WO2021220231A1 - Composition of propineb and metominostrobin - Google Patents

Composition of propineb and metominostrobin Download PDF

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Publication number
WO2021220231A1
WO2021220231A1 PCT/IB2021/053605 IB2021053605W WO2021220231A1 WO 2021220231 A1 WO2021220231 A1 WO 2021220231A1 IB 2021053605 W IB2021053605 W IB 2021053605W WO 2021220231 A1 WO2021220231 A1 WO 2021220231A1
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WO
WIPO (PCT)
Prior art keywords
propineb
metominostrobin
combination
composition
synergistic
Prior art date
Application number
PCT/IB2021/053605
Other languages
French (fr)
Inventor
Uma KUSHWAH
Vishwanath GADE
Santosh Shridhar AUTKAR
Ashim Kumar Dutta
Original Assignee
Pi Industries Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pi Industries Ltd. filed Critical Pi Industries Ltd.
Priority to CN202180032458.3A priority Critical patent/CN115515424A/en
Publication of WO2021220231A1 publication Critical patent/WO2021220231A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14Di-thio analogues thereof

Definitions

  • the present invention relates to a combination of propineb and metominostrobin and its composition.
  • the present invention relates to a composition comprising of propineb and metominostrobin, methods of preparation of said composition and use thereof for the control of a wide variety of undesired pathogenic microorganism.
  • the plants can be infested with multiple pathogens or bacteria as well as other diseases, for which growers are applying control measures either separately or by tank mixing various fungicides to manage a wide variety of undesired pathogenic microorganism.
  • This practice of mixing several fungicides might lead to poor efficacy and crop damage due to compatibility issues.
  • a premix of the best possible formulation for a combination of fungicides with different mode of actions would help growers to combat these pathogenic microorganisms more effectively.
  • the present invention relates to a fungicidal product that contains a combination of active substances, a method for controlling undesired pathogenic microorganism using this product, its use and the plant propagation organs treated with this product, as well as the use of this combination for the preparation of the product.
  • Propineb is a fungicidal compound belonging to the dithiocarbamate chemical class. Propineb was developed by Bayer Cropscience (Montedison SPA) and described in US 3178336. Propineb is classified under group M3 of the FRAC mode of action. It is used against downy mildew, black rots, gray mold, scab, leaf spot and blossom wilt. Chemically, it is [[2- [(dithiocarboxy)amino]-l-methylethyl]carbamodithioato(2-)-KS,KS']zinc. Metominostrobin is a fungicidal compound belonging to oximinoacetamides of the strobilurin type.
  • Metominostrobin was developed by Bayer (Shionogi and Co. Ltd.), as described in US 5185324. Metominostrobin is classified under group 11 of the FRAC mode of action. It is used for the control of Pyricularia oryzae of rice crop. Chemically, it is (E)-2- (methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide.
  • a combination comprising propineb and metominostrobin provides an effective composition in controlling a wide variety of undesired pathogenic microorganisms.
  • the present invention provides a combination of propineb and metominostrobin with enhanced efficacy and spectrum as compared to the use of propineb and metominostrobin alone.
  • the present invention provides a combination of propineb and metominostrobin, wherein optionally, addition of one or more insecticidal or fungicidal or acaricidal or nematicidal or herbicidal compounds or any combination thereof is possible.
  • the present invention provides a combination of propineb and metominostrobin to control a wide variety of undesired pathogenic microorganisms.
  • the present invention is to provide a longer residual control of the undesired pathogenic microorganisms treated with the combination of propineb and metomino strobin .
  • the present invention provides a synergistic composition of propineb, metominostrobin and agrochemically acceptable additives, wherein optionally, addition of one or more insecticidal or fungicidal or acaricidal or nematicidal or herbicidal compounds or any combination thereof is possible.
  • the present invention provides a synergistic composition of propineb and metominostrobin to control a wide variety of undesired pathogenic microorganisms.
  • the present invention provides a synergistic composition comprising propineb and metominostrobin, the composition possesses fungicidal activity.
  • the present invention provides a method for the preparation of the composition comprising propineb and metominostrobin.
  • the present invention provides a synergistic composition of propineb and metominostrobin, wherein the composition is used as a fungicidal composition.
  • the composition is selected from suspension concentrate (SC), wettable granules (WG), wettable powder (WP), a water dispersible granule (WDG), a water dispersible tablet (WT), an ultra- low volume (ULV) liquid (UL), an ultra-low volume (ULV) suspension (SU), a water soluble powder (SP), a suspo-emulsion (SE), granule (GR), an emulsifiable granule (EG), an oil-in- water emulsion (EW), an emulsifiable concentrate (EC), a micro-emulsion (ME), an oil dispersion (OD), a capsule suspension (CS), a dustable powder (DP) or an aerosol (AE).
  • SC suspension concentrate
  • WG wettable granules
  • WP wettable powder
  • the present invention provides a synergistic composition of propineb and metominostrobin, wherein propineb and metominostrobin having a particle size of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
  • the present invention provides a synergistic combination of propineb and metominostrobin, wherein propineb and metominostrobin having a particle size (d50, determined after dispersion in the water phase by laser diffraction) of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
  • the present invention provides a method for improving crop health (phyto-tonic effect), comprising treating a plant with an effective amount of the composition of propineb and metominostrobin.
  • compositions comprising, “comprising”, “includes”, “including”, or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated.
  • a composition or a method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, or method.
  • composition or “formulation” can be used interchangeably, unless stated otherwise, is meant to encompass, and are not limited to, compositions or formulations containing the combination of propineb and metominostrobin.
  • additive(s) refers to inert substances which are commonly used as diluent, to provide stability or to increase the activity profile of the composition or formulation with or without having agrochemical activity or direct effect on the undesired pathogenic microorganism.
  • surfactant(s) means a compound that, when dissolved in a liquid, reduces the surface tension of the liquid, which reduces the interfacial tension between two liquids or which reduces surface tension between a liquid and a solid.
  • stabilizer(s) refers to a substance capable of imparting resistance against physical or chemical deterioration or deformulation.
  • defoaming agent(s) refers to a chemical additive that reduces and hinders the formation of foam in the industrial process of liquids, semi-solids, or solids.
  • defoaming agent and anti-foaming agent can be used interchangeably.
  • thickener(s) refers to a polymeric material, which at a low concentration increases the viscosity of an aqueous solution and helps to stabilize the composition.
  • % refers to % weight; and % weight refers to % of the weight of respective component with respect to the total weight of the composition.
  • locus means a plant, plant parts, plant propagation material (preferably seed), soil, area, material or environment in which a pest is growing or may grow.
  • plant parts are understood to mean all above-ground and below ground parts and organs of plants, such as shoot, leaf, flower and root, examples including leaves, needles, stems, stalks, flowers, fruit-bodies, fruits and seeds, and also roots, tubers and rhizomes.
  • the plant parts also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
  • the term "effective amount" means the amount of the active substances in the compositions to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the effective amount can vary for the various compositions used in the present invention.
  • An effective amount of the compositions will also vary according to the prevailing conditions such as desired fungicidal effect and duration, weather, target species, locus, mode of application, and the like.
  • propineb encompasses propineb or its agrochemically acceptable salt(s), derivative(s) or any other modified form of propineb.
  • metalominostrobin encompasses metominostrobin or its agrochemically acceptable salt(s), derivative(s) or any other modified form of metomino strobin .
  • the present invention provides a combination of propineb and metominostrobin.
  • the present invention provides a combination of propineb and metominostrobin to control a wide variety of undesired pathogenic microorganisms.
  • the present invention provides a fungicidal combination of propineb and metominostrobin.
  • the present invention provides a longer residual control of the undesired pathogenic microorganisms treated with the combination of propineb and metomino strobin .
