A bactericidal composition comprising a pyridinecarboxamide compound and a method for controlling plant pathogenic bacteria using the same

Abstract

This invention relates to a bactericidal composition comprising pyridine amide compounds, containing active ingredient compound I and fluoxetine, wherein the weight ratio of compound I to fluoxetine is 50:1 to 1:25; this invention also provides a method for preventing or controlling the invasion of plant pathogens into plants, plant parts, plant propagation material and subsequently grown plant organs.

Description

Technical Field

[0001] This invention relates to a bactericidal composition comprising pyridine amide compounds; and also to a method for controlling plant pathogens. Background Technology

[0002] Fungicides containing a single active ingredient often have certain shortcomings in the control of agricultural diseases. Repeated use not only easily leads to drug resistance in pathogens but also easily causes food and environmental pollution. Rational mixing of fungicide active ingredients can improve the activity against plant pathogens while reducing the total amount of active compound applied, thereby reducing the application rate of known active compounds and improving their activity spectrum. This can thus reduce or even avoid pesticide pollution of food and the environment.

[0003] Compound I, known by WO2016109257A1, belongs to the pyridine amide class of compounds. Compound I can protect plants or seeds from pathogenic fungi of the Ascomycetes, Basidiomycetes, Deuteromycetes, and Oomycetes classes.

[0004]

[0005] Due to increasingly stringent environmental and economic requirements for fungicides, such as demands on activity spectrum, toxicity, selectivity, application rate, residue composition, and favorable preparative feasibility, as well as potential issues related to resistance, the development of safer, higher-performance, lower-dosage, easier-to-use, and more cost-effective fungicidal compositions remains a subject of ongoing research. Summary of the Invention

[0006] We have found that simultaneous, combined or separate application of Compound I and fluthiazopyrone, or sequential application of Compound I and fluthiazopyrone, results in better control of plant pathogens than application of each compound alone.

[0007]

[0008] Therefore, one object of the present invention is to provide a bactericidal composition comprising a pyridine amide compound, wherein compound I and fluoxetine are present in the composition in an amount that produces a synergistic effect. The synergistic effect is more pronounced when the weight ratio of compound I to fluoxetine is 50:1-1:25, preferably 25:1-1:25, more preferably 20:1-1:20, more preferably 20:1-1:10, more preferably 10:1-1:10, more preferably 10:1-1:5, and even more preferably 10:1-1:2.

[0009] Synergistic effect refers to the effect of a combination of active ingredients exceeding the sum of the effects of their individual components. For a given combination of active ingredients, the expected effect E can be calculated using the so-called "Colby formula" (see SR Colby, "Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20-22) as follows: If

[0010] X is the activity when active compound A is used at a dosage of mg / ha or a concentration of m ppm;

[0011] Y is the activity when active compound B is used at a dosage of ng / ha or a concentration of n ppm, expressed as a percentage of the untreated control;

[0012] E represents the activity when active compounds A and B are used at dosages of m and ng / ha or concentrations of m and n ppm.

[0013] So

[0014] ;

[0015] If the actual observed activity (O) is greater than the expected activity (E), then a synergistic effect exists.

[0016] The synergistic activity of compound I and fluthiazopyrone reduces the application rate of both compounds while maintaining the same level of efficacy. This means that even at such a low application rate range, where the two individual components have become generally ineffective, the composition can still achieve a high level of plant pathogen control. On the other hand, it substantially broadens the spectrum of plant pathogens that can be controlled.

[0017] The fungicidal compositions of the present invention, comprising pyridine amide compounds, can be used as foliar treatments in crop protection, as well as for seed dressing and soil treatment. The fungicidal compositions according to the present invention can be applied before or after infection of cultivated plants.

[0018] Another aspect of the present invention is to provide a method for preventing or controlling the infection of cultivated plants by plant pathogens, comprising applying a bactericidal composition comprising pyridine amide compounds of the present invention to plant pathogens and / or their environment, or to plants, plant propagation material and subsequently grown plant organs, soil or cultivation medium, material or space.

[0019] This invention provides a method for preventing or controlling the infection of cultivated plants by plant pathogens. The method includes applying the fungicidal composition of this invention to plant pathogens and / or their environment at an agronomically effective and substantially non-phytotoxic amount by means of seed treatment, foliar application, stem application, soaking, dripping, watering, spraying, misting, dusting, dispersing or fumigation.

