A fungicidal composition containing fluoxapiprolin

Abstract

The application discloses a fungicidal composition containing Fluoxapiprolin, and effective components of the composition are Fluoxapiprolin and thiabendazole, the mass ratio of Fluoxapiprolin to thiabendazole is 50:1 to 1:50, and the active component in the composition has a mass percentage of 5-80%. The composition can be prepared into dispersible oil suspensions, wettable powders, water dispersible granules and the like. The application of the fungicidal composition is in farmland, orchard and the like, and is used for preventing and treating various oomycete diseases such as downy mildew and late blight on crops such as vegetables, fruit trees and flowers, the composition of the application reduces the application amount and frequency of chemical pesticides through significant synergistic effect, improves the application efficiency, delays the occurrence of resistance, reduces pesticide residues, protects the ecological environment of farmland and guarantees the food safety of agricultural products.

Description

Technical Field

[0001] This invention relates to a fungicide composition containing Fluoxapiprolin, belonging to the field of agricultural fungicides. Background Technology

[0002] Downy mildew of cucumber, commonly known as "running dry" or "dry leaves," can affect both seedlings and mature plants, primarily damaging leaves and stems, while tendrils and flower stalks are less affected. The pathogen is *Pseudoperonospora cubensis*, a fungus belonging to the genus *Pseudoperonospora* of the subphylum Oomycetes. The sporangia of this fungus are spread by air currents and rainwater. Downy mildew is the most prevalent and damaging disease in cucumber cultivation. It develops rapidly, causes severe illness, and spreads quickly; without timely control, it can cause devastating losses to cucumber plants.

[0003] Late blight is a major disease affecting tomatoes, occurring in both greenhouses and open fields, and is particularly severe in years with prolonged periods of overcast and rainy weather. Severe infection causes stem rot, plant wilting, and browning of the fruit, ultimately impacting yield.

[0004] The control of downy mildew in cucumbers and late blight in tomatoes mainly relies on fungicides such as dimethomorph, metalaxyl, and some protective agents. However, long-term use of these agents has led to varying degrees of resistance, reducing their effectiveness. Furthermore, the excessive use of these agents increases pesticide residues, endangering food safety and exacerbating environmental pollution. Therefore, we propose a fungicide composition containing fluoxapiprolin. Summary of the Invention

[0005] The purpose of this invention is to provide a new bactericidal composition with low resistance risk, low cost, good efficacy, and long-lasting effect.

[0006] A bactericidal composition containing Fluoxapiprolin, wherein the active ingredients are Fluoxapiprolin and thiamethoxam.

[0007] The preferred mass ratio of Fluoxapiprolin to thiamethoxam is 50:1 to 1:50.

[0008] The preferred mass ratio of Fluoxapiprolin to thiamethoxam is 30:1 to 1:30.

[0009] Preferably, as a preferred embodiment of the present invention, the active component in the composition has a mass percentage content of 5-80%.

[0010] Preferably, as a preferred embodiment of the present invention, the composition can be formulated into any dosage form, with preferred dosage forms including dispersible oil suspensions, wettable powders, and water-dispersible granules.

[0011] Preferably, as an alternative to the present invention, the composition can be provided in the form of a finished formulation, that is, the substances in the composition have been mixed; the components of the composition can also be provided as a single-dose formulation, which is directly mixed in a barrel (can) before use.

[0012] Preferably, as a preferred embodiment of the present invention, the bactericidal composition is used to prevent and control downy mildew of cucumber and late blight of tomato.

[0013] Beneficial effects: First, the composition has a significant synergistic effect, greatly improving efficacy; second, the amount of pesticide used in the field is reduced, lowering production and usage costs, and reducing pesticide residues and environmental pollution; third, the composition consists of effective ingredients with different mechanisms of action, increasing the number of action sites, which helps to overcome and delay the development of pathogen resistance.

[0014] Through extensive indoor bioassays and field efficacy trials, the inventors unexpectedly discovered that a mixture of Fluoxapiprolin and Thiamethoxam in a certain ratio had a significant synergistic effect on diseases such as cucumber downy mildew and tomato late blight.