  • the combination ratio of propineb and metominostrobin depends on various factors such as, the undesired pathogenic microorganisms to be controlled, the degree of infestation, the climatic conditions, the characteristics of the soil and the application method, wherein ratio of propineb and metominostrobin is from 20:1 to 1:20, preferably from 12:1 to 4:1, more preferably 10:1 to 7:1.
  • the present invention provides a combination of propineb and metominostrobin, wherein propineb and metominostrobin, having a particle size of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
  • the present invention provides a combination of propineb and metominostrobin, wherein propineb and metominostrobin having a particle size (d50, determined after dispersion in the water phase by laser diffraction) of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
  • the present invention further provides a synergistic composition of propineb and metominostrobin for the control of a wide variety of undesired pathogenic microorganisms.
  • the present invention provides a synergistic composition of propineb and metominostrobin, wherein the composition is used as a fungicidal composition.
  • the synergistic composition of the present invention comprises of propineb and metominostrobin in a wider ratio, in relation to various factors such as, the undesired pathogenic microorganisms to be controlled, the degree of infestation, the climatic conditions, the characteristics of the soil and the application method, wherein the weight ratio of propineb and metominostrobin is from 20:1 to 1:20, preferably from 12:1 to 4:1, more preferably 10:1 to 7:1.
  • the present invention provides a synergistic composition, comprising of the weight percentage of propineb or its acceptable salt(s) thereof is 80% to 2%, the weight percentage of metominostrobin or its acceptable salt(s) thereof is 2% to 80% and the weight percentage of additives is 10% to 90%.
  • the present invention provides a synergistic composition of propineb and metominostrobin, wherein the active ingredients having a particle size of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
  • the present invention provides a synergistic composition of propineb and metominostrobin, wherein propineb and metominostrobin having a particle size (d50, determined after dispersion in the water phase by laser diffraction) of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
  • the combination or composition of propineb and metominostrobin of the present invention may further comprise of insecticide(s), fungicide(s), nematicide(s), acaricide(s), safener(s), or herbicide(s) or any combination thereof.
  • the composition is selected from a wettable powder (WP), a water dispersible granule (WDG), a water dispersible tablet (WT), an ultra-low volume (ULV) liquid (UL), an ultra-low volume (ULV) suspension (SU), a water soluble powder (SP), a soluble concentrate (SL), a water soluble granule (SG), a suspo-emulsion (SE), granule (GR), an emulsifiable granule (EG), an oil-in- water emulsion (EW), an emulsifiable concentrate (EC), a micro-emulsion (ME), an oil dispersion (OD), a capsule suspension (CS), an aerosol (AE) or a mixed formulation of ZC (CS + SC), ZE (CS+SE), ZW (CS+EW).
  • WP wettable powder
  • WDG water dispersible granule
  • WT water dispersible tablet
  • UUV ultra-low volume
  • UAV
  • compositions may be manufactured by any process know in the art, such as, “Pesticide Formulation Guide” (edited by Pesticide Science Society of Japan, The Agricultural Formulation and Application Committee, published by Japan Plant Protection Association, 1997).
  • the present invention provides a process for preparing a composition of propineb and metominostrobin, comprising steps of: a) addition of propineb and metominostrobin or its acceptable salt(s) thereof, b) addition of agrochemically acceptable additives selected from surfactant(s), carrier(s) and other additive(s) uniformly in a mixer; and c) optionally milling by a mill.
  • composition comprising organic or inorganic carrier material including agrochemically acceptable additives are selected from the group comprising of solid carrier(s), liquid carrier(s), gaseous carrier(s), surfactant(s), binder(s), disintegrating agent(s), pH adjuster(s), thickener(s), preservative(s), anti-freezing agent(s), defoaming agent(s), extender(s), stabilizer(s) and/or coloring agent(s) or a combination thereof.
  • the composition may also contain if desired, one or more auxiliaries customary for crop protection compositions.
  • Solid carrier(s) is selected from the group comprising of, but not limited to, natural minerals such as quartz, talc, kaolin, pyrophyllite, montmorillonite, attapulgite, bentonite, kieselguhr, chalk, zeolite, calcite, sericite, acid clay, diatomaceous earth, natural rock, Fuller’s earth, meerschaum, gibbsite, dolomite or pumice; synthetic minerals such as precipitated silica, fumed silica, sodium silicate, alumina, aluminum hydroxide; inorganic salts such as calcium carbonate, ammonium sulfate or other ammonium salts, sodium sulfate, potassium chloride; organic materials such as urea, solid polyoxyethylene, solid polyoxypropylene, polyethylene, polypropylene, lactose, starch, lignin, cellulose, cottonseeds hulls, wheat flour, soybean flour, wood flour, walnut shell flour, plant powders, sawdust,
  • Liquid carrier(s) is selected from the group comprising of, but not limited to, water; alcohols such as ethanol, propanol, n-octanol, isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerin; polyol ethers such as ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, isoparaffin, kerosene, mineral oil; aromatic hydrocarbons such as xylene, toluene, naphthene, solvent naphtha, solvent C9, solvent
  • Gaseous carrier(s) is selected from the group comprising of, but not limited to, liquefied petroleum gas, air, nitrogen, carbon dioxide or dimethyl ether. These gaseous carriers may be used alone or in combination thereof.
  • Surfactant(s) are nonionic or anionic surfactants or a combination of these surfactants. It is preferred to use one or more than one kind of surfactant.
  • Surfactant(s) is selected from the group comprising of, but not limited to, sugar esters such as sorbitan monolaurate, polyoxyethylene sorbitan monolaurate; alkyl poly gluco side such as decyl glucoside; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether or polyoxyethylene coconut fatty alcohol ether; polyoxyethylene alkynyl ether such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol ether; polyoxyethylene aryl ethers such as polyoxyethylene nonylphenyl ether or polyoxyethylene tristyrylphenyl ether; polyoxyethylene vegetable oil ethers such as polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil; polyoxyethylene fatty acid esters such as polyoxyethylene monolaurate, polyoxiethylene distearate or polyoxyethylene resin acid ester; polyoxyethylene polyoxypropylene block copolymers (such as Pluronic ® );
  • Binder(s) or adhesive-imparting agent(s) is selected from the group comprising of, but not limited to, polyvinyl alcohol, dextrin, denatured dextrin, soluble starch, guar gum, xanthan gum, sucrose, polyvinylpyrrolidone, gum arabic, polyvinyl acetate, sodium polyacrylate, carboxymethyl cellulose or its salt, carboxymethylcellulose dextrin, bentonite, polyethylene glycol having an average molecular weight of 6,000 to 20,000, polyethylene oxide having average molecular weight of 100,000 to 5,000,000, natural phosphatide such as cephalinic acid or lecithin. These binders or adhesive-imparting agents may be used alone or in combination thereof.
  • Disintegrating agent(s) is selected from the group comprising of, but not limited to, sodium tripolyphosphate, stearic acid metal salt, cellulose powder, dextrin, methacrylate copolymer, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compound, styrene sulfonate/isobutylene/maleic anhydride copolymer, starch/polyacrylonitrile graft copolymer, sodium hexametaphosphate, carboxymethyl cellulose, sodium polycarbonate, bentonite. These disintegrating agents may be used alone or in combination thereof.
  • pH adjuster(s) is selected from the group comprising of, but not limited to, sodium or potassium carbonate, sodium or potassium hydrogen carbonate, sodium or potassium dihydrogen phosphate, disodium or dipotassium hydrogen phosphate, citric acid, malic acid and triethanolamine. These pH adjusters may be used alone or in combination thereof.
