DESC:FIELD OF THE INVENTION
The present invention relates to a stable agrochemical composition and in particular a stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph and at least one triazole fungicide. The present invention also relates to the process for the preparation of synergistic fungicidal composition thereof and use of this combination for combating plant pathogenic fungi in and on the seeds and plants at different growth stages of crop for protection and good yields.
BACKGROUND OF THE INVENTION
Crop protection is the practice of protecting the crop yields from pests, weeds, plant diseases, and other organisms that damage agricultural crops, which is critical from early stages of crop development. Preventing pests and diseases in the entire crop cycle, i.e., from root development to maturing crops, leads to increased crop quality and yield. The control of plant diseases caused by fungi is extremely important in achieving high crop efficiency. Fungicides help to minimize this damage by controlling plant pathogenic fungi. The use of two or more appropriate active ingredient combinations in specific dose ratios leads to synergism in crop protection. In addition to this, often highly destructive plant diseases can be difficult to control and may develop resistance to commercial fungicides. Many products are commercially available for these purposes, but there is still a continues need to develop new fungicidal combinations which are more effective, less costly, less toxic, environmentally safer and have different sites of action.
The biggest challenge in the field of crop protection is to reduce the dosage rate of active ingredients to diminish or circumvent environmental or toxicological effects without compromising on effective crop protection against pathogenic fungi, in addition to long lasting and broad-spectrum protection from plant diseases. Another challenge is to reduce the excessive application of solo chemical compounds or insecticides which invariably help in rapid selection of pathogenic fungi and aid in developing natural or adapted resistance against the active compound in question.
Therefore, it is indeed necessary to use the fungicidal combination in lower doses, fast acting with the different modes of action that can provide long lasting control against broad spectrum of pathogenic fungi and check the resistance development in fungi. The composition should have high synergistic action, no cross resistance to existing fungicides, avoid excess loading of the toxicant to the environment and negligible impact to environmental safety. Thus, there is a need for synergistic fungicidal combinations which could be physico-compatible formulations in the form of storage stability, safe packaging and ready to use formulations.
Dimethomorph is a systemic fungicide known chemically as (EZ)-4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloyl]morpholine. It exhibits protective and curative activity against fungal pathogens, particularly those belonging to the Oomycete class. Dimethomorph is widely employed in agricultural practices for the control of diseases such as downy mildew and root rot, caused by organisms like Pythium and Phytophthora species. Its mode of action involves the inhibition of cell wall biosynthesis in target pathogens, leading to disrupted fungal growth and development.
Flusilazole is a systemic fungicide belonging to the triazole class of compounds. Chemically, it is known as 1-[bis(4-fluorophenyl)methyl]-1H-1,2,4-triazole-3-thiol. Flusilazole acts by inhibiting the biosynthesis of ergosterol, an essential component of fungal cell membranes. This disruption compromises membrane integrity, leading to the inhibition of fungal growth and reproduction. Flusilazole is primarily used for the control of a broad spectrum of fungal diseases in crops such as cereals, fruits, and vegetables. It is effective against pathogens responsible for powdery mildew, leaf spots, rusts, and blights. Due to its systemic properties, Flusilazole is absorbed by plant tissues and provides protective and curative action.
Myclobutanil is a systemic fungicide belonging to the triazole class of compounds. Chemically, it is described as (RS)-2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-ylmethyl)hexanenitrile. Myclobutanil functions as a demethylation inhibitor (DMI) by targeting the C14-demethylase enzyme involved in the biosynthesis of ergosterol, a critical component of fungal cell membranes. Due to its mode of action, Myclobutanil disrupts fungal growth and reproduction, offering both preventive and curative activity. It is widely used to control a broad range of fungal diseases including powdery mildew, rusts, scabs, and leaf spots on crops such as grapes, apples, cereals, and ornamental plants. Its systemic action allows for prolonged residual control, and it is particularly valued for its effectiveness in Integrated Pest Management (IPM) programs where resistance management is crucial.
Furthermore, in agrochemical applications, liquid concentrate compositions, are sometimes preferred over other types of formulations due to ease of making and using. Concentrated compositions have grown in popularity due to various benefits such as being free from dust, which may cause health hazard to people exposed to it during manufacturing as well as at the end user level. Concentrated compositions can be conveniently diluted to bigger volumes during application without involving sophisticated machinery before final use. Concentrated compositions such as Suspension Concentrate (SC) and Flowable Liquids (FL) are dispersion of an insoluble solid into a liquid carrier.
Although compositions containing mixtures of two or more fungicides in suspension concentrates have been practiced in the art, problems such as suspensibility, physical instability of such mixtures during manufacture, shelf life at dilution or at the time of application as well as long-term instability can adversely impact the efficacy associated with the fungicidal composition.
Thus, there remains a need for development of stable fungicidal compositions in suspension concentrate formulations, which address the challenges and also do not affect the efficacy associated with the fungicidal compositions.

OBJECTS OF THE INVENTION
It is a primary objective of the present invention to provide a stable agrochemical formulation.
It is another objective of the present invention to provide a stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph and at least one triazole fungicide.
It is another objective of the present invention to provide stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph, at least one triazole fungicide and at least one dispersing agent.
It is another objective of the present invention to provide a process for preparation of a stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph and at least one triazole fungicide.
SUMMARY OF THE INVENTION:
In one aspect, the present invention provides a stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph and at least one triazole fungicide.
In another aspect, the present invention to provide a process for preparation of a stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph and at least one triazole fungicide.
DETAILED DESCRIPTION OF THE INVENTION
The present invention / specification refers to a synergistic fungicidal composition and the process for the preparation for crop protection.
The term “combination” can be replaced with the words “mixture” or “composition” or “formulation” defined or refers to as combining two or more active ingredients formulated in desired formulations.
The expression of various quantities in terms of “% w/w” or “%” means the percentage by weight, relative to the weight of the total solution or composition unless otherwise specified.
The term “pesticide” as used in this specification refers to a substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest or weeds which causes damage to the crop. Herbicides, insecticides, and fungicides are mainly used as pesticides which control weeds and insect pests and disease-causing pathogens respectively that eventually leads to high yield of crops.
The term “fungicide” also called Antimycotic, as used in this specification refers to a type of chemical compound or substance specifically designed to protect crops and kill or inhibit the growth of fungi and their spores that cause economic damage to crop, ornamental plants or endanger the health of domestic animals or humans.
The term “synergism” as used in this specification refers to the interaction between two or more active compounds or other factors to produce a combined effect greater than the sum of their separate effects. The present invention involves the mixture of three active ingredients which has increased efficacy when compared to individual use and admixture of those components.
The conventional fungicides have poor activity, limited to certain insects, and are not satisfactorily maintained for prolonged periods. Even though some fungicides may bear satisfactory fungicidal effects, they require improvements in respect of environment and health safety and are also required to achieve high insecticidal effect at a smaller dosage and lack resistance management.
We found that this objective in part or complete can be achieved by the combination of active compounds defined at the outset. Thus, the present inventors have intensively studied to solve these problems and found that by combining fungicidal composition having carboxylic acid amides (CAA) and triazole fungicide in different formulation and percentages have astonishing effects in controlling the growth of fungi and by reducing the amount of dosage than in a case of using an active compound alone.
Therefore, the present invention provides a novel synergistic fungicidal composition with carboxylic acid amides (CAA) and triazole fungicide and purpose thereof. The synergy of this fungicidal composition having dimethomorph and myclobutanil with dual mode of action of sterol mainly ergo sterol biosynthesis pathway inhibition by demethylation and disruption of fungal cell wall biogenesis can generate efficient synergism and can enable broad spectrum satisfactory disease control from soil borne, seed borne and foliar plant diseases for prolonged period of time at lower dose, powered by preventive, curative and systemic activity, rain fastness, vapour activity and phyto-tonic effect.
Dimethomorph, a cinnamic acid derivative, is a member of the morpholine group of fungicides and carboxylic acid amides (CAA) fungicide group that consists of a mixture of the E and Z isomers in approximately equal proportions. Its mode of action is through the disruption of fungal cell wall biogenesis. CAA compounds are directly linked to the inhibition of cellulose synthesis in Oomycetes. CAA fungicides are grouped in the MoA Group H (cell wall biosynthesis inhibitors) with the target site code H5 (cellulose synthase inhibitors).
