A bactericidal composition containing bronopol and its use

Abstract

The application belongs to the technical field of pesticides, and discloses a kind of fungicidal composition containing bromonitril and purposes thereof, the fungicidal composition contains active ingredient A and active ingredient B, the active ingredient A is bromonitril, the active ingredient B is selected from any one of fluazinam, isopyrazam or carboxin, and the mass ratio of the active ingredient A to the active ingredient B is 1:35-35:1.The fungicidal composition has high activity on diseases on various crops, has significant synergistic effect, is superior to single agent in terms of quick-acting property and persistence, simultaneously reduces the use amount of pesticide in agricultural production, reduces pesticide residues in agricultural products, delays the generation of pathogenic bacteria resistance, and is beneficial to the comprehensive management of agricultural diseases.

Description

[0001] This invention application is a divisional application of application number CN202311812433.2, filed on May 20, 2022, entitled "A bactericidal composition containing bromonitroethanol and its use therein". Technical Field

[0002] This invention relates to the field of pesticide fungicide compositions and their application technology, specifically to a fungicide composition containing bromonitrol and its uses. Background Technology

[0003] Bronitrophenol, chemically known as 2-bromo-2-nitro-1,3-propanediol, also called bromonitrobanol, is a broad-spectrum bactericide belonging to the brominated nitro alcohol class. It exhibits good control effects against fungal and bacterial diseases of plants, particularly rice bakanae disease, and also shows some control efficacy against cotton angular leaf spot and wheat scab.

[0004] Fluopyram, ISO common name: pydiflumetofen, chemical name: 3-(difluoromethyl)-N-methoxy-1-methyl-N-[(RS)-1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide, CAS Registry Number: 1228284-64-7. Fluopyram is a pyridine amide fungicide developed by Syngenta that acts on succinate dehydrogenase. It primarily works by affecting the respiratory chain electron transport system of pathogens, acting on succinate dehydrogenase, the key link between oxidative phosphorylation and electron transport within the pathogen, leading to tricarboxylic acid cycle disorders, hindering energy metabolism, and thus inhibiting pathogen growth and death, thereby achieving the purpose of disease control. Fluopyram is broad-spectrum and highly effective, suitable for many crops, such as corn, small grains, soybeans, peanuts, rapeseed, and quinoa.

[0005] Pyrazam, ISO common name: isopyrazam, CAS Registry Number: 881685-58-1. Pyrazam is a succinate dehydrogenase inhibitor (SDHI) with both preventative and curative effects, primarily controlling foliar diseases of cereals, such as powdery mildew and eye spot. In addition to the pyrazole ring common to SDHI fungicides, pyrazam also contains a unique benzo[a]-bridged ring. These two ring structures allow pyrazam to bind strongly to the binding sites on mitochondrial membrane SDHI enzymes and the waxy layer on the leaf surface, giving it higher activity and ensuring highly effective disease control and a longer residual effect in the field. Furthermore, pyrazam significantly maintains crop health, greatly improving photosynthesis, increasing yield, and extending the harvest time.

[0006] Phenylopyr aniline, ISO common name: penflufen, chemical name: N-[2-(1,3-dimethylbutyl)phenyl]-5-1,3-dimethyl-1H-pyrazole-4-carboxamide, CAS Registry Number: 494793-67-8. Phenylopyr aniline is a pyrazole amide fungicide developed by Bayer. It exhibits good activity against a variety of plant pathogenic fungi. This fungicide is a succinate dehydrogenase inhibitor, primarily acting on the respiratory chain electron transport complex II, blocking energy metabolism. Phenylopyr aniline possesses systemic, preventative, and curative effects, with a long-lasting effect. It is mainly used as a seed treatment fungicide. After seed treatment, the agent penetrates into the germinating seed and is translocated throughout the plant via the xylem, thus protecting the growing seedling.

[0007] Succinate dehydrogenase inhibitors (SDHIs) act on succinate dehydrogenase in the respiratory chain of pathogenic fungi, blocking electron transport and interfering with fungal energy metabolism to exert their fungicidal effect. SDHIs are effective against a variety of plant pathogenic fungi due to their single site of action and broad spectrum of activity. However, due to widespread and frequent use, resistant strains have emerged in the field, leading to widespread resistance and reduced efficacy. Because of their single site of action, FRAC classifies SDHIs as having a medium to high risk of resistance. With the widespread development and frequent use of these products, resistance development and reduced efficacy are inevitable. To delay the occurrence and development of resistance and improve control efficacy, effective resistance management measures must be implemented in agricultural production. Therefore, the inventors, through extensive experimental research, discovered that combining bromonitol with an SDHI fungicide (any one of fluopyram, pyraclostrobin, or fluopyram) improves control efficacy, broadens the control spectrum, and delays the development of pathogen resistance. Summary of the Invention

[0008] Based on the above, the purpose of this invention is to provide a bactericidal composition containing bromonitol. This composition is effective against plant pathogens, significantly enhances efficacy, and is superior to single agents in terms of both rapid and sustained effects. At the same time, it reduces the amount of pesticides used in agricultural production, slows down the development of pesticide resistance in pathogens, reduces pesticide residues in agricultural products, and is beneficial to the integrated management of agricultural diseases.

[0009] To achieve the above objectives, the present invention adopts the following technical solution: a bactericidal composition containing bromonitol, wherein the bactericidal composition comprises active ingredient A and active ingredient B, wherein active ingredient A is bromonitol, and active ingredient B is selected from any one of fluopyram, pyraclostrobin, or fluopyram aniline, and the mass ratio of active ingredient A to active ingredient B is 1:35 to 35:1.

