Synergistic fungicidal composition

Abstract

To provide a novel fungicidal composition showing broader activity and synergistic effect.SOLUTION: The present invention provides a synergistic fungicidal composition. The synergistic fungicidal composition comprises a strobilurin-based compound, validamycin, and a compound A selected from the group comprising thifluzamide, hexaconazole, propiconazole, tricyclazole and difenoconazole.SELECTED DRAWING: None

Description

Detailed Description of the Invention

[0001] FIELD OF THEINVENTION The present invention relates to a synergistic fungicidal composition. More particularly, the present invention relates to a synergistic fungicidal composition comprising a strobilurin compound, validamycin, and a compound A selected from the group comprising thifluzamide, hexaconazole, propiconazole, tricyclazole and difenoconazole. The present invention also relates to a method for preparing such a composition.

[0002] BACKGROUND OF THEINVENTION Various compositions have been developed to control fungi, and are actually used as single agents or mixtures.Actual agricultural experience shows that the repeated and exclusive application of individual active compounds in the control of harmful fungi often leads to the rapid selection of fungal strains that naturally or adaptively develop resistance to the active compounds in question.Effective control of these fungi with the active compounds in question is very difficult in such cases.

[0003] European Patent Application No. 1872658A1 provides a composition for preventing harmful organisms, the composition comprising a diamine derivative represented by formula (1):

[0004] [ka]

[0005] In the formula, R1 represents a hydrocarbon having 1 to 6 carbon atoms substituted with halogen or the like, R2 and R7 each independently represent a hydrogen atom, a hydrocarbon having 1 to 6 carbon atoms, or the like, R3 and R4 each independently represent a hydrogen atom, a hydrocarbon having 1 to 6 carbon atoms which may be substituted, or R3 and R4 each independently represent a cycloalkyl group having 3 to 6 carbon atoms bonded thereto, R5 and R6 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or the like, and R8 represents an arylalkyl group which may be substituted, an aryl group which may be substituted, or a heteroaryl group which may be substituted. The composition further comprises, as an active ingredient, one or more compounds selected from the group consisting of other fungicides, insecticides, and acaricides.

[0006] WO2008075454 provides compositions comprising a compound of formula 1 or 5 in combination with an insecticide.

[0007] [ka]

[0008] In formulas (1) and (5), A1, A2, A3 and A4 each represent a carbon atom, a nitrogen atom or a nitrogen oxide atom, R1 and R2 each independently represent a hydrogen atom, a C1-C4 alkyl group or a C1-C4 alkylcarbonyl group, G1 and G2 each independently represent an oxygen atom or a sulfur atom, and X may be the same or different and represents a hydrogen atom, a halogen atom, a C1-C3 alkyl group or a trifluoromethyl group. This provides a long list of insecticides including metominostrobilurin, validamycin, tricyclazole, hexaconazole, propiconazole or thifluzamide.

[0009] EP 2094087 relates to insecticidal compositions comprising an anthranilamide compound or a salt thereof and other insecticides and / or fungicides.

[0010] In order to reduce the risk of selection of resistant strains, today, mixtures of various active compounds are commonly used to control harmful fungi.By combining active compounds with different mechanisms of action, it is possible to ensure good control over a relatively long period of time.

[0011] Therefore, there is a need to develop new fungicidal compositions that exhibit broader activity and synergistic effects to avoid or control the development of resistant strains to active ingredients or mixtures of known active ingredients used by farmers, while minimizing the amount of chemicals dispersed in the environment and reducing the cost of treatment. There is also a need for synergistic compositions that are physicochemically compatible formulations in the form of storage-stable, safely packaged, ready-to-use formulations.

[0012] Summary of the Invention The inventors of the present invention have surprisingly found that a composition comprising a strobilurin compound, validamycin and a compound A selected from the group comprising thifluzamide, hexaconazole, propiconazole, tricyclazole and difenoconazole provides an enhanced synergistic fungicidal effect.

[0013] Thus, the present invention provides a synergistic composition comprising a strobilurin compound, validamycin, compound A selected from the group comprising thifluzamide, hexaconazole, propiconazole, tricyclazole and difenoconazole, and at least one excipient.

[0014] In one embodiment, the composition of the invention comprises a strobilurin compound in an amount of 0.1-20% w / w, validamycin in an amount of 0.1-12% w / w, and compound A in an amount of 0.1-35% w / w.