Triazole fungicides (TFs) are systemic fungicides that work by inhibiting the biosynthesis of sterols specifically ergosterol, which is a vital component of the fungal cell membrane. This inhibition disrupts the cell membrane structure by demethylation that acts as sterol demethylation inhibitor (DMI fungicide), leading to the death of the fungus. It is a broad spectrum systemic and effective fungicide that will translocate into new growth with curative, preventative and protective effects against a wide range of plant pathogenic fungi. It is used in several crops and ornamental plants to control diseases like rust, powdery mildew, canker etc. caused by fungi.
This combination has the broadest spectrum of all antifungal treatment and shows its effectiveness against different classes of fungi mainly the ascomycota, deuteromycota, basidiomycota and oomycota. It controls many diseases in plants which include leaf spots, rusts, powdery mildew, downy mildew, net blotch and blight. It is registered as systemic fungicide for use in tomato, grape, cucumber, wheat, barley, oats, rye, soya, cotton, rice, strawberry, peas, beans, onions and many other vegetables and ornamental plants.
The synergistic fungicidal composition of the present invention controls wide verity of fungi including Ascomycota, Deuteromycota, Basidiomycota and the Oomycota on a wide variety of crops.
The synergistic fungicidal composition of the present invention is also used in seed treatment to protect against diseases which impair good seed germination and seedling development.
The synergistic fungicidal composition of the present invention controls many diseases in plants which include anthracnose, leaf spot, dollar spot, rusts, scab, powdery mildew, downy mildew, net blotch, blight, summer patch, brown patch and rot.
In an embodiment, the present invention provides a stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph and at least one triazole fungicide.
According to an embodiment of the present invention, triazole fungicide is selected from the group comprising myclobutanil, flusilazole, hexaconazole, tebuconazole, propiconazole, mefentrifluconazole or combinations thereof.
In an embodiment, the present invention provides a stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph and flusilazole.
In an embodiment, the present invention provides a stable synergistic fungicidal Suspension Concentrate formulation comprising dimethomorph and myclobutanil.
In an embodiment, the present invention provides a stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph and mefentrifluconazole.
In an embodiment, the present invention provides a stable synergistic fungicidal suspension concentrate formulation comprising dimethomorph and propiconazole.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises from about 5% to about 50% of dimethomorph, based on total weight of the stable composition.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises from about 15% to about 40% of dimethomorph, based on total weight of the stable composition.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises 37.5% of dimethomorph, based on total weight of the stable composition.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises 32.5% of dimethomorph, based on total weight of the stable composition.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises from about 0.5% to about 25% of triazole fungicide, based on total weight of the stable composition.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises from about 0.5% to about 10% of triazole fungicide, based on total weight of the stable composition.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises about 3.75% of triazole fungicide, based on total weight of the stable composition.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises about 3.25% of triazole fungicide, based on total weight of the stable composition.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises about 3.75% of flusilazole, based on total weight of the stable composition.
According to an embodiment of the present invention, the stable synergistic fungicidal composition comprises about 3.25% of myclobutanil, based on total weight of the stable composition.
According to a preferred embodiment, the present invention provides a fungicidal SC formulation comprising:
dimethomorph,
at least one triazole fungicide,
at least one dispersing agent; and
at least one agrochemically acceptable excipient.
According to a preferred embodiment, the present invention provides a fungicidal SC formulation comprising dimethomorph, at least one at least one triazole fungicide and at least one dispersing agent, wherein the triazole fungicide is flusilazole.
According to a preferred embodiment, the present invention provides a fungicidal SC formulation comprising dimethomorph, at least one at least one triazole fungicide and at least one dispersing agent, wherein the triazole fungicide is myclobutanil.
According to an embodiment of the disclosure, the fungicidal SC formulation comprising comprises dimethomorph, flusilazole, and at least one dispersing agent, wherein dimethomorph and flusilazole are present in a weight ratio of about 1:10 to about 10:1.
According to an embodiment of the disclosure, the fungicidal SC formulation comprising comprises dimethomorph, myclobutanil, and at least one dispersing agent, wherein dimethomorph and myclobutanil are present in a weight ratio of about 1:10 to about 10:1.
According to a preferred embodiment, the present invention provides a fungicidal SC formulation comprising:
dimethomorph from about 35 to 40%;
Flusilazole from about 3 to 4.5%;
at least one dispersing agent; and
at least one agrochemically acceptable excipient.
According to a preferred embodiment, the present invention provides a fungicidal SC formulation comprising:
dimethomorph from about 30- 40%;
Myclobutanil from about 2 - 4%;
at least one dispersing agent; and
at least one agrochemically acceptable excipient.
According to a preferred embodiment, the present invention provides a fungicidal SC formulation comprising dimethomorph, flusilazole and at least one dispersing agent.
According to a preferred embodiment, the present invention provides a fungicidal SC formulation comprising dimethomorph, myclobutanil and at least one dispersing agent.
According to an embodiment of the present invention, the dispersing agents comprise non-ionic dispersing agents/surfactants. Non-ionic surfactants may be selected from the group comprising fatty acid glycol ester surfactants, polyalkoxylated triglyceride surfactants, alkoxylated fatty alcohol surfactants, and sorbitan fatty acid ester surfactants, polyalkoxylated alkylphenol surfactants, polyalkoxylated alkarylphenol surfactants, amine oxide surfactants, alkanolamide surfactants, glycoside surfactants, fatty alcohol ethoxylate, ethylene oxide / propylene oxide (EO / PO) block copolymers (for example, non-ionic polyalkylene glycol ether, polyalkylene oxide block copolymer, low foaming block copolymers, alkyl EO / PO copolymer., non-ionic EO / PO block copolymer), or combinations thereof.
In a preferred embodiment, the dispersing agent is selected from Acrylic copolymer solution (graft comb polymer; Atlox 4913), fatty alcohol ethoxylate, ethylene oxide/propylene oxide (EO / PO) block copolymer, or combinations thereof.
According to one embodiment of the present invention, the dispersing agent is incorporated in the SC formulation to prevent agglomeration and settling of the active ingredients. This ensures consistent dosing, enhances shelf stability, and improves the applicability of the formulation in field conditions.
In another embodiment, the dispersing agent aids in achieving better wettability and re-dispersibility of the formulation upon dilution with water. This is particularly beneficial in ensuring that the active compounds dimethomorph and the triazole fungicide are evenly distributed during spraying. The dispersing agents also act as particle size regulators, preventing crystal growth during formulation or storage and improving its bioavailability by maintaining it in a fine particle suspension, enhancing foliar uptake and fungicidal action.
In an embodiment of the present invention, the fungicidal SC formulation comprising comprises from about 0.1% w/w to about 50% w/w of the dispersing agents, based on total weight of the agrochemical composition.
In an embodiment of the present invention, the fungicidal SC formulation comprising comprises from about 0.1% w/w to about 30% w/w of the dispersing agents, based on total weight of the agrochemical composition.
In an embodiment of the present invention, the fungicidal SC formulation comprising comprises from about 0.1% w/w to about 20% w/w of the dispersing agents, based on total weight of the agrochemical composition.
According to a preferred embodiment, the present invention provides a fungicidal SC formulation comprising:
dimethomorph;
at least one triazole fungicide;
at least one dispersing agent; and
at least one agrochemically acceptable excipient. Wherein, the agrochemically acceptable excipient is selected from the group comprising emulsifier(s), colorant(s), thickener(s)/binder(s), antifreeze agent(s), anti-foaming agent(s), antioxidant(s), solvent(s), preservative(s), glidant(s), anticaking agent(s), pH regulating agent(s), buffering agent(s), formulation aid(s), disintegrant(s), or combinations thereof.
According to an embodiment of the present invention, agrochemically acceptable excipients are selected from the group comprising emulsifier(s), colorant(s), thickener(s)/binder(s), antifreeze agent(s), anti-foaming agent(s), antioxidant(s), solvent(s), preservative(s), glidant(s), anticaking agent(s), pH regulating agent(s), buffering agent(s), formulation aid(s), disintegrant(s), or combinations thereof..
