RU2460293C1 - Fungicidal mixture, fungicides means and method for control pathogenic fungi on their basis - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture. Fungicidal mixture contains a compound (I) - prochloraz or its complex salt, a compound (II), selected from tebuconazole or cyproconazole, and the compound (III), which is thiabendazole. The weight ratio (in terms of prochloraz) of the compound (I) to the compound (II) is from 1:25 to 25:1, and the weight ratio (in terms of prochloraz) of the compound (I) to the compound (III) is from 1:25 to 25:1. These mixtures exhibit synergistic efficacy. Fungicide product contains these compounds and at least one surfactant and one solvent and, if necessary auxiliaries. Fungicidal agent can be represented in the form of suspension or emulsion.

EFFECT: means or a mixture is used to control phytopathogenic fungi on plants and seeds of agricultures; invention enables to improve the efficiency of processing.

7 cl, 9 tbl, 2 ex

Description

The present invention relates to the field of agriculture.

The subject of the present invention is a fungicidal mixture containing prochlorase (or its complex salt), tebuconazole or ciproconazole and additionally thiabendazole as active substances, a fungicidal agent based on a mixture of these substances, and also a method for controlling phytopathogenic fungi using the fungicidal mixture mentioned above and a fungicidal crop protection products.

Prochlorase (compound I) is the common name for the chemical compound N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] -1H-imidazole-1-carboxamide, which is known from US Pat. Nos. 3,991,071 and 4,080,462. Prochlorase is a systemic fungicidal substance against a wide range of pathogens of fungal diseases of the following species in various cultures: Pseudocercosporella, Pyrenophora, Rhynchosporium, Septoria, Erysiphe, Alternaria, Botrytis, Pyrenopeziza, Sclerotinia, etc. (The Pesticide Manual, 14th ed. BCPC, 2006). The biological effect of prochlorase is based on the mechanism of inhibition of ergosterol. Various commercial preparations were registered on the basis of prochlorase, for example, Mirage, KS (450 g / l of prochlorase) Makteshim-Agan Industries Ltd., Kinto Duo, KS, (20 g / l of triticonazole + 60 g / l of prochlorase contained in a complex with chloride zinc (+2)) company BASF Agro B.V. and others (“State catalog of pesticides and agrochemicals approved for use in the Russian Federation in 2010”, Ministry of Agriculture of the Russian Federation, Moscow, 2010).

In the present invention, the term "prochlorase" also encompasses its complex salts, of which the most preferred is a complex of prochlorase with manganese chloride with an oxidation state of manganese (+2).

Tebuconazole (compound IIa) - the common name for the chemical compound α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, belongs to the class triazoles, its synthesis is described in patents EP 0040345, US 4723984.

The biological effect of tebuconazole is based on the mechanism of inhibition of ergosterol biosynthesis. Tebuconazole is a substance of systemic fungicidal action against a wide range of pathogens of fungal diseases, in particular: Pyrenophora, Rhynchosporium, Septoria, Erysiphe graminis, Alternaria, Tilletia, Puccinia, Sphacelotheca, Ustilago, Cercospora, Podosphaera, Fusarium dr., Manual. , 14th ed., BCPC, 2006).

On the basis of tebuconazole, various commercial preparations have been registered, including it as one active component, for example, Raxil (60 g / l), CS; Raxil Ultra, (120 g / l) KS; Folicur (250 g / l), CE - Bayer Crop Science AG products; Bunker (60 g / l), VSK - CJSC Avgust Firm, and as part of multicomponent mixtures, for example, Vial-TT (80 g / l thiabendazole + 60 g / l tebuconazole), VSK; Kolosal Pro, KNE (300 g / l propiconazole + 200 g / l tebuconazole) - preparations of Augustus CJSC. (“The state catalog of pesticides and agrochemicals approved for use in the Russian Federation in 2010”, Ministry of Agriculture of the Russian Federation, Moscow, 2010)

Cyproconazole (compound IIb) is the common name for the chemical compound α- (4-chlorophenyl) -α- (1-cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol, which belongs to the class of triazoles, the synthesis of which is described in the patent US 4,664,696. The biological effect of ciproconazole is based, as with tebuconazole, on the ability to inhibit ergosterol biosynthesis.

