Fungicidal and bactericidal preparation and method for using same

Abstract

The invention relates to agriculture, and more particularly to plant cultivation, and concerns a fungicidal and bactericidal preparation based on copper and thiourea or derivatives thereof, as well as the use of said preparation in the cultivation of spring-sown and autumn-sown cereals and leguminous plants, field vegetable crops and protected vegetable crops, tree and shrub crops, fruit crops, berry crops, aromatic crops, horticultural crops, ornamental crops, cucurbitaceous crops, tilled crops, industrial crops and feed crops. The claimed fungicidal or bactericidal preparation contains a complex compound of copper (I) with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethylene thiourea, or N,N'-bis(dimethylaminomethyl)thiourea and a complex compound of silver with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethylene thiourea, or N,N'-bis(dimethylaminomethyl)thiourea. The claimed fungicidal or bactericidal preparation includes a mixed complex compound of copper (I) and silver with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethylene thiourea, or N,N'-bis(dimethylaminomethyl)thiourea.

Description

[0001] FUNGICIDAL AND BACTERICIDAL DRUG AND METHOD OF ITS USE

[0002] Field of technology

[0003] The invention relates to agriculture, namely, to plant growing, and concerns a fungicidal and bactericidal preparation based on copper, silver and thiourea or its derivatives, as well as the use of this preparation in growing spring and winter grain and leguminous crops, open and protected ground vegetables, woody and shrubby, fruit, berry, essential oil, garden, ornamental, melon, row crop, industrial and forage crops. The invention can be used for pre-sowing seed treatment, as well as for treating seedlings when growing plants in hothouses, garden plots, parks and farms, as well as in agro-complexes, forest nurseries, forestries, botanical gardens, and in landscaping.

[0004] State of the art

[0005] The intensive use of pesticides and their mixtures in agriculture leads to some slowdown in the growth and development of crops, which can not only negatively affect the growth of agricultural crops, especially in conditions of water deficit and global warming, but also the quality of agricultural products.

[0006] In this regard, when growing crops, there is a need to reduce the pesticide load when treating seeds and crops of crops.

[0007] Fungicides based on dithiocarbamic acid derivatives are well known from the prior art, for example mancozeb, which is a mixed salt where X is Zn and Mn; fungicides based on substituted benzimidazoles, such as benomyl, thiabendazole, fuberidazole, carbendazim; fungicides based on triazole derivatives, such as triadimefon, triadimenod, dichlobutrazole, flutrimazole, flutriafen, etaconazole, propiconazole, butrazole; fungicides based on imidazole derivatives, such as imazalil and prochloraz; fungicides based on esters and amides of phosphoric and thiophosphoric acids; fungicides based on amines, amidines and guanidines, such as those based on polyhexamethylene guanidine salts. In addition, fungicides based on chemical compounds belonging to other classes are widely used.

[0008] As an alternative to organic synthetic substances, pesticides based on copper (II) compounds are also widely used in agriculture. Such substances are relatively cheap and easy to produce, and also have the ability to suppress the growth of a wide range of not only fungal but also bacterial pathogens of plant diseases.

[0009] The first widely used agricultural antimicrobial compound in the world based on an insoluble copper compound was Bordeaux mixture, a mixture of copper sulfate and lime milk. Then other copper compounds began to be used, such as hydroxide, carbonate, oxychloride. Copper compounds are characterized by high efficiency, low probability of developing resistance in phytopathogens and low toxicity to plant and mammalian cells.

[0010] More effective fungicidal preparations are complex copper compounds. For example, Russian patent No. 2536404 discloses the use of [N,N'-bis(dimethylaminomethyl)thioureaoxalate] copper sulfate pentahydrate as a means of combating fungal diseases of plants.

[0011] When copper gets into the soil, it does not remain in it in a dissolved form, as it is easily bound by clay minerals and humus components. However, copper removal from the soil as a result of leaching, rainwater washout or absorption by plants is insignificant, so it can accumulate in the environment, especially in the upper 15 cm of soil, and cause biodegradation. Thus, the constant use of high concentrations of copper compounds for more than a century has led to the accumulation of this metal in the soil of agricultural lands in quantities exceeding the copper content in untreated soils by 40-50 times. For this reason, the use of copper compounds in agriculture is limited. In this regard, the development of new forms of copper preparations that retain their antimicrobial and fungicidal effectiveness at fairly low concentrations of the metal has become relevant.