In another embodiment, emulsifier(s) which can be advantageously employed herein can be readily determined by those skilled in the art and include various nonionic, anionic, cationic, and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of non-ionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts.
Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble salts or sulfated polyglycol ethers, appropriate salts of phosphated polyglycol ether, or combinations thereof.
In an embodiment, colorant(s) may be selected from iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace elements, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc, or combinations thereof.
In an embodiment, thickener(s) or gelling agent(s) may be selected from but not limited to molasses, granulated sugar, alginates, karaya gum, jaguar gum, tragacanth gum, polysaccharide gum, mucilage, xanthan gum, or combinations thereof.
In another embodiment, the binder(s) may be selected from silicates such as magnesium aluminium silicate, polyvinyl acetates, polyvinyl acetate copolymers, polyvinyl alcohols, polyvinyl alcohol copolymers, celluloses, including ethylcelluloses and methylcelluloses, hydroxymethyl celluloses, hydroxypropylcelluloses, hydroxymethylpropyl-celluloses, polyvinylpyrolidones, dextrins, malto-dextrins, polysaccharides, fats, oils, proteins, gum arabics, shellacs, vinylidene chloride, vinylidene chloride copolymers, calcium lignosulfonates, acrylic copolymers, starches, polyvinylacrylates, zeins, gelatin, carboxymethylcellulose, chitosan, polyethylene oxide, acrylimide polymers and copolymers, polyhydroxyethyl acrylate, methylacrylimide monomers, alginate, ethylcellulose, polychloroprene and syrups or mixtures thereof; polymers and copolymers of vinyl acetate, methyl cellulose, vinylidene chloride, acrylic, cellulose, polyvinylpyrrolidone and polysaccharide; polymers and copolymers of vinylidene chloride and vinyl acetate-ethylene copolymers; combinations of polyvinyl alcohol and sucrose; plasticizers such as glycerol, propylene glycol, polyglycols, or combinations thereof.
In another embodiment, antifreeze agent(s) added to the composition may be alcohols selected from the group comprising but not limited to ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-propylenediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 3-methyl-1,5pentanediol, 2,3-dimethyl-2,3-butanediol, trimethylol propane, mannitol, sorbitol, glycerol, pentaerythritol, 1,4-cyclohexanedimethanol, xylenol, bisphenols such as bisphenol A or the like. In addition, ether alcohols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyoxyethylene or polyoxypropylene glycols of molecular weight up to about 4000, diethylene glycol monomethylether, diethylene glycol monoethylether, triethylene glycol monomethylether, butoxyethanol, butylene glycol monobutylether, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, heptaglycerol, octaglycerol, or combinations thereof.
According to an embodiment, anti-foaming agent(s) may be selected from silicone defoamers, polydimethoxysiloxane, polydimethylsiloxane, alkyl poly acrylates, castor oil, fatty acids, fatty acids esters, fatty acids sulfate, fatty alcohol, fatty alcohol esters, fatty alcohol sulfate, foot olive oil, mono & di glyceride, paraffin oil, paraffin wax, poly propylene glycol, silicones oil, vegetable fats, vegetable fats sulfate, vegetable oil, vegetable oil sulfate, vegetable wax, vegetable wax sulfate, agents based on silicon or magnesium stearate, or combinations thereof.
The present invention may further include a rheology modifier. The preferred rheology modifier includes xanthan gum, Palygorskite and clay, which may be present in an amount of about 0.01% to about 3% by weight of the formulation.
In an embodiment, thickener(s) or gelling agent(s) may be selected from but not limited to molasses, xanthan gum (Rhodopol G), granulated sugar, alginates, karaya gum, jaguar gum, tragacanth gum, polysaccharide gum, mucilage, or combinations thereof.
The formulations according to the present invention may additionally comprise a biocide selected from Preservatives/biocide used may be benzothiazoles, benzisothiazolinone (Proxel GXL) or phonols, 2-bromo-2-nitropropane-1,3-diol (Bioban BP 30), 5-chloro-2-methyl-4- isothiazolin-3-one & 2 methyl-4-isothiazolin -3 one (Kathon CG/ICP), which may be present in an amount of about 0.01% to about 3% by weight of the formulation..
According to an embodiment, Wetting agents that can be added to the agrochemical formulation of the present invention include, but are not limited to: Oxirane, 2-methyl-, polymer with oxirane, block (Atlas G 5000), polyarylalkoxylated phosphate esters and their potassium salts (e.g., Soprophor FLK, Stepfac TSP PE- K. Other suitable wetting agents include sodium dioctylsulfosuccinates (e.g., Geropon SDS, Aerosol OT) and ethoxylated alcohols (e.g., Trideth-6; Rhodasurf BC 610; Tersperse 4894).
According to an embodiment, examples of suitable solvent(s)/inert carrier(s) are water, vegetable oils, or derivatives. In principle, solvent mixtures may also be used.
The agrochemical composition may also comprise one or more antioxidant(s). Preferably, agrochemical formulation comprises an antioxidant. Antioxidants are, for example, amino acids (e.g., glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazole and imidazole derivatives (e.g., urocanic acid), peptides, such as, for example, D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g., anserine), carotenoids, carotenes (e.g., alpha- carotene, beta- carotene, lycopene) and derivatives thereof, lipoic acid and derivatives thereof (e.g., dihydrolipoic acid), aurothioglucose, propylthiouracil and further thio compounds (e.g., thioglycerol, thiosorbitol, thioglycolic acid, thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl cholesteryl and glyceryl esters thereof), and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nueotides, nucleosides and salts), and sulfoximine compounds (e.g., buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine) in very low tolerated doses (e.g., pmol/kg to pmol/kg), also metal chelating agents (e.g., I-hydroxy fatty acids, EDTA, EGTA, phytic acid, acids (e.g., citric acid, lactic acid, malic acid), humic acids, bile extracts, gallic esters (e.g., propyl, octyl and dodecyl gallate), flavonoids, catechins, bilirubin, biliverdin and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g., ?-linolenic acid, linoleic acid, arachidonic acid, oleic acid), folic acid and derivatives thereof, hydroquinone and derivatives thereof (e.g., arbutin), ubiquinone and ubiquinol, and derivatives thereof, vitamin C and derivatives thereof (e.g., ascorbyl palmitate, stearate, dipalmitate, acetate, Mg ascorbyl phosphates, sodium and magnesium ascorbate, disodium ascorbyl phosphate and sulfate, potassium ascorbyl tocopheryl phosphate, chitosan ascorbate), isoascorbic acid and derivatives thereof, tocopherols and derivatives thereof (e.g., tocopheryl acetate, linoleate, oleate and succinate, tocophereth-5, tohereth-10, tocophereth-12, tocophereth-18, tocophereth-50, tocophersolan), vitamin A and derivatives (e.g., vitamin A palmitate), the coniferyl benzoate of benzoin resin, rutin, rutinic acid and derivatives thereof, disodium rutinyl disulfate, cinnamic acid and derivatives thereof (e.g., ferulic acid, ethyl ferulate, caffeeic acid), kojic acid, chitosan glycolate and salicylate, butylhydroxytoluene, buhydroxyanisol, nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, selenium and selenium derivatives (e.g., selenomethionine), stilbenes and stilbene derivatives (e.g., stilbene oxide, trans-stilbene oxide). According to the disclosure, suitable derivatives (salts, esters, sugars, nucleotides, nuosides, peptides, and lipids) and mixtures of these specified active ingredients or plant extracts (e.g., tea tree oil, rosemary extract and rosemarinic acid) which comprise these antioxidants can be used. In general, mixtures of the afore-mentioned antioxidants are possible.
In another embodiment of the present invention provides a synergistic fungicidal composition comprising: a) dimethomorph, b) at least one triazole fungicide, c) Dispersing agent, d) Antifreezing agent, e) Wetting agent, f) Antifoaming agent, g) Anticaking agent, h) Solvent / Diluent i) Thickening agent, j) Rheology modifier and k) Biocide / antibacterial agent; wherein, the triazole fungicide is selected from myclobutanil or flusilazole.