Cyproconazole is a systemic fungicidal substance against fungal pathogens such as Septoria, Rhynchosporium, Cercospora, Ramutaria, Mycena, Sclerotinia, Rhizoctonia and others (The Pesticide Manual, 14th ed., BCPC, 2006).

Various commercial preparations were registered on the basis of ciproconazole, in particular, Alcor, KS - a preparation of LLC Agruskhim; Recruit, KS - Sibagrohim LLC drug (the content of ciproconazole in the preparations is 400 g / l); mixed: Alto-super, CE (250 g / l propiconazole + 80 g / l ciproconazole), Amistar Extra, SC (200 g / l azoxystrobin + 80 g / l ciproconazole), Dividend Star, CE (30 g / l diphenoconazole + 6.3 g / l of cyproconazole) - Syngenta Krop Protekshi AG preparations (“State catalog of pesticides and agrochemicals approved for use in the Russian Federation in 2010”, Ministry of Agriculture of the Russian Federation, Moscow, 2010).

Thiabendazole (compound III) is the common name for the chemical compound 2- (thiazol-4-yl) benzimidazole, which is known from US Pat. No. 3,017415. Thiabendazole is a systemic fungicidal substance against a wide range of pathogens of fungal diseases of the following types: Aspergillus, Botrytis, Ceratoxystisis , Cercospora, Cladosporium, Colletotrichum, Corticium, Diaporthe, Diplodia, Fusarium, Gibberella, Gloeosporium, Oospora, Penicillium, Phoma, Podosphaera leucotricha, Rhizoctonia, Sclerotinia, Septoria, Thielavi Pest. Et al. , 2006). The biological effect of thiabendazole is based on the inhibition of the mitosis process due to the binding of tubulin. On the basis of thiabendazole, various commercial preparations were registered, for example, mixed ones: Vial Trast, VSK (80 g / l thiabendazole + 60 g / l tebuconazole) - a preparation of ZAO August Company; Vincit, SC (25 g / l thiabendazole + 25 g / l flutriafol) drug company Keminova A / C. (“The state catalog of pesticides and agrochemicals approved for use in the Russian Federation in 2010”, Ministry of Agriculture of the Russian Federation, Moscow, 2010).

The patent literature describes the combined use of thiabendazole with other systemic fungicidal preparations, for example, triazole derivatives such as tebuconazole in seed treatment compositions (patent RU 2264711), tebuconazole or ciproconazole in pesticidal compositions (international application WO 2005/029960).

Also known are methods of controlling phytopathogenic fungi using prochlorase and its complex salts together with other active substances, for example, tebuconazole in fungicidal mixtures and compositions (US patent 4845111, US application 2009215845 (prototype), CN 101019545), ciproconazole in fungicidal compositions ( GB 2191401 and EP 0714605).

However, information on the joint use of prochlorase with tebuconazole or cyproconazole and thiabendazole in the form of a three-component fungicidal mixture, the presence of synergism of this kind of three-component mixtures in assessing their biological effectiveness and fungicidal agents based on these mixtures to protect plants from phytopathogenic fungi are currently lacking.

An object of the present invention is to expand the spectrum of biological action and increase the biological effectiveness of the above compounds.

The problem is solved by creating a fungicidal mixture containing as active substances a mixture of three biologically active compounds: compound (I), which is prochlorase or its complex salt, compound (II) selected from tebuconazole (IIa) or ciproconazole (IIb), and compounds (III) which is thiabendazole taken in effective ratios, wherein the mass ratio (in terms of prochlorase) of compound (I) to compound (II) is from 1:25 to 25: 1 and the mass ratio (in terms of prochlorase) of the compound (I) to compound Senion (III) ranges from 1:25 to 25: 1.

The inventors have found that the fungicidal effect of such a mixture of biologically active substances is higher than the sum of the action of the same substances used individually, i.e. a synergistic effect takes place, and not a simple additive summation of their action.

Another object of the present invention is to provide a fungicidal agent consisting of compound (I), which is prochlorase (or its complex salt), compound (II) selected from tebuconazole (IIa) or ciproconazole (IIb) and, in addition, compound (III) which is thiabendazole, and containing at least one solvent (diluent) and one surfactant and, if necessary, auxiliary additives that improve the consumer properties of such agents. Moreover, the mass ratio (in terms of prochlorase) of compound (I) to compound (II) is from 1:25 to 25: 1 and the mass ratio (in terms of prochlorase) of compound (I) to compound (III) is from 1: 25 to 25: 1.