[0015] In another embodiment, the composition of the invention comprises a strobilurin compound selected from the group comprising azoxystrobin, dimoxystrobin, enstrobulin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin and enstrobulin.

[0016] In one preferred embodiment, the strobilurin compound in the composition of the invention is metominostrobin.

[0017] In one embodiment of the invention, when compound A is thifluzamide, the amount of thifluzamide present in the composition is 5-14% w / w. In an alternative embodiment of the invention, when compound A is hexaconazole, the amount of hexaconazole present in the composition is 0.1-10% w / w. In an alternative embodiment of the invention, when compound A is propiconazole, the amount of propiconazole present in the composition is 8-15% w / w. In an alternative embodiment of the invention, when compound A is tricyclazole, the amount of tricyclazole present in the composition is 15-30% w / w. In an alternative embodiment of the invention, when compound A is difenoconazole, the amount of difenoconazole present in the composition is 5-10% w / w.

[0018] In yet another embodiment, the composition of the present invention comprises: a) metominostrobin, validamycin, thifluzamide and at least one excipient; b) metominostrobin, validamycin, hexaconazole and at least one excipient; c) metominostrobin, validamycin, propiconazole and at least one excipient; d) metominostrobin, validamycin, tricyclazole and at least one excipient, or e) metominostrobin, validamycin, difenoconazole and at least one excipient; It is one of the following.

[0019] In one embodiment, the composition of the present invention comprises: a) metominostrobin present in an amount of 1-20% w / w, validamycin present in an amount of 0.1-12% w / w, thifluzamide present in an amount of 5-14% w / w, and at least one excipient; or b) metominostrobin present in an amount of 1-20% w / w, validamycin present in an amount of 0.1-12% w / w, hexaconazole present in an amount of 0.1-10% w / w, and at least one excipient; It is one of the following.

[0020] In another embodiment, the composition of the present invention comprises: a) metominostrobin present in an amount of 10% w / w, validamycin present in an amount of 6% w / w, thifluzamide present in an amount of 9% w / w, and at least one excipient; or b) metominostrobin present in an amount of 10% w / w, validamycin present in an amount of 6% w / w, hexaconazole present in an amount of 5% w / w, and at least one excipient; It is one of the following.

[0021] In another embodiment, the composition is a capsule suspension (CS), a dispersible concentrate (DC), a dustable powder (DP), a powder for dry seed treatment (DS), an emulsifiable concentrate (EC), an emulsifiable granule (EG), an emulsion water-in-oil (EO), an emulsifiable powder (EP), an emulsion for seed treatment (ES), an oil-in-water emulsion (EW), a flowable concentrate for seed treatment (FS), a granule (GR), a micro-emulsion (ME), an oil-dispersion (OD), an oil miscible flowable concentrate (OS ... concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (ST), Ultra-low volume (ULV) suspension, Tablet (TB), Ultra-low volume (ULV) liquidThey are formulated as water dispersible liquids, water dispersible granules (WG), wettable powders (WP), water dispersible powder for slurry seed treatment (WS), water dispersible tablets (WT), a mixed formulation of CS and SC (ZC), a mixed formulation of CS and SE (ZE), a mixed formulation of CS and EW (ZW).

[0022] In a preferred embodiment, the compositions of the present invention are formulated as suspension concentrates.

[0023] In one embodiment, the composition of the present invention comprises at least one excipient selected from the group comprising dispersants, wetting agents, antifreeze agents, antifoam agents, biocides and thickeners.

[0024] In yet another embodiment, the dispersing agent is selected from the group including, but not limited to, tristyrylphenol phosphate ethoxylated amine salts, acrylic copolymers, graft copolymers, and combinations thereof, and is present in an amount of 2-10% w / w.

[0025] In another embodiment, the wetting agent is selected from the group including, but not limited to, ethoxylated polyarylphenol phosphate esters, dioctyl sulfosuccinates, non-ionic ethoxylates, and combinations thereof, and is present in an amount of 1-5% w / w.

[0026] In one embodiment, the cryoprotectant is selected from the group including, but not limited to, propylene glycol, diethylene glycol, monoethylene glycol, and combinations thereof, and is present in an amount of 2-10% w / w.

[0027] In another embodiment, the antifoam agent is a dimethylpolysiloxane emulsion and is present in an amount of 0.01-0.5% w / w.