[0015] Benziothiazolinone, with the molecular formula C7H5SON and chemical name 1,2-benziothiazolin-3-one, is a novel, broad-spectrum fungicide with both preventative and curative effects against fungal diseases. It is primarily used to control downy mildew in cucumbers, pear scab, apple scab, citrus anthracnose, and grape black rot, and is highly effective against a variety of bacterial and fungal diseases.

[0016] Fluoxapiprolin's mechanism of action involves inhibiting a novel target, oxysterol-binding protein (OSBP), thereby affecting cholesterol metabolism and cell membrane composition. It can also act on CHS1 and FKS2 to influence cell wall composition. At extremely low concentrations, it operates at multiple stages of the pathogen's asexual reproductive lifecycle. On one hand, it inhibits zoospore release and prevents zoospore and sporangium germination, thus producing protective activity. On the other hand, it inhibits mycelial growth within the host plant before visible lesions occur, thereby achieving a therapeutic effect.

[0017] The mechanism of action of thiamethoxam: 1. It destroys the nuclear structure of pathogenic cells, causing them to lose their vital organs and die; 2. It interferes with the metabolism of pathogenic cells, causing physiological disorders and ultimately leading to death. Thiamethoxam can completely kill pathogens, achieving the ideal effect of eradicating diseases.

[0018] In summary, Fluoxapiprolin and thiamethoxam have different mechanisms of action and sites of action. Fluoxapiprolin interferes with the metabolism of cholesterol compounds, thereby affecting cell membrane composition, while thiamethoxam primarily damages the nuclear structure of pathogen cells, interfering with their metabolism. The combined use of both to control plant diseases can achieve a reduced dosage and increased efficacy, protecting the ecological environment while preventing plant pathogens from developing resistance to single agents, slowing down the rate of resistance development, and extending the lifespan of the agents. Furthermore, there are currently no reports of the combination of Fluoxapiprolin and thiamethoxam, either domestically or internationally.

[0019] Through quantitative analysis of the combined effects of the above-mentioned compositions, the inventors formulated the technical solution of this invention: a bactericidal composition containing Fluoxapiprolin, wherein the mass ratio of Fluoxapiprolin to thiamethoxam in the composition is 50:1 to 1:50, and the preferred mass ratio of Fluoxapiprolin to thiamethoxam is 30:1 to 1:30. The total mass percentage of the active ingredients in the composition is 5% to 80%.

[0020] The compositions of this invention can be prepared into any formulation suitable for agricultural use using known methods. Preferred formulations include dispersible oil suspensions, wettable powders, and water-dispersible granules. These formulations can be prepared by common methods, for example, by mixing the active substance with a liquid solvent and / or a solid carrier, while adding surfactants such as emulsifiers, dispersants, stabilizers, and wetting agents, and may also add binders, defoamers, oxidants, dyes, etc. The specific components listed in the following formulation examples are included, but not limited to.

[0021] For dispersible oil suspensions, dispersants such as polycarboxylates, lignin sulfonates such as sodium lignin sulfonate, and alkyl naphthalene sulfonates can be used; emulsifiers such as Agricultural Emulsion 700# (generic name alkylphenol formaldehyde resin polyoxyethylene ether), sodium dibutylnaphthalene sulfonate formaldehyde condensate, Agricultural Emulsion 2201#, Span-60# (generic name sorbitan monostearate), Agricultural Emulsion 1601# (generic name triphenylethylphenol polyoxypropylene polyoxyethylene block polymer), and TERSPERSE can also be used. One or more of 4894 (2500); wetting agents such as alkylphenol polyoxyethylene ether formaldehyde condensate phosphate, tea seed powder, alkylphenol polyoxyethylene ether phosphate, phenethylphenol polyoxyethylene ether phosphate, alkyl sulfate, alkyl sulfonate, naphthalene sulfonate; thickeners such as xanthan gum, polyvinyl alcohol, bentonite; preservatives such as formaldehyde, benzoic acid, sodium benzoate; defoamers such as silicone defoamers; antifreeze agents such as ethylene glycol, propylene glycol, glycerin, urea, inorganic salts such as sodium chloride.

