EA044049B1 - INSECTO-FUNGICIDAL COMPOSITION WITH SYNERGIC EFFECTIVENESS - Google Patents

Description

The invention relates to means for treating agricultural crops and treating seeds, namely to a preparation comprising a synergistically active mixture with fungicidal and insecticidal properties, where the active components in the composition are the fungicides prochloraz, pyraclostrobin, tebuconazole and one insecticide from the class of neonicotinoids acetamiprid, or thiamethoxam or imidacloprid.

Control of plant diseases caused by plant pathogenic fungi is extremely important in achieving high crop yields, as plant diseases can cause significant reductions in productivity. Pathogens that cause plant diseases are difficult to control and may develop resistance to industrial fungicides. New effective combinations of active compounds are needed to best suit specific plant disease control requirements.

Pests of cultivated plants attack seed material during storage and after introducing seed material into the soil, as well as during and immediately after plant germination. This phase is especially critical due to the great sensitivity of the root system and plant seedlings: even minor damage can lead to the death of the entire plant. Therefore, seed treatment with special compositions is used.

The combined use of active ingredients of fungicides and insecticides increases the spectrum of action, increases the efficiency of treatment and reduces the likelihood of resistance to pathogens of various crops due to the simultaneous action of different mechanisms of fungal damage.

Prochloraz - N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]-1H-imidazole-1-carboxamide, belongs to the class of imidazoles, is a substance with systemic fungicidal action against a wide range of pathogens of fungal diseases of the following types on various crops: Pseudocercosporella, Pyrenophora, Rhynchosporium, Septoria, Erysiphe, Alternaria, Botrytis, Pyrenopeziza, Sclerotinia, etc. (The Pesticide Manual, 18th ed., WSRS, 2018). The biological action of prochloraz is based on the mechanism of ergosterol inhibition.

Tebuconazole - a-[2-(4-chlorophenyl)ethyl]-a-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol, belongs to the class of triazoles. Tebuconazole is a substance with systemic fungicidal action against a wide range of pathogens of fungal diseases, in particular: Pyrenophora, Rhynchosporium, Septoria, Erysiphe graminis, Altemaria, Tilletia, Puccinia, Sphacelotheca, Ustilago, Cercospora, Podosphaera, Fusarium, Venturia, etc. (The Pesticide Manual , 18th ed., WSRS, 2018). It has an eradicating and therapeutic effect. It is an inhibitor of steroid demethylation in the biosynthesis of ergosterol. The fungicide is intended to combat various fungal diseases of grains, legumes, gardens, vegetables and many other crops.

Pyraclostrobin - [Methyl N-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}(Nmethoxy)carbamate, a fungicide from the class of strobilurins of contact and deep action. Pyraclostrobin inhibits the respiration of the pathogen. It is concentrated on the surface of the leaf, then gradually redistributed into the internal tissues. Preparations based on pyraclostrobin are used against diseases of corn (fusarium, smut, root and stem rot, helminthoriosis), soybean (downy mildew, ascochyta blight), etc. (List of pesticides and agrochemicals approved for use on the territory of the Russian Federation, 2019). It is also known that the strobilurin fungicide pyraclostrobin can be used as a fungicide to control fungal plant diseases. Pyraclostrobin is described, for example, in The Pesticide Manual, 13th ed. (2003), published by the British Crop Protection Council, or also in WO 96/01256 A1.

The mixture of the proposed fungicide composition additionally contains an insecticide from the neonicotinoid class, namely acetamiprid, or thiamethoxam, or imidacloprid.

Acetamiprid - [K1-methyl-K1-[(6-chloro-3-pyridyl)methyl]-N-cyanoacetamidine], belongs to the class of neonicotinoids, used in agriculture to control harmful insects. The active substance blocks nicotine-dependent acetylcholine receptors in the nervous system, namely, it disrupts the transmission of nerve impulses through the synapse and the insect dies from severe nervous overexcitation. Preparations based on acetamiprid are used against pests of wheat (bug bug, ground beetle), wheat and barley (ground beetle, grain flies, striped flea beetle), etc. The effectiveness of acetamiprid is high, however, in relation to individual pests and in some cases it does not respond high requirements for insecticides.

Thiamethoxam, 5-methyl-3-(2-chlorothiazol-5-ylmethyl)-1,3,5-oxadiazinan-4-ylidene-K-nitroamine, C ₈ H ₁₀ ClN ₅ O ₃ S insecticide from the neonicotinoid class. An insecticide of systemic and contact-intestinal action with translaminar activity (absorbed into the vascular system of plants and distributed through it, making them poisonous to insects), suppresses piercing-sucking and gnawing insects, agricultural pests, including secretive living and feeding on the lower part of the leaf.