[0028] In another embodiment, the biocide is selected from the group including, but not limited to, 1,2-benzisothiazolin-3-one in 20% dipropylene glycol in water, formaldehyde, and combinations thereof, and is present in an amount of 0.01-0.50% w / w.

[0029] In another embodiment, the thickening agent is xanthan gum and is present in an amount of 0.01-0.50% w / w.

[0030] In another embodiment, the present invention provides a method for producing a synergistic fungicidal composition comprising the steps of mixing a strobilurin compound, validamycin, compound A selected from the group comprising thifluzamide, hexaconazole, propiconazole, tricyclazole and difenoconazole, and at least one excipient.

[0031] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1. Flow chart for preparing a synergistic fungicidal composition containing metominostrobin, validamycin and thifluzamide in the form of a suspension concentrate.

[0032] FIG. 2. Flow chart for preparing a synergistic fungicidal composition comprising metominostrobin, validamycin and hexaconazole in the form of a suspension concentrate.

[0033] Detailed Description of the Invention Several representative embodiments of the present invention are described below. The present invention, in its broader aspects, is not limited to the specific details and representative methods. Illustrative examples are described in this section in connection with the embodiments and methods provided. The present invention according to its various aspects is particularly pointed out and distinctly claimed in the appended claims in view of this specification and appropriate equivalents.

[0034] It should be noted that, as used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing "a compound" includes a mixture of two or more compounds. Also, the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0035] The expression of various amounts in the terms "% w / w" or "%" means percent by weight based on the weight of the total solution or composition, unless otherwise specified.

[0036] The term "active ingredient" (ai) or "active agent" as used herein refers to the component of the composition that is responsible for controlling insects or pests.

[0037] Strobilurins are a group of compounds used as fungicides in agriculture. Strobilurins are part of a larger group of quinone external inhibitors (QoIs), which act to inhibit the respiratory chain at the level of complex III. Strobilurins have an inhibitory effect on other fungi, reducing their competitors for nutrients. Strobilurins inhibit electron transport in mitochondria, disrupting metabolism and preventing the growth of target fungi. Some of the strobilurins are azoxystrobin, kresoxim-methyl, picoxystrobin, fluoxastrobin, oryzatrobin, dimoxystrobin, pyraclostrobin, trifloxystrobin, cumoxystrobin, enoxastrobin, flufenoxystrobin, mandestrobin, fenaminostrobin and metominostrobin.

[0038] Metominostrobin (IUPAC name: (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide) acts by inhibiting the cytochrome pathway between cytochrome b and cytochrome c1 at the site of ubiquinol oxidation. Metominostrobin is used on rice to control Pyricuaria oryzae.

[0039] Validamycin (IUPAC name: (1R,2R,3S,4S,6R)-2,3-dihydroxy-6-hydroxymethyl-4-[(1S,4R,5S,6S)-4,5,6-trihydroxy-3-hydroxymethylcyclohex-2-enylamino]cyclohexyl-β-D-glucopyranoside) is a non-systemic antibiotic with bacteriostatic activity. Validamycin causes abnormal branching of the tips of the pathogen and subsequently arrest of further development. Validamycin inhibits trehalase, the enzyme that mediates the digestion of the carbohydrate trehalose and the transport of glucose to the hyphal tips. Validamycin controls the fungus Rhizoctonia solani in rice, potato, vegetables, strawberry, tobacco, ginger and other crops, and damping-off disease in cotton, rice, sugar beet, etc.

[0040] Thifluzamide (IUPAC name: 2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4-trifluoromethyl-1,3-thiazole-5-carboxanilide) is a fungicide commonly used to control basidiomycetes on rice, potato, corn, and amenity grass. Thifluzamide inhibits succinate dehydrogenase (complex II) in the tricarboxylic acid cycle.

[0041] Hexaconazole (IUPAC name: (RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol) is a systemic fungicide with protective and curative action. Hexaconazole inhibits the biosynthesis of ergosterol (sterol demethylation inhibitor). Hexaconazole controls many fungi, especially ascomycetes and basidiomycetes, in apple, vine, coffee, peanut, banana, cucumber, pepper and other crops.

[0042] Propiconazole ((IUPAC name: 2RS,4RS;2RS,4SR)-1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole) is a systemic foliar fungicide with preventive and curative action, which translocates favorably into the xylem. Propiconazole is used on cereals, bananas, rice, coffee, peanuts, stone fruits and corn for the control of a wide variety of fungal species by acting as a sterol demethylation (ergosterol biosynthesis) inhibitor.

