A bactericidal composition containing fluoxapiprolin and its application

Abstract

The present invention belongs to the technical field of pesticide fungicides and discloses a fungicide composition containing fluoxapiprolin. The composition comprises an active ingredient A and an active ingredient B, wherein the active ingredient A is famoxadone and the active ingredient B is fluoxapiprolin. The weight ratio of the active ingredient A to the active ingredient B is 1:40 to 50:1. The composition has high activity against a variety of diseases on various crops, exhibits significant synergistic effects, and has a broad fungicide spectrum.

Description

[0001] This invention application is a divisional application with application number CN202211217889.X, application date September 30, 2022, and invention name “A bactericidal composition containing fluoxapiprolin and its application”. Technical Field

[0002] The present invention relates to the field of pesticide fungicides, and in particular to a fungicide composition containing fluoxapiprolin and application thereof. Background Art

[0003] Fungal diseases have always been one of the most important constraints in agricultural production. During the growth process of crops, they may be infected by a variety of fungi or bacteria and suffer from various diseases.

[0004] Fluoxapiprolin is a newly developed piperidinylthiazolylisoxazoline fungicide developed by Bayer. Fluoxapiprolin is a racemic isomer, and both isomers possess identical biological activity. Its chemical name is 2-{(5RS)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}-4-piperidinyl)thiazol-4-yl]-4,5-dihydroisoxazol-5-yl}-3-chlorophenyl methanesulfonate, and its CAS number is 1360819-11-9.

[0005] Due to the increasing environmental and economic demands placed on fungicides and the increasing attention paid to resistance, the development of new fungicides that outperform existing ones in certain aspects is an ongoing task. Fungicides containing a single ingredient often suffer from drawbacks in crop disease control: they can easily develop resistance with continuous use, have a narrow spectrum of activity, fail to provide comprehensive crop protection, and incur high costs for farmers. Combinations of two or more active ingredients can overcome these shortcomings to a certain extent. Synergistic blends of two or more active ingredients can improve efficacy, reduce the dosage of the active ingredients, save farmers money on pesticides, slow the development of disease resistance, and broaden the control spectrum. Summary of the Invention

[0006] Based on the above situation, the purpose of the present invention is to provide a fungicidal composition containing fluoxapiprolin, which can have a synergistic effect on various diseases, can alleviate the development of pathogen resistance, and reduce production costs.

[0007] To achieve the above object, the present invention provides the following technical solution: a fungicide composition containing fluoxapiprolin, comprising an active ingredient A and an active ingredient B, wherein the active ingredient A is selected from mancozeb and famoxadone, and the active ingredient B is fluoxapiprolin, and the weight ratio of the active ingredient A to the active ingredient B is 1:40 to 50:1;

[0008] Furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1:40 to 35:1.

[0009] Furthermore, the mass ratio of mancozeb to fluoxapiprolin is 1:25 to 25:1;

[0010] Furthermore, the mass ratio of mancozeb to fluoxapiprolin is 1:25, 1:17, 1:10, 1:5, 7:2, 6:1, 15:1, and 25:1;

[0011] Furthermore, the mass ratio of famoxadone to fluoxapiprolin is 1:40 to 35:1;

[0012] Furthermore, the mass ratio of famoxadone to fluoxapiprolin is 1:40, 1:20, 1:6, 1:1, 5:1, 10:1, 20:1, and 35:1;

[0013] Furthermore, the mass ratio of mancozeb to fluoxapiprolin is 1:10 to 6:1;

[0014] Furthermore, the mass ratio of mancozeb to fluoxapiprolin is 1:10, 1:5, 7:2, and 6:1;

[0015] Furthermore, the mass ratio of famoxadone to fluoxapiprolin is 1:6 to 20:1;

[0016] Furthermore, the mass ratio of famoxadone to fluoxapiprolin is 1:6, 1:1, 5:1, 10:1, and 20:1;

[0017] Furthermore, based on the total weight of the bactericidal composition being 100 wt%, the sum of the content of the active ingredient A and the active ingredient B in the bactericidal composition is 5 to 90 wt%;