The fungicidal agent exhibits greater biological efficacy in relation to the selected comparison drugs, including at lower consumption rates of the active substances that make up the composition, resulting in a decrease in the environmental load on the environment. At the same time, through the use of active substances with different biological mechanisms of action, the risk of resistance in pathogenic organisms is reduced.

The fungicidal agent in accordance with the present invention can be presented in the form of a suspension, preferably in the form of a suspension concentrate (abbreviation SK) or emulsion, preferably in the form of an emulsion concentrate (abbreviated CE), nanoemulsion concentrate (abbreviated CNE) and microemulsion concentrate (abbreviated designation KME).

Suspension concentrates can be obtained by grinding a mixture of active substances with a diluent, surfactants in bead mills to achieve the desired particle size. After grinding, auxiliary additives are added to the suspension - acidity regulator, thickener, dye or biocide.

Emulsion concentrates (CE) are obtained by dissolving a mixture of active substances in a hydrophobic solvent and emulsifier system. When diluted with water for practical use, CEs form white emulsions with a particle size of 1 to 40 microns.

Microemulsion concentrates (CME) and nanoemulsion concentrates (CNE) are obtained by selecting the components of the organic phase and their quantitative content to obtain a thermodynamically stable product over time. In the preparation of spraying solutions (working solutions), these formulations form micro- and nanoemulsions (respectively) and are stable and transparent solutions with a particle size of 200-300 nm for CME and up to 200 nm for CNE. Fungicidal agents in accordance with the present invention retain their original physicochemical properties and biological activity under the influence of high or low temperatures during storage for a long period of time.

The following can be used as the main components of fungicidal agents: solvents (diluents) - such as oil distillation products, in particular aromatic hydrocarbons, preferably C ₈ -C ₁₂ fractions, such as xylene mixtures or substituted naphthalenes; phthalic acid esters such as dibutyl or dioctyl phthalate; aliphatic hydrocarbons such as cyclohexane or paraffins; alcohols and glycols, as well as their ethers and esters, such as ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; ketones like cyclohexanone; mineral or vegetable oils; polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide, water; surfactants - both nonionic and cationic and / or anionic surfactants with emulsifying, dispersing and wetting properties, it is also possible to use a mixture of surfactants. In particular, ethoxylated (di) tristyrylphenols, ethoxylated tristyrylphenol sulfates (phosphates), salts of ethoxylated tristyrylphenol sulfates (phosphates), ethoxylated alkylphenols, condensed alkylnaphthalenesulfonates, alkylbenzene, alkyl diphenylsulfonyl (alkylene diphenylsulfonyl) -phenyl sulfonates aryl) sulfonates, ethylene / propylene oxide block copolymers, ethoxy (propoxylated) polyarylphenols, polycarboxylate salts, polyethylene glycol fatty acid esters and m polyhydric alcohols.

As auxiliary additives, the described fungicidal agents may contain:

- antifreezes, due to which an increase in the stability of the product is achieved under long-term storage at high and low temperatures. As antifreeze agents, it is preferable to use glycolic antifreeze agents or glycerol. The use of glycerin allows combining the function of antifreeze and homogenizing agent for the mineral or vegetable oil introduced into the composition of the compositions;

- mineral or vegetable oils, the addition of which ensures the formation of a uniform film on the objects treated with a fungicidal agent and increases the adhesion of the drug;

- acidity regulators or buffer additives necessary to maintain the range of acidity of the medium (pH value); citric acid and its salts, as well as salts of inorganic acids, preferably alkali metals of inorganic acids, such as sodium carbonate or sodium bicarbonate, can be used as such;

anti-foaming agents to reduce foaming, preferably organosilicon, such as Penta 469 polydimethylsiloxane defoamer (Penta company, Russia), Rodorsil (Rodia company, Italy), Amersil (Ametek company, Italy);

- dyes such as varnishes, for example Lac Rubin 2SK and Lac Rubin SK, which are calcium salts of 2-hydroxy-4 - [(4-methyl-2-sulfo (phenyl)] - azo-2-naphthalene carboxylic acid (GOST 7436- 74), the purpose of which is to ensure uniform coloring of the treated object;

- thickeners, which can be used xanthan gum, mineral substances, as well as polysaccharides, including cellulose thickeners;

- mold inhibiting biocides, such as 1,2-benzisothiazolin-3-one (CAS No. 2634-33-5) and 1,3,5-tris (2-hydroxyethyl) hexahydro-1,3,5-triazine (CAS No. 4719-04-4).