[0010] Furthermore, the active ingredient B is fluopyram, and the mass ratio of active ingredient A to active ingredient B is 1:30 to 30:1.

[0011] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:15 to 20:1;

[0012] Furthermore, the active ingredient B is pyraclostrobin, and the mass ratio of active ingredient A to active ingredient B is 1:30 to 30:1;

[0013] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:20 to 30:1;

[0014] Furthermore, the active ingredient B is fluopyram aniline, and the mass ratio of active ingredient A to active ingredient B is 1:25 to 25:1;

[0015] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:15 to 25:1.

[0016] Furthermore, based on a total weight of 100 wt%, the total weight of active ingredient A and active ingredient B accounts for 1% to 80% of the total weight of the bactericidal composition.

[0017] Furthermore, the bactericidal composition includes other auxiliary components in addition to the active ingredients, and the auxiliary components are selected from one or more of the following: wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, warning colors, film-forming agents, synergists, and carriers.

[0018] The wetting agent is selected from one or more of the following: alkylbenzene sulfonates, alkylnaphthalene sulfonates, lignin sulfonates, sodium dodecyl sulfate, sodium dioctyl succinate sulfonate, α-olefin sulfonates, alkylphenol polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkylphenol ethoxylates, fatty alcohol ethoxylates, sodium fatty alcohol polyoxyethylene ether sulfate, silkworm excrement, soapberry powder, soapberry powder, SOPA, detergents, emulsifiers 2000 series, and wetting and penetrating agents F; and / or

[0019] The dispersant is selected from one or more of the following: lignin sulfonates, alkyl naphthalene sulfonates formaldehyde condensates, naphthalene sulfonates, tristyrylphenol ethoxylate phosphates, fatty alcohol ethoxylates, alkylphenol polyoxyethylene ethers, alkylphenol polyoxyethylene ether methyl ether condensates sulfates, fatty amine polyoxyethylene ethers, glycerol fatty acid ester polyoxyethylene ethers, polycarboxylates, polyacrylic acids, phosphates, EO-PO block copolymers, and EO-PO graft copolymers; and / or

[0020] The emulsifier is selected from one or more of the following: calcium dodecylbenzenesulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrene-phenol polyoxyethylene ether, castor oil polyoxyethylene ether, and alkylphenol ether phosphate; and / or

[0021] The thickener is selected from one or more of xanthan gum, organobentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose, and silica; and / or

[0022] The disintegrant is selected from one or more of sodium sulfate, ammonium sulfate, aluminum chloride, sodium chloride, ammonium chloride, bentonite, glucose, sucrose, starch, cellulose, urea, sodium carbonate, sodium bicarbonate, citric acid, and tartaric acid; and / or

[0023] Antifreeze is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons, and inorganic salts; and / or

[0024] Defoamer selected from C 10 -C 20 Saturated fatty acid compounds, silicone oil, silicone compounds, C8-C 10 One or more of the fatty alcohols; and / or

[0025] The solvent is selected from one or more of benzene, toluene, xylene, mesitylene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, hydrocarbon carbonates, diesel oil, solvent oil, vegetable oil, vegetable oil derivatives, and water; and / or

[0026] The preservative is selected from one or more of propionic acid, sodium propionate, sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium p-hydroxybenzoate, methyl p-hydroxybenzoate, Kathon, and 1,2-benzisothiazolin-3-one; and / or

[0027] The stabilizer is selected from one or more of the following: disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2,6-di-tert-butyl-p-cresol, triethanolamine oleate, epoxidized vegetable oil, kaolin, bentonite, attapulgite, silica, talc, montmorillonite, and starch; and / or

[0028] Warning colors are selected from one or more of the following: blue, green, red, and purple; and / or

[0029] Film-forming agents are selected from one or more of sodium carboxymethyl starch, cellulose derivatives (sodium carboxymethyl cellulose, sodium alginate, polyvinyl alcohol), and polyacrylic acid; and / or

[0030] Synergists are selected from synergistic phosphorus, synergistic ether; and / or

[0031] The carrier is selected from one or more of the following: ammonium salts, ground natural minerals, ground artificial minerals, silicates, resins, waxes, solid fertilizers, water, organic solvents, mineral oils, vegetable oils, and vegetable oil derivatives.

[0032] Furthermore, the bactericidal composition can be prepared into any agriculturally acceptable formulation, which may be a solid formulation, a liquid formulation, and / or a seed treatment formulation.

[0033] Furthermore, the solid dosage form is a direct-use solid dosage form, a dispersible solid dosage form, or a soluble solid dosage form;

[0034] Furthermore, the directly usable solid dosage form is a powder, granule, ball, tablet, or strip;

[0035] The dispersible solid dosage form is a wettable powder, an oil-dispersible powder, an emulsion powder, a water-dispersible granule, an emulsion granule, or a water-dispersible tablet;

[0036] The soluble solid dosage form is a soluble powder, soluble tablet, or soluble granule;

[0037] Furthermore, the liquid formulation is a solution formulation, a dispersed liquid formulation, an emulsion formulation, a suspension formulation, or a multiphase formulation;

[0038] Furthermore, the solution formulation is a soluble agent, a soluble gel, an oil, or a film-spreading oil;

[0039] The dispersed liquid formulation is an emulsifiable concentrate, latex, dispersible liquid, or ointment;

[0040] The emulsion formulation is an aqueous emulsion, an oil emulsion, a microemulsion, or a lipid formulation;

[0041] The suspension formulation is a suspension agent, microcapsule suspension agent, oil suspension agent, or dispersible oil suspension agent;

[0042] The multiphase formulation is a suspension emulsion, a microcapsule suspension-suspension, a microcapsule suspension-water emulsion, or a microcapsule suspension-suspension emulsion;

[0043] Furthermore, the seed treatment formulation includes a solid seed treatment formulation or a liquid seed treatment formulation;

[0044] Furthermore, the seed treatment solid formulation is a seed treatment dry powder or a seed treatment dispersible powder;

[0045] The seed treatment liquid formulation is a seed treatment liquid, a seed treatment emulsion, or a seed treatment suspension;

[0046] Furthermore, the solid formulation is a water-dispersible granule and / or a wettable powder, the liquid formulation is a suspension concentrate, and the seed treatment formulation is a seed treatment suspension concentrate.

