Fludioxonil-containing bactericide and preparation method therefor

Abstract

A fludioxonil-containing bactericide and a preparation method therefor. In the bactericide, fludioxonil is used as an active ingredient, and florylpicoxamid is used as another active ingredient, wherein the mass ratio of fludioxonil to florylpicoxamid is 1:10-10:1. The bactericide is composed of two active ingredients with different action mechanisms, and the two active ingredients compounded in a certain ratio have a significant synergistic effect, and same improves the prevention and control effect and is beneficial to overcoming and delaying the generation of drug resistance of pathogenic bacteria. The compounding of agents reduces the dosage, so that the cost is reduced and the pollution to the environment is alleviated.

Description

A fungicide containing fludioxonil and preparation method thereof Technical Field

[0001] The present invention relates to a fungicide, in particular to a fungicide containing fludioxonil and a preparation method thereof. Background Art

[0002] Fludioxonil, also known as fludioxonil, belongs to the phenylpyrrole fungicide class and its chemical name is 4-(2,2-difluoro-1,3-benzodioxy-4-yl)pyrrole-3-carbonitrile. Its unique mechanism of action inhibits glucose phosphorylation-related transfer, phosphorylation of mitogen-activated protein kinases / histidine kinases in osmotic signaling, and the increase of polyols such as glycerol. This inhibits conidial germination and fungal mycelial growth, while also promoting crop seedling growth and increasing the activity of enzymes associated with disease resistance.

[0003] Florylpicoxamid is a broad-spectrum pyridineamide fungicide with inhibitory effects on more than 20 plant pathogenic fungi from the Ascomycetes and Basidiomycetes. The 100 g / L pyridineamide emulsifiable concentrate, approved by the Canadian PMRA at the same time, is used to control various diseases such as powdery mildew, early blight, and gray mold in cucurbits and grapes. A 50 g / L pyridineamide + 100 g / L pyraclostrobin emulsifiable concentrate product is registered for the control of various crop diseases such as leaf spot, black shank, sclerotinia rot, and lentil anthracnose in wheat, rapeseed, and sugar beets. Its structural formula is , CAS registration number: 1961312-55-9.

[0004] Long-term use of a single dose of fludioxonil can easily lead to the development of resistance in pests, resulting in increased dosage, reduced efficacy, and a shortened duration of effectiveness, which is detrimental to environmental sustainability. Combining active ingredients with different mechanisms of action is a common method for delaying the development of resistance in pests. Whether such combinations have synergistic or antagonistic effects is determined by their effectiveness in actual production applications. In most cases, the effects of pesticide combinations are additive; truly synergistic combinations are rare, and those with particularly pronounced synergistic effects are even rarer.

[0005] CN102017954A discloses that fludioxonil is mixed with one of propiconazole, carbendazim, thiram, cyanocobalamin, fludioxonil, and polyoxin within a certain range, showing a good synergistic effect against diseases such as powdery mildew, seedling disease, rice blast, sheath blight, damping-off, gray mold, and root rot. CN108184861A discloses that fludioxonil is mixed with pyraziflumid, showing a significant synergistic and long-lasting effect. CN103651364A discloses a fungicide and disease-fighting composition containing lentinan and fludioxonil, containing 0.5% to 10% lentinan and 0.5% to 30% fludioxonil by weight; the weight ratio of lentinan to fludioxonil is 5:1 to 1:5. This fungicide composition has good fungicidal effect and low drug cost.

[0006] Although there have been reports in the prior art on the compounding of fludioxonil with different fungicides, there is still a need to develop more compound fungicides in the pesticide field to improve fungicidal efficiency and reduce resistance. Currently, there are no reports on the mixing technology of fludioxonil and pyridamole. Summary of the Invention

[0007] The object of the present invention is to provide a bactericidal and anti-disease composition containing fludioxonil which is highly effective, safe and beneficial for the management of pathogen resistance.

[0008] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0009] The fludioxonil-containing fungicide of the present invention comprises fludioxonil as one active ingredient and pyridoxamide as another active ingredient, wherein the mass ratio of fludioxonil to pyridoxamide is 1:10 to 10:1, more preferably 1:5 to 5:1, and most preferably 1:3 to 3:1.

[0010] Preferably, the fungicidal composition of the present invention contains, in addition to the active ingredient, adjuvants commonly used in pesticides. These adjuvants may include wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoaming agents, solvents, preservatives, stabilizers, and the like, and may be added as needed for the formulation.

[0011] The wetting agent is selected from one or more of sodium lauryl sulfate, calcium dodecylbenzenesulfonate, sodium dibutylnaphthalenesulfonate, sodium dioctylsulfosuccinate, Morwet EFW, GY-WS10 and the like.

[0012] The dispersant is selected from one or more of naphthalene or alkylnaphthalene formaldehyde condensate sulfonate, fatty alcohol ethylene oxide adduct sulfonate, lignin and its derivative sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, fatty alcohol polyoxyethylene ether sulfate, acrylic acid homopolymer sodium salt, disodium maleate, etc.