[0018] Furthermore, based on the total weight of the bactericidal composition being 100 wt%, the sum of the content of the active ingredient A and the active ingredient B in the bactericidal composition is 10 to 80 wt%;

[0019] Furthermore, based on the total weight of the bactericidal composition being 100 wt%, the sum of the content of the active ingredient A and the active ingredient B in the bactericidal composition is 10 to 60 wt%;

[0020] Furthermore, the bactericidal composition is added with corresponding adjuvants to prepare any one of wettable powder, water dispersible granules or suspension concentrate;

[0021] Furthermore, the auxiliary agent is one or more of a wetting agent, a dispersant, an emulsifier, a thickener, a disintegrant, an antifreeze agent, a defoaming agent, a solvent, a preservative, a stabilizer, a synergist or a carrier;

[0022] The wetting agent is selected from one or more of alkylbenzene sulfonate, alkylnaphthalene sulfonate, lignin sulfonate, sodium lauryl sulfate, sodium dioctyl sulfosuccinate, α-olefin sulfonate, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, alkylphenol ethoxylate, fatty alcohol ethoxylate, fatty alcohol polyoxyethylene ether, tea saponin, silkworm feces, soapberry powder, soapberry powder, SOPA, detergent, emulsifier 2000 series and wetting penetrant F;

[0023] The dispersant is selected from one or more of lignin sulfonate, alkylnaphthalene sulfonate formaldehyde condensate, alkylnaphthalene formaldehyde condensate sodium sulfonate, naphthalene sulfonate, tristyrylphenol ethoxylate phosphate, fatty alcohol ethoxylate, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether methyl ether condensate sulfate, fatty amine polyoxyethylene ether, glycerol fatty acid ester polyoxyethylene ether, polycarboxylates, polyacrylic acids, phosphates, EO-PO block copolymers and EO-PO graft copolymers;

[0024] The emulsifier is selected from one or more of calcium dodecylbenzenesulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenylethylphenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, fatty alcohol polyoxyethylene ether, styrylphenol polyoxyethylene ether, sodium salt of dioctyl sulfosuccinate, castor oil polyoxyethylene ether and alkylphenol ether phosphate;

[0025] The thickener is selected from one or more of xanthan gum, gum arabic, organic bentonite, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose and white carbon black;

[0026] The disintegrant is selected from one or more of ammonium sulfate, sodium sulfate, aluminum chloride, sodium chloride, ammonium chloride, bentonite, glucose, sucrose, starch, cellulose, urea, sodium carbonate, sodium bicarbonate, citric acid and tartaric acid;

[0027] The antifreeze agent is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons and inorganic salts;

[0028] Defoaming agent selected from C 10 -C20 Saturated fatty acid compounds, silicone oil, silicone compounds, C8-C 10 one or more of fatty alcohols;

[0029] The solvent is selected from one or more of benzene, toluene, xylene, durene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, alkylene carbonate, diesel, solvent oil, vegetable oil, vegetable oil derivatives and water;

[0030] The preservative is selected from one or more of propionic acid, sodium propionic acid, sorbic acid, sodium sorbic acid, potassium sorbic acid, benzoic acid, sodium benzoic acid, sodium p-hydroxybenzoic acid, methyl p-hydroxybenzoate, kasone and 1,2-benzisothiazol-3-one;

[0031] The stabilizer is selected from one or more of disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2,6-di-tert-butyl-p-methylphenol, triethanolamine oleate, epoxidized vegetable oil, kaolin, bentonite, attapulgite, white carbon black, talc, montmorillonite and starch;

[0032] The synergist is selected from synergist phosphine and piperonyl butoxide;

[0033] pH regulator is selected from oxalic acid, citric acid, sodium carbonate, sodium tripolyphosphate;

[0034] The warning pigment is selected from acid red, rose essence, and brilliant blue;

[0035] The carrier is selected from one or more of ammonium salts, ground natural minerals, ground artificial minerals, silicates, resins, waxes, solid fertilizers, water, organic solvents, mineral oils, vegetable oils and vegetable oil derivatives;

[0036] A fungicidal composition containing fluoxapiproli is used for controlling plant pathogenic fungi.