[0047] The present invention also discloses the use of the bactericidal compositions and / or their formulations as described above in the prevention or control of crop pathogens.

[0048] Furthermore, the crops are selected from food crops, cash crops, fruits and vegetables, and / or lawn and garden crops;

[0049] Furthermore, the pathogenic bacteria are pathogenic bacteria of the genus Fusarium, including Fusarium oxysporum, Fusarium incarnatum, Fusarium proliferatum, Fusarium equiseti, Fusarium verticillicides, Fusarium graminearum, and Fusarium moniliforme.

[0050] Furthermore, the pathogenic Fusarium species mentioned are selected from Fusarium graminearum and Fusarium moniliforme.

[0051] The present invention also discloses a method for preventing and controlling crop pathogens, wherein the fungicidal composition and / or its preparations are applied in an effective and substantially non-phytotoxic amount to plants, plant propagation materials and subsequently grown plant organs, cultivation media, materials or spaces by means of seed treatment, foliar application, stem application, soaking, dripping, watering, spraying, misting, dusting, dispersing or fumigation.

[0052] Compared with the prior art, the advantages of the present invention are as follows:

[0053] 1) The rational combination of bromonitol with any one of fluopyram, pyraclostrobin or fluopyram has a significant synergistic effect, which improves the control effect against pathogens.

[0054] 2) Bronitrofurazone has a different mechanism of action than any of the fluopyram, pyraclostrobin, or fluopyram, which helps to delay the development of drug resistance in pathogenic bacteria.

[0055] 3) It reduces the amount of pesticides used in agricultural production, reduces pesticide residues in agricultural products, is environmentally friendly, and is conducive to the comprehensive management of agricultural diseases. Detailed Implementation

[0056] To better understand the essence of the present invention, the following embodiments further illustrate the content of the present invention, but these should not be regarded as limitations on the present invention. The content mentioned in the embodiments is not a limitation of the present invention, and the selection of material formulations can be adapted to local conditions without having a substantial impact on the results.

[0057] Formulation preparation example:

[0058] Preparation Example 1: 30% Bronitrofurazone·Fluoropyram aniline seed treatment suspension (1:1)

[0059] By weight percentage: 15% bromonitroethanol, 15% fluopyram aniline, 4% alkylphenol polyoxyethylene ether, 5% alkylphenol polyoxyethylene ether phosphate salt, 3% sodium lignosulfonate, 2% polyacrylic acid, 0.2% xanthan gum, 6% rose red pigment, 5% ethylene glycol, 1% magnesium aluminum silicate, 0.5% silicone defoamer, 1% sodium benzoate, deionized water to make up the balance.

[0060] Preparation method: The active ingredients, additives, and water are mixed and stirred evenly under high shear according to the formula. Then, the mixture is ground in a sand mill for 2.5 hours to achieve an average particle size of 1-5 micrometers. Finally, thickeners, preservatives, and film-forming agents are added and the mixture is further sheared and stirred evenly to obtain the seed treatment suspension.

[0061] Preparation Example 2: 24% Bronitrofurazone·Fluoropyram aniline seed treatment suspension (1:3)

[0062] By weight percentage: 6% bromonitroethanol, 18% fluopyram aniline, 4% tristyrene-phenol polyoxyethylene ether polyoxypropylene ether, 3% styrene-phenol polyoxyethylene ether phosphate salt, 2% sodium polycarboxylate salt, 1% polyacrylic acid, 0.2% xanthan gum, 1% magnesium aluminum silicate, 5% glycerol, 5% rose red pigment, 1% methylparaben, 0.5% silicone defoamer, deionized water to make up the balance.

[0063] Preparation method: Same as in preparation example 1.

[0064] Preparation Example 3: 30% Bronitrofurazone·Fluoropyram aniline seed treatment suspension (5:1)

[0065] By weight percentage: 25% bromonitroethanol, 5% fluopyram aniline, 4% fatty alcohol polyoxyethylene ether, 5% glycerol fatty acid ester polyoxyethylene ether phosphate, 2% sodium polycarboxylate, 0.2% xanthan gum, 5% rose red pigment, 2% sodium carboxymethyl starch, 5% propylene glycol, 0.5% silicone defoamer, 2% sodium sorbate, deionized water to make up the balance.

[0066] Preparation method: Same as in preparation example 1.

[0067] Preparation Example 4: 28% Bronitrofurazone·Fluoropyram seed treatment suspension (3:1)

[0068] By weight percentage: 21% bromonitroethanol, 7% fluopyram, 3% isotridecyl alcohol polyoxyethylene ether, 3% alkylphenol polyoxyethylene ether phosphate, 2% sodium polycarboxylate, 1% polyacrylic acid, 0.2% xanthan gum, 4% rose red pigment, 5% propylene glycol, 1% magnesium aluminum silicate, 3% sodium benzoate, 0.5% silicone defoamer, deionized water to make up the balance.