[0020] The fungicidal compositions of the present invention, comprising pyridine amide compounds, are particularly effective against the following plant diseases: wheat brown rust (Puccinia striiformis); wheat stripe rust (Mycosphaerella graminicola); wheat leaf spot (Septoria tritici); wheat glume blight (Leptosphaeria nodorum); barley spot (Cochliobolus sativum); wheat root rot (Helminthosporium sativum); beet brown spot (Cercospora beticola); peanut leaf spot (Mycosphaerella argentea). arachidis); peanut cercariae (Cercospora arachidicola); cucumber anthracnose (Colletotrichum Iagenarium); cucurbitaceous spur spores (Colletotrichum lagenarium); banana leaf spot (Mycosphaerella fijiensis); white mold (Sclerotinia sclerotiorum); apple scab (Venturia inaequalis); grape powdery mildew (Erysiphe necator); barley scald (Rhynchosporium secalis); rice blast (Pyricularia oryzae); soybean rust (Phakopsora pachyrhizi); wheat powdery mildew (Blumeria graminis f.sp.).Tritici); Powdery mildew of cucurbits (Erysiphecichoracearum); Early blight of tomatoes (Alternaria solani); Watermelon vine blight (Didymella bryoniae); Powdery mildew of apples (Podosphaeraleucotricha); Gray mold (Botrytis cinerea); White mold of sclerotinia (Sclerotinia sclerotiorum); Rice fever (Pyricularia oryzae); Brown rot of stone fruit (Monilinia fructicola); Downy mildew of cucumbers (Pseudoperonosporacubensis (Berk. et Curt.) Rostov.); Late blight of tomatoes (Phytophthora festans); Damping-off of cucumbers (Bythium drizzleum). deliense Meurs. ). .

[0021] Suitable plants for this invention include: grapevines; cereals (e.g., wheat, barley, rye, or oats); beets (e.g., sugar beets or fodder sugar beets); fruits (e.g., pome fruits, drupes, or berries, such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, or blackberries); legumes (e.g., broad beans, green beans, peas, or soybeans); oilseed plants (e.g., rapeseed, mustard, poppies, olives, sunflowers, coconuts, castor oil plants, cocoa beans, or peanuts); and cucurbits (e.g., young gourds, cucumbers, or melons). ); fiber plants (such as cotton, flax, hemp, or jute); citrus fruits (such as oranges, lemons, grapefruits, or tangerines); vegetables (such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, gourds, or red peppers); Lauraceae (such as avocados, cinnamon, or camphor); corn; tobacco; nuts; coffee; sugarcane; tea; vines; hops; durian; bananas; natural rubber trees; turf or ornamental plants (such as flowers, shrubs, broadleaf trees, or evergreens such as conifers).

[0022] The bactericidal compositions of the present invention, comprising pyridine amide compounds, can be used to protect plants, plant parts, plant propagation material, and subsequently grown plant organs from plant pathogens.

[0023] "Plant" refers to all plants and plant populations, including desirable and undesirable wild plants, cultivated plants, and plant varieties (whether or not protected by plant variety or plant breeder rights). Cultivated plants and plant varieties can be plants obtained through conventional propagation and cultivation methods, which may be supplemented by one or more biotechnological methods, such as the use of double haploids, protoplast fusions, random and directed mutations, molecular or genetic markers, or the use of bioengineering and genetic engineering methods.

[0024] "Plant parts" refers to all above-ground and underground parts and organs of a plant, such as buds, leaves, flowers, and roots, including leaves, needles, stems, branches, flowers, fruiting bodies, fruits, and seeds, as well as roots, bulbs, and rhizomes. Crops, as well as materials for vegetative and sexual reproduction, such as cuttings, bulbs, rhizomes, stolons, and seeds, are also considered plant parts.

[0025] "Plant propagation material" should be understood to refer to all plant parts capable of reproduction, such as seeds, which can be used to propagate the latter, and plant materials such as cuttings or tubers (e.g., potatoes). Therefore, the term used in this article...

[0026] "Plant parts" include plant propagation material. This may include, for example, seeds, roots, fruits, tubers, bulbs, rhizomes, and plant parts. This includes germinating plants and viable plants that have been suppressed after sprouting from the soil or after emergence. Young plants can be protected by whole or partial treatment with immersion before transplanting.