[0012] One of the strategies to maximize the effectiveness of copper compounds has become a reduction in the particle size of the active substance, since smaller particles provide increased uniformity of coating, distribution and adhesion and increase the resistance of the drug to dripping. In addition, having a larger specific surface area, the surface-to-volume ratio, such particles provide a faster release of active Cu ions 2+ However, the possibilities of this approach are limited by technological constraints that do not allow obtaining aggregation-stable particles with a diameter of less than 1 µm with sufficient economic efficiency.

[0013] Another approach to increasing the effectiveness of copper-based pesticides is to find more active chemical forms of the metal, such as copper (I) compounds. For example, monovalent copper in the form of Cu2O oxide is the main active ingredient, 860 g / kg, of the commercially available fungicide NORDOX 75 V G from Nordox, Norway. The disadvantage of this product is the large size of the copper oxide particles, which reduces the effectiveness of the product.

[0014] The prior art discloses a fungicidal and bactericidal preparation disclosed in Russian Federation Patent No. 2022126588 of 12.10.2022, comprising at least one complex compound of copper (I) with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethyl thiourea, or N,N'-bis(dimethylamino _methyl)thiourea. In this preparation, copper is in the form of a solution, which significantly increases the biological activity of the preparation compared to analogues. However, the effectiveness of fungicidal or bactericidal treatment with this preparation may be insufficient in some cases.

[0015] In this regard, the task arises of developing more effective fungicidal and bactericidal preparations based on copper.

[0016] The specified technical result is achieved by using a fungicidal and bactericidal preparation and a method for its use, described in more detail below. Description of the invention

[0017] In an experimental study of the biological activity of various complex compounds with thiourea and its derivatives, it was found that such complexes, including Cu ions + and Ag +, are characterized by high fungicidal and bactericidal activity, as well as chemical resistance acceptable for use in agriculture, low phytotoxicity. At the same time, the combined use of silver and copper complexes is more effective than their use separately.

[0018] This allows us to conclude that these preparations can be used in agriculture as fungicides and bactericidal preparations when growing plants.

[0019] The claimed invention relates to a fungicide or bactericide preparation that can be used in growing plants, including spring and winter grain and legume crops, open and protected ground vegetables, trees and shrubs, fruits, berries, essential oil, garden, ornamental, melon, row crops, industrial and forage crops.

[0020] The claimed invention relates to a fungicidal and / or bactericidal preparation comprising at least one complex compound of copper (I) with thiourea or yl methylthiourea, or yl N,N'-dimethylthiourea, or ethylthiourea, or yl N,N'-diethylthiourea, or yl ethylenethiourea, or N,N'-bis(dimethylaminomethyl)thiourea and at least one complex compound of silver with thiourea or yl methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethylenethiourea, or N,N'-bis(dimethylaminomethyl)thiourea, or at least one mixed complex compound of copper (I) and silver with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethylthiourea, or N,N'-bis(dimethylaminomethyl)thiourea.

[0021] The claimed invention relates to a fungicidal or bactericidal preparation in which the ratio of copper and silver by weight is from 50:1 to 1:10.

[0022] The claimed invention relates to a fungicidal or bactericidal preparation, in which the counterion in a copper (I) or silver complex compound, or a mixed copper (I) and silver complex compound is selected from a group comprising succinate, malate, citrate, lactate, formate, acetate, salicylate, phosphate, phosphite, thiocyanate, methosulfate, monocarboxylic acids with an alkyl saturated or unsaturated radical containing from 8 to 18 carbon atoms, iodide, alkyl phosphonates, borate, glycinate, glutamate, ethylenediaminetetraacetate, orthoethylidenediphosphonate.

[0023] The claimed invention also relates to a method for using a fungicide or bactericide preparation when growing plants, including spring and winter grains and legumes, open and protected ground vegetables, woody shrubs, fruits, berries, essential oil, garden, ornamental, melons, row crops, industrial and forage crops.

[0024] The claimed invention relates to a method for using a fungicide or bactericide preparation when growing plants, in which plant seeds or vegetative plants are treated with a solution including the preparation.

[0025] The invention is illustrated by examples of alternative embodiments of its implementation.

[0026] Example 1

[0027] A mixture of complex compounds of copper (I) with ethylenethiourea (ETU) and silver with ethylenethiourea - bis-imidazolidine-2-thionyl copper (I) formate [CuETU2] - was used as a fungicidal and bactericidal preparation. +HCOO- and bis-imidazolidine-2-thionylsilver nitrate [AgETU2] + NO3- in a ratio of 10:1 by weight of copper and silver.

[0028] The drug was obtained as follows.