[0043] Tricyclazole (IUPAC name: 5-methyl-1,2,4-triazolo[3,4-b][1,3]benzothiazole) is a systemic fungicide that is rapidly absorbed by roots and leaves and translocated to the xylem and apoplast within the plant. Tricyclazole is a melanin biosynthesis inhibitor (reduction of 1,3,8-trihydroxynaphthalene and bermellone). Tricyclazole controls rice shoot borer in transplanted and direct-sown rice.

[0044] Difenoconazole (IUPAC name: 3-chloro-4-[(2RS,4RS;2RS,4SR)-4-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxolan-2-yl]phenyl 4-chlorophenyl ether) is a systemic fungicide with preventive and curative action. Difenoconazole is absorbed by the leaves with acropetal and strong translaminar translocation. Difenoconazole provides long-lasting preventive and curative activity against saccharomycetes, basidiomycetes and imperfect fungi by inhibition of sterol demethylation and inhibition of cell membrane ergosterol biosynthesis, resulting in the cessation of development of said fungi. Difenoconazole is used against disease complexes in grapes, pome fruits, stone fruits, potatoes, sugar beets, oilseed rape, bananas, cereals, rice, soybeans, ornamental plants and vegetable crops.

[0045] The present invention provides a synergistic fungicidal composition comprising a strobilurin compound, validamycin, compound A selected from the group comprising thifluzamide, hexaconazole, propiconazole, tricyclazole and difenoconazole, and at least one excipient.

[0046] In one embodiment, the composition according to the present invention comprises a strobilurin compound in an amount of 0.1 to 20% w / w, validamycin in an amount of 0.1 to 12% w / w, and compound A in an amount of 0.1 to 35% w / w.

[0047] Non-limiting examples of strobilurin compounds according to the present invention may include azoxystrobin, dimoxystrobin, enstrobulin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin and enstrobulin. In a preferred embodiment, the strobilurin compound is metominostrobin.

[0048] In one embodiment of the invention, when compound A is thifluzamide, the amount of thifluzamide present in the composition is 5-14% w / w. In an alternative embodiment of the invention, when compound A is hexaconazole, the amount of hexaconazole present in the composition is 0.1-10% w / w. In an alternative embodiment of the invention, when compound A is propiconazole, the amount of propiconazole present in the composition is 8-15% w / w. In an alternative embodiment of the invention, when compound A is tricyclazole, the amount of tricyclazole present in the composition is 15-30% w / w. In an alternative embodiment of the invention, when compound A is difenoconazole, the amount of difenoconazole present in the composition is 5-10% w / w.

[0049] Non-limiting examples of suitable compositions according to the present invention may include mixtures of: a) metominostrobin, validamycin, thifluzamide and at least one excipient; b) metominostrobin, validamycin, hexaconazole and at least one excipient; c) metominostrobin, validamycin, propiconazole and at least one excipient; d) metominostrobin, validamycin, tricyclazole and at least one excipient, or e) metominostrobin, validamycin, difenoconazole and at least one excipient.

[0050] A preferred example of a suitable composition according to the invention may be the following mixture: a) metominostrobin present in an amount of 1-20% w / w, validamycin present in an amount of 0.1-12% w / w, thifluzamide present in an amount of 5-14% w / w, and at least one excipient; or b) metominostrobin present in an amount of 1-20% w / w, validamycin present in an amount of 0.1-12% w / w, hexaconazole present in an amount of 0.1-10% w / w, and at least one excipient.

[0051] In a most preferred embodiment, the synergistic fungicidal composition comprises metominostrobin in an amount of 10% w / w, validamycin in an amount of 6% w / w, thifluzamide in an amount of 9% w / w, and at least one excipient.

[0052] In another most preferred embodiment, the synergistic fungicidal composition comprises metominostrobin in an amount of 10% w / w, validamycin in an amount of 6% w / w, hexaconazole in an amount of 5% w / w, and at least one excipient.

[0053] In one embodiment, the ratio of metominostrobin:(validamycin+thifluzamide) is 1:1 to 1:2. In a preferred embodiment, the ratio between validamycin and thifluzamide is 1:1 to 1:2.

[0054] In another embodiment, the ratio of metominostrobin:(validamycin + hexaconazole is 1:0.5 to 1:2. In a preferred embodiment, the ratio between validamycin and hexaconazole is 0.5:1 to 1.5:1.