In another preferred embodiment of the present invention provides a synergistic fungicidal composition comprising: a) Dimethomorph, b) at least one triazole fungicide, c) Acrylic copolymer (graft comb polymer) d) Palygorskite, e) Benzisothiazolinone, f) Silicone defoamers, g) Propylene glycol, h) Atlas G 5000, i) Xanthan gum, j) Distilled water; wherein, the triazole fungicide is selected from myclobutanil or flusilazole.
In yet another preferred embodiment of the present invention provides a synergistic fungicidal composition comprising: a) Dimethomorph 36-40%, b) at least one triazole fungicide 2.5-4.5, c) Acrylic copolymer (graft comb polymer) 2-6 d) Palygorskite 0.20-0.70, e) Benzisothiazolinone 0.01-0.025, f) Silicone defoamers 0.30-0.70, g) Propylene glycol 4-9, h) Atlas G 5000 2-6, i) Xanthan gum 4-8 and j) Distilled water Q.S of the fungicidal composition ; wherein, the triazole fungicide is selected from myclobutanil or flusilazole.
In another embodiment, alternative or multiple embodiments of the disclosure disclosed herein are not to be construed as limitations. Each embodiment can be referred to and claimed individually or in any combination with other embodiments of the disclosure. One or more embodiments of the disclosure can be included in, or deleted from, the disclosure for reasons of convenience and/or patentability.
The disclosure will now be described in more details with reference to the following examples. While the foregoing written description of the disclosure enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate the existence of variations, combinations, and equivalents of the specific embodiment, method, and examples herein. The disclosure should therefore not be limited by the above-described embodiment, method, and following examples, but by all embodiments and methods within the scope and spirit of the disclosure.

EXAMPLES:
Example 1: Suspension Concentrate (SC) formulation of Dimethomorph and Flusilazole
Ingredients Quantity (% w/w)
Dimethomorph 35 - 40
Flusilazole 3 - 4.5
Acrylic copolymer
(graft comb polymer) 2 - 6
Palygorskite 0.20 - 0.70
Benzisothiazolinone 0.01- 0.25
silica 0 - 0.25
Silicone defoamers 0.30 - 0.70
Propylene glycol 4 – 9
Atlas G 5000 2 – 6
Xanthan gum 4 – 8
Distilled water Q. S
Total 100
Example 2: Suspension concentrate (SC) formulation of Dimethomorph and Myclobutanil
Ingredients Quantity (% w/w)
Dimethomorph 30- 40
Myclobutanil 2 - 4
Propylene glycol 5 - 9
Atlas G 5000 02 - 06
Acrylic copolymer
(graft comb polymer) 02 - 06
benzisothiazolinone 0.01 - 0.2
silica 0 - 0.25
Silicone defoamers 0.1 5 - 0.60
Palygorskite 0.20 - 0.80
Xanthan gum Q. S
DW water Q. S
Total 100

Process:
Premix slurry preparation: Charge required quantity of Propylene Glycol. Under continue stirring charge required quantity of the defoamer followed by required quantity of Palygorskite clay, dispersing & wetting agent. After homogenizing the above solution add required quantity of DM water slowly. After homogenizing the above solution, add lot wise required quantity of dimethomorph and myclobutanil.
Wet milling: The resulting premix slurry was subjected to a wet milling process. The milling was performed under controlled conditions, with the slurry temperature maintained below 25°C. Milling was continued until the average particle size (D90) of the active ingredients was reduced to less than 10 µm, as determined by laser diffraction particle size analysis.
Gel preparation: In a separate clean vessel, Propylene Glycol and benzisothiazolinone (BIT) were mixed. To this mixture, xanthan gum was added slowly under high-speed stirring to ensure uniform dispersion. The gum mixture was then transferred into DM water, pre-warmed to a temperature not exceeding 50°C, and stirred continuously until complete hydration and gel formation was achieved.
Finished good preparation: In a separate clean reactor, the milled slurry from Step 2 was charged and agitation was started. To this slurry, 1.0 part by weight of hydrophobic fumed silica was added and mixed until a uniform dispersion was obtained. Finally, a calculated quantity of the 2% xanthan gum gel prepared in Step 3 was added gradually under stirring to achieve the desired rheological properties and viscosity suitable for suspension concentrate formulations. The final formulation was homogenized and filled into containers for storage and field evaluation.

Example 3: Stability study data of Suspension concentrate (SC) formulation of Dimethomorph and Flusilazole.
A stability study of the present composition was performed at ambient as well as accelerated heat conditions and the results are tabulated in Table 1.
Table 1: Stability Study Data
S.No Parameters Specification Ambient Temperature AHS-14 Days
1 Appearance White to off white coloured suspension free from any visible extraneous matter White coloured suspension free from any visible extraneous matter
2 Active Content (g/L)
a) dimethomorph
b) Flusilazole
235-265 g/L
188-212 g/L
261.5
261.5
261.5
261.5
3 Suspensibility
(%, gravimetric) 70.0 (Minimum) 98.05 92.67
4 pH (1% aqueous suspension) 5 – 8 7.10 6.80
5 Specific gravity @20°C 1.18 ± 0.02 1.1882 1.1879
6 Persistence Foam Maximum 60 mL Foam in Water D after 1 minute Nil Nil
7 Wet Sieve passing through 200 BSS test sieve (%w/w) Minimum 98% w/w of formulation should pass through 75micron sieve Complies Complies
8 Particle Size Distribution (PSD D-50: 3-5 microns D-90 <12 microns D-99 <25 microns 3.88
8.62
17.37 4.05
10.4
17.7
9 Stability at 0°C Sample should comply with the Wet Sieve Test, after storage at 0°C for 7 days Complies NA
10 Spontaneity of Dispersion (% a.i. Minimum 80% w/w of a.i.in suspension after 5 min. water D at 30 ± 2°C 89.22 87.57
NA=Not Applicable
The composition of the present invention was evaluated for various physicochemical parameters. It was observed that the composition comprising dimethomorph and flusilazole resulted in >90% suspensibility at ambient as well as AHS temperatures.
Example 4: Stability study data of Suspension concentrate (SC) formulation of Dimethomorph and Myclobutanil. A stability study of the present composition was performed at ambient as well as accelerated heat conditions and the results are tabulated in Table 2.
Table 2: Stability Study Data
S.No Parameters Specification Ambient Temperature AHS-14 Days
1 Appearance White to off white coloured suspension free from any visible extraneous matter White coloured suspension free from any visible extraneous matter
2 Active Content (g/L)
a) dimethomorph
b) Myclobutanil
235-265 g/L
188-212 g/L
261.5
261.5
261.5
261.5
3 Suspensibility
(%, gravimetric) 70.0 (Minimum) 98.05 92.67
4 pH (1% aqueous suspension) 5 – 8 7.10 6.80
5 Specific gravity @20°C 1.18 ± 0.02 1.1882 1.1879
6 Persistence Foam Maximum 60 mL Foam in Water D after 1 minute Nil Nil
7 Wet Sieve passing through 200 BSS test sieve (%w/w) Minimum 98% w/w of formulation should pass through 75micron sieve Complies Complies
8 Particle Size Distribution (PSD D-50: 3-5 microns D-90 <12 microns D-99 <25 microns 3.88
8.62
17.37 4.05
10.4
17.7
9 Stability at 0°C Sample should comply to Wet Sieve Test, after storage at 0°C for 7 days Complies NA
10 Spontaneity of Dispersion (% a.i.) Minimum 80% w/w of a.i.in suspension after 5 min. water D at 30 ± 2°C 89.22 87.57
The composition of the present invention was evaluated for various physicochemical parameters. It was observed that the composition comprising dimethomorph and Myclobutanil resulted in >90% suspensibility at ambient as well as AHS temperatures.
Example – 5: Bio-efficacy Study
The said combinations of Dimethomorph (Dimethomorph + Myclobutanil, Dimethomorph + Flusilazole) have been evaluated among various pathogens of different crops. The fungicidal combination has been tested at three different doses levels viz., low, medium, and high, the same solo molecules as individual treatments and current competitive market standards were taken into note and the efficacy of all the molecules are evaluated and compared. The treatment details are mentioned in Table 1 along with the pathogen against which were tested.