[0022] For water-dispersible granules, the following dispersants may be used: one or more of polycarboxylate, lignin sulfonate, NNO4, and alkyl naphthalene sulfonate; wetting agents such as nonylphenol polyoxyethylene ether, polyoxyethylene alcohol, alkyl sulfate, alkyl sulfonate, and naphthalene sulfonate; disintegrants such as ammonium sulfate, urea, sucrose, and glucose; binders such as diatomaceous earth, corn starch, PVA, and carboxymethyl (ethyl) cellulose; and fillers such as diatomaceous earth, calcium bicarbonate, kaolin, silica, talc, and clay.

[0023] For wettable powders, the following dispersants may be used: one or more of polycarboxylate, lignin sulfonate, and alkyl naphthalene sulfonate; wetting agents may be used: one or more of alkyl sulfate, alkyl sulfonate, and naphthalene sulfonate; and fillers may be used: one or more of ammonium sulfate, urea, sucrose, glucose, diatomaceous earth, kaolin, silica, light calcium carbonate, talc, attapulgite, and clay.

[0024] The compositions of this invention can be provided as finished formulations, i.e., the substances in the composition are already mixed; the components of the composition can also be provided as single-dose formulations, which are directly mixed in a container before use. The concentrates of this invention are typically mixed with water to obtain the desired concentration of active substances.

[0025] The compositions of this invention can be used to control important diseases caused by oomycetes, and are particularly suitable for controlling downy mildew and blight. The compositions of this invention can be applied to farmland, orchards, etc.

[0026] The compositions of the present invention can also be used in combination with other compounds having herbicidal, insecticidal or fungicidal properties, especially protective fungicides, or in combination with nematicides, protective agents, growth regulators, phytonutrients or soil conditioners.

[0027] This invention also includes a method for in-situ fungal control, by applying the composition of this invention to the crop and / or fruit and its growing or storage location before or after infection. Application can be performed using conventional methods such as watering, spraying, misting, dusting, or spreading. The application rate of this invention varies depending on weather conditions or crop condition. The duration of the protective effect is generally related to the content of individual compounds in the composition and is influenced by external factors such as climate, but the effects of climate can be mitigated by using appropriate formulations. Detailed Implementation

[0028] When different active ingredients in pesticides are mixed, they typically exhibit three types of effects: additive, synergistic, and antagonistic. However, the specific type of effect is unpredictable and can only be determined through extensive testing. Well-formulated pesticide mixtures with excellent synergistic effects significantly improve actual control efficacy, reduce pesticide usage, and thus greatly slow down the development of pesticide resistance in pathogens, making them an important means of scientifically controlling diseases.

[0029] The inventors conducted extensive indoor bioassays and field efficacy trials, and found that the combination of Fluoxapiprolin and thiamethoxam has a significant synergistic effect on cucumber downy mildew and tomato late blight, rather than simply the sum of the two agents (see bioassay examples 1 and 2 for details).

[0030] Bioassay Example 1: Indoor toxicity assay of Fluoxapiprolin combined with thiamethoxam to Pseudoperonospora cubensis, the causal agent of cucumber downy mildew.

[0031] This experiment used the pot method. Two cucumber seedlings with uniform growth at the true leaf stage were selected, with five pots used for each treatment, and each pot was numbered. A Potter sprayer was used at a pressure of 50 PSI, spraying 5 mL per pot. Five concentration gradients were set up for each agent, with a blank control consisting of a spray of an equal volume of water. Twenty-four hours after treatment, a sporangium suspension of cucumber downy mildew was sprayed in. The preparation process for the sporangium suspension was as follows: cucumber leaves infected with downy mildew were collected from the field, and the sporangia on the back were washed off with distilled water at approximately 10°C using a brush, preparing a suspension with a concentration of 3 × 10⁻⁶. 5 A sporangium suspension of 1 sporangium / mL was prepared. After inoculation, cucumber seedlings were placed in an artificial climate chamber (100% relative humidity, 15-20℃) for cultivation. After 24 hours, the temperature was maintained at 15-24℃ and the relative humidity at about 90% to induce disease. After 10 days, the disease incidence was investigated and recorded, and the disease index and control effect were calculated.