[0037] A fungicidal composition containing fluoxapiproli for controlling pathogenic fungi on cereals, fruits and vegetables;

[0038] The fungicidal composition of the present invention can be used to control plant pathogenic fungi, which are particularly selected from the group consisting of Ascomycetes, Basidiomycetes, Phycomycetes, Deuteromycetes, Oomycetes, and Plasmodiophoromycetes.

[0039] Furthermore, the diseases caused by the pathogenic fungi include downy mildew, blight, and powdery mildew;

[0040] Furthermore, the disease caused by the pathogenic fungus is downy mildew.

[0041] A fungicidal composition containing fluoxapiproli is applied to the pest to be controlled or to its growth medium at an effective dose.

[0042] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0043] 1) Fluoxapiprolin mixed with mancozeb and famoxadone has high activity against a variety of diseases and a broad fungicidal spectrum;

[0044] 2) It has obvious synergistic effect within a certain range, is safe and efficient, and can alleviate the development of pathogen resistance and reduce production costs. DETAILED DESCRIPTION

[0045] In order to make the technical solutions, objectives and advantages of the present invention more clearly understood, the present invention is described with reference to the following specific embodiments. However, the present invention can be implemented in various forms and should not be limited to the embodiments described herein.

[0046] The present invention has been described in detail below using general descriptions and specific implementation plans. However, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. All equivalent changes made on the basis of the technical solution of this application fall within the scope of protection of the present invention.

[0047] Indoor toxicity assay

[0048] Example 1

[0049] Pesticide Indoor Bioassay Test Guidelines: The test refers to NY / T 1156.6-2006 "Pesticide Indoor Bioassay Test Guidelines Fungicides Part 6: Determination of Combined Action of Mixtures" and NY / T 1156.7-2006 "Pesticide Indoor Bioassay Test Guidelines Fungicides Part 7: Test Pot Method for Control of Cucumber Downy Mildew"

[0050] Test target: Cucumber downy mildew (Pesudoperonospora cubensis);

[0051] Test materials: Select 4 cucumber seedlings in the true leaf stage with consistent growth. Select 5 pots of test cucumber seedlings for each treatment and number them for future use.

[0052] Test agents: mancozeb technical, famoxadone technical, fluoxapiprolin technical, all of which are provided by the group's R&D center.

[0053] Chemical Treatment: Dissolve the above active ingredients in a suitable solvent and then dilute with 0.1% Tween 80 solution. Set up five concentration gradients for each agent and spray the solution evenly on both sides of the leaves until they are completely wet. Allow the solution to air-dry and set aside. A treatment without chemical was used as a blank control.

[0054] Preparation of sporangium suspension: Take cucumber leaves with downy mildew from the field, use a brush dipped in distilled water at about 10℃ to wash off the sporangium on the back, and prepare a concentration of 3×10 5 The sporangium suspension was stored at 4°C until use.

[0055] Experimental treatment: Sporangium suspension of cucumber downy mildew was sprayed and inoculated 24 hours after the pesticide treatment. After inoculation, the cucumber seedlings were placed in an artificial climate box for cultivation at a temperature of 17-22°C and a relative humidity of more than 90%.

[0056] According to the disease situation of the blank control, the inoculated leaves were graded. The following grading method was used:

[0057] Level 0: no lesions on leaves;

[0058] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0059] Level 3: The lesion area accounts for 6-10% of the entire leaf area;

[0060] Level 5: The lesion area accounts for 11-25% of the entire leaf area;

[0061] Level 7: The lesion area accounts for 26-50% of the entire leaf area;

[0062] Level 9: The lesion area accounts for more than 50% of the entire leaf area.

[0063] Data statistics and calculations: Based on data surveys, calculate the disease index and prevention and control effects of each treatment.