Crops Tomato
Grape
Cucumber
Irrigated / Rainfed Irrigated
Design RBD
No. of treatments 12
No. of replications 3
Plot size 5 m x 5 m
No. of Sprays
Spray interval Three sprays
10 days
Water volume 500 l/ha
Equipment used Knapsack sprayer
Table 3. Treatment Details
Treatment Dose (ml or gm / Ha)
Dimethomorph 37.5% + Flusilazole 3.75% 1000
Dimethomorph 37.5% + Flusilazole 3.75% 1250
Dimethomorph 37.5% + Flusilazole 3.75% 1500
Dimethomorph 32.5% + Myclobutanil 3.25% 996
Dimethomorph 32.5% + Myclobutanil 3.25% 1245
Dimethomorph 32.5% +Myclobutanil 3.25% 1494
Dimethomorph 50% WP 1000
Flusilazole 40% EC 120
Myclobutanil 10% WP 200
Ametoctradin 27% + Dimethomorph 20.27% w/w SC 1000
Dimethomorph 12% + Pyraclostrobin 6.7% WG 1250
Untreated Check -
Method of Observations:
Disease observations: select 5 random plants in the plot and the disease symptoms are scored based on disease rating scale and then the percentage disease index will be calculated.
The observations were taken 1 day before spraying and at 10 Days after spraying.
Take the observation on the crop safety of the fungicide i.e., Phytotoxicity / softener observation of fungicide after application at 5 and 10 Days after application.
Parameters of Observations:
The disease severity is measured by an index, measured as Percent disease index (PDI) will be calculated by using following formula:
PDI = (Sum of all disease ratings)/(Total no.of leaves x Maximum disease grade) x 100
The percent reduction is calculated by the following formula:
% Reduction = ( PDI in control plot-PDI in treated plot )/(PDI in control plot)× 100
Colby’s Method: The combined effect of Pesticidal combinations is the sum of their individual effects. Colby’s method is an approach to evaluate the synergistic, additive, or antagonistic effects due to the interactions of two pesticides as a combination.
Colby’s method calculates expected response, and a ratio is calculated between expected response and observed response.
The formula for expected response is as follows-
E = (A+B)-((A*B)/100)
A represents pesticide A and B represents pesticide 2.
The observed response is the actual percent control achieved.
Colby’s ratio = Observed response (O) / Expected response (E).
If the ratio is,
< 1 = Antagonistic effect
= Additive effect
> 1 = Synergistic effect
The effect of these fungicides in combination and alone when applied on crops were assessed based on the yield (quintal per hectare). This parameter defines the crop quality.
Statistical Analysis:
The observations recorded are statistically analysed using RBD design in ANOVA and presented in the result tables.
Results:
The fungicide combinations of Dimethomorph (Dimethomorph 37.5% + Flusilazole 3.75%, Dimethomorph 32.5% + Myclobutanil 3.25%) were effective against wide range of diseases, so the different diseases controlled in different crops in the field experiments were enlisted below,
Tomato: Late Blight (Phytophthora infestans), Powdery Mildew (Leveillula taurica / Oidiopsis neolycopersici); Grape: Downy Mildew (Plasmopara viticola); Cucumber: Powdery Mildew (Erysiphe cichoracearum)

Tomato - Late Blight:
Table 4. Efficacy of Fungicide Dimethomorph Combinations against Late Blight Disease Incidence on Tomato Crop
Treatments Dose (g or ml / ha) Percent Disease Incidence % Reduction in PDI after 3 Sprays Colby’s Ratio
Pre 1 2 3
Dimethomorph 37.5% + Flusilazole 3.75% 1000 5.30 (13.30) 0.00
(0.00) 0.59
(3.60) 1.07
(5.94) 93.96 1.11
Dimethomorph 37.5% + Flusilazole 3.75% 1250 5.40
(13.43) 0.00
(0.00) 0.00
(0.00) 0.55
(3.46) 96.92 1.15
Dimethomorph 37.5% + Flusilazole 3.75% 1500 5.20
(13.18) 0.00
(0.00) 0.00
(0.00) 0.22
(1.56) 98.74 1.17
Dimethomorph 32.5% + Myclobutanil 3.25% 996 5.43
(13.47) 0.00
(0.00) 0.33
(1.91) 1.12
(6.06) 93.71 1.13
Dimethomorph 32.5% + Myclobutanil 3.25% 1245 5.23
(13.22) 0.00
(0.00) 0.00
(0.00) 0.66
(3.81) 96.29 1.16
Dimethomorph 32.5% + Myclobutanil 3.25% 1494 5.17
(13.13) 0.00
(0.00) 0.00
(0.00) 0.17
(1.35) 99.06 1.19
Dimethomorph 50% WP 1000 5.27
(13.26) 4.69
(12.51) 5.55
(13.62) 7.31
(15.68) 58.84 -
Flusilazole 40% EC 120 5.30
(13.30) 4.88
(12.76) 5.12
(13.07) 6.65
(14.94) 62.57 -
Myclobutanil 10% WP 200 5.23
(13.22) 5.13
(13.09) 5.04
(12.96) 7.30
(15.67) 58.91 -
Ametoctradin 27% + Dimethomorph 20.27% w/w SC 1000 5.40
(13.43) 4.04
(11.59) 4.44
(12.16) 5.03
(12.96) 71.67 -
Dimethomorph 12% + Pyraclostrobin 6.7% WG 1250 5.33
(13.34) 3.93
(11.43) 3.93
(11.43) 4.53
(12.28) 74.50 -
Untreated Check - 5.40
(13.43) 9.40
(17.85) 13.34
(21.41) 17.77
(24.92) 0.00 -
SE(m) ± 0.162 0.068 0.75 2.81 - -
CD NS 0.199 2.21 0.95 - -
Figures in parenthesis are arc sine transformed values
The efficacy of dimethomorph combinations against Phytophthora infestans (late blight) in tomato crops was assessed through percent disease incidence (PDI) measured pre-treatment and after three successive sprays (Table 2).
The results we can conclude that the fungicidal combination is highly effective against late blight in tomato when applied in combination than when applied alone. The results significantly varied among treatments; the pre-treatments data indicated that there has been no significant difference in PDI among the treatments. At the end of the last spray i.e., Third spray the treatments of Dimethomorph combinations of highest dose persisted in recording lowest PDI such as Dimethomorph 37.5% + Flusilazole 3.75% @ 1500 ml/ha with 0.22% and Dimethomorph 32.5% + Myclobutanil 3.25% @ 1494 ml/ha with 0.17% respectively. This was followed by Dimethomorph 37.5% + Flusilazole 3.75% @ 1250ml/ha with 0.55% and Dimethomorph 32.5% + Myclobutanil 3.25% @ 1245 ml/ha with 0.66% which were at par with each other. The results indicate that all the three doses of Dimethomorph 37.5% + Flusilazole 3.75% and Dimethomorph 32.5% + Myclobutanil 3.25% recorded low PDI at the end of three sprays while the market standards recorded viz., Ametoctradin 2% + Dimethomorph 20.27% SC @ 1000 ml/ha and Dimethomorph 12% + Pyraclostrobin 6.7% WG @ 1290 gm/ha recorded 5.03% and 4.53% PDI respectively. The highest PDI was recorded in Untreated check with 17.77% PDI.
The percent reduction in disease in comparison with control and Colby’s Ratio indicated that >95% control was recorded in the highest doses of Dimethomorph 37.5% + Flusilazole 3.75% with 98.74% control, 1.17 Colby’s Ratio and Dimethomorph 32.5% + Myclobutanil 3.25% with 99.06% control with 1.19 as Colby’s Ratio. As for the solo molecules i.e., Dimethomorph 50% WP @ 1000 g/ha, Flusilazole 40% EC @ 120ml/ha and Myclobutanil 10% WP @ 200 gm/ha recorded 77.86%, 70.98% and 69.74% reduction in control respectively. For both combinations, higher doses (1500 and 1494 ml/ha) resulted in near-complete disease control (PDI = 0.66%), outperforming lower doses. All dimethomorph combinations at higher doses outperformed individual fungicides, highlighting synergistic or additive effects (Colby’s Ratio = 1.19). The Colby’s Ratios for all dimethomorph combinations (Dimethomorph 37.5% + Flusilazole 3.75%, Dimethomorph 32.5% + Myclobutanil 3.25%) ranged from 1.11 to 1.19, indicating additive interactions between Dimethomorph and Flusilazole / Myclobutanil.