[0029] The calculated amount of crushed copper carbonate was placed in a flask equipped with a stirrer and a thermometer with the required amount of distilled water at room temperature. The resulting mixture was stirred for 10 minutes to form an aqueous suspension. Solutions containing the calculated amounts of the complexing agent ethylenethiourea, the reducing agent ascorbic acid and formic acid were successively introduced into the resulting suspension with stirring through a dropping funnel. Then the reaction mixture was heated to 60° C and stirred for 2 hours. Intensive release of carbon dioxide was observed during the reaction. After 2 hours, the suspension was almost completely dissolved, and the reaction mixture was a transparent solution of bis-imidazolidine-2-thionyl copper (I) formate [CuETU2] + HCOO-. After this, the reaction mixture was cooled to room temperature, stirred for another 30 minutes and filtered.

[0030] The calculated amount of silver nitrate was placed in a flask equipped with a stirrer and a thermometer with the required amount of distilled water at room temperature. A solution containing the calculated amount of the complexing agent ethylenethiourea was added to the resulting solution with stirring through a dropping funnel. The reaction mixture was then heated to 60°C and stirred. The reaction mixture was a clear solution of bis-imidazolidine-2-thionyl silver (I) nitrate [AgETU2] + NO3-. After this, the reaction mixture was cooled to room temperature, stirred for another 30 minutes and filtered.

[0031] The mixture of the obtained filtrates was used as a bactericidal and fungicidal preparation P-1.

[0032] The bactericidal and fungicidal activity of the obtained preparation was studied.

[0033] P-1 in vitro against phytopathogenic microorganisms Erwinia atroseptica,

[0034] Sclerotinia sclerotiorum and UgLaTF7 Fusarium equiseti, which are the causative agents of such plant diseases as bacterial burn, sclerotypiosis, root and stem rot. In addition, the microbiological activity of the obtained preparation was compared with two commercially available analogues: "Coside 2000" (based on copper hydroxide, USA) and "Zeroks" (based on colloidal silver, Russia).

[0035] The bactericidal effect against Erwinia atroseptica was determined by counting the number of colony-forming units (CFU). For this purpose, the bacteria were grown on an agarized LB medium for 24 hours at 28°C, then washed off with sterile water and diluted in a 1 / 1 ratio. The wash was placed in a test tube, where the preparation was added in such an amount that the final concentration of the active substance was calculated, and kept for 30 minutes. Water in the same volume, including the fungicide, was added to the control test tubes. After incubation, 50 μl of the suspension was resuspended and distributed with a sterile spatula over the surface of the agarized medium, and after 72 hours of incubation at +28°C, the number of colonies was calculated.

[0036] The preparations were studied in various dilutions P1-4, in which the concentration of the active substance was 2, 20, 200 and 600 ppm, ppm - millionth part, 10 -6, by the total content of copper and silver, or 0.2, 2, 20, 60 ppm by silver or 2, 20, 200, 600 ppm by copper for comparison samples. The preparations in dilutions P1-4 contained: the preparation obtained according to the invention, P1 - 0.18 Ag and 1.8 Cu, P2 - 1.8 Ag and 18 Cu, P3 - 18.2 Ag and 182 Cu, P4 - 54.5 Ag and 545 Cu; comparison samples P1 - 0.2 Ag or 2 Cu, P2 - 2 Ag or 20 Cu, P3 - 20 Ag or 200 Cu, P4 - 60 Ag or 600 Cu.

[0037] The fungicidal effect against Sclerotinia sclerotiorum and UgLaTF7 Fusarium equiseti was assessed in Petri dishes as the ratio (expressed as a percentage) of the radial growth of the phytopathogen mycelium on an agarized pea medium with the addition of the preparation to its growth on the control agarized medium without the fungicide (a ratio of 100 means no fungicidal effect, and 0 means complete suppression of the phytopathogen growth). An agar block with 5 mm diameter mycelium was placed in the center of a Petri dish, after which it was incubated at a temperature of +23-25°C and natural light. The studied fungal colonies were measured when their diameter in the control reached 0.5 to 0.75 of the Petri dish size. The radial growth was assessed at 4 concentrations of fungicides (2, 20, 60 and 200 ppm for the total content of copper and silver, or 0.2, 2, 6 and 20 ppm for silver for the comparison sample) in two replicates.

[0038] The results of laboratory tests (Tables 1, 2) showed that the drug P-1 [CuETU2]+ HCOO-+[AgETU2] + NO3- is able to suppress the growth of all three studied phytopathogens more effectively than the studied analogues.

[0039] The obtained data indicate that the manufactured preparation has pronounced antimicrobial activity against bacterial, taacca and fungal phytopathogens at a low concentration of the active substance.