[0027] "Subsequently grown plant organs" refers to any part of a plant produced from plant propagation material such as seeds. Plant parts, plant organs, and plants can also benefit from protection against pathogen damage obtained by applying a fungicide composition to the plant propagation material. Certain plant parts and subsequent plant organs in certain locations can also be considered plant propagation material and can themselves be treated with a fungicide composition; thus, plants produced from treated plant parts and treated plant organs, as well as other plant parts and other plant organs, can also benefit from the application of the fungicide composition.

[0028] The bactericidal composition of the present invention, comprising pyridine amide compounds, can be used to protect seeds from harmful soil bacteria and to protect the roots and shoots of the resulting plants from harmful soil pathogens. Protection of plant roots and shoots is preferred.

[0029] This invention provides a method for protecting seeds, seedling roots, and shoots from plant pathogens, comprising contacting the seeds with an effective amount of the fungicidal composition of this invention before sowing and / or after germination. This treatment protects the seeds from plant pathogens and safeguards the roots and shoots of the resulting plant.

[0030] Seeds treated with the fungicidal composition comprising pyridine amide compounds of the present invention provide protection against pathogens not only for the seeds themselves but also for the plants that emerge from them after germination. Therefore, it is unnecessary to treat the plants directly at sowing time or shortly thereafter.

[0031] The seeds mentioned are selected from potato, sunflower, coffee, tobacco, canola, rapeseed, sugar beet, tomato, cucumber, green bean, Brassica oleracea, onion, soybean, wheat, barley, rye, oat, sorghum, peanut, sugarcane, rice, cabbage, cowpea, carrot, cotton and corn seeds.

[0032] On the other hand, the present invention also provides a method for preventing and controlling harmful bacteria in soil, wherein the bactericidal composition containing pyridine amide compounds described in the present invention is applied to the soil before, after, or before and after seed germination and / or directly applied to the soil in contact with plant roots or soil suitable for plant growth.

[0033] The bactericidal composition containing pyridine amide compounds of the present invention can be primarily in the form of a formulation, i.e., the substances in the composition are already mixed. Alternatively, the components of the composition can be provided as single-agent preparations, mixed in a container or tank before use, and then diluted to the desired concentration. Preferably, the formulation provided by the present invention is the primary form.

[0034] The bactericidal compositions of the present invention, comprising pyridine amide compounds, can be used in any conventional formulation form. Examples include emulsifiable concentrates, aqueous suspensions, oil suspensions, seed treatment dry powders, seed treatment solutions, seed treatment emulsions, suspension seed coating agents, water-dispersible granules, wettable powders, suspension emulsions, granules, water-in-oil emulsions, microcapsule suspensions, dry suspensions, ultra-low volume liquids, electrostatic oils, and microparticles.

[0035] In formulation form, it includes 1% to 90% by weight of active ingredient, 0% to 20% of agriculturally acceptable surfactant and 10% to 99% of filler.

[0036] According to the present invention, the term "filler" refers to a natural or synthetic organic or inorganic compound that can be combined or combined with an active compound to make it easier to apply to an object (e.g., a plant, crop, or grass). Therefore, the filler is preferably inert and should at least be agriculturally acceptable. The filler can be solid or liquid.

[0037] The inactive medium that can be used in this invention can be either solid or liquid. For example, solid medium materials include: talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar substances.

[0038] The following materials can be selected as liquid mediators: water, petroleum ether, vegetable oil, methyl ethyl ketone, cyclohexanone, amyl acetate, 2-butanone, butylene carbonate, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, diethanolamine, diethylene glycol, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 2-heptanone, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glyceryl acetate, glyceryl diacetate, glyceryl triacetate, and hexadecyl acetate. Alkane, hexanediol, isopentyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl myristate, lactic acid, laurylamine, isopropyl acetone, methoxypropanol, methyl isopentyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleyleneamine, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, triethyl phosphate, triethylene glycol, paraffin, mineral oil, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, ethanol, isopropanol, and alcohols with higher molecular weights, such as pentanol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0039] Suitable surfactants include, for example, fatty alcohol polyoxyethylene ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene higher fatty acid esters, phosphate esters of polyoxyethylene alcohols or phenols, fatty acid esters of polyols, alkyl aryl sulfonic acids, naphthalene sulfonic acid polymers, lignin sulfonates, branched copolymers in the form of combs, butyl naphthalene sulfonates, alkyl aryl sulfonates, sodium alkyl sulfosuccinate, oils and fats, fatty alcohol and ethylene oxide condensates, polyacrylates such as alkyl taurates, and protein hydrolysates. Suitable oligosaccharides or polymers, for example, based on a single ethylene monomer, acrylic acid, polyoxyethylene and / or polyoxypropylene, or their combination with, for example, (poly)ols or (poly)amines.