[0055] In yet another embodiment, the synergistic composition of the present invention is a capsule suspension (CS), a dispersible concentrate (DC), a dustable powder (DP), a powder for dry seed treatment (DS), an emulsifiable concentrate (EC), an emulsifiable granule (EG), an emulsion water-in-oil (EO), an emulsifiable powder (EP), an emulsion for seed treatment (ES), an emulsion for seed treatment (E ... treatment (ES), Emulsion oil-in-water (EW), Flowable concentrate for seed treatment (FS), Granules (GR), Micro-emulsion (ME), Oil-dispersion (OD), Oil miscible flowable concentrate (OF), Oil miscible liquid (OL), Oil dispersible powder (OP), Suspension concentrate (SC), Suspension concentrate for direct application (SD), Suspo-emulsion (SE), Water soluble granule (SG), Soluble concentrate (SL), Spreading oil (SO), Water soluble powder (SP), Water soluble tablet (Water soluble tablet (ST), ULV-suspension (Ultra-low volume (ULV) suspension), tablet (TB), ULV-liquid (Ultra-low volume (ULV) liquid), Water dispersible granules (WG), Wettable powder (WP), Water dispersible powder for slurry seed treatment (WS), Water dispersible tablet (WT), A mixed formulation of CS and SC (ZC), A mixed formulation of CS and SE (ZC), It can be formulated as a mixed formulation of CS and SE (ZE) and a mixed formulation of CS and EW (ZW).

[0056] In a preferred embodiment, the compositions of the present invention are formulated as suspension concentrates (SC). As used herein, the term "suspension concentrate" refers to a suspension of active ingredients and excipients in a small volume of liquid, usually water.

[0057] Generally, solid particles in a liquid are observed to naturally aggregate to form clumps. Therefore, it is recommended to add a dispersant that prevents the aggregation of the solid particles and keeps them suspended in the fluid. Thus, the composition of the present invention contains a dispersant such as tristyrylphenol ethoxylated amine salt phosphate, acrylic copolymer, graft copolymer, naphthalene sulphonate of formaldehyde condensate, acrylic copolymer, lignin-based sulphonate, etc. In the synergistic composition of the present invention, one or more dispersants can be used. The dispersant is present in an amount of 2-10% w / w.

[0058] Wetting is the first stage of dispersion, where the air surrounding the granular composition is replaced by water. If the surface tension of the liquid is very high, wetting of the composition by water cannot occur. Therefore, it is recommended to add a wetting agent to the composition to facilitate the dispersion process of the granules in the liquid. Non-limiting examples of wetting agents that can be used in the present invention include ethoxylated polyarylphenol phosphate esters, dioctyl sulphosuccinate, nonionic ethoxylates, dioctyl sulfosuccinate, sodium lauryl sulfate, and naphthalene alkylaryl sulfonates. In the alkylaryl sulfonates, the alkyl group contains about 1 to 5 carbon atoms and the aryl nucleus is selected from the group consisting of benzene and naphthalene. One or more wetting agents can be used in the synergistic composition of the present invention. The wetting agent is present in an amount of 1 to 5% w / w.

[0059] To prevent the aqueous composition from freezing, a cryoprotectant is generally added to the composition. Suitable cryoprotectants useful herein include, but are not limited to, propylene glycol, diethylene glycol, monoethylene glycol, and combinations thereof. Preferably, the cryoprotectant is present in an amount of 2-10% w / w.

[0060] Defoamers are also called antifoaming agents. Defoamers are generally added to compositions because foam formation prevents efficient filling of containers. Preferably, the defoamer is a polydimethylsiloxane emulsion. In the compositions of the present invention, the defoamer is present in an amount of 0.01-0.5% w / w.

[0061] The synergistic germicidal composition includes a biocide selected from the group consisting of 1,2-benzisothiazolin-3-one in 20% dipropylene glycol, formaldehyde, and combinations thereof, present in an amount of 0.01-0.50% w / w. The biocide is added to the composition of the present invention for protection against spoilage from bacteria, yeasts, and fungi.

[0062] The addition of a thickening agent to the composition is necessary to reduce the tendency of the composition to disperse when sprayed and to reduce the likelihood of it being rinsed off the crop. Preferably, the synergistic fungicidal composition contains xanthan gum as a thickening agent in an amount of 0.01-0.50% w / w. The xanthan gum used in the present invention is obtained from commercial sources.