Imidacloprid (4,5-dihydro-N-nitro-1-[(6-chloro-3-pyridyl)methyl]imidazolidin-2-ylenamine), C ₉ H ₁₀ ClN ₅ O ₂ , is the most widely used neonicotinoid insecticide. Imidacloprid has a pronounced systemic effect: it penetrates the vascular system of plants, and the plant becomes toxic to insects.

Based on the patent search, the following patents related to the fungicides and insecticides listed above were selected.

Pyraclostrobin is used in fungicidal compositions in combination with other active compounds, often in synergistically effective amounts. For example, with pyridylethylbenzamide derivatives (RF No. 2360417), with an amide derivative of a carboxylic acid (RF No. 2483541), with a 1,2,3-thiadiazole derivative (RF No. 2165144), with N-sulfonylvalinamide (RF No. 2270564), and other compounds , having fungicidal activity (RF No. 2417590, 2547554).

To expand the spectrum of action and enhance the biological activity, tebuconazole is used in various mixed preparations (RF patent No. 2024228, 2040899, 2232504, 2483541, 2192743).

A known fungicidal composition (RU No. 2672493) includes the fungicides prochloraz, the strobilurin fungicide azoxystrobin, prothioconazole, the insecticide acetamiprid and auxiliary components. Used for seed treatment. The disadvantage of this composition is the low effectiveness of the drug.

A fungicidal composition for plant protection is also known (WO 2009098210), which contains as active components an insecticidal compound selected from the following: acetamiprid, fungicidal compounds prochloraz and pyraclostrobin.

A known fungicidal composition for pre-sowing treatment of wheat seeds (RU 2656965), which includes the active ingredients tebuconazole and prochloraz, auxiliary components and additionally includes the strobilurin fungicide kresoxim-methyl.

A two-component plant protection agent is known (EA No. 016724), comprising a synergistically active mixture of at least one substance selected from the group that includes (a) acetamiprid with at least one substance selected from the group that includes (b) pyraclostrobin. Prochloraz or tebuconazole can be used as a fungicide. This product is used to treat seed material to combat pests and diseases that affect plants or seed material.

The closest technical solution to the claimed composition is a two-component mixture, including component (a), which is a fungicide from the pyrazole derivative class; component (b) includes at least one fungicide selected from two different groups, pyraclostrobin, tebuconazole, prochloraz. The composition is used to protect a plant or plant seeds from diseases caused by pathogenic fungi, contains. The composition may contain as (b) at least one agent for controlling invertebrate pests, for example acetamiprid or thiamethoxam or imidacloprid (RF patent No. 2572202).

The disadvantage of the known compositions is that they do not provide complete control over diseases of cultivated plants or require increased consumption rates during processing.

The objective of the invention is to expand the range of active insecticidal-fungicidal compositions for plant protection. Specifically for seed treatment to control disease at an early stage of growth, which will reduce the environmental load by minimizing the doses of chemicals while maintaining the high efficiency of protective treatments. Also, the technical objective of this invention is to preserve seed material from spoilage while maintaining high seed germination and growth during the initial growing season.

The technical result is the creation of a composition with synergistic effectiveness, prolonged phytopathogenic activity and high seed germination. The composition exhibits greater biological effectiveness at lower consumption rates of the active substances included in the composition. At the same time, due to the use of active substances with different biological mechanisms of action, the risk of resistance in pathogenic organisms is reduced. Thanks to this, there is no need for additional processing of the crop during sowing or a short period after it.

The technical result is achieved through the use of an insecticidal-fungicidal composition for the treatment of agricultural crops, including a mixture of fungicides consisting of tebuconazole and pyraclostrobin, and an insecticide.

In this case, the composition additionally contains the fungicide prochloraz and as an insecticide contains an insecticide from the class of neonicotinoids, acetamiprid, thiamethoxam or imidacloprid with a synergistic ratio of components in the composition, insecticide: prochloraz: pyraclostrobin: tebuconazole, equal, respectively, to (2+13): (2+15) :(0.2+5.0):1.

The insecticidal-fungicidal agent in accordance with the present invention retains its original physicochemical properties and biological activity under standard storage conditions for a long period of time.

The effectiveness of the known compounds is high, however, in small quantities and in relation to individual pathogens, in some cases it does not meet the high requirements for fungicides. Therefore, fungicides are often combined in mixtures to expand the spectrum of fungicidal activity, to achieve a synergistic effect and to delay pathogen resistance to one of the components of the mixture.