[0069] Preparation method: Same as in preparation example 1.

[0070] Preparation Example 5: 30% Bronitrofurazone·Fluoropyram seed treatment suspension (1:1)

[0071] By weight percentage: 15% bromonitroethanol, 15% fluopyram, 2% fatty alcohol polyoxyethylene ether, 3% alkylphenol polyoxyethylene ether phosphate, 3% naphthalene sulfonate formaldehyde condensate, 2% polyvinyl alcohol, 0.3% xanthan gum, 5% rose red pigment, 4% ethylene glycol, 1.5% magnesium aluminum silicate, 0.5% silicone defoamer, 0.1% Kathon, deionized water to make up the balance.

[0072] Preparation method: Same as in preparation example 1.

[0073] Preparation Example 6: 32% Bronitrofurazone·Fluoropyram seed treatment suspension (7:1)

[0074] By weight percentage: 28% bromonitroethanol, 4% fluopyram, 4% isotridecyl alcohol polyoxyethylene ether, 3% EO / PO block copolymer, 3% glycerol fatty acid ester polyoxyethylene ether phosphate, 3% sodium lignosulfonate, 2% sodium carboxymethyl cellulose, 5% glycerol, 0.3% xanthan gum, 1.5% magnesium aluminum silicate, 0.5% silicone defoamer, 6% rose red pigment, 1% potassium benzoate, deionized water to make up the balance.

[0075] Preparation method: Same as in preparation example 1.

[0076] Preparation Example 7: 20% Bronitrofurazone·Fluoropyram hydroxylamine suspension (1:1)

[0077] By weight percentage, 10% bromonitol, 10% fluopyram, 2% sodium dodecyl sulfate, 1% alkylphenol polyoxyethylene ether, 3% styrene-phenol polyoxyethylene ether phosphate, 0.2% xanthan gum, 1% magnesium aluminum silicate, 3% ethylene glycol, 1% sodium benzoate, 0.5% silicone oil, and deionized water to make up the balance.

[0078] Preparation method: According to the formula ratio, the active ingredients, surfactants and other functional additives are placed in the reaction vessel in sequence, water is added and mixed evenly, and then subjected to high-speed shearing, wet sand milling and finally homogenization filtration to obtain the suspension product.

[0079] Preparation Example 8: 36% Bronitrofurazone·Fluoropyram hydroxylamine water-dispersible granules (3:1)

[0080] By weight percentage, 27% bromonitol, 9% fluopyram, 8% sodium lignosulfonate, 6% naphthalenesulfonate formaldehyde condensate, 3% bleaching powder BX, 5% white sugar, and kaolin to make up the balance.

[0081] Preparation method: According to the formulation ratio in the example, add the active ingredient to the carrier, and add surfactants and other functional additives therein, mix, and after air jet pulverization, add 10-25% water, and then knead, granulate, dry and sieve to obtain water-dispersible granules; or spray water, granulate and dry the pulverized powder in a fluidized bed granulator, and then sieve to obtain the product.

[0082] Preparation Example 9: 48% Bronitrofurazone·Fluoropyram wettable powder (1:5)

[0083] By weight percentage, 8% bromonitol, 40% fluopyram, 12% naphthalene sulfonate formaldehyde condensate, 3% calcium lignosulfonate, 2% sodium lignosulfonate, 2% sodium dodecyl sulfate, and kaolin to make up the balance.

[0084] Preparation method: According to the formula ratio, the active ingredients, dispersant, wetting agent and filler are mixed and stirred evenly in a stirring tank. The mixture is then pulverized and mixed evenly multiple times by an air jet mill to prepare the wettable powder of the composition of the present invention.

[0085] Preparation Example 10: 30% Bronitrofurazone·Pyrazothiamethoxam Suspension (1:3)

[0086] By weight percentage: 7.5% bromonitol, 22.5% pyraclostrobin, 2% fatty alcohol polyoxyethylene ether, 3% alkylphenol polyoxyethylene ether phosphate, 2% sodium lignosulfonate, 0.3% xanthan gum, 1.5% magnesium aluminum silicate, 5% propylene glycol, 0.5% silicone oil, 0.01% potassium benzisothiazolinone, deionized water to make up the balance.

[0087] Preparation method: Same as in preparation example 7.

[0088] Preparation Example 11: 32% Bronitrofurazone·Pyrazothiamethoxam Water Dispersible Granules (1:1)

[0089] By weight percentage, 16% bromonitol, 16% pyraclostrobin, 3% sodium dodecyl sulfate, 6% sodium lignosulfonate, 10% naphthalenesulfonate formaldehyde condensate, 10% ammonium sulfate, and starch to make up the balance.

[0090] Preparation method: Same as in preparation example 8.

[0091] Preparation Example 12: 44% Bronitrofurazone·Pyrazothiamethoxam Wettable Powder (1:10)

[0092] By weight percentage, 4% bromonitol, 40% pyraclostrobin, 3% sodium polycarboxylate, 4% sodium lignosulfonate, 6% dispersant NNO, 3% sodium dodecyl sulfate, and kaolin to make up the balance.

[0093] Preparation method: Same as in preparation example 9.

[0094] Indoor activity assay:

[0095] Example 1: Indoor activity assay of bromonitol combined with any one of fluopyram or fluopyram aniline against rice bakanae disease.

[0096] Test basis: The test refers to NY / T 1156.2-2006, the agricultural industry standard of the People's Republic of China, "Guidelines for Indoor Bioassay Tests of Pesticides - Fungicides Part 2: Test on Inhibition of Mycelial Growth of Pathogenic Fungi - Plate Method".