[0063] The compositions of the present invention may further comprise additional ingredients such as surfactants, agriculturally acceptable supports, carriers or fillers, protective colloids, adhesives, thixotropic agents, penetrating agents, stabilizers, sequestering agents, and the like.

[0064] In one embodiment, the invention provides a method for preparing a synergistic fungicidal composition, the method comprising the steps of mixing a strobilurin compound, validamycin, a compound selected from the group comprising thifluzamide, hexaconazole, propiconazole, tricyclazole or difenoconazole, and at least one excipient.

[0065] In another embodiment, the present invention provides a method for preparing a synergistic germicidal composition in the form of a suspension concentrate. The method includes diluting a dispersant and a wetting agent in deionized water and solubilizing them by high shear mixing to obtain a solution. The active ingredient, antifreeze agent, antifoam agent, and biocide are added to the solution and mixed to obtain a homogenous mass. The mass is then ground in a mill to obtain an average particle size of less than 5 microns. An aqueous solution of a thickener is added to the ground mass under low agitation to obtain the synergistic germicidal composition of the present invention in the form of a suspension concentrate.

[0066] The synergistic compositions of the present invention have been found to be effective in controlling a wide range of fungal diseases, such as, for example, budworm (neck and leaf), sheath blight, and bacterial leaf blight in paddy fields. The synergistic compositions are also effective in controlling mildew, early and late blight, rot in fruits and vegetables, cereals and other crops.

[0067] The inventors have surprisingly found that the compositions of the present invention are synergistic in nature.The synergistic compositions of the present invention are more effective than their individual counterparts or when two active substances are incorporated together.The synergistic compositions of the present invention can also use significantly less active ingredients compared to their individual counterparts.This allows the application rate of each of these active ingredients to be substantially reduced while maintaining good efficacy.The reduction in application rate reduces the processing cost to farmers and also reduces the environmental burden from both waste generation and chemical residues that protect crops.

[0068] The synergistic fungicidal compositions of the present invention provide broad spectrum control of fungi, delay the emergence of resistant strains, minimize the risk of resistance development, and achieve effective and economical control of undesirable fungi.

[0069] The synergistic compositions of the present invention provide many other advantages, -Improved efficacy over the study period compared with other formulations tested; Economically beneficial for farmers as it reduces the number of sprays and improves crop yields; -Reduces the risk to farmers from occupational exposure due to reduced frequency of spraying; Storage stable, Non-phytotoxic, -Environmentally friendly.

[0070] Since numerous modifications and variations within the scope of the invention will be apparent to those skilled in the art, embodiments of the invention are more particularly described in the following examples, which are intended as illustrations only. Unless otherwise specified, all parts, percentages and ratios reported in the following examples are by weight, and all reagents used in the examples were obtained or are available from chemical suppliers.

[0071] [Example] A synergistic fungicidal composition of the present invention in the form of a suspension concentrate containing metominostrobin, validamycin and thifluzamide is shown in Table 1. The units of each component of the composition are expressed as "% w / w", that is, as a weight percentage based on the weight of the entire solution or composition.

[0072] [Table 1]

[0073] Table 2 provides the amount of active ingredients and raw materials charged to produce the synergistic composition of the present invention in SC form. The active ingredients are technical grade. The entries for the active ingredients in Table 2 are different from those in Table 1 because the entries in Table 1 are for 100% pure compounds, while the entries in Table 2 are for technical ones with a certain percentage of impurities. Thus, 10% w / w metominostrobin, 6% w / w validamycin and 9% w / w thifluzamide of 100% purity in Table 1 correspond to 10.10 g of metominostrobin of 99% purity, 9.38 g of validamycin of 64% purity and 9.47 g of thifluzamide of 95% purity in Table 2.

[0074] [Table 2]

[0075] Example 1: Method for preparing a synergistic insecticidal composition in the form of a suspension concentrate (SC) containing metominostrobin, validamycin and thifluzamide All ingredients were weighed as per Table 2. Graft copolymer (5 g) and nonionic ethoxylate (3 g) were diluted with deionized water and solubilized by high shear mixing. Propylene glycol (4 g), metominostrobin (10.10 g), validamycin (9.38 g) and thifluzamide (9.47 g), dimethylpolysiloxane emulsion (0.15 g), 1,2-benzisothiazolin-3-one 20% in dipropylene glycol (0.20 g) were then added and mixed to obtain a homogenous mass. The homogenous mass was milled in a bead mill. Milling was continued until an average particle size of less than 5 (D-90) microns was obtained. After milling, a 2% aqueous solution of xanthan gum was added under low agitation to obtain the title fungicidal composition.