The high fungicidal effectiveness of this composition is evident from the examples below.

Example 1: Laboratory tests. Determination of fungicidal synergistic effect (see.

table 1-3)

Methodology for conducting the experiment:

An experimental study of the fungicidal and fungistatic activity of the samples was carried out using the agar cutting method. For analysis, working solutions of samples were prepared with a concentration that was determined by the field consumption rate of active substances, taking into account the consumption rate of the working fluid. To obtain comparative data and avoid achieving maximum efficiency, the consumption rate was reduced by 5 times. Then, 180 μl of a working solution of a fungicidal disinfectant was poured into sterile Petri dishes (consumption rates per 1 ton of seeds were recalculated to the surface area of a Petri dish with a diameter of 87 mm), poured into a KSA nutrient medium that had been previously sterilized and cooled to 45°C, and mixed until completely mixed. environment and drug. After the agar had solidified, mushroom blocks 1 cm in diameter, cut using a sterile punch, were placed in the center of each plate. The experiment was repeated 3 times. They were thermostated at a temperature of 825°C for 7-20 days (depending on the growth rate of the fungi), after which the presence or absence of zones of mycelial growth around the agar blocks was recorded and compared with the control.

The growth rate of fungi was calculated as the ratio of the diameter of mycelium growth in the experimental variant to the control, expressed in %.

The biological activity of active substances and their mixtures was calculated using the following formula: 100% - (growth rate).

Repetition - 4 times.

The expected efficiency is calculated using the Colby formula - Y + V 'J expected, - T D' ₁₀₀ where

X and Y are the observed effectiveness for separately applied fungicides at the indicated dose in g/ha or g/t;

E _expected - expected result for a mixture of fungicides;

E _exp - the result obtained as a result of the experiment.

If the ratio between the experimentally observed efficiency ( _Eexp .) and the expected efficiency ( _Eexpected ) - synergetic factor (SF) - is more than 1, the mixture exhibits a synergistic effect

E

SF = ---zksp^e

expect

This synergistic effect guarantees increased reliability in the fight against crop diseases, leading to a significant reduction in the amount of active component required to achieve the same biological effect, or maintaining the rate of consumption of the active substance while increasing biological effectiveness. The results are presented in table. 13

Example 2: Laboratory tests. Determination of insecticidal synergistic effect (see Table 4-6)

Wheat seeds are treated with the product in accordance with the standards indicated in the table. 4. Wireworm larvae (family Elateridae) are planted on the treated seeds, and after 3 days the mortality of the larvae is determined, expressed as a percentage. It is believed that 100% means that all larvae are dead, 0% means all larvae are alive.

Synergism is calculated using the Colby formula

^J EXPECTED,— Λ τ D' ₁₀₀ where

X is the death of larvae in%, calculated in relation to the untreated control (active substance A);

Y is the death of larvae in %, calculated in relation to the untreated control (group of active substances B);

EO _liquid - expected death of larvae in % relative to untreated control when using a synergistic mixture of substances A + B in the indicated ratios.

If the ratio between the experimentally observed efficiency (E _exp .) and the expected efficiency (Eolid) - synergetic factor (SF) - is more than 1, the mixture exhibits a synergistic effect:

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E

SF =-e expected

For synergy coefficients of insecticidal mixtures when treating seeds, see table. 4-6.

Example 3. Field small-plot tests (see Table 8-9)

The effectiveness of the claimed composition was studied under field conditions when treating grain seeds. Method of application - seed treatment The test results are given in table. 8-9.

The proposed mixture (150 g/l acetamiprid +100 g/l prochloraz + 20 g/l tebuconazole +15 g/l pyraclostrobin) was tested on spring and winter wheat, spring and winter barley against diseases: hard smut, fusarium, helminthosporium and rhizoctonia root rot, septoria, seed mold, powdery mildew, cercosporella rot, root collar, pythium root rot, snow mold; against pests: grain fly, wireworm, flea beetle, aphid, leech, leafhopper, bread ground beetle. Pre-sowing treatment of these crops was carried out.

The resulting composition, in addition to its protective effect against a wide range of pests and diseases, has a pronounced positive effect on the germination of seed material and further plant growth.

To take into account phytotoxicity, the laboratory germination of seeds was determined, which was expressed as a percentage; the data was processed statistically. Laboratory germination of seeds was determined in accordance with GOST 12038-84 - 07/01/86. Agricultural seeds. Methods for determining germination. When taking into account germination, normally germinated seeds were counted. The arithmetic mean of the results of determining the germination of all analyzed samples was taken as the result of the analysis (Table 7).