[0040] To facilitate the dispersion, stabilization, adhesion, and / or binding of the active ingredient compounds, adjuvants such as xanthan gum, magnesium aluminum silicate, gelatin, starch, cellulose methyl ether, polyvinyl alcohol, polyvinyl acetate, and natural and synthetic phospholipids, as well as bentonite, sodium lignosulfonate, etc., may be used.

[0041] Antifreeze agents can include ethylene glycol, propylene glycol, glycerol, and sorbitol. Antiflocculation agents for suspending products can be auxiliary agents such as naphthalene sulfonic acid polymers and polyphosphates.

[0042] Organosilicon defoamers can be used as defoamers.

[0043] Colorants that can be used include inorganic pigments such as iron oxide, titanium dioxide, and Prussian blue; organic pigments / dyes such as alizarin dyes, azo dyes, and metallic phthalocyanine dyes; and trace elements such as iron salts, manganese salts, boron salts, copper salts, cobalt salts, molybdenum salts, and zinc salts.

[0044] Optionally, it may also contain other additional components, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, and masking agents.

[0045] The compound I and fluthiazopyrone of the present invention can also be used in combination with other active ingredients, for example, to broaden the activity spectrum or prevent the formation of resistance. These other active ingredients include, for example, fungicides, bactericides, attractants, insecticides, acaricides, nematicides, growth regulators, herbicides, safeners, fertilizers, or chemical pheromones. Detailed Implementation

[0046] The technical grade compounds I and fluthiazopyrone were dissolved in acetone to prepare single-agent stock solutions, which were then diluted with an aqueous solution containing 0.1% Tween-80 to the required concentration.

[0047] The fungicidal activity of the agent against tomato late blight was determined using a live pot method. Tomato seedlings were planted in plastic pots with a vegetable growing substrate. The potted plants were cultivated until they had 2-4 true leaves before use.

[0048] The pathogen used in the experiment was cultured on a suitable culture medium. After sporangia were produced, 4 o The sporangia were rinsed with distilled water at room temperature, filtered through double-layered gauze to prepare a sporangia suspension, and then placed at 4°C. o At a low temperature (C), treat in the dark for 0.5-3 hours to induce the release of zoospores, and adjust the spore concentration to 1×10⁻⁶. 5 Quantity / mL, for later use.

[0049] The potted seedlings were sprayed evenly with the foliage. The leaves of the plants to be inoculated were sprayed with each treatment until moistened, and inoculated 24 hours later. Each treatment consisted of 3 pots, with 4 replicates. A blank control was provided, containing no treatment (containing organic solvents and emulsifiers).

[0050] Spray the sporangium suspension evenly onto the underside of tomato leaves using an inoculation sprayer. After inoculation, the tomato seedlings are kept under alternating light and dark conditions for 12 hours each day, with a light intensity of 10000 Lux and a temperature of 18 degrees Celsius. O C-20 O C, and keep the leaf surface covered with a water film within 24 hours after inoculation, and then culture for 7 days under conditions of relative humidity above 90%.

[0051] Once the disease rate in the blank control reaches 50% or higher, conduct a graded survey of the disease incidence in each treatment. At least 30 leaves should be surveyed for each treatment.

[0052] The grading method is as follows:

[0053] Grade 0: No lesions or spots;

[0054] Grade 1: The area of ​​lesions accounts for less than 10% of the total leaf area;

[0055] Grade 3: Lesions cover 10%-25% of the total leaf area;

[0056] Level 5: Lesions cover 25%-50% of the total leaf area;

[0057] Level 7: The lesions cover more than 50% of the total leaf area;

[0058] Level 9: All leaves are infected and wither.

[0059] Calculate the disease index and prevention efficacy using the following formulas.

[0060] .

[0061] Table 1. Efficacy of the compositions of the present invention against late blight of tomato.

[0062]

[0063] Table 1 clearly shows that the actual control efficacy of the fungicidal composition containing pyridine amide compounds of the present invention against tomato late blight is higher than the control efficacy calculated by the Colby formula, that is, there is a synergistic effect.