  • Thickener(s) is selected from the group comprising of, but not limited to, water-soluble polymer and inorganic fine powder, wherein water-soluble polymer such as xanthan gum, welan gum, guar gum, polyvinyl alcohol, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative or polysaccharide; or an inorganic fine powder selected from high purity silica, bentonite, white carbon. These thickeners may be used alone or in combination thereof.
  • water-soluble polymer such as xanthan gum, welan gum, guar gum, polyvinyl alcohol, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative or polysaccharide
  • inorganic fine powder selected from high purity silica, bentonite, white carbon.
  • Preservative(s) is selected from the group comprising of, but not limited to, potassium sorbate, 4-hydroxybenzoic acid esters, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4- isothiazolin-3-one, l,2-benzisothiazolin-3-one (Proxel ® GXL). These preservatives may be used alone or in combination thereof.
  • Anti-freezing agent(s) is selected from the group comprising of, but not limited to, polyhydric alcohol such as ethylene glycol, polyethylene glycol, diethylene glycol, propylene glycol, and glycerol. These anti-freezing agents may be used alone or in combination thereof.
  • Defoaming agent(s) is selected from the group comprising of, but not limited to, silicone compounds such as polysiloxane, polydimethyl siloxane and organic fluorine compounds. These defoaming agents may be used alone or in combination thereof.
  • Extender(s) is selected from the group comprising of, but not limited to, silicon type surfactant, a cellulose powder, dextrin, processed starch, a polyaminocarboxylic acid chelate compound, crosslinked polyvinylpyrrolidone, maleic acid and styrene, methacrylic acid copolymer, half ester of polymer of polyhydric alcohol with dicarboxylic anhydride, or water-soluble salt of polystyrene sulfonic acid. These extenders may be used alone or in combination thereof.
  • Stabilizer(s) is selected from the group comprising of, but not limited to, drying agents such as zeolite, quicklime or magnesium oxide; antioxidant agents such as phenol type, amine type, sulfur type or phosphorus type; or ultraviolet absorbers such as salicylic acid type or a benzophenone type. These stabilizers may be used alone or in combination thereof.
  • Coloring agent(s) is selected from the group comprising of, but not limited to, inorganic pigments such as iron oxide, titanium oxide or prussian blue; organic dye such as alizarin dye, azo dye, metal phthalocyanine dye. These coloring agents may be used alone or in combination thereof.
  • the content of the carrier is selected typically in a weight range from 5% to 95%, preferably from 20% to 90%; the content of the surfactant is selected from the range of typically from 0.1% to 30%, preferably from 0.5% to 10%, and the content of the other additives is selected from the range of typically from 0.1% to 30%, preferably from 0.5% to 10%.
  • the present invention provides a water dispersible granule (WDG) composition of propineb and metominostrobin.
  • WDG water dispersible granule
  • the present invention provides a wettable powder (WP) composition of propineb and metominostrobin.
  • WP wettable powder
  • the present invention provides a suspension concentrate (SC) composition of propineb and metominostrobin.
  • the present invention provides an oil dispersion (OD) composition of propineb and metominostrobin.
  • the present invention provides a general process for preparing water dispersible granules (WDG) formulation, comprising steps of: a) mix sodium lauryl sulphate (SLS) & sodium lignosulfonate (SLS) with the actives propineb and metominostrobin thoroughly. b) slowly add kaolin and silica to the above mixture under constant mixing at low speed (10-15 rpm) c) dissolve lactose in water 2%w/w and add to the material in step 1 and 2 under constant stirring. d) slowly add the sodium sulphate powder under constant mixing to obtain a uniformly wet powdery material. e) extrude the above material through an extruder to obtain granules of required shape and size. f) dry the granules in a fluid bed dryer for a final moisture content of 0.2%w/w.
  • SLS sodium lauryl sulphate
  • SLS sodium lignosulfonate
  • composition of the present invention can be applied by any one of the methods selected from atomization, spreading, dusting, spraying, diffusion, immersion, irrigation, injection, mixing, sprinkling (water immersion), foaming, dressing, coating, blasting, fumigation, smoking, smog and painting.
  • the present invention provides a method of controlling a wide variety of undesired pathogenic microorganism, with an effective amount of a composition of propineb and metominostrobin.
  • the present invention provides a fungicidal combination or composition comprising of propineb and metominostrobin to control the pathogenic microorganism on economically important crops such as rice, peppers, soybean, cotton, chick pea, pigeon pea, tea, potato, and tomato.
  • the present invention further provides a composition for the control of a wide variety of, pathogenic microorganism, wherein the weight percentage of propineb or its acceptable salt(s) thereof is 80% to 2% and the weight percentage of metominostrobin or its acceptable salt(s) thereof is 2% to 80%.
  • the total content of propineb and metominostrobin in the composition is selected in the weight range typically from 10% to 90%, preferably from 20% to 80%.
  • the composition of the present invention used to control a wide variety of undesired pathogenic microorganism is advantageous, for several purposes, e.g.: a) useful for addressing a wider range of undesired pathogenic microorganisms e.g. fungicidal activity; b) offering a single application as a uniform composition in place of separate applications of fungicides; c) offering crop health improvement in comparison to separate applications of fungicides; d) offers longer residual control after application of the composition.
  • the present invention provides a combination/composition that shows enhanced action against undesired pathogenic microorganisms, in comparison to the control rates that are possible with the individual compounds and/or suitable for improving the health of plants when applied to plants, parts of plants, plant propagation materials, or at their locus of their growth.
  • the present invention provides a method of controlling a wide variety of undesired pathogenic microorganism with an effective amount of the combination/ composition of propineb and metominostrobin with fungicidal compound.
  • the undesired pathogenic microorganism for the present invention is selected from the group comprising of Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. Candida) and sunflowers (e.g. A. tragopogonis), Alternaria spp. (Alternaria leaf spot) on vegetables, citrus fruits (A. citri), rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e.g. A.
  • spot blotch B. sorokiniana
  • cereals e.g. B. oryzae on rice and turfs and on oats
  • Blumeria originally Erysiphe
  • graminis prowdery mildew
  • cereals e.g. on wheat or barley
  • Botrytis cinerea teleomorph: Botryotinia fuckeliana: grey mold
  • fruits and berries e.g. strawberries
  • vegetables e.g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • Bremia lactucae downy mildew
  • Ceratocystis syn. Ophiostoma
  • Cercosporidium spp. on peanut e.g. C. personatum: late leaf spot
  • Cladosporium spp. on tomatoes e.g. C. fulvum: leaf mold
  • cereals e.g. C. herbarum (black ear) on wheat, C. caryigenum (pecan scab) on pecan
  • Cylindrocladium spp. on peanut C. crotalariae: cylindrocladium black rot
  • Cochliobolus anamorph: Helminthosporium of Bipolaris
  • spp. leaf spots
  • gloeosporioides and soybeans (e.g. C. truncatum or C. gloeosporioides), Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e.g. C.
  • liriodendri Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia ) necatrix (root and stem rot) on soybeans; Diplodia spp. e.g. Diplodia boll rot on cotton, Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans, D. citri (melanose) on citrus fruits; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora ) spp. on com, cereals, such as barley (e.g. D. D.
  • oats e.g. D. avenae, leaf spot
  • wheat e.g. D. tritici-repentis : tan spot
  • Esca dieback, apoplexy
  • on vines caused by Formitiporia (syn. Phellinus ) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum ), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa Elsinoe spp. on pome fruits (F. pyri), on citrus fruits (F.
  • peas and bean e.g. E. polygoni
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis
  • Exserohilum syn. Elelminthosporium
  • com e.g. E. turcicum
  • Fusarium teleomorph: Gibberella
  • spp. wilt, root or stem rot
  • Microsphaera diffusa prowdery mildew
  • Myeosphaerella citri greasy spot
  • Monilinia spp. e.g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Myeosphaerella spp. on peas and beans, cereals, bananas, soft fruits and ground nuts, such as e.g. M. graminicola (anamorph: Septoria tritici, Septoria blotch ) on wheat or M.