[0097] Test strain: Fusarium moniliforme, provided by Shenyang Chemical Research Institute.

[0098] Equipment: Autoclave, laminar flow hood, incubator, electric drying oven, 0.01% electronic balance, pipette, alcohol lamp, beaker (50mL), volumetric flask, Erlenmeyer flask (100mL), petri dish (Φ9cm), hole punch (Φ0.6cm), inoculator, ruler, etc.

[0099] Culture conditions for the test target: Fusarium moniliforme stored at 4°C in an indoor refrigerator was transferred to potato dextrose agar medium and incubated in the dark at 25°C for 5 days to activate it for later use.

[0100] Test reagents: 95% bronitrothion technical, 98% fluopyram technical, and 95% fluopyram technical. All of the above reagents were provided by the R&D Center of Hailier Pharmaceutical Group.

[0101] Other reagents: acetone (analytical grade), Tween 80 (chemically pure).

[0102] Preparation of pharmaceutical stock solution: Dissolve the above raw materials separately in acetone to prepare high-concentration stock solutions, then dilute with 0.1% Tween 80 aqueous solution to prepare single-agent stock solutions. Design different ratios according to the purpose of mixing and the activity of the pharmaceuticals. Prepare each single agent and each group of mixed solutions to the required series of mass concentrations.

[0103] Experimental replication: Four petri dishes were used for each concentration of the test reagent, with one petri dish for each replicate, for a total of four replicates. A 0.1% Tween 80 aqueous solution without the reagent was used as a blank control.

[0104] Drug processing: Under aseptic conditions, use a pipette to add 5 mL of drug solution of different concentrations to pre-calibrated sterile Erlenmeyer flasks. Then, add the melted and cooled culture medium to the Erlenmeyer flasks, shake well, and pour the mixture into 4 petri dishes in equal amounts to prepare drug-containing PDA plates of the corresponding concentrations.

[0105] Inoculation: Under aseptic conditions, use a sterile punch to cut off a mycelial cake from the edge of the pre-cultured Fusarium moniliforme. Inoculate the mycelial cake into the center of the drug-containing plate using an inoculator, cover with the cap, and place in a constant temperature incubator at 25°C for dark incubation.

[0106] Data collection: An experimental investigation was conducted based on the colony growth to 2 / 3 to 4 / 5 of the petri dish diameter in the control treatment. The colony diameter (cm) was measured using a ruler, and the diameter of each colony was measured once using the cross-sectional method, and the average value was taken.

[0107] Data statistics and analysis: Based on the survey results, the inhibition rate of mycelial growth of the tested target bacteria by each treatment concentration was calculated, in percentage (%). The calculation results were retained to two decimal places.

[0108] D = D1 - D2

[0109] In the formula:

[0110] D – Colony growth diameter;

[0111] D1—colony diameter;

[0112] D2 – Diameter of the mushroom cake.

[0113]

[0114] In the formula:

[0115] I – Mycelial growth inhibition rate;

[0116] D0—Correlation diameter of the blank control group;

[0117] D T — Diameter of colonies grown after chemical treatment.

[0118] The data were processed using probability value analysis. IBM SPSS Statistics 20 statistical analysis system was used to analyze the data and derive the toxicity regression line and EC5. 50 Values ​​and correlation coefficient R 2 To evaluate the activity of the test reagent on biological materials.

[0119] Sun Yunpei's method: The synergistic effect of drug mixtures is evaluated based on the co-toxicity coefficient (CTC). A CTC ≥ 120 indicates a synergistic effect; a CTC ≤ 80 indicates an antagonistic effect; and a CTC < 120 indicates an additive effect.

[0120] Calculation of the co-toxicity coefficient (CTC value) of the mixture:

[0121]

[0122] In the formula:

[0123] ATI – Actual Measured Toxicity Index of Mixtures;

[0124] S—EC of standard reagent 50 The unit is milligrams per liter (mg / L);

[0125] M – EC of the mixture 50 The unit is milligrams per liter (mg / L).

[0126] TTI = TI A *P A +TI B *P B

[0127] In the formula:

[0128] TTI – Theoretical Toxicity Index of Mixtures;

[0129] TI A —A. Toxicity index of drug A;

[0130] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0131] TI B —Toxicity index of drug B;

[0132] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0133]

[0134] In the formula:

[0135] CTC – Cotoxicity Coefficient;

[0136] ATI – Actual Measured Toxicity Index of Mixtures;

[0137] TTI – Theoretical Toxicity Index of Mixtures.

[0138] The test results are shown in the table below:

[0139] Table 1. Results of indoor activity tests of bronitrocellulose combined with fluopyram aniline against rice bakanae disease.

[0140]

[0141] Table 2. Results of indoor activity tests of bronitrocellulose and fluopyram combined with rice bakanae disease control.

[0142]

[0143] As shown in Tables 1 and 2, the indoor activity tests indicate that the combination of bromonitol with either fluopyram or fluopyram aniline exhibits good control effects against rice bakanae disease.

[0144] Table 1 shows that the tested agents bromonitol and fluopyram aniline have good control effects on rice bakanae disease pathogens, and their EC50 values ​​are [not specified]. 50 The concentrations were 4.628 mg / L and 5.344 mg / L, respectively. The co-toxicity coefficients of bronitrophenol and fluopyram aniline in the mass ratio range of 1:35 to 35:1 were all greater than 120, which showed a synergistic effect on rice bakanae disease. Among them, the co-toxicity coefficient was the largest and the synergistic effect was the most significant when bronitrophenol and fluopyram aniline were combined in a mass ratio of 1:1.

