences at the P < 0.05 level.

[0426] The results in Table 24 show that under the condition of the same effective dose, ZJS178 has excellent control effect on watermelon wilt disease after being combined with azoxystrobin, and the control efficacy is significantly higher than that of the single agent. The test agents are safe for the test crops.

[0427] Potted Fungicidal Efficacy Test for Controlling Rice Stem Borer

[0428] The control of rice sheath blight is carried out in accordance with the provisions of <GB-T 17980.104-2004 Guidelines for Pesticide Package Potency Tests (II) - Control of Rice Sheath Blight by Fungicides>. Sampling is carried out at 5 points in each area, and 100 plants are surveyed at each point, recording the total number of plants and the number of diseased plants. Before transplanting the main crop, 5 points are randomly sampled in each area, and 20 tillers are surveyed at each point. The test plot is in Dongpu Town, Shaoxing City. The medicament solution is diluted to a certain dilution and soaked for 72 hours. The soil type of the test plot is loam, the fertility is medium, and the pH is neutral. The rice variety is Zhongzao 39 (a susceptible variety). Seedlings are raised using loam, and the seedling raising process is strictly carried out in accordance with the mechanical transplanting seedling raising process. The seed amount, soil fertility, etc. of each treatment are all the same. 20 seedling trays are used for each treatment, and the seed usage per tray is 150 g. The sheath blight incidence situation is surveyed 1 day before rice transplanting and before the main crop emergence. Medicament efficacy calculation method:

[0429] According to the survey results, the disease incidence and control efficacy are calculated using the following formulas (1) and (2). The test data is statistically analyzed by Duncan's new multiple range test (DMRT).

[0430] Diseased plant rate (%) = × 100 (1)

[0431] Control efficacy (%) = × 100 (2)

[0432] Table 25: Results of Pesticide Package Potency Test for Control of Rice Sheath Blight

[0433]

[0434] * Different lowercase letters behind the data in the same row indicate significant differences at the P < 0.05 level.

[0435] The results in Table 25 show 24% ZJS178 Pyraclostrobin suspension exhibits very good efficacy against rice blast disease in soaking treatments at dilutions of 3,000 to 2,000, with a control efficacy of 89.8% to 96.2%, demonstrating significant superiority over the single agent. The test agent is safe for the test crop.

[0436] In summary, the results of indoor bioassays and field efficacy tests demonstrate the following: The composition of the present invention has reasonable components, combines therapeutic and protective effects, exhibits excellent fungicidal effects, reduces the frequency of drug treatments, and has low drug costs. Furthermore, its activity and fungicidal effects are not merely superpositions of the activities of each component but exhibit a significant enhancement of efficacy. The composition consists of active ingredients with different mechanisms of action, which increases the site of action and is advantageous for overcoming and delaying the development of drug resistance in pathogens. Additionally, there are no distinct side effects on any of the test crops, and leaf color and growth conditions are all normal. Its excellent safety meets the safety requirements of pesticide formulations. The present invention has an excellent control effect against diseases caused by Fusarium.

[0437] The present invention has an excellent control effect against seed-borne and soil-borne crop diseases caused by Fusarium.

Claims

Claim 1 In a sterilization composition, the active ingredient of the composition comprises a compound ZJS178 represented by the structural formula (I) and a fungicide; the fungicide is selected from at least one of a triazole fungicide, a succinate dehydrogenase inhibitor fungicide, a pyrrole fungicide, an imidazole fungicide, and a methoxyacrylate fungicide; the triazole fungicide is tebuconazole or metconazole, and the mass ratio of compound ZJS178 to the triazole fungicide in the composition is 8:1 to 1:8; A bactericidal composition characterized in that the succinate dehydrogenase inhibitor-based disinfectant is pidiflumetofen or fenflufen, and the mass ratio of compound ZJS178 to the succinate dehydrogenase inhibitor-based disinfectant in the composition is 7:1 to 1:5; the pyrrole-based disinfectant is fludioxonil, and the mass ratio of compound ZJS178 to the pyrrole-based disinfectant in the composition is 3:1 to 1:3; the imidazole-based disinfectant is prochloraz, prochloraz manganese salt, or thiophanate-methyl, and the mass ratio of compound ZJS178 to the imidazole-based disinfectant in the composition is 15:1 to 1:15; and the methoxyacrylate-based disinfectant is azoxystrobin or pyraclostrobin, and the mass ratio of compound ZJS178 to the methoxyacrylate-based disinfectant in the composition is 8:1 to 1:

12. (I). Claim 2 A sterilization composition according to claim 1, wherein the fungicide is a triazole-based fungicide, and the mass ratio of compound ZJS178 to the fungicide in the composition is 4:1 to 1:5, or 5:1 to 1:3, or 3:1 to 1:3, or 2:1 to 1:

3. Claim 3 A sterilization composition according to claim 1, wherein the fungicide is a pyrrole-based fungicide, and the mass ratio of compound ZJS178 to the fungicide in the composition is 3:1 to 1:2, or 1:1 to 3, or 1:2 to 3, or 1:1 to 2. Claim 4 A sterilization composition according to claim 1, wherein the fungicide is an imidazole-based fungicide or a methoxyacrylate-based fungicide, and the mass ratio of compound ZJS178 to the fungicide in the composition is 6:1 to 1:6 or 3:1 to 1:

3. Claim 5 A sterilization composition according to claim 1, wherein the sterilization composition further comprises an auxiliary component necessary for a pesticide formulation; and wherein the auxiliary component is a carrier and an adjuvant acceptable to the pesticide. Claim 6 A bactericidal composition according to claim 1, wherein the fungicide is a triazole-based bactericidal agent and the mass ratio of the active ingredient in the composition is 1 to 90%. Claim 7 A bactericidal composition according to claim 1, wherein the fungicide is a succinate dehydrogenase inhibitor-based bactericidal agent, and the mass ratio of the active ingredient in the composition is 1 to 90%. Claim 8 A bactericidal composition according to claim 1, characterized in that the fungicide is a pyrrole-based bactericidal agent and the mass ratio of the active ingredient in the composition is 1 to 90%. Claim 9 A sterilization composition according to claim 1, wherein the fungicide is an imidazole-based sterilizer or a methoxyacrylate-based sterilizer, and the mass ratio of the active ingredient in the composition is 0.5 to 90%. Claim 10 A sterilization composition according to claim 1, characterized in that the formulation of the sterilization composition is a water-dispersible granule, a suspension, an aqueous emulsion, a microemulsion, or a suspension for seed treatment. Claim 11 Fusarium Fusarium spp. A method for controlling crop diseases caused by ), wherein the fungicide composition of claim 1 is applied to the crop to be controlled. Claim 12 In Clause 11, the above Fusarium ( Fusarium spp. ) is Fusarium Graminia Room( Fusarium graminearum ) Compound species, Fusarium fuzicuroi( Fusarium fujikuroi ) complex species, Fusarium oxysporum( Fusarium oxysporum A method characterized by being a composite species, Fusarium moniliforme. Claim 13 In Clause 12, the above Fusarium fuzikuroy ( Fusarium fujikuroi ) Composite paper Fusarium fujikuroyi( Fusarium fujikuroi ), Fusarium verticilioid( Fusarium verticillioides ) and Fusarium proliferatum ( Fusarium proliferatum A method characterized by including ). Claim 14 A method according to any one of claims 11 to 13, characterized in that the crop disease includes wheat red mold, rice blast, strawberry wilt, cucurbit wilt, tomato wilt, banana wilt, cotton wilt, wheat stem rot, corn red mold, corn stem rot, soybean root rot, and tobacco wilt. Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 delete Claim 30 delete Claim 31 delete Claim 32 delete Claim 33 delete Claim 34 delete Claim 35 delete Claim 36 delete Claim 37 delete Claim 38 delete Claim 39 delete Claim 40 delete Claim 41 delete Claim 42 delete Claim 43 delete Claim 44 delete Claim 45 delete Claim 46 delete Claim 47 delete Claim 48 delete Claim 49 delete Claim 50 delete Claim 51 delete Claim 52 delete

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