Table 5. Efficacy of Fungicide Dimethomorph Combinations against Powdery Mildew Disease Incidence on Tomato Crop
Treatments Dose
(g or ml / ha) Percent Disease Incidence % Reduction in PDI after 3 sprays Colby’s Ratio
Pre 1 2 3
Dimethomorph 37.5% + Flusilazole 3.75% 1000 12.74
(20.90) 0.37
(2.01) 1.40
(6.76) 3.65
(10.99) 81.77 1.19
Dimethomorph 37.5% + Flusilazole 3.75% 1250 12.66
(20.84) 0.33
(1.91) 1.07
(5.92) 3.27
(10.41) 83.65 1.22
Dimethomorph 37.5% + Flusilazole 3.75% 1500 12.47
(20.67) 0.17
(1.35) 0.33
(1.91) 2.33
(8.74) 88.33 1.29
Dimethomorph 32.5% + Myclobutanil 3.25% 996 12.53
(20.72) 0.33
(1.91) 0.95
(5.58) 3.33
(10.49) 83.33 1.40
Dimethomorph 32.5% + Myclobutanil 3.25% 1245 12.48
(20.68) 0.20
(1.48) 0.67
(3.83) 2.95
(9.89) 85.23 1.43
Dimethomorph 32.5% + Myclobutanil 3.25% 1494 12.61
(20.79) 0.10
(1.05) 0.60
(3.62) 1.93
(7.99) 90.33 1.51
Dimethomorph 50% WP 1000 12.45
(20.65) 9.81
(18.24) 10.85
(19.22) 13.00
(21.13) 34.98 -
Flusilazole 40% EC 120 12.55
(20.74) 7.40
(15.78) 8.71
(17.15) 9.63
(18.07) 51.85 -
Myclobutanil 10% WP 200 12.78
(20.94) 10.37
(18.78) 11.78
(20.07) 12.41
(20.62) 37.93 -
Ametoctradin 27% + Dimethomorph 20.27% w/w SC 1000 12.67
(20.84) 9.32
(17.76) 8.74
(17.18) 9.93
(18.36) 50.33 -
Dimethomorph 12% + Pyraclostrobin 6.7% WG 1250 12.77
(20.93) 7.14
(15.49) 7.46
(15.84) 9.14
(17.57) 54.30 -
Untreated check - 12.80
(20.96) 16.19
(23.71) 18.55
(25.50) 20.00
(26.55) 0.00 -
SE(m) ± 0.001 0.87 0.91 0.34 - -
CD NS 2.65 2.69 1.02 - -
Figures in parenthesis are arc sine transformed values
The efficacy of dimethomorph combinations against Leveillula taurica / Oidiopsis neolycopersici (powdery mildew) in tomato crops was assessed through percent disease incidence (PDI) measured pre-treatment and after three successive sprays (Table 3).
The results significantly varied among treatments; the pre-treatments data indicated that there has been no significant difference in PDI among the treatments which ranged between 12.47% to 12.80%. After Third spray the treatments of Dimethomorph combinations of highest dose persisted in recorded lowest PDI such as Dimethomorph 37.5% + Flusilazole 3.75% @ 1500ml/ha with 2.33% and Dimethomorph 32.5% + Myclobutanil 3.25% @ 1494 ml/ha with 1.93% respectively. This was followed by Dimethomorph 37.5% + Flusilazole 3.75% @ 1250ml/ha with 3.27% and Dimethomorph 32.5% + Myclobutanil 3.25% @ 1245 ml/ha with 2.95% which were at par with each other. The results indicate that all the three doses of Dimethomorph 37.5% + Flusilazole 3.75% and Dimethomorph 32.5% + Myclobutanil 3.25% recorded low PDI at the end of three sprays while the market standards recorded viz., Ametoctradin 2% + Dimethomorph 20.27% SC @ 1000 ml/ha and Dimethomorph 12% + Pyraclostrobin 6.7% WG @ 1290 gm/ha recorded 9.93% and 9.14% PDI respectively. The highest PDI was recorded in Untreated check with 20% PDI.
Table 6. Effect of Dimethomorph Combinations and other Fungicides on Yield of Tomato
Treatments Dose (g or ml / ha) Yield (t/ha)
Dimethomorph 37.5% + Flusilazole 3.75% 1000 39.78 (6.39)
Dimethomorph 37.5% + Flusilazole 3.75% 1250 41.82 (6.54)
Dimethomorph 37.5% + Flusilazole 3.75% 1500 42.89 (6.63)
Dimethomorph 32.5% + Myclobutanil 3.25% 996 40.33 (6.43)
Dimethomorph 32.5% + Myclobutanil 3.25% 1245 42.98 (6.63)
Dimethomorph 32.5% + Myclobutanil 3.25% 1494 43.26 (6.65)
Dimethomorph 50% WP 1000 37.11 (6.17)
Flusilazole 40% EC 120 35.59 (6.05)
Myclobutanil 10% WP 200 33.81 (5.90)
Ametoctradin 27% + Dimethomorph 20.27% w/w SC 1000 30.44 (5.61)
Dimethomorph 12% + Pyraclostrobin 6.7% WG 1250 28.21 (5.41)
Untreated Check - 25.00 (5.10)
SE(m) ± 0.022
CD 0.065
Figures in parentheses are square root transformed
The percent reduction in disease in comparison with control and Colby’s Ratio indicated that >85% control was recorded in the highest doses of Dimethomorph 37.5% + Flusilazole 3.75% with 88.33% control, 1.29 Colby’s Ratio and Dimethomorph 32.5% + Myclobutanil 3.25% with 90.33% control with 1.51 as Colby’s Ratio. For both combinations, higher doses (1500 and 1494 ml/ha) resulted in near-complete disease control (PDI = 1.93%), outperforming lower doses. All dimethomorph combinations at higher doses outperformed individual fungicides, highlighting synergistic or additive effects (Colby’s Ratio = 1.00). The Colby’s Ratios for all dimethomorph combinations (Dimethomorph 37.5% + Flusilazole 3.75%, Dimethomorph 32.5% + Myclobutanil 3.25%) ranged from 1.51 to 1.196, indicating additive interactions between Dimethomorph and Flusilazole / Myclobutanil.
Table 7. Phytotoxicity of Dimethomorph combinations and other fungicides on Tomato
Treatments Days Visual Rating Scale
Yellowing Necrosis Wilting Vein
Clearing Leaf Tip / Margin Dying Stunting / Dwarfing
Dimethomorph 37.5% + Flusilazole 3.75% @ 1000ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 37.5% + Flusilazole 3.75% @ 1250ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 37.5% + Flusilazole 3.75% @ 1500ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 32.5% + Myclobutanil 3.25% @ 996 ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 32.5% + Myclobutanil 3.25% @ 1245ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 32.5% + Myclobutanil 3.25% @ 1494 ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 50% WP @ 1000g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Flusilazole 40% EC @ 120ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Myclobutanil 10% WP @ 200 g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Ametoctradin 27% + Dimethomorph 20.27% w/w SC @ 1000 ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 12% + Pyraclostrobin 6.7% WG @ 1250 g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Untreated Check 5 0 0 0 0 0 0
10 0 0 0 0 0 0
The phytotoxicity effect of the fungicide Dimethomorph combinations (Dimethomorph 37.5% + Flusilazole 3.75%, Dimethomorph 32.5% + Myclobutanil 3.25%) and other fungicides showed no signs of phytotoxicity in the tomato crop. Hence, the combination is safe for the usage of Late Blight and Powdery Mildew control in tomato crops (Table 7).