  • fijiensis black Sigatoka disease
  • Peronospora spp. downy mildew
  • cabbage e.g. P. brassicae
  • rape e.g. P. parasitica
  • onions e.g. P. destructor
  • tobacco P . tabacina
  • soybeans e.g. P. manshuricaf, Phyllosticta maydis (yellow leaf blight) on corn
  • Phakopsora pachyrhizi and P. meibomiae saloybean rust
  • Phialophora spp. e.g. on vines e.g. P. tracheiphila and P.
  • soybeans e.g. P. gregata: stem rot; Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets, Phoma exigua (ascochyta blight) on peas and beans, phoma blight, boll rot on cotton, Phoma arachidicola (web blotch) on peanut; Phomopsis spp. on sunflowers, vines (e.g. P. viticola: can and leaf spot) and soybeans (e.g.
  • stem rot phaseoli, teleomorph: Diaporthe phaseolorumf, Phykopsora spp. e.g. rust on cotton, Physoderma maydis (physoderma brown spot) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e.g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e.g. P. infestans: late blight), broad-leaved trees (e.g. P. ramorum : sudden oak death) and peas and beans (e.g. P.
  • nicotianae downy mildew
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e.g. P. viticola (downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew
  • Polymyxa spp. e.g. on cereals, such as barley and wheat ( P . graminis ) and sugar beets ( P .
  • Pseudocercosporella herpotrichoides eyespot, teleomorph: Tapesia yallundae
  • Pseudoperonospora downy mildew
  • Pseudopezicula tracheiphila red fire disease or rotbrenner, anamorph: Phialophora
  • Puccinia spp. rusts on various plants, e.g. P. triticina (brown or leaf rust), P.
  • feres net blotch on barley, or P. avenae (leaf blotch) on oats; Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e.g. P. ultimum or P. aphanidermatum), Ramularia spp., e.g. R.
  • P. ultimum or P. aphanidermatum
  • Ramularia spp. e.g. R.
  • collo-cygni Ramularia leaf spots, physiological leaf spots
  • R. beticola on sugar beets
  • Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e.g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice and peanut, or R.
  • Erysiphe ) necator prowdery mildew, anamorph: Oidium tuckeri ) on vines
  • Setospaeria spp. leaf blight
  • com e.g. S. turcicum, syn. Helminthosporium turcicum
  • turf e.g. Sphacelotheca spp. (smut) on com, (e.g. S. reiliana : head smut), sorghum und sugarcane
  • Sphaerotheca fuliginea prowdery mildew
  • Spongospora subterranea powdery scab
  • S. nodorum Stagonospora blotch, teleomorph: Leptosphaeria (syn. Phaeosphaeria ) nodorum ) on wheat, septrotia leaf and glume blotch on rye; Stemphyllium spp. e.g. stemphy Ilium leaf spot on cotton, Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp.
  • T. basicola syn. Chalara elegansf Tilletia spp. (common bunt or stinking smut) on cereals, such as e.g. T. tritici (syn. T. caries , wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e.g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e.g. U.
  • U. phaseoli e.g. U. phaseoli
  • sugar beets e.g. U. betae
  • Ustilago spp. loose smut on cereals (e.g. U. nuda and U. avaenae ), com (e.g. U. maydis: corn smut) and sugar cane
  • Venturia spp. scab
  • apples e.g. V. inaequalis
  • pears e.g. Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e.g. V. dahliae on strawberries, rape, potatoes and tomatoes.
  • the fungicidal composition or combination according to the present invention is distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-bome fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the combination or composition of the present invention provides a non-agronomic (other than field crops) application such as application on horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.).
  • horticultural crops e.g., greenhouse, nursery or ornamental plants not grown in a field
  • turf e.g., sod farm, pasture, golf course, lawn, sports field, etc.
  • the combination or the composition of the present invention is particularly important for controlling a multitude of undesired pathogenic microorganisms, on various cultivated plants or plant parts, such as cereals, e.g. wheat, rye, barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g.
  • the rate of application amount varies depending on, for example, the blending ratio of an active ingredient, a metrological condition, a dosage form, an application time, an application method, an application place, a pest to be controlled, and a target crop, in ordinary cases.
  • the application rates of the active ingredients in the mixture according to the invention are preferably from 5000 to 2500g/l/ha, more preferably from 3000 to 1500g/l/ha, most preferably from 2500 to lOOOg/l/ha.
  • the present invention provides a method for improving crop health (phyto-tonic effect), comprising treating a plant with an effective amount of composition of propineb and metominostrobin.
  • Example 1 Water Dispersible Granule (WDG)
  • Example 2 Water Dispersible Granule (WDG)
  • Example 3 Water Dispersible Granule (WDG)
  • Example 4 Wettable Powder (WP)
  • Trials were conducted in the field to test the efficacy of the combination of propineb and metominostrobin for controlling leaf spots, blast, late blight in rice and fruits and vegetable pathogens at different test concentrations.
  • Crop vigour was recorded at 30 days after application.
  • the composition comprising the compound of component (1) and the component (2) may show a synergistic effect.
  • a synergistic effect of the combination is always present when the pesticidal activity of the active compound combinations exceeds the total of the activities of the individual combining partners when applied individually.
  • the expected activity for a given combination of two active compounds can be calculated by using the Colby’s formulas (COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination", Weeds, Vol. 15, pages 20-22; 1967).
  • E represents the expected percentage of inhibition of the disease for the combination of two pesticides at defined doses (for example equal to x and y respectively)
  • x is the percentage of inhibition observed for the disease by the compound (1) at a given dose (equal to x)
  • y is the percentage of inhibition observed for the disease by the compound (2) at a defined dose (equal to y).
  • E represents the expected percentage of inhibition of the disease for the combination of two pesticides at defined doses (for example equal to x and y respectively)
  • x is the percentage of inhibition observed for the disease by the compound (1) at a given dose (equal to x)
  • y is the percentage of inhibition observed for the disease by the compound (2) at a defined dose (equal to y).
  • the composition according to the invention can also have further surprising advantageous properties.
  • Example 1 Pyricularia oryzae (Rice blast):
  • Rhizoctonia solani (Rice sheath blight/ Potato black scurf):
  • Example 5 Phytophthora infestans (Late blight of potato & tomato):
  • a visual assessment of the compound performance was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7 and 10 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with the one in the untreated control. The treated plants were also assessed for phytotoxic effects by recording symptoms like necrosis, chlorosis & stunting. The percentage efficacy of Compound A, Compound B and mixtures thereof were calculated against Pyricularia oryzae. The results were tabulated as hereunder:
  • a visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7 and 10 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatments with the one of the untreated control. The treated plants were also assessed for plant compatibility by recording symptoms like necrosis, chlorosis & stunting. The percentage efficacy of Compound A, Compound B and mixtures thereof were calculated 5 against Alt e maria solani and Phytopthora infestans. The results were tabulated as hereunder:
  • a visual assessment of compound’s performance was carried by rating the disease severity 15 (0-100% scale) on treated plants on 3, 7, 10 and 15 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with untreated control. The sprayed plants were also assessed for compound’s phytotoxic effects by recording symptoms like necrosis, chlorosis and stunting. The percentage efficacy of Compound A, Compound B and mixtures thereof were calculated against Rhizoctonia 20 solani. The results were tabulated as hereunder:
  • the novel agrochemical composition of the invention also exhibits vigorous growth in crop. Vigour, here refers to early leaf area development and growth rate of the crop, has often been associated with improved competitive ability. Rapid canopy closure allows crops to quickly shade the ground and competing plants. Vigorous early growth may also promote greater root growth and improve WUE (Siddique el ah, 1990; Richards el ah, 2007; Richards, 2008), which may contribute to higher yields in water and nutrient-limited environments overall a potent strengthening effect in plants is observed. Accordingly, they can be used for mobilizing the defenses of the plant against the attack by undesirable microorganisms.