[0145] As shown in Table 2, the tested fungicide fluopyram has high toxicity against rice bakanae disease, with an EC50 value of [missing information]. 50 At a concentration of 0.053 mg / L, the co-toxicity coefficient of bronitrofurazone and fluopyram at a mass ratio of 1:35 to 35:1 was greater than 80, showing different additive or synergistic effects against rice bakanae disease. When the mass ratio of bronitrofurazone to fluopyram was 1:15 to 25:1, the co-toxicity coefficient was greater than 120, showing a synergistic effect against rice bakanae disease.

[0146] Example 2: Indoor activity assay of bromonitol combined with any one of fluopyram or pyraclostrobin against wheat scab.

[0147] Test basis: The test refers to NY / T 1156.2-2006, the agricultural industry standard of the People's Republic of China, "Guidelines for Indoor Bioassay Tests of Pesticides - Fungicides Part 2: Test on Inhibition of Mycelial Growth of Pathogenic Fungi - Plate Method".

[0148] Experimental target: Fusarium graminearum, collected from diseased wheat plants in the experimental field of Shandong Agricultural University, isolated, identified and preserved by the laboratory of Shandong Agricultural University.

[0149] Instruments and equipment: moist heat sterilizer, ultra-clean workbench, constant temperature and light incubator, electric heating drum and windproof drying oven, 0.01% electronic balance, pipette, alcohol lamp, small beakers, volumetric flasks, Erlenmeyer flasks, petri dishes (Φ9cm), hole punch, inoculator (Φ0.6cm), ruler, etc.

[0150] Culture conditions for the test target: Fusarium graminearum stored at 4°C in an indoor refrigerator was transferred to potato dextrose agar medium and incubated in the dark at 26°C for 4 days to activate it for later use.

[0151] Test reagents: 95% bronitrothion technical, 98% fluopyram technical, and 92% pyraclostrobin technical. All of the above reagents were provided by the R&D Center of Hailier Pharmaceutical Group.

[0152] Other reagents: solvent acetone (analytical grade), emulsifier Tween 80 (chemically pure).

[0153] Preparation of pharmaceutical stock solution: Dissolve the above raw materials separately in acetone to prepare high-concentration stock solutions, then dilute with 0.1% Tween 80 aqueous solution to prepare single-agent stock solutions. Design different ratios according to the purpose of mixing and the activity of the pharmaceuticals. Prepare each single agent and each group of mixed solutions to the required series of mass concentrations.

[0154] Experimental replication: Four petri dishes were used for each concentration of the test reagent, with one petri dish for each replicate, for a total of four replicates. A 0.1% Tween 80 aqueous solution without the reagent was used as a blank control.

[0155] Chemical treatment: Under aseptic conditions, pre-melted and sterilized PDA medium was quantitatively added to sterile Erlenmeyer flasks according to the experimental treatment. 10 mL of each prepared treatment solution, from low to high concentration, was quantitatively pipetted into the respective Erlenmeyer flasks, thoroughly mixed, and then poured into four 9 cm diameter petri dishes to prepare the corresponding concentration of drug-containing plates. A 0.1% Tween 80 aqueous solution without added drug was set up as a blank control. Each treatment was repeated four times.

[0156] Inoculation: Under aseptic conditions, cut a mycelial cake from the edge of the pre-cultured Fusarium graminearum using a sterile punch, inoculate the mycelial cake into the center of the drug-containing plate using an inoculator, cover with the cap, and place in a constant temperature and light incubator at 26℃ for dark incubation.

[0157] Data collection: The growth of pathogenic fungal hyphae was investigated based on the growth of hyphae in the blank control culture dishes. The diameter of the colonies was measured in centimeters (cm) using a ruler. The diameter of each colony was measured once using the cross-sectional method, and the average value was taken. The original data of all replicates for each treatment were recorded.

[0158] Data statistics and analysis: Based on the survey results, the inhibition rate of mycelial growth of the tested target bacteria by each treatment concentration was calculated, in percentage (%). The calculation results were retained to two decimal places.

[0159] D = D1 - D2

[0160] In the formula:

[0161] D – Colony growth diameter;

[0162] D1—colony diameter;

[0163] D2 – Diameter of the mushroom cake.

[0164]

[0165] In the formula:

[0166] I – Mycelial growth inhibition rate;

[0167] D0—Correlation diameter of the blank control group;

[0168] D T — Diameter of colonies grown after chemical treatment.

[0169] The data were processed using probability value analysis. IBM SPSS Statistics 20 statistical analysis system was used to analyze the data and derive the toxicity regression line and EC5. 50 Values ​​and correlation coefficient R 2 To evaluate the activity of the test reagent on biological materials.

[0170] Sun Yunpei's method: The synergistic effect of drug mixtures is evaluated based on the co-toxicity coefficient (CTC). A CTC ≥ 120 indicates a synergistic effect; a CTC ≤ 80 indicates an antagonistic effect; and a CTC < 120 indicates an additive effect.

[0171] Calculation of the co-toxicity coefficient (CTC value) of the mixture:

[0172]

[0173] In the formula:

[0174] ATI – Actual Measured Toxicity Index of Mixtures;

[0175] S—EC of standard reagent 50 The unit is milligrams per liter (mg / L);

[0176] M – EC of the mixture 50 The unit is milligrams per liter (mg / L).

[0177] TTI = TI A *PA +TI B *P B

[0178] In the formula:

[0179] TTI – Theoretical Toxicity Index of Mixtures;

[0180] TI A —A. Toxicity index of drug A;

[0181] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0182] TI B —Toxicity index of drug B;

[0183] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0184]

[0185] In the formula:

[0186] CTC – Cotoxicity Coefficient;

[0187] ATI – Actual Measured Toxicity Index of Mixtures;

[0188] TTI – Theoretical Toxicity Index of Mixtures.