[0032] Grading standards for cucumber downy mildew:

[0033] Grade 0: Leaves show no disease spots;

[0034] Grade 1: The lesion area accounts for less than 5% of the total leaf area;

[0035] Grade 3: Lesions cover 6-10% of the total leaf area;

[0036] Level 5: Lesions cover 11-25% of the total leaf area;

[0037] Level 7: Lesions cover 26-50% of the total leaf area;

[0038] Level 9: The lesion area accounts for more than 50% of the total leaf area.

[0039]

[0040]

[0041] The concentration of EC in the inhibition zone was calculated using the least squares method. 50Then, the cotoxicity coefficient (CTC) is calculated according to Sun Yunpei's method.

[0042] Actual Toxicity Index (ATI) = (Standard reagent EC) 50 / Test reagent EC 50 )×100

[0043] Theoretical Toxicity Index (TTI) = Toxicity Index of Agent A × Percentage of A in the Mixture + Toxicity Index of Agent B × Percentage of B in the Mixture

[0044] Co-toxicity coefficient (CTC) = [Actual toxicity index (ATI) of mixture / Theoretical toxicity index (TTI) of mixture] × 100.

[0045] CTC≤80 indicates an antagonistic effect, 80<CTC<120 indicates an additive effect, and CTC≥120 indicates a synergistic effect.

[0046] As shown in Table 1, the co-toxicity coefficient of Fluoxapiprolin and Thiamethoxam in the combination of 50:1 to 1:50 is above 120, which has a synergistic effect on cucumber downy mildew. In particular, the co-toxicity coefficient is above 170 in the ratio of 30:1 to 1:30.

[0047] Table 1. In vivo test results of Fluoxapiprolin combined with thiamethoxam against cucumber downy mildew (indoors).

[0048]

[0049]

[0050] Bioassay Example 2: Indoor toxicity assay of Fluoxapiprolin combined with thiamethoxam against Phytophthora festans, the causal agent of tomato late blight.

[0051] The toxicity of the agent was determined using the mycelial growth rate method (containing toxic kidney bean culture medium). The co-toxicity coefficient was evaluated in the same manner as in Example 1 of the bioassay.

[0052] As shown in Table 2, the co-toxicity coefficient of Fluoxapiprolin and Thiamethoxam in the combination of 50:1 to 1:50 is above 120, which has a synergistic effect on tomato late blight pathogen. Especially in the ratio of 30:1 to 1:30, the co-toxicity coefficient is above 170.

[0053] Table 2. In vivo test results of Fluoxapiprolin combined with thiamethoxam against tomato late blight pathogen (indoors).

[0054]

[0055] The present invention is further illustrated below with specific embodiments, but the invention is by no means limited to these examples. The following descriptions are merely preferred embodiments of the invention and are used only to explain the invention; they should not be construed as limiting the scope of the patent. It should be noted that any modifications, equivalent substitutions, and improvements made within the spirit and principles of the invention should be included within the scope of protection of the invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

[0056] All percentages in the formulation are by mass.

[0057] Examples of dispersible oil suspensions

[0058] According to the formula ratio, the active ingredients, dispersants, wetting agents, thickeners, antifreeze agents and oil bases are mixed evenly and then ground or sheared at high speed to make a dispersible oil suspension.

[0059] Example 1: 31% Fluoxapiprolin·Thiamethoxam Dispersible Oil Suspension

[0060] Fluoxapiprolin 30%, thiamethoxam 1%, sodium methylnaphthalenesulfonate formaldehyde condensate (dispersant) 10%, sodium dodecyl sulfate (wetting agent) 3%, xanthan gum (thickener) 2%, bentonite (thickener) 1%, glycerin (antifreeze agent) 5%, soybean oil to make up to 100%.