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Abstract

The present invention discloses a combination of propineb and metominostrobin with its composition and a method for controlling a broad variety of pathogenic microorganism, for a plant, including the treatment of plant/plant parts and a region around the plant. The present invention also discloses an enhanced efficacy against pests in comparison to individual components of the said combination. The combination also has a broader spectrum and is able to increase plant health.

Description

TITLE OF THE INVENTION: COMPOSITION OF PROPINEB AND METOMINOSTROBIN
FIELD OF THE INVENTION:
The present invention relates to a combination of propineb and metominostrobin and its composition. Particularly, the present invention relates to a composition comprising of propineb and metominostrobin, methods of preparation of said composition and use thereof for the control of a wide variety of undesired pathogenic microorganism.
BACKGROUND OF THE INVENTION:
In economically important crops, such as rice, peppers, soybean, chick pea, pigeon pea, cotton, tea, potato, tomato and other agricultural, horticultural and dry-land crop production, the plants can be infested with multiple pathogens or bacteria as well as other diseases, for which growers are applying control measures either separately or by tank mixing various fungicides to manage a wide variety of undesired pathogenic microorganism. This practice of mixing several fungicides might lead to poor efficacy and crop damage due to compatibility issues. Hence, a premix of the best possible formulation for a combination of fungicides with different mode of actions would help growers to combat these pathogenic microorganisms more effectively.
A typical challenge in the field of crop protection is to reduce the dose rates of an active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective control. Therefore, a combined application of an effective amount of fungicides in uniform composition is a practical necessity. The present invention relates to a fungicidal product that contains a combination of active substances, a method for controlling undesired pathogenic microorganism using this product, its use and the plant propagation organs treated with this product, as well as the use of this combination for the preparation of the product.
Propineb is a fungicidal compound belonging to the dithiocarbamate chemical class. Propineb was developed by Bayer Cropscience (Montedison SPA) and described in US 3178336. Propineb is classified under group M3 of the FRAC mode of action. It is used against downy mildew, black rots, gray mold, scab, leaf spot and blossom wilt. Chemically, it is [[2- [(dithiocarboxy)amino]-l-methylethyl]carbamodithioato(2-)-KS,KS']zinc.
Figure imgf000003_0001
Metominostrobin is a fungicidal compound belonging to oximinoacetamides of the strobilurin type. Metominostrobin was developed by Bayer (Shionogi and Co. Ltd.), as described in US 5185324. Metominostrobin is classified under group 11 of the FRAC mode of action. It is used for the control of Pyricularia oryzae of rice crop. Chemically, it is (E)-2- (methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide.
Figure imgf000003_0002
Various patent applications disclose the mixtures of fungicides for e.g. IN 201631026703. However, there is no effective composition available that act simultaneously on a wide variety of undesired pathogenic microorganisms.
It has been found that, as a solution to the above mentioned problems, a combination comprising propineb and metominostrobin provides an effective composition in controlling a wide variety of undesired pathogenic microorganisms. The present invention provides a combination of propineb and metominostrobin with enhanced efficacy and spectrum as compared to the use of propineb and metominostrobin alone.
SUMMARY OF THE INVENTION: Accordingly, in one aspect, the present invention provides a combination of propineb and metominostrobin, wherein optionally, addition of one or more insecticidal or fungicidal or acaricidal or nematicidal or herbicidal compounds or any combination thereof is possible.
In another aspect, the present invention provides a combination of propineb and metominostrobin to control a wide variety of undesired pathogenic microorganisms.
In yet another aspect, the present invention is to provide a longer residual control of the undesired pathogenic microorganisms treated with the combination of propineb and metomino strobin .
In one aspect, the present invention provides a synergistic composition of propineb, metominostrobin and agrochemically acceptable additives, wherein optionally, addition of one or more insecticidal or fungicidal or acaricidal or nematicidal or herbicidal compounds or any combination thereof is possible.
In another aspect, the present invention provides a synergistic composition of propineb and metominostrobin to control a wide variety of undesired pathogenic microorganisms.
In yet another aspect, the present invention provides a synergistic composition comprising propineb and metominostrobin, the composition possesses fungicidal activity.
In a further aspect, the present invention provides a method for the preparation of the composition comprising propineb and metominostrobin.
In one aspect, the present invention provides a synergistic composition of propineb and metominostrobin, wherein the composition is used as a fungicidal composition. The composition is selected from suspension concentrate (SC), wettable granules (WG), wettable powder (WP), a water dispersible granule (WDG), a water dispersible tablet (WT), an ultra- low volume (ULV) liquid (UL), an ultra-low volume (ULV) suspension (SU), a water soluble powder (SP), a suspo-emulsion (SE), granule (GR), an emulsifiable granule (EG), an oil-in- water emulsion (EW), an emulsifiable concentrate (EC), a micro-emulsion (ME), an oil dispersion (OD), a capsule suspension (CS), a dustable powder (DP) or an aerosol (AE). In another aspect, the present invention provides a synergistic composition of propineb and metominostrobin, wherein propineb and metominostrobin having a particle size of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm. In a specific aspect, the present invention provides a synergistic combination of propineb and metominostrobin, wherein propineb and metominostrobin having a particle size (d50, determined after dispersion in the water phase by laser diffraction) of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm. In one aspect, the present invention provides a method for improving crop health (phyto-tonic effect), comprising treating a plant with an effective amount of the composition of propineb and metominostrobin.
The above aspects and other objectives will become more apparent in view of the description given below.
DETAILED DESCRIPTION OF THE INVENTION:
ABBREVIATIONS
Figure imgf000005_0001
DEFINITIONS The foregoing definitions provided herein for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit the scope of the present invention disclosed in the present disclosure.
It will be understood that the terminology used herein is for the purpose of describing embodiments only, and is not intended to be limiting. As used in this specification, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, the reference to "a surfactant" includes one or more such surfactants.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which the invention pertains. Although other methods and materials similar, or equivalent, to those described herein can be used in the practice of the present invention, the preferred materials and methods are described herein.
As used herein, the terms "comprises", "comprising", "includes", "including", or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition or a method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, or method.
As used herein, the term “composition” or "formulation" can be used interchangeably, unless stated otherwise, is meant to encompass, and are not limited to, compositions or formulations containing the combination of propineb and metominostrobin.
As used herein, the term “additive(s)” refers to inert substances which are commonly used as diluent, to provide stability or to increase the activity profile of the composition or formulation with or without having agrochemical activity or direct effect on the undesired pathogenic microorganism.
As used herein, the term “surfactant(s)” means a compound that, when dissolved in a liquid, reduces the surface tension of the liquid, which reduces the interfacial tension between two liquids or which reduces surface tension between a liquid and a solid. As used herein, the term “stabilizer(s)” refers to a substance capable of imparting resistance against physical or chemical deterioration or deformulation.
As used herein, the term “defoaming agent(s)” refers to a chemical additive that reduces and hinders the formation of foam in the industrial process of liquids, semi-solids, or solids. The terms defoaming agent and anti-foaming agent can be used interchangeably.
As used herein, the term “thickener(s)” refers to a polymeric material, which at a low concentration increases the viscosity of an aqueous solution and helps to stabilize the composition.
Unless otherwise specified, % refers to % weight; and % weight refers to % of the weight of respective component with respect to the total weight of the composition.