[0076] [Table 3]

[0077] Table 4 provides the amount of active ingredient and raw materials charged to produce the synergistic composition of the present invention in SC form. The active ingredient is technical grade. The entries for the active ingredient in Table 4 are different from the entries in Table 3 because the entries in Table 3 are for compounds with 100% purity, while the entries in Table 4 are for technical ones with a certain percentage of impurities. Thus, 10% w / w metominostrobin with 100% purity, 6% w / w validamycin and 5% w / w hexaconazole in Table 3 correspond to 10.10 g of 99% pure metominostrobin, 9.38 g of 64% pure validamycin and 5.44 g of 92% pure hexaconazole in Table 4.

[0078] [Table 4]

[0079] Example 2: Method for preparing a synergistic insecticidal composition in the form of a suspension concentrate (SC) containing metominostrobin, validamycin and hexaconazole All ingredients were weighed as per Table 4. Graft copolymer (5 g) and nonionic ethoxylate (3 g) were diluted with deionized water and solubilized by high shear mixing. Propylene glycol (5 g), metominostrobin (10.10 g), validamycin (9.38 g) and hexaconazole (5.44 g), dimethylpolysiloxane emulsion (0.12 g), 1,2-benzisothiazolin-3-one 20% in dipropylene glycol (0.20 g) were then added and mixed to obtain a homogenous mass. The homogenous mass was milled in a bead mill. Milling was continued until an average particle size of less than 5 (D-90) microns was obtained. After milling, a 2% aqueous solution of xanthan gum was added under low agitation to obtain the title fungicidal composition.

[0080] [Evaluation of the synergistic effect of the disinfectant composition of the present invention] A synergistic effect exists whenever the action of a combination of active ingredients is greater than the sum of the actions of the individual ingredients. Synergistic effects were calculated using the method of Colby, Weeds, vol. 15, No. 1 (Jan. 1967), pp. 20-2.

[0081] The expected synergistic effect for a given combination of two active ingredients can be calculated as follows:

[0082]

number

[0083] The expected synergistic effect for a given combination of three active ingredients can be calculated as follows:

[0084]

number

[0085] During the ceremony, E represents the expected percentage of fungicidal control for a combination of three fungicides at defined doses (e.g., equal to x, y, and z, respectively); X is the percentage of fungicidal control observed by compound (I) at a defined dose (equal to x); Y is the percentage of fungicidal control observed by compound (II) at a defined dose (equal to y); Z is the percentage of fungicidal control observed by compound (III) at a defined dose (equal to z).

[0086] Synergy exists when the rate of fungicidal control observed for a combination is greater than the expected rate.

[0087]

number

[0088] [Greenhouse experiment on synergistic effects] To evaluate synergistic effects, test plants (paddy rice seedlings) are grown in a greenhouse. Seedlings are transplanted into trays measuring 1 mts x 0.5 mts and grown for one week before application of the test compound. Test plants are inoculated with shoots (neck and leaves), sheath blight, and bacterial leaf blight. Treated plants are maintained at 21°C to 28°C in the greenhouse for the duration of the experiment.

[0089] Test compounds were weighed out according to the treatment details provided in Tables 5 and 6. Required amount of sample is diluted with demineralized water. Mixtures are prepared within 0.5 h before spraying. Test compounds are applied as foliar spray applications 6 days after inoculation. For each treatment, each of four trays is sprayed in a spray chamber with approximately 20 ml of spray wash. After drying, plants are returned to the greenhouse and maintained at 20°C-25°C. Treated plants are evaluated for disease control compared to controls (untreated plants).

[0090] The percentage of infected leaf area is estimated for three separate leaves per pot. The % disease control for each treatment is determined using the formula shown below.

[0091]

number

[0092] For all combinations, the expected % control is calculated using the Colby formula above.

[0093] Tables 5 and 6 summarize the synergistic effects of the compositions of the present invention, namely Metominostrobin 10% + Validamycin 6% + Thifluzamide 9% SC and Metominostrobin 10% + Validamycin 6% + Hexaconazole 5% SC.