Patented fungicidal agents contain, in g / l, usually from 10 to 440 prochlorase (calculated as prochlorase), from 5 to 400 tebuconazole or cyproconazole, from 15 to 440 thiabendazole, from 5 to 215 surfactants or surfactant mixtures -active substances, the rest is a solvent and, if necessary, auxiliary additives, up to 1 liter.

Another object of the present invention is a method of combating phytopathogenic fungi, in which phytopathogenic fungi, their habitat or requiring protection from damage to plants, seeds, tubers, soil or agricultural land are treated with the inventive fungicidal mixture or fungicidal agent based on prochlorase, tebuconazole or ciproconazole and thiabendazole.

The following are examples of fungicidal preparations, their technical characteristics and biological efficacy assessments. The following examples illustrate but do not limit the present invention.

Example 1

Obtaining sample No. 1 in the form of a suspension concentrate

216.5 g of water, 55 g of diethylene glycol, 27.5 g of antifoam and 5 g of sodium alkylaryl sulfonate are loaded into the reactor, 33 g of ethylene propylene oxide block copolymer preheated to a temperature of 45-60 ° C are added with stirring. Stirred for 10-15 minutes, after which 440 g of thiabendazole, 440 g of the complex salt of prochlorase (in terms of prochlorase) and 17.6 g of ciproconazole are added. Mix thoroughly until a homogeneous suspension is formed and grind in a bead mill. 3.3 g of acidity regulator, 1.1 g of dye, 33 g of thickener and 0.5 g of biocide are added to the resulting product, after which the physicochemical characteristics of the preparation are determined.

Similarly receive samples No. 5-10 and 12.

Example 2

Obtaining sample No. 2 in the form of an emulsion concentrate

661.8 g of cyclohexanone are charged to the reactor and 15 g of thiabendazole, 100 g of prochlorase, 100 g of tebuconazole are added, whisked to a temperature of 45-50 ° C, 80.0 g of alkylbenzenesulfonate and 5.5 g of ethoxy (propoxylated) fatty alcohol are added, and 11.0 g of polyethylene glycol fatty acid ester and polyhydric alcohol. Stirred for 20-30 minutes until a homogeneous clear liquid was obtained, then 8.8 g of an acidity regulator and 8 g of antifoam were added. Filter through a filter and determine the physico-chemical characteristics of the drug. Similarly receive samples of emulsions No. 3-4 and 11 different types. Table No. 1 presents the compositions of the obtained samples of fungicidal agents.

Evaluation of the quality indicators of fungicidal agent samples was carried out as follows: the viscosity of the obtained drug samples was determined on a Brookfield viscometer, stability was determined according to GOST 16484-79 and the CIPAC MT 161 method, dispersion was determined on a Fritsch Analysette 22 laser particle analyzer according to the CIPAC MT 187 method, the pH value was according to GOST R 50550.

In tables No. 2 and No. 3 the physicochemical properties of the obtained samples are presented. As can be seen from these results, the samples obtained have high stability and dispersion.

Synergistic Evaluation

The effectiveness for a mixture of three biologically active substances in% is calculated according to the Colby formula and is determined as follows (COLBY LR "Calculating synergistic and antagonistic responses of herbicide combinations" ("Calculation of the synergistic and antagonistic expected action of mixtures of herbicides"). Weeds 15, p.20- 22, 1967), (LIMPEL et al. 1962 "Weeds control by certain combinations". Proc. NEWCL. Vol.16, pp. 48-53):

E _xyz = (X + Y + Z) - (X * Y + X * Z + Y * Z) / 100 + X * Y * Z / 10000,

Where

X biological effectiveness when using thiabendazole with a consumption rate of m, g / ton of seeds;

Y biological effectiveness when using prochlorase with a consumption rate of n, g / ton of seeds;

Z biological effectiveness when using tebuconazole (or ciproconazole) with a consumption rate of l, g / ton of seeds;

E _xyz biological effectiveness with the combined use of thiabendazole, prochlorase and tebuconazole (or ciproconazole) with consumption rates of m, n and 1 g / ton of seeds.