[0040] Table 1. Comparison of the bactericidal activity of CFU against Erwinia atroseptica of the drug P-1 and analogues Table 2. Comparison of fungicidal activity - the ratio of colony diameters on the medium with the addition of the preparation and in the control, % - in relation to Sclerotinia sclerotiorum and in relation to UgLaTF7 Fusarium equiseti of the preparation P-1 and analogues

[0041] Example 2

[0042] A mixed complex compound of copper (I) and silver with ethylenethiourea was used as a fungicide and bactericide.

[0043] The preparation was obtained as follows. The calculated amount of crushed copper oxide (I) Cu2O and silver nitrate in a molar ratio of 1:1 - in a ratio of 1:1.7 by weight of copper and silver - was placed in a flask equipped with a stirrer and thermometer with the required amount of distilled water at room temperature.

[0044] The resulting mixture was stirred for 10 minutes to form an aqueous suspension. Solutions containing the calculated amounts of the complexing agent ethylenethiourea and citric acid were successively introduced into the resulting suspension while stirring through a dropping funnel. Then the reaction mixture was heated to 60°C and stirred for 2 hours. During the reaction, intense release of carbon dioxide was observed. After 2 hours, the suspension was almost completely dissolved, and the reaction mixture was a transparent solution of the complex compound. After this, the reaction mixture was cooled to room temperature, stirred for another 30 minutes and filtered. The resulting filtrate was used as the bactericidal and fungicidal preparation P-2.

[0045] The bactericidal and fungicidal activity of the obtained preparation P-2 was studied similarly to Example 1. The preparation was studied in various dilutions P1-4, in which the concentration of the active substance was 2, 20, 200 and 600 ppm for the total content of copper and silver, or, for comparison samples, for silver or copper. The preparations in dilutions P1-4 contained: the preparation obtained according to the invention, P1 - 1.25 Ag and 0.75 Cu, P2 - 12.5 Ag and 7.5 Cu, P3 - 125 Ag and 75 Cu, P4 - 375 Ag and 225 Cu; comparison samples P1 - 2 Ag or Cu, P2 - 20 Ag or Cu, P3 - 200 Ag or Cu, P4 - 600 Ag or Cu.

[0046] The results of laboratory tests (Tables 3, 4) showed that the drug P-2 is capable of suppressing the growth of all three studied phytopathogens more effectively than the studied analogues.

[0047] The obtained data indicate that the manufactured preparation has pronounced antimicrobial activity against bacterial, taacca and fungal phytopathogens at a low concentration of the active substance.

[0048] Table 3. Comparison of the bactericidal activity of CFU against Erwinia atroseptica of the drug P-2 and analogues

[0049] Table 4. Comparison of fungicidal activity - the ratio of colony diameters on the medium with the addition of the preparation and in the control, % - in relation to Sclerotinia sclerotiorum and in relation to UgLaTF7 Fusarium equiseti of the preparation P-2 and analogues

[0050] Example group 1

[0051] In group 1 of examples, mixtures of complex compounds of copper (I) and silver with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethylenethiourea, or N,N'-bis(dimethylaminomethyl)thiourea were used as a fungicidal or bactericidal preparation in a ratio of 50:1 to 1:10 by weight of copper and silver; succinate, malate, citrate, lactate, formate, acetate, salicylate, phosphate, phosphite, thiocyanate, methosulfate, iodide, borate, glycinate, glutamate, ethylenediaminetetraacetate, orthoethylidenediphosphonate were used as a counterion. The preparations were obtained and tested similarly to example 1. For comparison, analog preparations were used [CuETU2] + HCOO-, "Zerox", copper hydroxide "Coside 2000" (tables 5-7).

[0052] In all cases, the effectiveness of the obtained preparations in relation to the tested strains was higher than the effectiveness of analog preparations, which indicates the achievement of the stated technical result.

[0053] Table 5. Codes of the declared preparations - mixtures of complex compounds of copper (I) and silver - and analogues; K сu and K Ag — complexing agent, respectively, of copper (I) and silver; P сu and P Ag - counterion in a complex compound of copper (I) and silver, respectively; Cu:Ag - the ratio of copper and silver by weight

[0054] Table 6. Comparison of bactericidal activity of CFU against Erwinia atroseptica of preparations - mixtures of complex compounds of copper (I) and silver - and analogues

[0055] Table 7. Comparison of fungicidal activity - the ratio of colony diameters on the medium with the addition of the preparation and in the control, % - in relation to Sderotinia sclerotiorum preparations - mixtures of complex compounds of copper (I) and silver - and analogues Example group 2

[0056] In group 2 of examples, mixed complex compounds of copper (I) and silver with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethylenethiourea, or N,N'-bis(dimethylaminomethyl)thiourea were used as a fungicidal or bactericidal preparation; succinate, malate, citrate, lactate, formate, acetate, salicylate, phosphate, phosphite, thiocyanate, methosulfate, iodide, borate, glycinate, glutamate, ethylenediaminetetraacetate, orthoethylidenediphosphonate with a copper:silver molar ratio of 3:1, 1:1, 1:3 were used as a counterion. The preparations were obtained and tested similarly to example 2. For comparison, analog preparations were used [CuETU2]+ HCOO-, "Zerox", copper hydroxide "Coside 2000" (tables 8-10).