[0064] The disease index is calculated according to the following formula:

[0065]

[0066] The control effect is calculated according to the following formula:

[0067]

[0068] Statistical analysis: IBM SPSS Statistics 20 statistical analysis system was used to calculate the toxicity regression line and EC 50 Value and correlation coefficient R 2 ,

[0069] The co-toxicity coefficient (CTC value) of the mixture is calculated according to the following formula:

[0070]

[0071] Where:

[0072] ATI - measured toxicity index of mixture;

[0073] S——EC of standard agent 50 , the unit is milligrams per liter (mg / L);

[0074] M——EC of the mixture 50 , the unit is milligrams per liter (mg / L).

[0075] TTI=TI A ×P A +TI B ×P B

[0076] Where:

[0077] TTI – Theoretical Toxicity Index of Mixtures;

[0078] TI A ——Agent toxicity index;

[0079] P A ——The percentage of agent A in the mixture, in percentage (%);

[0080] TI B ——Toxicity index of agent B;

[0081] P B ——The percentage of agent B in the mixture, in percentage (%).

[0082] Calculation of co-toxicity coefficient (CTC) according to Sun Yunpei method

[0083]

[0084] Where:

[0085] CTC – Co-toxicity coefficient;

[0086] ATI - measured toxicity index of mixture;

[0087] TTI - Theoretical Toxicity Index of Mixture.

[0088] The synergistic effect of mixed drugs was evaluated based on the co-toxicity coefficient (CTC), that is, CTC ≤ 80 was antagonistic, 80 < CTC < 120 was additive, and CTC ≥ 120 was synergistic.

[0089] Results and Analysis:

[0090] As shown in Table 1, mancozeb and fluoxapiprolin alone and their combination have good fungicidal activity against cucumber downy mildew. 50 The value is 142.421 mg / L, fluoxapiprolin single dose EC 50 The value is 2.394 mg / L.

[0091] The mass ratio of mancozeb to fluoxapiprolin was 1:25-1:35, with no antagonistic effect, and 1:25-25:1, with a synergistic effect. When the mass ratio of mancozeb to fluoxapiprolin was 1:10-6:1, the co-toxicity coefficient was greater than 150, and the synergistic effect was obvious.

[0092] Table 1 Indoor combined toxicity results of different ratios of mancozeb and fluoxapiprolin against downy mildew

[0093]

[0094]

[0095] It can be seen from Table 2 that the single agent of fluoxapiprolin and famoxadone and their combination have good fungicidal activity against cucumber downy mildew. 50 The value is 55.517 mg / L.

[0096] The mass ratio of famoxadone to fluoxapiprolin was 1:40 to 50:1, which showed no antagonistic effect. The mass ratio of famoxadone to fluoxapiprolin was 1:40 to 35:1, which showed synergistic effect. 50 It is 4.358 mg / L, the co-toxicity coefficient is 269.928, and the synergistic effect is obvious.

[0097] Table 2 Indoor combined toxicity results of different ratios of famoxadone and fluoxapiprolin against cucumber downy mildew

[0098]

[0099] Specific preparation example:

[0100] Preparation Example 1:

[0101] 30% mancozeb and fluoxapiprolin suspension (5+25)

[0102] Formula: Mancozeb 5%, fluoxapiprolin 25%, polyether 3%, phenylethylphenol polyether phosphate 2.5%, Guerbet alcohol polyoxyethylene ether (XP-70) 2%, fatty amine polyoxyethylene ether 1%, magnesium aluminum silicate 1%, xanthan gum 0.5%, propylene glycol 4%, glycerin 1%, benzisothiazolinone 0.02%, dimethicone 0.4%, deionized water to make up;

[0103] Preparation method: Add mancozeb and additives (except preservatives and thickeners) to a feeding kettle and initiate shearing to completely dissolve the additives. Add fluoxapiprolin under high shear stirring, shear evenly, and then sand grind. After sand grinding, transfer to a homogenizer, add preservatives and thickeners, add the remaining water to make up the balance, shear, and homogenize to obtain the corresponding suspension concentrate.