[0189] The test results are shown in the table below:

[0190] Table 3. Results of indoor activity tests of bronitrocellulose and fluopyram combined with wheat scab virus.

[0191]

[0192] Table 4. Results of indoor activity tests of bromonitrile combined with pyraclostrobin against wheat scab.

[0193]

[0194] As shown in Tables 3 and 4, the indoor activity tests indicate that bromonitol combined with any one of fluopyram or pyraclostrobin showed good control effects against wheat scab.

[0195] Table 3 shows that the tested agent fluopyram has a good control effect on wheat scab pathogen, and its EC50 value is [missing information]. 50The concentration was 0.079 mg / L. The co-toxicity coefficient of bromonitol and fluopyram at a mass ratio of 1:35 to 35:1 was greater than 120, which showed a synergistic effect on wheat scab. The co-toxicity coefficient was the largest and the synergistic effect was the most significant when bromonitol and fluopyram were combined at a mass ratio of 1:1.

[0196] Table 4 shows that both bronitrofurazone and pyraclostrobin, the tested agents, have good control effects on wheat scab. 50 The concentrations were 6.572 mg / L and 4.221 mg / L, respectively. When bromonitol and pyraclostrobin were combined in a mass ratio of 1:30 to 30:1, the co-toxicity coefficient was greater than 120, showing a synergistic effect against wheat scab.

[0197] Field efficacy trials:

[0198] Example 3: Field efficacy trial of compound formulation for controlling rice bakanae disease

[0199] Experimental basis: The experiment was conducted in accordance with GB / T 17980.104-2004 "Guidelines for Field Efficacy Tests of Pesticides (II) Part 104: Control of Rice Bakanae Disease by Fungicides".

[0200] Experimental target: Rice bakanae disease.

[0201] Experimental crop: Rice (Ewan 17).

[0202] Experimental site: Bailianhe Village, Bailianhe Township, Luotian County, Huanggang City, Hubei Province. Bakanae disease is a common disease in rice production in this region, and a mild outbreak occurred in the experimental field in 2018. The soil at the experimental site was gleyed paddy soil with a pH of 5.5, an organic matter content of 1.5%, and moderate soil fertility.

[0203] Water and fertilizer management in the experimental field: Before rice transplanting (May 8), apply 50 kg of 30% (15-7-8) Ezhong compound fertilizer per mu as base fertilizer, apply 12 kg of 46.4% urea per mu as topdressing on May 17, and apply 6 kg of 46.4% urea per mu as the second topdressing on July 1.

[0204] Meteorological data: The weather was cloudy on March 31, 2019, the day of pesticide application, with temperatures ranging from 5 to 19°C. No severe weather that would have affected the test results occurred during the experiment.

[0205] Plot arrangement: The plots for the experimental drug, control drug, and blank control were arranged in a randomized block design.

[0206] Cell area: 24m² per experimental cell 2 Each interval has a protected row, and each process is repeated 4 times.

[0207] Dosage of the tested reagents: The reagents and dosages are shown in the table below:

[0208] Table 4. Tested pesticides and dosages for field efficacy trials of rice bakanae disease.

[0209] 1 30% Bronitrofurazone·Fluoropyram Aniline Seed Treatment Suspension (1:1) 50 2 32% Bronitrofurazone·Fluoropyram seed treatment suspension (7:1) 50 3 28% Bronitrofurazone·Fluoropyram seed treatment suspension (3:1) 50 4 24% Bronitrofurazone·Fluoropyram Aniline Seed Treatment Suspension (1:3) 50 5 200 g / L fluopyram suspension 100 6 22.4% Fluopyram Aniline Seed Treatment Suspension 60 7 20% Bronitrocellulose wettable powder 85 8 Blank control -

[0210] Application method: Coat rice seeds before sowing. Weigh the seeds for each treatment according to the seed quantity per acre, put them in sealed bags for later use, and thoroughly mix the pesticide solution with the seeds according to the experimental protocol until the solution is evenly distributed on the seed surface. After drying, sow the seeds.

[0211] Sowing: Sow 4 trays (55cm*25cm) per plot in the seedbed, placing them in different locations within the plot. Each tray contains approximately 3900 seeds, which are used for seedling emergence rate surveys.

[0212] Application time and number of applications: Seed coating was carried out on March 31, 2019, with a total of 1 application.

[0213] Experimental survey: A total of three surveys were conducted. The first survey was conducted when the seedlings emerged in the seedbed, investigating the emergence time and emergence rate. Four trays of rice were sown at fixed points in each plot, and half of each tray was investigated. The second survey was conducted before the rice seedlings were transplanted, investigating the disease incidence rate. Five samples were taken from each plot, with 100 plants sampled at each point. The number of diseased plants and the total number of plants in each treatment were investigated, and the control effect was calculated. The third survey was conducted before the rice heading stage, investigating the disease situation. Five samples were taken from each plot, with 20 clumps sampled at each point. The number of diseased plants and the total number of plants in each treatment were investigated, and the control effect was calculated.

[0214] Safety investigation: Field observations were conducted after the experiment. Rice growth in all pesticide-treated areas was normal, basically consistent with the blank control area. No phytotoxicity, chlorosis, deformity, or other adverse effects were observed in rice caused by any of the tested pesticides. Compared with the blank control, no effects were observed on other target organisms by any of the treatments.