Table 1. Efficacy of mixtures of active ingredients for the control of Bipolavis sorokiniana _________________ (helminthosporium root rot) ____________

Active components Dose, g DV/t Ratio of DV Prochloraz: Tebuconazole: Pyraclostrobin exp. expected SF 1 Prochloraz Tebuconazole 150 thirty 52.1 Pyraclostrobin 22.5 22.4 Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 5:1:0.75 73.5 62.8 1.17 2 Prochloraz Tebuconazole 150 10 44.6 Pyraclostrobin 2 11.5 Prochloraz Tebuconazole Pyraclostrobin 150 10 2 15:1:0.2 55.1 51.0 1.08 3 Prochloraz Tebuconazole 40 20 21.2 Pyraclostrobin 100 68.1 Prochloraz Tebuconazole Pyraclostrobin 40 20 100 2:1:5 80.6 74.9 1.08

Table 2. Efficacy of mixtures of active ingredients for the control of Fusarium Oxysporum (Fusarium root rot)

Active components Dose, g DV/t DV ratio (Prochloraz: Tebuconaz ol: Pyraclostrobin) exp. expected SF 1 Prochloraz Tebuconazole 150 thirty 54.3 Pyraclostrobin 22.5 26.1 Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 5:1:0.75 76.2 66.2 1.15 2 Prochloraz Tebuconazole 150 10 50.8 Pyraclostrobin 2 12.2 Prochloraz Tebuconazole Pyraclostrobin 150 10 2 15:1:0.2 63.0 56.8 1.11 3 Prochloraz Tebuconazole 40 20 26.7 Pyraclostrobin 100 52.1 Prochloraz Tebuconazole Pyraclostrobin 40 20 100 2:1:5 68.1 64.9 1.05

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Table 3. Efficacy of mixtures of active ingredients for the control of Microdochium nivale ______________________ (snow mold) ___________________

Active components Dose, g DV/t DV ratio (Prochloraz: Tebuconaz ol: Pyraclostrobin) e _exp uh expected SF 1 Prochloraz Tebuconazole 150 thirty 71.2 Pyraclostrobin 22.5 14.8 Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 5:1:0.75 89.0 75.5 1.18 2 Prochloraz Tebuconazole 150 10 70.5 Pyraclostrobin 2 8.8 Prochloraz Tebuconazole Pyraclostrobin 150 10 2 15:1:0.2 80.5 73.1 1.10 3 Prochloraz Tebuconazole 40 20 38.4 Pyraclostrobin 100 32.7 Prochloraz Tebuconazole Pyraclostrobin 40 20 100 2:1:5 64.0 58.5 1.09

Table . 4. Determination of insecticidal synergistic effect (acetamiprid)

Active components Dose, g DV/t DV ratio exp. E EXPECT. SSF 1 A Acetamiprid 225 83.3 IN Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 6.7 Acetamiprid Prochloraz Tebuconazole Pyraclostrobin 225 150 thirty 22.5 7.5:5:1:0.75 90.0 84.4 1.07 2 A Acetamiprid 60 40.0 IN Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 0 Acetamiprid Prochloraz Tebuconazole Pyraclostrobin 225 150 thirty 22.5 2:5:1:0.75 50.0 40.0 1.25 3 A Acetamiprid 390 90.0 IN Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 3.3 Acetamiprid Prochloraz Tebuconazole Pyraclostrobin 225 150 thirty 22.5 13:5:1:0.75 96.7 90.33 1.07

Table 5. Determination of insecticidal synergistic effect (thiamethoxam)

Active components Dose, g DV/t DV ratio 9 EXP. uh expected SSF 1 A Thiamethoxam 225 80.0 IN Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 3.3 Thiamethoxam Prochloraz Tebuconazole Pyraclostrobin 225 150 thirty 22.5 7.5:5:1:0.75 83.3 80.7 1.03 2 A Thiamethoxam 60 43.3 IN Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 3.3 Thiamethoxam Prochloraz Tebuconazole Pyraclostrobin 225 150 thirty 22.5 2:5:1:0.75 53.3 45.2 1.18 3 A Thiamethoxam 390 83.3 IN Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 0 Thiamethoxam Prochloraz Tebuconazole Pyraclostrobin 225 150 thirty 22.5 13:5:1:0.75 90.0 83.3 1.08

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Table 6. Determination of insecticidal, synergistic, effect (imidacloprid)