[0104] Preparation Example 2:

[0105] 25% fluoxapiprolin suspension (20+5)

[0106] Formula: 20% famoxadone, 5% fluoxapiprolin, 2.5% polyether, 2.5% phenylethylphenol polyether phosphate, 2% dioctyl sodium sulfosuccinate, 1% magnesium aluminum silicate, 0.45% xanthan gum, 5% propylene glycol, 0.02% benzisothiazolinone, 0.3% dimethicone, and deionized water to make up.

[0107] Preparation method: Same as Preparation Example 1.

[0108] Preparation Example 3:

[0109] 40% mancozeb·fluoxapiprolin wettable powder (8+32)

[0110] Formula: Mancozeb 8%, fluoxapiprolin 32%, sodium lignin sulfonate 7%, polycarboxylate 0.5%, sodium naphthalene sulfonate 2%, BX powder 4%, sodium lauryl sulfate 3.5%, attapulgite 2.5%, and kaolin to make up the balance;

[0111] Preparation method: The active ingredients, dispersant, wetting agent and filler are mixed according to the formula ratio, stirred evenly in a mixer, crushed in a jet mill and mixed evenly again to prepare the wettable powder of the composition of the present invention.

[0112] Preparation Example 4:

[0113] 50% fluoxapiprolin wettable powder (25+25)

[0114] Formula: 25% famoxadone, 25% fluoxapiprolin, 7% sodium lignin sulfonate, 0.2% potassium phosphate, 3% sodium polycarboxylate, 3% BX powder, 3% sodium lauryl sulfate, 5% talc, and starch to make up the balance;

[0115] Preparation method: Same as Preparation Example 3.

[0116] Preparation Example 5:

[0117] 60% Mancozeb and Fluoxapiprolin Water Dispersible Granules (30+30)

[0118] Formula: Mancozeb 30%, fluoxapiprolin 30%, lignin sulfonate 5%, sodium dodecylbenzene sulfonate 7.5%, aluminum chloride 4%, bentonite 10%, white carbon black as the balance;

[0119] Preparation method: According to the formula ratio of the embodiment, the active ingredient is added to the carrier, and the surfactant and other functional additives are added thereto, mixed, and after air flow grinding, 10-25% water is added, and then the water-dispersible granule product is obtained by kneading, granulating, drying and screening.

[0120] Preparation Example 6:

[0121] 55% fluoxapiprolin water dispersible granules (35+20)

[0122] Formula: 35% of famoxadone, 20% of fluoxapiprolin, 5% of lignin sulfonate, 8% of sodium dodecylbenzenesulfonate, 5% of ammonium sulfate, 8% of starch, and diatomaceous earth to make up the balance;

[0123] Preparation method: Same as Preparation Example 5.

[0124] Controlling cucumber downy mildew in the field

[0125] Example 1:

[0126] Experimental site: The experiment was conducted in a solar greenhouse in Zhucheng, Weifang City, Shandong Province. The soil fertility was above average and the terrain was flat.

[0127] Test basis: The test refers to GB / T 17980.26-2000 "Guidelines for field efficacy tests (I) Fungicides for the control of cucumber downy mildew".

[0128] Test object: downy mildew.

[0129] Experimental crop: cucumber (Nongda No. 12).

[0130] Experimental design: The experiment set up 10 treatments, each treatment was repeated 4 times, and the plots were arranged in random blocks, with an area of ​​20m2 .

[0131] Application time: The experiment was carried out on March 25, 2022. The first application was carried out, and the second application was carried out after an interval of 7 days, for a total of 2 applications.

[0132] Investigation method: The control results were investigated 7 days after the last application of pesticides. Five points were randomly selected in each plot for investigation, two plants were investigated at each point, and all leaves of each plant were investigated. The disease index and control effect were calculated.

[0133] Grading method (leaf-based)

[0134] Level 0: no lesions;

[0135] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0136] Level 3: The lesion area accounts for 6% to 10% of the entire leaf area;

[0137] Level 5: The lesion area accounts for 11% to 25% of the entire leaf area;

[0138] Level 7: The lesion area accounts for 26% to 50% of the entire leaf area;

[0139] Level 9: The lesion area accounts for more than 50% of the entire leaf area.