As used herein, the term “locus" means a plant, plant parts, plant propagation material (preferably seed), soil, area, material or environment in which a pest is growing or may grow. As used herein, the term “plant parts” are understood to mean all above-ground and below ground parts and organs of plants, such as shoot, leaf, flower and root, examples including leaves, needles, stems, stalks, flowers, fruit-bodies, fruits and seeds, and also roots, tubers and rhizomes. The plant parts also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
As used herein, the term "effective amount" means the amount of the active substances in the compositions to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The effective amount can vary for the various compositions used in the present invention. An effective amount of the compositions will also vary according to the prevailing conditions such as desired fungicidal effect and duration, weather, target species, locus, mode of application, and the like.
As used herein, the term “propineb” encompasses propineb or its agrochemically acceptable salt(s), derivative(s) or any other modified form of propineb. As used herein, the term “metominostrobin” encompasses metominostrobin or its agrochemically acceptable salt(s), derivative(s) or any other modified form of metomino strobin .
Accordingly, the present invention provides a combination of propineb and metominostrobin.
In one embodiment, the present invention provides a combination of propineb and metominostrobin to control a wide variety of undesired pathogenic microorganisms.
In another embodiment, the present invention provides a fungicidal combination of propineb and metominostrobin.
In yet another embodiment, the present invention provides a longer residual control of the undesired pathogenic microorganisms treated with the combination of propineb and metomino strobin .
In a specific embodiment, the combination ratio of propineb and metominostrobin depends on various factors such as, the undesired pathogenic microorganisms to be controlled, the degree of infestation, the climatic conditions, the characteristics of the soil and the application method, wherein ratio of propineb and metominostrobin is from 20:1 to 1:20, preferably from 12:1 to 4:1, more preferably 10:1 to 7:1.
In another embodiment, the present invention provides a combination of propineb and metominostrobin, wherein propineb and metominostrobin, having a particle size of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
In a specific embodiment, the present invention provides a combination of propineb and metominostrobin, wherein propineb and metominostrobin having a particle size (d50, determined after dispersion in the water phase by laser diffraction) of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
In one embodiment, the present invention further provides a synergistic composition of propineb and metominostrobin for the control of a wide variety of undesired pathogenic microorganisms. In another embodiment, the present invention provides a synergistic composition of propineb and metominostrobin, wherein the composition is used as a fungicidal composition.
In yet another embodiment, the synergistic composition of the present invention comprises of propineb and metominostrobin in a wider ratio, in relation to various factors such as, the undesired pathogenic microorganisms to be controlled, the degree of infestation, the climatic conditions, the characteristics of the soil and the application method, wherein the weight ratio of propineb and metominostrobin is from 20:1 to 1:20, preferably from 12:1 to 4:1, more preferably 10:1 to 7:1.
In a specific embodiment, the present invention provides a synergistic composition, comprising of the weight percentage of propineb or its acceptable salt(s) thereof is 80% to 2%, the weight percentage of metominostrobin or its acceptable salt(s) thereof is 2% to 80% and the weight percentage of additives is 10% to 90%.
In another embodiment, the present invention provides a synergistic composition of propineb and metominostrobin, wherein the active ingredients having a particle size of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
In a specific embodiment, the present invention provides a synergistic composition of propineb and metominostrobin, wherein propineb and metominostrobin having a particle size (d50, determined after dispersion in the water phase by laser diffraction) of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
In one embodiment, the combination or composition of propineb and metominostrobin of the present invention may further comprise of insecticide(s), fungicide(s), nematicide(s), acaricide(s), safener(s), or herbicide(s) or any combination thereof.
In another embodiment, the composition is selected from a wettable powder (WP), a water dispersible granule (WDG), a water dispersible tablet (WT), an ultra-low volume (ULV) liquid (UL), an ultra-low volume (ULV) suspension (SU), a water soluble powder (SP), a soluble concentrate (SL), a water soluble granule (SG), a suspo-emulsion (SE), granule (GR), an emulsifiable granule (EG), an oil-in- water emulsion (EW), an emulsifiable concentrate (EC), a micro-emulsion (ME), an oil dispersion (OD), a capsule suspension (CS), an aerosol (AE) or a mixed formulation of ZC (CS + SC), ZE (CS+SE), ZW (CS+EW).
These compositions may be manufactured by any process know in the art, such as, “Pesticide Formulation Guide” (edited by Pesticide Science Society of Japan, The Agricultural Formulation and Application Committee, published by Japan Plant Protection Association, 1997).
In a specific embodiment, the present invention provides a process for preparing a composition of propineb and metominostrobin, comprising steps of: a) addition of propineb and metominostrobin or its acceptable salt(s) thereof, b) addition of agrochemically acceptable additives selected from surfactant(s), carrier(s) and other additive(s) uniformly in a mixer; and c) optionally milling by a mill.
The composition comprising organic or inorganic carrier material including agrochemically acceptable additives are selected from the group comprising of solid carrier(s), liquid carrier(s), gaseous carrier(s), surfactant(s), binder(s), disintegrating agent(s), pH adjuster(s), thickener(s), preservative(s), anti-freezing agent(s), defoaming agent(s), extender(s), stabilizer(s) and/or coloring agent(s) or a combination thereof. The composition may also contain if desired, one or more auxiliaries customary for crop protection compositions.
Solid carrier(s) is selected from the group comprising of, but not limited to, natural minerals such as quartz, talc, kaolin, pyrophyllite, montmorillonite, attapulgite, bentonite, kieselguhr, chalk, zeolite, calcite, sericite, acid clay, diatomaceous earth, natural rock, Fuller’s earth, meerschaum, gibbsite, dolomite or pumice; synthetic minerals such as precipitated silica, fumed silica, sodium silicate, alumina, aluminum hydroxide; inorganic salts such as calcium carbonate, ammonium sulfate or other ammonium salts, sodium sulfate, potassium chloride; organic materials such as urea, solid polyoxyethylene, solid polyoxypropylene, polyethylene, polypropylene, lactose, starch, lignin, cellulose, cottonseeds hulls, wheat flour, soybean flour, wood flour, walnut shell flour, plant powders, sawdust, coconut shellflower, com cob, tobacco stem. These solid carriers may be used alone or in combination thereof. Liquid carrier(s) is selected from the group comprising of, but not limited to, water; alcohols such as ethanol, propanol, n-octanol, isopropanol ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerin; polyol ethers such as ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethers such as dipropyl ether, dioxane, tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, isoparaffin, kerosene, mineral oil; aromatic hydrocarbons such as xylene, toluene, naphthene, solvent naphtha, solvent C9, solvent CIO, solvent C12, solvesso 100, solvesso 150, solvesso 200; chlorinated aliphatic or aromatic hydrocarbons such as chlorobenzene, chloroethylene, methylene chloride; esters such as ethyl acetate, diisopropyl phthalate, dimethyl adipate, methyl oleate, methyl tallowate; lactones such as gamma-butyrolactone; amides such as dimethylformamide, N-methyl-2-pyrrolidone, N-octylpyrolidone, N,N- dimethyldecanamide; nitriles such as acetonitrile; organosulfur compound such as dimethyl sulfoxide; vegetable oils such as soybean oil, rapeseed oil, cotton seed oil. These liquid carriers may be used alone or in combination thereof.
Gaseous carrier(s) is selected from the group comprising of, but not limited to, liquefied petroleum gas, air, nitrogen, carbon dioxide or dimethyl ether. These gaseous carriers may be used alone or in combination thereof.