[0013] The emulsifier is selected from one or more of sodium lauryl sulfate, calcium dodecylbenzenesulfonate, castor oil polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate, fatty alcohol polyoxyethylene ether, triphenyl phenol polyoxyethylene polyoxypropylene ether, alkylnaphthalene sulfonate, fatty acid polyoxyethylene ester, AEO series, etc.

[0014] The thickener is selected from one or more of white carbon black, kaolin, bentonite, xanthan gum, sodium carboxymethyl cellulose and the like.

[0015] The disintegrant is selected from one or more of urea, bentonite, aluminum chloride, ammonium sulfate, succinic acid, sodium bicarbonate and the like.

[0016] The antifreeze agent is selected from one or more of glycerol, ethylene glycol, propylene glycol and the like.

[0017] The defoaming agent is selected from one or more of organic silicone defoaming agents, C 8-10 fatty alcohol defoaming agents and the like.

[0018] The solvent is one or more of toluene, xylene, cyclohexanone, aromatic solvent, methanol, ethyl acetate, soybean oil, epoxidized soybean oil, castor oil and the like.

[0019] The preservative is selected from one or more of sodium benzoate, benzoic acid, potassium sorbate, and kason.

[0020] The stabilizer is selected from one or more of triphenyl phosphite, acetic anhydride, epichlorohydrin, resorcinol, sodium citrate and the like.

[0021] On the other hand, the present invention provides a method for preparing a fungicide containing fludioxonil, which comprises the following steps: weighing fludioxonil and pyridoxam in proportion, adding an adjuvant acceptable to pesticides, and mixing them evenly.

[0022] On the other hand, the present invention can be prepared into a dosage form suitable for agricultural use using known methods. The composition can be processed into any dosage form acceptable for pesticide applications by combining the active ingredients with adjuvants and carriers (fillers), depending on various factors such as the crop to be controlled, the environmental conditions, the control method, and the control cost. Preferred dosage forms include seed suspensions, granules, microcapsule suspensions, emulsions in water, suspensions, wettable powders, water-dispersible granules, or emulsifiable concentrates. The adjuvants, carriers, and processing techniques used are known components. In each of these various dosage forms, the total mass percentage of the active ingredient in the composition is 0.5% to 85%.

[0023] On the other hand, the product (composition) described in the present invention can be provided in the form of a finished formulation, that is, the substances in the composition are already mixed. The components of the composition can also be provided in the form of a single dose, which is directly mixed in a bucket or tank before use and then diluted to the desired concentration.

[0024] On the other hand, the fungicidal composition of the present invention is particularly suitable for preventing and controlling diseases of crops, including grain crops, legume crops, oil crops, fiber crops, sugar crops, melon crops, fruit crops, dry fruit crops, root crops, flower crops, medicinal crops, raw material crops, and green manure and forage crops.

[0025] Preferably, the diseases include: gray mold, target spot, canker, vine blight, rust, ring rot, sclerotinia, smut, take-all, root rot, damping-off, sheath blight, seedling blight, wilt, sclerotinia, white spot, downy mildew, damping-off, brown spot, powdery mildew, anthracnose, early blight, leaf mold, leaf spot, black spot, black mole, blight, stem base rot, verticillium wilt, clubroot, sooty mold and other fungal diseases.

[0026] On the other hand, the composition of the present invention can be applied by conventional methods such as pouring, seed dressing, spraying, dusting or fumigation, and the application rate varies depending on weather conditions or the state of the crop.

[0027] On the other hand, the composition of the present invention can be mixed with other compounds having herbicidal or fungicidal properties, or with insecticides, nematicides, protectants, growth regulators, plant nutrients or soil conditioners.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The fungicide of the present invention is composed of two active ingredients with different mechanisms of action. When compounded in a certain ratio, they have a significant synergistic effect, improving the control effect and also helping to overcome and delay the development of drug resistance in pathogens.

[0030] 2. Mixing of drugs reduces the amount of drugs used, thereby reducing costs and alleviating pollution to the environment. DETAILED DESCRIPTION

[0031] To make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described below with reference to the following examples, but the present invention is by no means limited to these examples. The specific examples are only used to explain the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the patent of the present invention should be based on the appended claims.

[0032] The present invention will be further explained below with reference to specific embodiments.

[0033] Example 1 Indoor toxicity determination

[0034] Weigh fludioxonil and pyridoxamide stock drugs separately using an electronic balance and dissolve in a trace amount of acetone to prepare a stock solution at a concentration of 100 μg / mL. Dilute each stock drug with sterile water to form a series of concentration gradient solutions. Inoculate the pathogen cake in the center of a plate, using a drug-free plate as a control. Repeat three times for each treatment. Incubate in a dark incubator at 20°C for 72 hours. Measure colony diameters using the cross-hatch method, and calculate inhibition rates and correlation coefficients.