[0064] Experiment 2: Apple Black Spot Disease

[0065] The technical grade compounds I and fluthiazopyrone were dissolved in acetone to prepare single-agent stock solutions, which were then diluted with an aqueous solution containing 0.1% Tween-80 to the required concentration.

[0066] Take apple leaves infected with black spot disease and incubate them in a moist environment for 3-4 days to induce spore production. Use a brush to apply 10... O Wash the underside of diseased leaves with distilled water at approximately 5°C to obtain fungal spores, and prepare a solution with a concentration of 5×10⁻⁶. 4 A spore suspension of approximately 1 spore per mL.

[0067] The fungicidal activity of the agent against apple scab was determined using a live pot method. Greenhouse potted apple seedlings were used as experimental materials. One plant was selected per pot. Seedlings with two newly unfolded leaves at the top were chosen (old leaves at the bottom of the plant were removed).

[0068] The potted seedlings were sprayed evenly with the foliage. The leaves of the plants to be inoculated were sprayed with the respective treatment agents until moist, and inoculated 24 hours later. Each treatment consisted of one pot, with four replicates. A blank control was provided, containing no agents (but containing organic solvents and emulsifiers).

[0069] Spray the spore suspension onto the tender leaves at the tips of vigorously growing new shoots, immediately place them on a tray lined with a damp towel, with the undersides of the leaves facing up, seal with plastic film, and incubate at 25°C. O Cultured in a climate-controlled chamber under humidity. After 15 days, the disease incidence was investigated.

[0070] Grading standards:

[0071] Level 0: No disease;

[0072] Grade 1: The area of ​​lesions accounts for less than 5% of the total leaf area;

[0073] Grade 3: Lesions cover 6%-10% of the entire leaf area;

[0074] Level 5: Lesions cover 11%-20% of the entire leaf area;

[0075] Level 7: Lesions cover 21%-40% of the entire leaf area;

[0076] Level 9: The lesion area accounts for more than 40% of the total leaf area.

[0077] Calculate the disease index and prevention efficacy using the following formulas.

[0078] ;

[0079] .

[0080] Table 2. Efficacy of the compositions of the present invention against apple scab.

[0081]

[0082] Table 2 clearly shows that the actual control efficacy of the bactericidal composition containing pyridine amide compounds of the present invention against apple black spot disease is higher than the control efficacy calculated by the Colby formula, that is, there is a synergistic effect.

Claims

1. A bactericidal composition comprising a pyridine amide compound, characterized in that, The active ingredient is composed of compound I ; It is composed of compound I and fluthiazopyrone, wherein the weight ratio of compound I to fluthiazopyrone is 10:1 to 1.25:

1.

2. The bactericidal composition comprising a pyridine amide compound according to claim 1, characterized in that, The weight ratio of compound I to fluthiazopyrone is 5:1 to 1.25:

1.

3. The bactericidal composition comprising a pyridine amide compound according to claim 1, characterized in that, The weight ratio of compound I to fluthiazopyrone is 2.5:1 to 1.25:

1.

4. The bactericidal composition comprising a pyridine amide compound according to claim 1, characterized in that, The bactericidal composition further comprises fillers and / or surfactants.

5. The use of the bactericidal composition comprising pyridine amide compounds as described in claim 1 for the prevention or control of tomato late blight and apple scab.

6. A method for preventing or controlling the invasion of plant, plant parts, plant propagation material, and subsequently grown plant organs from plant pathogens, characterized in that, This includes applying the bactericidal composition comprising pyridine amide compounds as described in claim 1 to plants, plant parts, plant propagation materials, or soil or cultivation media in which plants are growing or need to grow, wherein the plant pathogen is *Phytophthora indicum* or *Phytophthora macrantha*.

7. The method according to claim 6, characterized in that, This includes applying the fungicidal composition comprising a pyridine amide compound as described in claim 1 to a plant, plant part, plant propagation material, or soil or cultivation medium in which the plant is growing or needs to grow, before or after the plant is infected by pathogens.

8. A method for protecting seeds, seedling roots, and branches from plant pathogens, characterized in that, This includes contacting the seeds with the fungicidal composition comprising a pyridine amide compound as described in claim 1 before sowing and / or after germination, wherein the plant pathogen is *Phytophthora indicum* or *Phytophthora macrantha*.

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