Surfactant(s) (a dispersing agent, a wetting agent, a spreader, an adjuvant for penetration enhancement, rain fastness, soil leaching control etc.) are nonionic or anionic surfactants or a combination of these surfactants. It is preferred to use one or more than one kind of surfactant. Surfactant(s) is selected from the group comprising of, but not limited to, sugar esters such as sorbitan monolaurate, polyoxyethylene sorbitan monolaurate; alkyl poly gluco side such as decyl glucoside; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether or polyoxyethylene coconut fatty alcohol ether; polyoxyethylene alkynyl ether such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol ether; polyoxyethylene aryl ethers such as polyoxyethylene nonylphenyl ether or polyoxyethylene tristyrylphenyl ether; polyoxyethylene vegetable oil ethers such as polyoxyethylene castor oil or polyoxyethylene hydrogenated castor oil; polyoxyethylene fatty acid esters such as polyoxyethylene monolaurate, polyoxiethylene distearate or polyoxyethylene resin acid ester; polyoxyethylene polyoxypropylene block copolymers (such as Pluronic®); polyoxyethylene polyoxypropylene alkyl ether such as polyoxyethylene polyoxypropylene lauryl ether; polyoxyethylene polyoxypropylene aryl ether such as polyoxyethylene polyoxypropylene styrylphenyl ether; polyoxyethylene alkyl amines such as polyoxyethylene stearyl amine; polyoxyethylene fatty acid amide such as lauric acid diethanolamid; fluorinated surfactant; alkyl sulfates such as sodium lauryl sulfate, sodium alkylbenzene sulphonate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate; polyoxyethylene aryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate or ammonium polyoxyethylene tristyrylphenyl ether sulfate; aryl sulfonate such as calcium dodecyl benzene sulfonate, sodium naphthalene sulfonate or sodium naphthalene sulfonate formaldehyde condensate; ‘alpha’ -olefin sulfonate; alkyl sulfosuccinate such as sodium dioctyl sulfosuccinate; lignin sulfonate such as sodium lignosulfonate; polycarboxylic acid sodium salt; N-methyl fatty acid sarcosinate; polyoxyethylene alkyl ether phosphate; polyoxyethylene aryl ether phosphates such as polyoxyethylene phenyl ether phosphate or polyoxyethylene nonylphenyl ether phosphate; polyoxyethylene polyoxypropylene block copolymer phosphate; graft copolymer such as polymethyl methacrylate-polyethylene glycol graft copolymer. These surfactants may be used alone or in combination thereof.
Binder(s) or adhesive-imparting agent(s) is selected from the group comprising of, but not limited to, polyvinyl alcohol, dextrin, denatured dextrin, soluble starch, guar gum, xanthan gum, sucrose, polyvinylpyrrolidone, gum arabic, polyvinyl acetate, sodium polyacrylate, carboxymethyl cellulose or its salt, carboxymethylcellulose dextrin, bentonite, polyethylene glycol having an average molecular weight of 6,000 to 20,000, polyethylene oxide having average molecular weight of 100,000 to 5,000,000, natural phosphatide such as cephalinic acid or lecithin. These binders or adhesive-imparting agents may be used alone or in combination thereof.
Disintegrating agent(s) is selected from the group comprising of, but not limited to, sodium tripolyphosphate, stearic acid metal salt, cellulose powder, dextrin, methacrylate copolymer, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compound, styrene sulfonate/isobutylene/maleic anhydride copolymer, starch/polyacrylonitrile graft copolymer, sodium hexametaphosphate, carboxymethyl cellulose, sodium polycarbonate, bentonite. These disintegrating agents may be used alone or in combination thereof. pH adjuster(s) is selected from the group comprising of, but not limited to, sodium or potassium carbonate, sodium or potassium hydrogen carbonate, sodium or potassium dihydrogen phosphate, disodium or dipotassium hydrogen phosphate, citric acid, malic acid and triethanolamine. These pH adjusters may be used alone or in combination thereof.
Thickener(s) is selected from the group comprising of, but not limited to, water-soluble polymer and inorganic fine powder, wherein water-soluble polymer such as xanthan gum, welan gum, guar gum, polyvinyl alcohol, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative or polysaccharide; or an inorganic fine powder selected from high purity silica, bentonite, white carbon. These thickeners may be used alone or in combination thereof.
Preservative(s) is selected from the group comprising of, but not limited to, potassium sorbate, 4-hydroxybenzoic acid esters, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4- isothiazolin-3-one, l,2-benzisothiazolin-3-one (Proxel® GXL). These preservatives may be used alone or in combination thereof.
Anti-freezing agent(s) is selected from the group comprising of, but not limited to, polyhydric alcohol such as ethylene glycol, polyethylene glycol, diethylene glycol, propylene glycol, and glycerol. These anti-freezing agents may be used alone or in combination thereof.
Defoaming agent(s) is selected from the group comprising of, but not limited to, silicone compounds such as polysiloxane, polydimethyl siloxane and organic fluorine compounds. These defoaming agents may be used alone or in combination thereof.
Extender(s) is selected from the group comprising of, but not limited to, silicon type surfactant, a cellulose powder, dextrin, processed starch, a polyaminocarboxylic acid chelate compound, crosslinked polyvinylpyrrolidone, maleic acid and styrene, methacrylic acid copolymer, half ester of polymer of polyhydric alcohol with dicarboxylic anhydride, or water-soluble salt of polystyrene sulfonic acid. These extenders may be used alone or in combination thereof.
Stabilizer(s) is selected from the group comprising of, but not limited to, drying agents such as zeolite, quicklime or magnesium oxide; antioxidant agents such as phenol type, amine type, sulfur type or phosphorus type; or ultraviolet absorbers such as salicylic acid type or a benzophenone type. These stabilizers may be used alone or in combination thereof. Coloring agent(s) is selected from the group comprising of, but not limited to, inorganic pigments such as iron oxide, titanium oxide or prussian blue; organic dye such as alizarin dye, azo dye, metal phthalocyanine dye. These coloring agents may be used alone or in combination thereof.
When additive ingredients are incorporated into the composition of the present invention, the content of the carrier is selected typically in a weight range from 5% to 95%, preferably from 20% to 90%; the content of the surfactant is selected from the range of typically from 0.1% to 30%, preferably from 0.5% to 10%, and the content of the other additives is selected from the range of typically from 0.1% to 30%, preferably from 0.5% to 10%.
In one embodiment, the present invention provides a water dispersible granule (WDG) composition of propineb and metominostrobin.
In another embodiment, the present invention provides a wettable powder (WP) composition of propineb and metominostrobin.
In yet another embodiment, the present invention provides a suspension concentrate (SC) composition of propineb and metominostrobin.
In one another embodiment, the present invention provides an oil dispersion (OD) composition of propineb and metominostrobin.
In an embodiment, the present invention provides a general process for preparing water dispersible granules (WDG) formulation, comprising steps of: a) mix sodium lauryl sulphate (SLS) & sodium lignosulfonate (SLS) with the actives propineb and metominostrobin thoroughly. b) slowly add kaolin and silica to the above mixture under constant mixing at low speed (10-15 rpm) c) dissolve lactose in water 2%w/w and add to the material in step 1 and 2 under constant stirring. d) slowly add the sodium sulphate powder under constant mixing to obtain a uniformly wet powdery material. e) extrude the above material through an extruder to obtain granules of required shape and size. f) dry the granules in a fluid bed dryer for a final moisture content of 0.2%w/w.
In another embodiment, the composition of the present invention can be applied by any one of the methods selected from atomization, spreading, dusting, spraying, diffusion, immersion, irrigation, injection, mixing, sprinkling (water immersion), foaming, dressing, coating, blasting, fumigation, smoking, smog and painting.
In another embodiment, the present invention provides a method of controlling a wide variety of undesired pathogenic microorganism, with an effective amount of a composition of propineb and metominostrobin. In a preferred another preferred embodiment, the present invention provides a fungicidal combination or composition comprising of propineb and metominostrobin to control the pathogenic microorganism on economically important crops such as rice, peppers, soybean, cotton, chick pea, pigeon pea, tea, potato, and tomato.