Active components Dose, g DV/t DV ratio e exp. uh expected SSF 1 A Imidacloprid 225 86.6 IN Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 0 Imidacloprid Prochloraz Tebuconazole Pyraclostrobin 225 150 30 22.5 7.5:5:1:0.75 90.0 86.6 1.04 2 A Imidacloprid 60 40.0 IN Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 10.0 Imidacloprid Prochloraz Tebuconazole Pyraclostrobin 225 150 30 22.5 2:5:1:0.75 50.0 46.0 1.09 3 A Imidacloprid 390 96.6 IN Prochloraz Tebuconazole Pyraclostrobin 150 thirty 22.5 0 Imidacloprid Prochloraz Tebuconazole Pyraclostrobin 225 150 thirty 22.5 13:5:1:0.75 100 96.6 1.04

Table 7. Determination of laboratory germination of spring barley seeds

Experience Option Rate of drug use, l/t Energy of seed germination, % Laboratory seed germination, % 150 g/l acetamiprid + 100 g/l prochloraz + 20 g/l tebuconazole + 15 g/l pyraclostrobin 1.2 93.5 97.5 150 g/l acetamiprid + 100 g/l prochloraz + 20 g/l tebuconazole + 15 g/l pyraclostrobin 1.5 93.0 97.0 Control (without processing) - 88.5 92.5

Table 8. Efficacy of the product against the complex of seed and soil infections of spring barley (variety Nutans 642) in the conditions of the Volgograd region

Experience Option Norm applied IA means l/t Field germination of seed, % Plant density ^pcs./m2 BIPOSO + FUS ASP DRECTE USTINU USTIHO tillering formation of the 2nd node development, % efficiency, % develop tie, % efficiency, % development, % efficiency, % amazed tion, % efficiency, % amazed tion, % efficiency, % 150 g/l acetamiprid + 100 g/l prochloraz + 20 g/l tebuconazole + 15 g/l pyraclostrobin 1.2 92.2 328 3.7 60.6 I,4 39.0 3.8 28.3 0.0 100 0.0 100 150 g/l acetamiprid + 100 g/l prochloraz + 20 g/l tebuconazole + 15 g/l pyraclostrobin 1.5 92.5 329 2.6 72.3 9.9 47.1 3.3 360.2 0.0 100 0.0 100 Control (without processing) - 86.5 309 9.4 - 18.7 - 8.3 - 1.35 - 4.05 -

Note: BIPOSO + FUSASP - Bipolaris sorokiniana+ Fusarium spp. (helminthosporium-fusarium root rots) DRECTE - Drechslera teres (net spot) USTINU - Ustilago nuda (smut) USTIHO - Ustilago hordei (stone smut)

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Claims (2)

Table 9. Biological effectiveness of the product in the fight against wheat fly (Phorbia fumigata Meigen) on spring barley (variety Nutans 642) in the conditions of the Volgograd region Experience Option Consumption rate of the drug, l/t Repetition Average number of larvae per linear m of row after emergence by day of recording Reduction in pest numbers relative to control after emergence by day of survey, % Biological grain yield, c/ha 12 19 26 12 19 26 1 0 0 0 100 100 100 32.8 150 g/l acetamiprid +100 g/l 2 0 0 0 100 100 100 32.4 prochloraz + 20 g/l tebuconazole + 1.2 3 0 0 0 100 100 100 32.6 15 g/l pyraclostrobin 4 0 0 0 100 100 100 33.1 avg. 0 0 0 100 100 100 32.7 1 0 0 0 100 100 100 32.7 2 0 0 0 100 100 100 33.3 150 g/l acetamiprid +100 g/l 3 0 0 0 100 100 100 32.4 prochloraz + 20 g/l tebuconazole 1.5 4 O 0 O 100 100 100 32 9 + 15 g/l pyraclostrobin sr· 0 0 0 100 100 100 32.8 1 12.5 11.5 11.0 - — — 22.4 2 11.5 10.5 10.0 — — — 21.7 Control — 3 13.5 12.5 11.5 - — — 22.8 4 13.5 12.0 10.5 — — — 21.9 sr· 12.8 11.6 10.8 - - - 22.2 CLAIM An insecticidal-fungicidal composition for treating seeds of agricultural crops, including a mixture of fungicides consisting of tebuconazole and pyraclostrobin, and an insecticide, characterized in that the composition additionally contains the fungicide prochloraz and as an insecticide contains an insecticide from the class of neonicotinoids, selected from acetamiprid, thiamethoxam or imidacloprid at synergistic ratio of components in the composition insecticide: prochloraz: pyraclostrobin: tebuconazole, equal, respectively, to (2+13): (2+15): (0.2+5.0): 1. Eurasian Patent Organization, EAPO Russia, 109012, Moscow, Maly Cherkassky lane, 2