An efficacy of 0% corresponds to an efficacy without fungicide treatment, an efficacy of 100% means a complete suppression of pathogens. A synergistic effect always exists if the fungicidal effect of a mixture of biologically active substances is greater than the sum of the actions of the individual biologically active substances used.

From the examples given in tables No. 4 and No. 5, it can be seen that in all cases the actual effectiveness for the mixture of active substances is higher than that calculated by the Colby formula, i.e. there is a synergistic effect.

Biological Efficiency Assessment

Field trials of the obtained samples for assessing biological effectiveness were carried out by treating spring barley seeds (Stimul variety) against root rot of Fusarium etiology and winter wheat plants (Pobeda variety 50) against a complex of diseases caused by phytopathogenic fungi.

The tests were carried out in comparison with well-known commercial preparations, such as VIAL TT, VSK and Kolosal, CE. The tests were carried out in accordance with the "Methodological guidelines for registration testing of fungicides in agriculture", ed. V.I.Dolzhenko, St. Petersburg, VIZR, 2009

During the growing season, the test samples were sprayed at the heading phase. Spraying was carried out with a backpack sprayer. The working fluid flow rate is up to 200 l / ha. The experiment was repeated four times, the area of each plot was 10 m ² . The degree of damage to plants by pathogens at the date of registration was estimated by the surface area covered by the disease.

Biological effectiveness (%) was evaluated by the formula:

,

,

Where

BE - biological effectiveness,%;

About - the degree of damage to plants on the date of accounting,%;

To - the degree of damage to plants in the control on the date of accounting,%.

Evaluation of the effectiveness of the test samples as dressing agents was carried out by dressing the seeds with moisture before sowing. The working fluid flow rate is up to 10 l / t of seeds. The experiment was repeated four times, the area of each plot was 10 m ² . On each plot, the counts were performed twice: in the spring in the tillering phase and in the phase of formation of the 2nd node.

The development of the disease (%) was evaluated by the formula:

,

,

Where

R is the development of the disease,%;

a is the number of plants with the same lesion score (b);

N is the total number of plants;

K - the highest score of the accounting scale, equal to 4.

Biological effectiveness (%) was evaluated by the formula:

, где

where

BE - biological effectiveness,%;

Rk - the development of the disease in the control,%;

Rb is the development of the disease in the experiment,%.

The results are shown in tables No. 6-9.

These data clearly demonstrate the high biological effectiveness of the claimed objects in the protection of seeds and plants of crops from diseases caused by phytopathogenic fungi.

Claims (7)

1. A fungicidal mixture containing compound (I), which is prochlorase or its complex salt and compound (II) selected from tebuconazole or cyproconazole, characterized in that it further comprises compound (III), which is thiabendazole, and the mass ratio in in terms of the coolness of compound (I) to compound (II) is from 1:25 to 25: 1 and the mass ratio (in terms of cool) of compound (I) to compound (III) is from 1:25 to 25: 1. 2. The fungicidal mixture according to claim 1, characterized in that the compounds (I), (II) and (III) are taken in a synergistically effective amount. 3. A fungicidal agent containing compound (I), which is prochlorase or its complex salt and compound (II) selected from tebuconazole or ciproconazole, characterized in that it further comprises compound (III), which is thiabendazole and at least , one surfactant and one diluent solvent and, if necessary, auxiliary additives, the mass ratio in terms of prochlorase of compound (I) to compound (II) being from 1:25 to 25: 1 and the mass ratio in terms of prochlor the az of compound (I) to compound (III) is from 1:25 to 25: 1. 4. The fungicidal agent according to claim 3, characterized in that it contains, g / l:
compound (I) in terms of coolant from 10 to 440,
compound (II) from 5 to 400,
compound (III) from 15 to 440
surfactant or
a mixture of surfactants from 5 to 215,
solvent-diluent and, if necessary, auxiliary additives up to 1 l. 5. The fungicidal agent according to claim 3 or 4, characterized in that it contains a dye or antifreeze as an auxiliary additive. 6. The fungicidal agent according to claim 3, characterized in that it is presented in the form of a suspension or emulsion. 7. A method for controlling phytopathogenic fungi, characterized in that phytopathogenic fungi, their habitat or requiring protection from damage to plants, seeds, tubers, soil, agricultural areas are treated with the fungicidal mixture or fungicidal agent according to any one of claims 1 to 6.