[0140] The efficacy is calculated according to the following formula:

[0141]

[0142]

[0143] Results and Analysis:

[0144] Table 3 Field efficacy test results of different fungicides against cucumber downy mildew

[0145]

[0146] Example 2:

[0147] Experimental site: The experiment was conducted in a solar greenhouse in Qingzhou City, Shandong Province, where the soil fertility was above average and the terrain was flat.

[0148] Test basis: The test refers to GB / T 17980.26-2000 "Guidelines for field efficacy tests (I) Fungicides for the control of cucumber downy mildew".

[0149] Test object: downy mildew.

[0150] Experimental crop: Cucumber (Catriocarpus vinifera).

[0151] Experimental design: The experiment set up 10 treatments, each treatment was repeated 4 times, and the plots were arranged in random blocks, with an area of ​​20m 2 .

[0152] Application time: The experiment was conducted on April 1, 2022, with the first application of pesticides. The second application was carried out after an interval of 7 days, for a total of 2 applications.

[0153] Investigation method: The control results were investigated 7 days after the last application of pesticides. Five points were randomly selected in each plot for investigation, two plants were investigated at each point, and all leaves of each plant were investigated. The disease index and control effect were calculated.

[0154] Grading method (leaf-based)

[0155] Level 0: no lesions;

[0156] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0157] Level 3: The lesion area accounts for 6% to 10% of the entire leaf area;

[0158] Level 5: The lesion area accounts for 11% to 25% of the entire leaf area;

[0159] Level 7: The lesion area accounts for 26% to 50% of the entire leaf area;

[0160] Level 9: The lesion area accounts for more than 50% of the entire leaf area.

[0161] The efficacy is calculated according to the following formula:

[0162]

[0163]

[0164] Results and Analysis:

[0165] Table 4 Field efficacy test results of different fungicides against cucumber downy mildew

[0166]

[0167] The pesticide composition or formulation obtained by the present invention exhibits significant pest control efficacy, outperforming single agents in delaying the development of resistance and extending the duration of efficacy. Furthermore, no crop damage was observed with the combined formulation in testing, demonstrating that the improved synergistic fungicidal efficacy of the resulting pesticide composition or formulation can reduce production and usage costs and is safe for crops.

[0168] Although the present invention has been described in detail above using general descriptions and specific implementation plans, it is obvious to those skilled in the art that some modifications or improvements can be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention shall fall within the scope of protection claimed by the present invention.

Claims

1. A bactericidal composition containing fluoxapiprolin, characterized in that: The invention comprises an active ingredient A and an active ingredient B, wherein the active ingredient A is famoxadone, the active ingredient B is fluoxapiprolin, and the weight ratio of the active ingredient A to the active ingredient B is 1:40-35:

1.

2. The bactericidal composition according to claim 1, characterized in that The mass ratio of famoxadone to fluoxapiprolin is 1:6-20:

1.

3. The bactericidal composition according to claim 1, characterized in that Based on the total weight of the bactericidal composition being 100 wt %, the sum of the contents of the active ingredient A and the active ingredient B in the bactericidal composition is 5 to 90 wt %.

4. The bactericidal composition according to claim 1, characterized in that The bactericidal composition is added with corresponding adjuvants to prepare any one of wettable powder, water-dispersible granules or suspension.

5. The bactericidal composition according to claim 4, characterized in that The auxiliary agent is one or more of a wetting agent, a dispersant, an emulsifier, a thickener, a disintegrant, an antifreeze agent, a defoaming agent, a solvent, a preservative, a stabilizer, a synergist or a carrier.

6. Use of the fungicidal composition according to any one of claims 1 to 5 for controlling plant pathogenic fungi, characterized in that: The disease caused by the pathogenic fungus is downy mildew.

7. The use according to claim 6, characterized in that The fungicidal composition is applied to the disease to be controlled or its growth medium at an effective dose.

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