Grape Downy mildew:
Table 8. Effect of Dimethomorph combinations and other fungicides on Downy mildew of Grape
Treatments Dose (g or ml / ha) Percent Disease Incidence % Reduction in PDI after 3 sprays Colby’s Ratio
Pre 1 2 3
Dimethomorph 37.5% + Flusilazole 3.75% 1000 16.71
(24.12) 8.00
(16.42) 11.09
(19.44) 13.40
(21.47) 82.05 1.08
Dimethomorph 37.5% + Flusilazole 3.75% 1250 16.53
(23.98) 6.13
(14.33) 8.76
(17.21) 11.26
(19.60) 84.92 1.12
Dimethomorph 37.5% + Flusilazole 3.75% 1500 16.63
(24.06) 5.83
(13.97) 6.40
(14.64) 9.04
(17.49) 87.89 1.16
Dimethomorph 32.5% + Myclobutanil 3.25% 996 16.83
(24.21) 5.00
(12.91) 8.11
(16.54) 9.29
(17.74) 87.55 1.14
Dimethomorph 32.5% + Myclobutanil 3.25% 1245 16.80
(24.19) 3.89
(11.37) 7.00
(15.33) 7.63
(16.03) 89.78 1.16
Dimethomorph 32.5% + Myclobutanil 3.25% 1494 16.90
(24.26) 3.07
(10.08) 5.20
(13.18) 6.20
(14.41) 91.70 1.19
Dimethomorph 50% WP 1000 16.75
(24.15) 28.67
(32.36) 30.42
(33.45) 38.67
(38.43) 48.21 -
Flusilazole 40% EC 120 16.61
(24.04) 30.22
(33.34) 30.93
(33.78) 34.56
(35.99) 53.72 -
Myclobutanil 10% WP 200 16.79
(24.18) 26.19
(30.77) 27.85
(31.84) 33
(35.05) 55.80 -
Ametoctradin 27% + Dimethomorph 20.27% w/w SC 1000 16.86
(24.23) 23.90
(29.26) 25.16
(30.09) 28.67
(32.36) 61.60 -
Dimethomorph 12% + Pyraclostrobin 6.7% WG 1250 16.82
(24.21) 24.07
(29.37) 26.03
(30.66) 30.15
(33.29) 59.63 -
Untreated check - 16.93
(24.29) 33.83
(35.55) 48.33
(44.03) 74.67
(59.76) 0.00 -
SE(m) ± 0.120 0.165 0.202 0.209 - -
CD N/A 0.486 0.596 0.616 - -
Figures in parenthesis are arc sine transformed values
The efficacy of dimethomorph combinations against Plasmopara viticola (Downy Mildew) in grape crops was assessed through percent disease incidence (PDI) measured pre-treatment and after three successive sprays (Table 8).
The results we can conclude that the fungicidal combination is highly effective against downy mildew in grape when applied in combination than when applied alone. The pre-treatments data indicated that there has been no significant difference in PDI among the treatments ranging between 16.53% to 16.93%. At third spray, similar trend was observed where the lowest PDI was recorded in Dimethomorph 32.5% + Myclobutanil 3.25% @ 1494ml/ha with 6.20%. The highest PDI was recorded in Untreated check with 74.64% PDI. The PDI values indicated that Dimethomorph 32.5% + Myclobutanil 3.25% and Dimethomorph 37.5% + Flusilazole 3.75% at all the three doses significantly reduced the spread of downy mildew in grapes.
Table 9. Effect of Dimethomorph combinations and other fungicides on yield of Grape
Treatments Dose (g or ml / ha) Yield (t/ha)
Dimethomorph 37.5%+Flusilazole 3.75% 1000 18.75 (4.44)
Dimethomorph 37.5%+Flusilazole 3.75% 1250 21.00 (4.69)
Dimethomorph 37.5%+Flusilazole 3.75% 1500 23.07 (4.91)
Dimethomorph 32.5%+Myclobutanil 3.25% 996 20.55 (4.64)
Dimethomorph 32.5%+Myclobutanil 3.25% 1245 22.26 (4.82)
Dimethomorph 32.5%+Myclobutanil 3.25% 1494 24.16 (5.02)
Dimethomorph 50% WP 1000 14.33 (3.92)
Flusilazole 40% EC 120 12.33 (3.65)
Myclobutanil 10% WP 200 11.67 (3.56)
Ametoctradin 27%+ Dimethomorph 20.27% w/w SC 1000 16.00 (4.12)
Dimethomorph 12% + Pyraclostrobin 6.7% WG 1250 15.33 (4.04)
Untreated check - 6.33 (2.71)
SE(m) ± 0.036
CD 0.107
Figures in parentheses are square root transformed
The percent reduction in disease in comparison with control and Colby’s Ratio indicated that >85% control was recorded in the highest dose of Dimethomorph 37.5% + Flusilazole 3.75% with 87.89% control, 1.16 Colby’s Ratio and all the three doses of Dimethomorph 32.5% + Myclobutanil 3.25% with 91.70%, 89.78%, 87.55% control with 1.19, 1.16, 1.14 as Colby’s Ratio respectively. As for the solo molecules i.e., Dimethomorph 50% WP @ 1000 g/ha, Flusilazole 40% EC @ 120ml/ha and Myclobutanil 10% WP @ 200 gm/ha recorded 48.21%, 53.72% and 55.80% reduction in control respectively. For both combinations, higher doses (1500 and 1494 ml/ha) resulted in near-complete disease control (PDI = 6.20%), outperforming lower doses. All dimethomorph combinations at higher doses outperformed individual fungicides, highlighting synergistic or additive effects (Colby’s Ratio = 1.19). The Colby’s Ratios for all dimethomorph combinations (Dimethomorph 37.5% + Flusilazole 3.75%, Dimethomorph 32.5% + Myclobutanil 3.25%) ranged from 1.08 to 1.19, indicating additive interactions between Dimethomorph and Flusilazole / Myclobutanil.
Table 10. Phytotoxicity of Dimethomorph combinations and other fungicides on Grape
Treatments Days Visual Rating Scale
Yellowing Necrosis Wilting Vein
Clearing Leaf Tip / Margin Dying Stunting / Dwarfing
Dimethomorph 37.5% + Flusilazole 3.75% @ 1000ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 37.5% + Flusilazole 3.75% @ 1250ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 37.5% + Flusilazole 3.75% @ 1500ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 32.5% + Myclobutanil 3.25% @ 996 ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 32.5% + Myclobutanil 3.25% @ 1245ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 32.5% + Myclobutanil 3.25% @ 1494 ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 50% WP @ 1000g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Flusilazole 40% EC @ 120ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Myclobutanil 10% WP @ 200 g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Ametoctradin 27% + Dimethomorph 20.27% w/w SC @ 1000 ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 12% + Pyraclostrobin 6.7% WG @ 1250 g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Untreated Check 5 0 0 0 0 0 0
10 0 0 0 0 0 0

The phytotoxicity effect of the fungicide Dimethomorph combinations (Dimethomorph 37.5% + Flusilazole 3.75%, Dimethomorph 32.5% + Myclobutanil 3.25%) and other fungicides showed no signs of phytotoxicity in the grape crop. Hence, the combination is safe for the usage of Downy Mildew control in Grape crops (Table 10).
Cucumber Powdery mildew:
Table 11. Effect of Dimethomorph combinations and other fungicides on Powdery mildew of Cucumber
Treatments Dose (g or ml / ha) Percent Disease Incidence % Reduction in PDI after 3 Sprays Colby’s Ratio
Pre 1 2 3
Dimethomorph 37.5% + Flusilazole 3.75% 1000 4.93
(12.82) 2.50
(9.09) 2.07
(8.24) 2.00
(8.13) 84.96 1.11
Dimethomorph 37.5% + Flusilazole 3.75% 1250 4.74
(12.57) 1.80
(7.71) 1.73
(7.56) 1.87
(7.85) 85.96 1.13
Dimethomorph 37.5% + Flusilazole 3.75% 1500 4.80
(12.65) 1.17
(6.20) 0.80
(5.03) 1.02
(5.76) 92.31 1.21
Dimethomorph 32.5% + Myclobutanil 3.25% 996 4.67
(12.47) 2.06
(8.26) 1.63
(7.33) 1.77
(7.63) 86.72 1.15
Dimethomorph 32.5% + Myclobutanil 3.25% 1245 4.37
(12.06) 1.36
(6.70) 1.05
(5.88) 1.15
(6.15) 91.35 1.21
Dimethomorph 32.5% + Myclobutanil 3.25% 1494 4.73
(12.55) 1.01
(5.76) 0.41
(3.63) 0.90
(5.45) 93.23 1.23
Dimethomorph 50% WP 1000 4.75
(12.58) 4.73
(12.55) 5.11
(13.05) 7.00
(15.34) 47.37 -
Flusilazole 40% EC 120 4.43
(12.15) 4.14
(11.73) 4.60
(12.38) 6.00
(14.17) 54.89 -
Myclobutanil 10% WP 200 4.70
(12.51) 4.41
(12.12) 3.67
(11.03) 6.16
(14.36) 53.71 -
Ametoctradin 27% + Dimethomorph 20.27% w/w SC 1000 4.76
(12.59) 4.35
(12.04) 3.22
(10.34) 3.89
(11.37) 70.78 -
Dimethomorph 12% + Pyraclostrobin 6.7% WG 1250 4.70
(12.52) 4.10
(11.68) 3.00
(9.97) 3.68
(11.06) 72.31 -
Untreated Check - 5.00
(12.91) 7.57
(15.96) 11.16
(19.50) 13.30
(21.38) 0.00 -
SE(m) ± 0.203 0.057 0.260 0.193 - -
CD NS 0.168 0.767 0.569 - -
Figures in parenthesis are arc sine transformed values
The efficacy of dimethomorph combinations against Erysiphe cichoracearum (Powdery Mildew) in cucumber crop was assessed through percent disease incidence (PDI) measured pre-treatment and after three successive sprays (Table 11).