[0035] Fluoxetine and pyridamole were mixed in the ratio of 20:1, 10:1, 5:1, 3:1, 1:1, 1:3, 1:5, 1:10, and 5:20, and diluted with sterile water to prepare a series of drug-containing plates with a final drug content and a concentration gradient. Other measurement and calculation methods were the same as for a single dose.

[0036] The combined action mode was determined by the co-toxicity coefficient (CTC) method to determine the synergistic effect of the mixture.

[0037] Taking a single agent in the mixture as the standard agent (usually the one with the lower EC50), the formula for calculating the co-toxicity coefficient is as follows:

[0038] Single-dose toxicity index = standard agent EC50 / a single-dose EC50×100;

[0039] Measured toxicity index (ATI) = (EC50 of standard single dose / EC50 of mixture) × 100;

[0040] Theoretical toxicity index (TTI) = toxicity index of single agent A × the proportion of single agent A in the mixture + toxicity index of single agent B × the proportion of single agent B in the mixture;

[0041] Co-toxicity coefficient (CTC) = [Actual toxicity index (ATI) of the mixture / Theoretical toxicity index (TTI) of the mixture] × 100

[0042] When CTC≤80, the composition exhibits an antagonistic effect; when 80<CTC<120, the composition exhibits an additive effect; and when CTC≥120, the composition exhibits a synergistic effect.

[0043] The test results of the combined toxicity test of fludioxonil and pyridamole against wheat powdery mildew are as follows.

[0044]

[0045] The invention uses fluoxetine and pyridoxamide as active ingredients, can maintain a good additive effect within a wide mass ratio range, and has a co-toxicity coefficient of more than 80. When the mass ratio of fluoxetine to pyridoxamide is 1-10:10-1, it has a significant synergistic effect on wheat powdery mildew. It can be seen that the combination of fluoxetine and pyridoxamide can become an ideal agent for preventing and controlling wheat powdery mildew.

[0046] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A bactericide containing fludioxonil, characterized in that: Fluoxetine is used as one active ingredient, and pyridoxamide is used as another active ingredient, wherein the mass ratio of fluoxetine to pyridoxamide is 1:10 to 10:

1.

2. The bactericide according to claim 1, characterized in that: The mass ratio of fludioxonil to pyridoxamide is 1:5 to 5:

1.

3. The bactericide according to claim 1, characterized in that: The mass ratio of fludioxonil to pyridoxamide is 1:3 to 3:

1.

4. The bactericide according to any one of claims 1 to 3, characterized in that The fungicide also includes adjuvants commonly used in pesticides, wherein the adjuvants are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, and stabilizers.

5. The bactericide according to claim 4, characterized in that: The wetting agent is selected from one or more of sodium dodecyl sulfate, calcium dodecylbenzene sulfonate, sodium dibutylnaphthalene sulfonate, sodium dioctyl sulfosuccinate, Morwet EFW, and GY-WS10; The dispersant is selected from one or more of naphthalene or alkylnaphthalene formaldehyde condensate sulfonate, fatty alcohol ethylene oxide adduct sulfonate, lignin and its derivative sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, fatty alcohol polyoxyethylene ether sulfate, acrylic acid homopolymer sodium salt, and maleic acid disodium salt; The emulsifier is selected from one or more of sodium dodecyl sulfate, calcium dodecylbenzene sulfonate, castor oil polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate, fatty alcohol polyoxyethylene ether, triphenyl phenol polyoxyethylene polyoxypropylene ether, alkylnaphthalene sulfonate, fatty acid polyoxyethylene ester, and AEO series; The thickener is selected from one or more of white carbon black, kaolin, bentonite, xanthan gum, and sodium carboxymethyl cellulose; The disintegrant is selected from one or more of urea, bentonite, aluminum chloride, ammonium sulfate, succinic acid, and sodium bicarbonate; The antifreeze agent is selected from one or more of glycerol, ethylene glycol and propylene glycol; The defoaming agent is selected from one or more of organic silicone defoaming agents and C 8-10 fatty alcohol defoaming agents; The solvent is selected from one or more of toluene, xylene, cyclohexanone, aromatic solvents, methanol, ethyl acetate, soybean oil, epoxidized soybean oil, and castor oil; The preservative is selected from one or more of sodium benzoate, benzoic acid, potassium sorbate and kason; The stabilizer is selected from one or more of triphenyl phosphite, acetic anhydride, epichlorohydrin, resorcinol and sodium citrate.

6. The bactericide according to any one of claims 1 to 3, characterized in that The fungicide is made into any dosage form acceptable in pesticide application, and the dosage form is selected from suspension seed coating agent, granule, microcapsule suspension, aqueous emulsion, suspension, wettable powder, water dispersible granule or emulsifiable concentrate.

7. The method for preparing the fungicide according to any one of claims 1 to 3, comprising the following steps: weighing fludioxonil and pyridoxamide in proportion, adding an adjuvant acceptable to pesticides, and mixing them evenly.

8. The fungicide according to any one of claims 1 to 6 or its use in preventing and controlling powdery mildew of crops.

9. The use according to claim 8, characterized in that The crop powdery mildew is wheat powdery mildew.

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