[0094] [Table 5] JPEG2025041943000012.jpg197169

[0095] [Table 6] JPEG2025041943000014.jpg149169

[0096] From Tables 5 and 6 it is clear that the fungicidal compositions of the present invention (Metominostrobin 10% + Validamycin 6% + Thifluzamide 9% SC and Metominostrobin 10% + Validamycin 6% + Hexaconazole 5% SC) have a synergistic effect.

[0097] Biological effectiveness of the antiseptic composition of the present invention Experimental details Field trials were conducted in paddy fields to evaluate the control of diseases, namely leaf and neck blast, sheath blight, and bacterial leaf blight, using metominostrobin, validamycin, thifluzamide, and hexaconazole alone, in binary mixtures (tank mix), and in ternary mixtures as foliar applications. The ternary mixtures were prepared as described in Examples 1 and 2. The formulations metominostrobin 20% SC, validamycin 3% L, thifluzamide 24% SC, and hexaconazole 5% SC were diluted with water to the specified concentrations of active compounds. Treatment details are given in the second column of Tables 7 and 8.

[0098] The experiment was designed in a randomized block design (RBD) with four replications. The plot size was 25 square meters. All recommended agricultural practices were followed throughout the cropping period. Application was done using a domestic sprayer fitted with a pressure regulator and hollow cone nozzle. The application rate was 500 l / ha for all tests. Various fungicide compositions listed in Tables 7 and 8 were sprayed on paddy fields to evaluate the control of leaf and neck shoots, sheath blight, and bacterial leaf blight. Based on the various doses, weighed amounts of the test articles were dissolved in 1.25 liters of water per treatment and sprayed evenly twice at 15 days interval. After each application, the disease incidence (PDI) per hill was evaluated 14 days after application (DAA) on 10 hills per plot. The average of the percentage disease index (PDI) after two applications was recorded and is shown in the table below. The yield was also recorded.

[0099] [Table 7] JPEG2025041943000016.jpg30169

[0100] [Table 8] JPEG2025041943000018.jpg30169

[0101] [Phytotoxic Effects] In the above field test, phytotoxicity was evaluated for the synergistic composition of the present invention. In the phytotoxicity evaluation in paddy field, the following observations were made by observing temporary or long-term damage of leaves, i.e. leaf damage at the tip and leaf surface, withering, vein removal, necrosis, epigastric growth and hypogastric growth, after 3, 5, 7 and 14 DAS of the synergistic fungicidal composition of the present invention. The average scores are shown in the table. Crop damage was observed with a visual rating of 1 to 10 grades as shown in Table 9. Table 10 shows the phytotoxicity effect of the synergistic composition of the present invention in paddy field.

[0102] [Table 9]

[0103] [Table 10]

[0104] The synergistic fungicidal composition of the present invention provided better control of fungal diseases compared to the reference product. Furthermore, the use of the synergistic fungicidal composition resulted in better crop condition, i.e., fresh green leaves, and no phytotoxic symptoms in the plants.

[0105] From the foregoing, it will be appreciated that numerous modifications and variations may be made without departing from the true spirit and scope of the novel concept of the present invention. It should be understood that no limitation with respect to the specific embodiments described is intended or should be inferred. All such modifications and improvements have been omitted from this specification for brevity and readability, but are understood to be appropriate within the scope of the following claims. [Brief description of the drawings]

[0106] [Figure 1] 1 is a flow chart for preparing a synergistic fungicidal composition comprising metominostrobin, validamycin and thifluzamide in the form of a suspension concentrate. [Diagram 2] 1 is a flow chart for preparing a synergistic fungicidal composition comprising metominostrobin, validamycin and hexaconazole in the form of a suspension concentrate.

Claims

[Claim 1] a) comprising metominostrobin present in an amount of 1-20% w / w, validamycin present in an amount of 0.1-12% w / w, thifluzamide present in an amount of 5-14% w / w, and at least one excipient, wherein the ratio of metominostrobin:(validamycin+thifluzamide) is 1:1 to 1:2, and the ratio between validamycin and thifluzamide is 1:1 to 1:2, or b) metominostrobin present in an amount of 1-20% w / w, validamycin present in an amount of 0.1-12% w / w, hexaconazole present in an amount of 0.1-10% w / w, and at least one excipient, wherein the ratio of metominostrobin:(validamycin+hexaconazole) is 1:0.5-1:2 and the ratio between validamycin and hexaconazole is 0.5:1-1.5:1; A synergistic fungicidal composition characterized by being used on rice seedlings.

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