The results we can conclude that the fungicidal combination is highly effective against powdery mildew in cucumber when applied in combination than when applied alone. The pre-treatments data indicated that there has been no significant difference in PDI among the treatments ranging from 4.37% to 5%. At third spray, similar trend was observed where the lowest PDI was recorded in Dimethomorph 32.5% + Myclobutanil 3.25% @ 1494ml/ha with 0.09% followed by Dimethomorph 37.5% + Flusilazole 3.75% @ 1500ml/ha with 1.02% PDI. The highest PDI was recorded in Untreated check with 13.30% PDI. The PDI values indicated that Dimethomorph 32.5% + Myclobutanil 3.25% and Dimethomorph 37.5% + Flusilazole 3.75% at all the three doses reduced the disease incidence but the highest doses of both the combinations were highly effective in managing powdery mildew in cucumber.
The percentage reduction in disease in comparison with control and Colby’s Ratio indicated that >85% control was recorded in the highest dose of Dimethomorph 37.5% + Flusilazole 3.75% with 92.31% control, 1.21 Colby’s Ratio and two doses of Dimethomorph 32.5% + Myclobutanil 3.25% with 93.23%, 91.35% control with 1.21, 1.23 as Colby’s Ratio respectively. As for the solo molecules i.e., Dimethomorph 50% WP @ 1000 g/ha, Flusilazole 40% EC @ 120ml/ha and Myclobutanil 10% WP @ 200 gm/ha recorded 47.37%, 54.89% and 53.71% reduction in control respectively. For both combinations, higher doses (1500 and 1494 ml/ha) resulted in near-complete disease control (PDI = 1.04%), outperforming lower doses. All dimethomorph combinations at higher doses outperformed individual fungicides, highlighting synergistic or additive effects (Colby’s Ratio = 1.23). The Colby’s Ratios for all dimethomorph combinations (Dimethomorph 37.5% + Flusilazole 3.75%, Dimethomorph 32.5% + Myclobutanil 3.25%) ranged from 1.11 to 1.23, indicating additive interactions between Dimethomorph and Flusilazole / Myclobutanil.
Table 12. Effect of Dimethomorph combinations and other fungicides on yield of Cucumber
Treatments Dose (g or ml / ha) Yield (t/ha)
Dimethomorph 37.5% + Flusilazole 3.75% 1000 8.83 (3.13)
Dimethomorph 37.5% + Flusilazole 3.75% 1250 9.60 (3.25)
Dimethomorph 37.5% + Flusilazole 3.75% 1500 9.33 (3.21)
Dimethomorph 32.5% + Myclobutanil 3.25% 996 8.10 (3.02)
Dimethomorph 32.5% + Myclobutanil 3.25% 1245 9.80 (3.29)
Dimethomorph 32.5% + Myclobutanil 3.25% 1494 9.90 (3.30)
Dimethomorph 50% WP 1000 7.27 (2.88)
Flusilazole 40% EC 120 6.97 (2.82)
Myclobutanil 10% WP 200 6.33 (2.71)
Ametoctradin 27% + Dimethomorph 20.27% w/w SC 1000 7.97 (2.99)
Dimethomorph 12% + Pyraclostrobin 6.7% WG 1250 7.93 (2.99)
Untreated Check - 5.70 (2.59)
SE(m) ± 0.065
CD 0.192
Figures in parenthesis are square root transformed

Table 13. Phytotoxicity of Dimethomorph combinations and other fungicides on Cucumber
Treatments Days Visual Rating Scale
Yellowing Necrosis Wilting Vein
Clearing Leaf Tip / Margin Dying Stunting / Dwarfing
Dimethomorph 37.5% + Flusilazole 3.75% @ 1000ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 37.5% + Flusilazole 3.75% @ 1250ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 37.5% + Flusilazole 3.75% @ 1500ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 32.5% + Myclobutanil 3.25% @ 996 ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 32.5% + Myclobutanil 3.25% @ 1245ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 32.5% + Myclobutanil 3.25% @ 1494 ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 50% WP @ 1000g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Flusilazole 40% EC @ 120ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Myclobutanil 10% WP @ 200 g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Ametoctradin 27% + Dimethomorph 20.27% w/w SC @ 1000 ml/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Dimethomorph 12% + Pyraclostrobin 6.7% WG @ 1250 g/ha 5 0 0 0 0 0 0
10 0 0 0 0 0 0
Untreated Check 5 0 0 0 0 0 0
10 0 0 0 0 0 0

The phytotoxicity effect of the fungicide Dimethomorph combinations (Dimethomorph 37.5% + Flusilazole 3.75%, Dimethomorph 32.5% + Myclobutanil 3.25%) and other fungicides showed no signs of phytotoxicity in the cucumber crop. Hence, the combination is safe for the usage of Powdery Mildew control in Cucumber crop (Table 13). ,CLAIMS:We Claim:
1. A stable synergistic fungicidal suspension concentrate formulation comprising:
Dimethomorph;
at least one triazole fungicide;
at least one dispersing agent; and
at least one agrochemically acceptable excipient.
2. The formulation as claimed in claim 1, wherein the triazole fungicide is selected from the group comprising myclobutanil, flusilazole, hexaconazole, tebuconazole, propiconazole, mefentrifluconazole or combinations thereof.
3. The formulation as claimed in claim 1, wherein dimethomorph and triazole fungicide are present in the weight ratio from about (1-10) to about (10-1).
4. The formulation as claimed in claim 1, wherein the formulation comprises from about 5% w/w to about 50% w/w dimethomorph and from about 0.5% w/w to about 25% w/w triazole fungicide of total weight of the composition.
5. The formulation as claimed in claim 1, wherein the dispersing agent is selected from fatty alcohol ethoxylate, acrylic copolymer solution (graft comb polymer), polyalkylene glycol ether block copolymer, ethylene oxide / propylene oxide block copolymer, or combinations thereof; wherein, the composition comprises from about 0.1% w/w to about 10% w/w dispersing agents of total weight of the composition.
6. The formulation as claimed in claim 1, wherein the agrochemically acceptable excipient is selected from the group comprising anti-foaming agents, solvents, emulsifiers, colorants, thickeners/binders, anticaking agents, anti-freeze agents, antioxidants, preservatives, glidants, pH-regulating agents, buffering agents, formulation aids, disintegrants, or combinations thereof.
7. A stable synergistic fungicidal suspension concentrate formulation comprising:
dimethomorph;
flusilazole;
at least one dispersing agent; and
at least one agrochemically acceptable excipient.
8. The formulation as claimed in claim 7, wherein the formulation comprises from about 10% w/w to about 50% w/w dimethomorph and from about 0.5% w/w to about 25% w/w flusilazole of total weight of the composition.
9. A stable synergistic fungicidal suspension concentrate formulation comprising:
dimethomorph;
myclobutanil;
at least one dispersing agent; and
at least one agrochemically acceptable excipient.
10. The formulation as claimed in claim 9, wherein the formulation comprises from about 10% w/w to about 50% w/w dimethomorph and from about 0.5% w/w to about 25% w/w myclobutanil of total weight of the composition.