[0215] Methods for calculating drug efficacy:

[0216]

[0217]

[0218]

[0219] The test results are shown in the table below:

[0220] Table 5. Results of field efficacy trials of compound formulations for controlling rice bakanae disease.

[0221]

[0222] The efficacy of the compound formulation in the field trial was analyzed: Rice seeds were coated with the compound formulation of this invention. The germination rate survey results showed that the germination rates of each treatment were basically the same as or even better than the control treatment. Before rice seedling transplanting, the disease incidence rate was investigated. The average disease incidence rate in the blank control treatment reached 8.50%, while the control effect of the compound formulation was higher than 84.12%. The control effect survey conducted before rice heading showed that the control effect of the compound formulation on rice bakanae disease ranged from 84.71% to 94.76%, all of which were superior to the single-agent control.

[0223] Example 4: Field efficacy trial of compound formulation for controlling wheat scab

[0224] Experimental basis: The experiment was conducted in accordance with NY / T 1464.15-2007 "Guidelines for Field Efficacy Tests of Pesticides Part 15: Control of Wheat Fusarium Head Blight by Fungicides".

[0225] Experimental target: Wheat scab.

[0226] Experimental crop: Wheat (Jimai 22).

[0227] Experimental site: A field in Sanlitun Village, Zhanghuang Town, Yutai County, Jining City, Shandong Province, where rice and wheat rotation has been practiced for many years. Wheat scab disease has been a serious problem in recent years. The seed rate was 20 kg per mu. The soil in the experimental site was clay loam with moderate fertility. The cultivation conditions of all experimental plots were consistent and met the local good agricultural practices.

[0228] Experimental plot arrangement: The experimental, control, and blank control treatments were arranged in a randomized block design, with each plot measuring 20 m². 2 Each treatment was repeated 4 times.

[0229] Dosage of the tested reagents: The reagents and dosages are shown in the table below:

[0230] Table 6. Tested pesticides and dosages used in field efficacy trials for wheat scab.

[0231]

[0232]

[0233] Application time: The experiment involved applying the pesticide once during the wheat flowering stage, using a Linong HD-400 backpack sprayer for whole-plant spraying to ensure even and thorough droplet distribution. The amount of pesticide solution applied per acre was 35 kg.

[0234] Investigation methods and time: The efficacy of the control was investigated once 15 days after the application of the pesticide (wheat milk stage). During the investigation, five points were sampled diagonally in each plot, and 100 ears were investigated at each point. The control was classified according to the percentage of dead ears to the total ear area, and the number of diseased ears at each level and the total number of ears were recorded.

[0235] Grading standards for wheat scab:

[0236] Grade 0: Disease-free entire ear of grain;

[0237] Grade 1: The area of ​​withered ears accounts for less than 1 / 4 of the total ear area;

[0238] Grade 3: The area of ​​withered ears accounts for 1 / 4 to 1 / 2 of the total ear area;

[0239] Grade 5: The area of ​​withered ears accounts for 1 / 2-3 / 4 of the total ear area;

[0240] Level 7: The area of ​​dead ears accounts for more than 3 / 4 of the total ear area.

[0241] Methods for calculating drug efficacy:

[0242]

[0243]

[0244] The test results are shown in the table below:

[0245] Table 5. Results of field efficacy trials of the compound formulation against wheat scab.

[0246]

[0247]

[0248] Field efficacy results showed that the combination of bromonitol with any one of fluopyram or pyraclostrobin showed good control effect against wheat scab. The overall control efficacy of each combination treatment was above 86.25%, which was better than the blank control group with a single agent.

[0249] Indoor toxicity tests and field efficacy tests show that the bactericidal composition containing bromonitrile of the present invention exhibits good control effect against Fusarium pathogens, is safe for crops, delays the development of drug resistance in pathogens, and reduces the dosage of the agent while reducing the pesticide residue in agricultural products.

[0250] Although the present invention has been described in detail above with general description and specific embodiments, some modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention are within the scope of protection claimed by the present invention.

Claims

1. A bactericidal composition containing bromonitroethanol, characterized in that, The bactericidal composition comprises active ingredient A and active ingredient B, wherein active ingredient A is bromonitol and active ingredient B is fluopyram aniline, and the mass ratio of active ingredient A to active ingredient B is 1:35 to 35:

1.

2. The bactericidal composition according to claim 1, characterized in that, The mass ratio of active ingredient A to active ingredient B is 1:25 to 25:

1.

3. The bactericidal composition according to claim 2, characterized in that, The mass ratio of active ingredient A to active ingredient B is 1:15 to 25:

1.

4. The bactericidal composition according to claim 1, characterized in that, The total weight of the bactericidal composition is calculated as 100 wt%, and the total weight of active ingredient A and active ingredient B accounts for 1% to 80% of the total weight of the bactericidal composition.

5. The bactericidal composition according to claim 1, characterized in that, The bactericidal composition includes, in addition to the active ingredient, other auxiliary ingredients selected from one or more of the following: wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, warning colors, film-forming agents, synergists, and carriers.

6. The bactericidal composition according to claim 1, characterized in that, The bactericidal composition is prepared into any agriculturally acceptable formulation, wherein the formulation is a solid formulation, a liquid formulation, and / or a seed treatment formulation; wherein the solid formulation is a water-dispersible granule or a wettable powder, the liquid formulation is a suspension concentrate, and the seed treatment formulation is a seed treatment suspension concentrate.

7. The use of the bactericidal composition and / or its formulation according to any one of claims 1-6 in the prevention or control of crop pathogens, characterized in that, The pathogenic bacteria mentioned are Fusarium pathogens, and the Fusarium pathogen is Fusarium moniliforme.

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