[0061] Example 2: 31% Fluoxapiprolin·Thiamethoxam Dispersible Oil Suspension

[0062] Fluoxapiprolin 1%, thiamethoxam 30%, polycarboxylate (dispersant) 10%, tea seed cake powder (wetting agent) 3%, polyvinyl alcohol (thickener) 2%, bentonite (thickener) 1%, ethylene glycol (antifreeze agent) 5%, turpentine oil to make up to 100%.

[0063] Example 3: 5% Fluoxapiprolin·Thiamethoxam Dispersible Oil Suspension

[0064] Fluoxapiprolin 2.5%, thiamethoxam 2.5%, sodium methylnaphthalenesulfonate formaldehyde condensate (dispersant) 10%, sodium dodecyl sulfate (wetting agent) 3%, xanthan gum (thickener) 2%, bentonite (thickener) 1%, urea (antifreeze agent) 5%, soybean oil to make up to 100%.

[0065] Example 4: 16% Fluoxapiprolin·Thiamethoxam Dispersible Oil Suspension

[0066] Fluoxapiprolin 15%, thiamethoxam 1%, polycarboxylate (dispersant) 10%, tea seed cake powder (wetting agent) 3%, polyvinyl alcohol (thickener) 2%, bentonite (thickener) 1%, propylene glycol (antifreeze agent) 5%, turpentine oil to make up to 100%.

[0067] Examples of wettable powders

[0068] The active ingredients, adjuvants, and fillers of pesticides are mixed in a certain proportion, then pulverized by air jet milling, and finally mixed again to obtain a wettable powder. Main equipment: mixer, air jet mill.

[0069] Example 5: 80% Fluoxapiprolin·Thiamethoxam wettable powder

[0070] Fluoxapiprolin 50%, thiamethoxam 30%, sodium dodecyl sulfate (wetting agent) 2%, sodium lignosulfonate (dispersant) 3%, silica 10% (filler), kaolin to make up to 100%.

[0071] Example 6: 51% Fluoxapiprolin·Thiamethoxam wettable powder

[0072] Fluoxapiprolin 50%, thiamethoxam 1%, alkyl sulfate (wetting agent) 3%, polycarboxylate (dispersant) 3%, silica (filler) 11%, bentonite to make up to 100%.

[0073] Example 7: 16% Fluoxapiprolin·Thiamethoxam wettable powder

[0074] Fluoxapiprolin 1%, thiamethoxam 15%, alkyl sulfonate (wetting agent) 3%, sodium lignosulfonate (dispersant) 3%, silica (filler) 11%, clay to make up to 100%.

[0075] Water-dispersible granules example

[0076] According to the formula ratio, the active ingredient, powdered carrier, wetting and spreading agent, and binder are mixed and pulverized, then water is added and kneaded, and then the mixture is fed into a granulator equipped with a sieve of a certain size for granulation. After drying and sieving (according to the sieve range), granular product is obtained.

[0077] Example 8: 51% Fluoxapiprolin·Thiamethoxam water-dispersible granules

[0078] Fluoxapiprolin 1%, thiamethoxam 50%, polycarboxylate (dispersant) 5%, sodium lignosulfonate (dispersant) 7%, sodium dodecyl sulfate (wetting agent) 2%, ammonium sulfate (disintegrant) 5%, and light calcium carbonate to make up to 100%.

[0079] Example 9: 40% Fluoxapiprolin·Thiamethoxam water-dispersible granules

[0080] Fluoxapiprolin 20%, thiamethoxam 20%, sodium alkylnaphthalene sulfonate (dispersant) 5%, sodium lignin sulfonate (dispersant) 7%, sodium dodecyl sulfate (wetting agent) 2%, urea (disintegrant) 5%, and light calcium carbonate to make up to 100%.

[0081] Field Application Example 1: Field Efficacy Trial of Fluoxapiprolin Combined with Thiamethoxam for Cucumber Downy Mildew

[0082] The experiment was conducted in Zhaoqing, Guangdong Province. Fields with a history of severe cucumber downy mildew infection were selected. Field trial methods and results were conducted according to the guidelines for field efficacy trials of fungicides for controlling cucumber downy mildew, GB / T 17980.26-2000. The tested fungicides and dosages are shown in Table 3. Each treatment was replicated in four plots, with each plot covering 20 square meters.