[0057] In all cases, the effectiveness of the obtained preparations in relation to the tested strains was higher than the effectiveness of analog preparations, which indicates the achievement of the stated technical result.

[0058] Table 8. Codes of the declared preparations of mixed complex compounds of copper (I) and silver - and analogues; Cu:Ag - molar ratio of copper and silver

[0059] Sample code complexing agent, counterion Cu:Ag

[0060] P-10 thiourea, nitrate 3:1

[0061] P-11 methylthiourea, acetate 1:1

[0062] P-12 M,1Ch'-dimethylthiourea, phosphite 1:3

[0063] P-13 ethylthiourea, succinate 3:1

[0064] P-14 1H,1\G-diethylthiourea, citrate 1:1

[0065] P-15 ethylenethiourea, lactate 1:3

[0066] P-16 1M,M'-bis(dimethylamino-methyl)thiourea, salicylate 1:1

[0067] Table 9. Comparison of the bactericidal activity of CFU against Erwinia atroseptica of preparations - mixed complex compounds of copper (I) and silver - and analogues

[0068] Table 10. Comparison of fungicidal activity - the ratio of colony diameters on the medium with the addition of the preparation and in the control, % - in relation to Sclerotinia sclerotiorum preparations - mixed complex compounds of copper (I) and silver - and analogues

Claims

CLAUSE OF INVENTION 1. A fungicidal or bactericidal preparation comprising at least one complex compound of copper (I) with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethylenethiourea, or N,N'-bis(dimethylaminomethyl)thiourea, characterized in that it additionally comprises at least one complex compound of silver with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, OR N,N'-DIETHYLTHIOUREA, or ethylenethiourea, or N,N'-bis(dimethylaminomethyl)thiourea.

2. A fungicidal or bactericidal preparation according to paragraph 1, characterized in that the ratio of copper and silver by weight in the preparation is from 50:1 to 1:

10.

3. A fungicidal or bactericidal preparation according to claim 1, characterized in that the counterion in the copper (I) or silver complex compound is selected from the group consisting of succinate, malate, citrate, lactate, formate, acetate, salicylate, phosphate, phosphite, thiocyanate, methosulfate, monocarboxylic acids with an alkyl saturated or unsaturated radical containing from 8 to 18 carbon atoms, iodide, alkyl phosphonates, borate, glycinate, glutamate, ethylenediaminetetraacetate, orthoethylidenediphosphonate.

4. A fungicidal or bactericidal preparation according to paragraph 1, characterized in that it can be used in the cultivation of plants, including spring and winter grain and leguminous crops, open and protected ground vegetables, trees and shrubs, fruits, berries, essential oil, garden, ornamental, melons, row crops, industrial and forage crops.

5. A fungicidal or bactericidal preparation comprising at least one mixed complex compound of copper (I) and silver with thiourea or methylthiourea, or N,N'-dimethylthiourea, or ethylthiourea, or N,N'-diethylthiourea, or ethylenethiourea, or N,N'-bis(dimethylaminomethyl)thiourea.

6. A fungicidal or bactericidal preparation according to paragraph 5, characterized in that it can be used in the cultivation of plants, including spring and winter grains and legumes, vegetables in open and protected ground, trees and shrubs, fruits, berries, essential oil plants, garden plants, ornamental plants, melons, row crops, industrial and forage crops.

7. A fungicidal or bactericidal preparation according to claim 5, characterized in that the counterion in the mixed complex compound of copper (I) and silver is selected from the group consisting of succinate, malate, citrate, lactate, formate, acetate, salicylate, phosphate, phosphite, thiocyanate, methosulfate, monocarboxylic acids with an alkyl saturated or unsaturated radical containing from 8 to 18 carbon atoms, iodide, alkyl phosphonates, borate, glycinate, glutamate, ethylenediaminetetraacetate, orthoethylidenediphosphonate.

8. A method for using a fungicide or bactericide according to any of paragraphs 1 to 7 in growing plants, in which plant seeds or vegetative plants are treated with a solution that includes, respectively, a fungicide or bactericide.

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