[0083] The first application of pesticide was carried out at the early stage of disease occurrence, spraying the entire plant evenly until the leaves were dripping wet. A water-treated control was used as a blank control. A second application was carried out 7 days later. The incidence of cucumber downy mildew was investigated before the first application and 7 days after the second application. Five sampling points were used in each plot, with 5 plants sampled at each point. All leaves of each plant were examined, and the percentage of diseased area to the total leaf area was recorded for classification. The disease index and control effect of each treatment were calculated.

[0084] Grading standards:

[0085] Grade 0: No lesions;

[0086] Grade 1: The lesion area accounts for less than 5% of the total leaf area;

[0087] Grade 3: Lesions cover 6%-15% of the total leaf area;

[0088] Level 5: Lesions cover 16%-25% of the total leaf area;

[0089] Level 7: Lesions cover 26%-50% of the total leaf area;

[0090] Level 9: The lesion area accounts for more than 50% of the total leaf area.

[0091] Methods for calculating drug efficacy:

[0092]

[0093]

[0094] Table 3 shows that the control efficacy of Fluoxapiprolin and thiamethoxam alone against cucumber downy mildew was 76.9% and 72.4%, respectively. The fungicidal composition of this invention significantly improved the control efficacy, with a minimum efficacy of 88.3% and a maximum of 92.8%. Field trials clearly demonstrate that the combination of Fluoxapiprolin and thiamethoxam has a significant synergistic effect against cucumber downy mildew, resulting in a substantial increase in control efficacy even with a reduced dosage of active ingredient per acre. Therefore, the composition of this invention has the beneficial effects of reducing costs, delaying resistance development, reducing the number of applications, and minimizing pesticide residues.

[0095] Table 3. Field trial results of Fluoxapiprolin combined with thiamethoxam against cucumber downy mildew.

[0096]

[0097]

[0098] Field Application Example 2: Field Efficacy Trial of Fluoxapiprolin Combined with Thiamethoxam for Tomato Late Blight

[0099] The test site was Tai'an, Shandong Province. The field trial methods and results were conducted in accordance with the "Guidelines for Field Efficacy Trials of Fungicides for the Control of Tomato Late Blight" (GB / T 17980.31-2000).

[0100] Table 4 shows that the control efficacy of Fluoxapiprolin and thiamethoxam alone against tomato late blight was 77.9% and 75.1%, respectively. The fungicidal composition of this invention significantly improved the control efficacy, with a minimum efficacy of 88.3% and a maximum of 93.0%. Field trials clearly demonstrate that the combination of Fluoxapiprolin and thiamethoxam has a significant synergistic effect against tomato late blight, resulting in a substantial increase in control efficacy even with a reduced dosage of active ingredient per acre. Therefore, the composition of this invention has the beneficial effects of reducing costs, delaying resistance development, reducing the number of applications, and minimizing pesticide residues.

[0101] Table 4. Field trial results of Fluoxapiprolin combined with thiamethoxam against tomato late blight.

[0102]

Claims

1. A bactericidal composition, characterized in that: The active ingredients are Fluoxapiprolin and Thiamethoxazole, in a mass ratio of 50:1 to 1:

50.

2. The bactericidal composition according to claim 1, characterized in that: The mass ratio of Fluoxapiprolin to thiamethoxam is 30:1 to 1:

30.

3. The bactericidal composition according to any one of claims 1-2, characterized in that: The active component in the composition has a mass percentage of 5-80%.

4. The bactericidal composition according to claim 1, characterized in that: The composition can be formulated into dosage forms, including dispersible oil suspensions, wettable powders, and water-dispersible granules.

5. The bactericidal composition according to claim 1, characterized in that: The composition can be provided as a finished product, meaning that the substances in the composition have already been mixed; or the components of the composition can be provided as a single-dose formulation, which is mixed directly in the container before use.

6. The bactericidal composition according to claim 1 is used to prevent and control downy mildew of cucumber and late blight of tomato.

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