In a specific embodiment, the present invention further provides a composition for the control of a wide variety of, pathogenic microorganism, wherein the weight percentage of propineb or its acceptable salt(s) thereof is 80% to 2% and the weight percentage of metominostrobin or its acceptable salt(s) thereof is 2% to 80%. The total content of propineb and metominostrobin in the composition is selected in the weight range typically from 10% to 90%, preferably from 20% to 80%.
In an embodiment, the composition of the present invention used to control a wide variety of undesired pathogenic microorganism, is advantageous, for several purposes, e.g.: a) useful for addressing a wider range of undesired pathogenic microorganisms e.g. fungicidal activity; b) offering a single application as a uniform composition in place of separate applications of fungicides; c) offering crop health improvement in comparison to separate applications of fungicides; d) offers longer residual control after application of the composition.
In another embodiment, the present invention provides a combination/composition that shows enhanced action against undesired pathogenic microorganisms, in comparison to the control rates that are possible with the individual compounds and/or suitable for improving the health of plants when applied to plants, parts of plants, plant propagation materials, or at their locus of their growth.
In yet another embodiment, the present invention provides a method of controlling a wide variety of undesired pathogenic microorganism with an effective amount of the combination/ composition of propineb and metominostrobin with fungicidal compound. The undesired pathogenic microorganism for the present invention is selected from the group comprising of Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. Candida) and sunflowers (e.g. A. tragopogonis), Alternaria spp. (Alternaria leaf spot) on vegetables, citrus fruits (A. citri), rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e.g. A. solani or A. alternata), tomatoes (e.g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cotton, cereals and vegetables, e.g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp. for e.g. Cochliobolus carbonum (northern corn leaf blight)), e.g. Southern leaf blight ( D . maydis) or Northern leaf blight (B. zeicola) on corn, e.g. spot blotch (B. sorokiniana) on cereals, e.g. B. oryzae on rice and turfs and on oats; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.g. strawberries), vegetables (e.g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broadleaved trees and evergreens, e.g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn and cotton, (Cercospora blight spots) on cotton, (e.g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e.g. C. beticola), sugar cane, vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchii) and rice, sunflower (e.g. cercospora leaf spot: C. helianthi), peanut (e.g. early leaf spot: C. arachidicola) Cercosporidium spp. on peanut (e.g. C. personatum: late leaf spot); Cladosporium spp. on tomatoes (e.g. C. fulvum: leaf mold) and cereals, e.g. C. herbarum (black ear) on wheat, C. caryigenum (pecan scab) on pecan; Cylindrocladium spp. on peanut (C. crotalariae: cylindrocladium black rot); Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e.g. C. sativus (black point), anamorph: B. sorokiniana) and rice (e.g. C. miyabeanus, anamorph: H. oryzae)·, Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e.g. C. gossypii), corn (e.g. C. graminicola : Anthracnose stalk rot), soft fruits, potatoes (e.g. C. coccodes: black dot), beans (e.g. C. Iindemuthianum), citrus fruits (e.g. C. acutatum (post bloom fruit drop), C. gloeosporioides ) and soybeans (e.g. C. truncatum or C. gloeosporioides), Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e.g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia ) necatrix (root and stem rot) on soybeans; Diplodia spp. e.g. Diplodia boll rot on cotton, Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans, D. citri (melanose) on citrus fruits; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora ) spp. on com, cereals, such as barley (e.g. D. teres , net blotch), oats (e.g. D. avenae, leaf spot), and wheat (e.g. D. tritici-repentis : tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus ) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum ), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa Elsinoe spp. on pome fruits (F. pyri), on citrus fruits (F. fawcetti ), soft fruits ( E . veneta : anthracnose) and vines {F. ampelina : anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets ( E . betae ), (powdery mildew) on rye ( E . gramini ), vegetables (e.g. E. pisi ), such as cucurbits (e.g. E. cichoracearum), cabbages, sunflower, rape (e.g. E. crucifer arum), peas and bean (e.g. E. polygoni)·, Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Elelminthosporium) spp. on com (e.g. E. turcicum), Fusarium (teleomorph: Gibberella ) spp. (wilt, root or stem rot) on various plants, such as hardlock, boll rot of cotton, F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e.g. wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e.g. wheat or barley) and corn; Gibberella spp. on cereals (e.g. G. zeae) and rice (e.g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fmits and other plants and G. gossypii on cotton; Grain staining complex on rice; Guignardia bidwellii (black rot) on vines, Guignardia citricarpa (balck spot) on citrus fmits; Gymnosporangium spp. on rosaceous plants and junipers, e.g. G. sabinae (mst) on pears; Elelmintho sporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e.g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Kabatiella zeae (eyespot) on corn; Leptosphaeria maculans (blackleg) on oilseed crops; Leptosphaerulina spp. on peanut (e.g. L. crassiasca: pepperspot); Macrophomina phaseolina (syn. phaseoli ) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium ) nivale (pink snow mold) on cereals (e.g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Myeosphaerella citri (greasy spot) on citrus fruit, Monilinia spp., e.g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Myeosphaerella spp. on peas and beans, cereals, bananas, soft fruits and ground nuts, such as e.g. M. graminicola (anamorph: Septoria tritici, Septoria blotch ) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e.g. P. brassicae), rape (e.g. P. parasitica), onions (e.g. P. destructor), tobacco ( P . tabacina ) and soybeans (e.g. P. manshuricaf, Phyllosticta maydis (yellow leaf blight) on corn; Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e.g. on vines (e.g. P. tracheiphila and P. tetraspora ) and soybeans (e.g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets, Phoma exigua (ascochyta blight) on peas and beans, phoma blight, boll rot on cotton, Phoma arachidicola (web blotch) on peanut; Phomopsis spp. on sunflowers, vines (e.g. P. viticola: can and leaf spot) and soybeans (e.g. stem rot: phaseoli, teleomorph: Diaporthe phaseolorumf, Phykopsora spp. e.g. rust on cotton, Physoderma maydis (physoderma brown spot) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e.g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e.g. P. infestans: late blight), broad-leaved trees (e.g. P. ramorum : sudden oak death) and peas and beans (e.g. P. nicotianae : downy mildew); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e.g. P. viticola (downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e.g. P. leucotricha on apples; Polymyxa spp., e.g. on cereals, such as barley and wheat ( P . graminis ) and sugar beets ( P . betae ) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae ) on cereals, e.g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e.g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or rotbrenner, anamorph: Phialophora ) on vines; Puccinia spp. (rusts) on various plants, e.g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e.g. wheat, barley or rye ( P . recondita), P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus, P. coronata (crown rust) and P. graminis (stem rust) on oats, P. arachidis (rust) on peanut; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat, P. feres (net blotch) on barley, or P. avenae (leaf blotch) on oats; Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e.g. P. ultimum or P. aphanidermatum), Ramularia spp., e.g. R. collo-cygni ( Ramularia leaf spots, physiological leaf spots) on barley and mint, and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e.g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice and peanut, or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e.g. S. sclerotiorum ) and soybeans (e.g. S. rolfsii or S. sclerotiorum ), S. minor (sclerotinia blight) on peanut, S. sclerotiorum (white mold) on potato; Sclerotium spp. on peanut (e.g. S. rolfsii ); Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. nodorum (syn. Stagonospora ) (Stagonospora blotch) on cereals, S. avenae (septoria blotch) on oats, S. linicola (pasmo) on flax seed; Uncinula (syn. Erysiphe ) necator (powdery mildew, anamorph: Oidium tuckeri ) on vines; Setospaeria spp. (leaf blight) on com (e.g. S. turcicum, syn. Helminthosporium turcicum ) and turf; Sphacelotheca spp. (smut) on com, (e.g. S. reiliana : head smut), sorghum und sugarcane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e.g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria (syn. Phaeosphaeria ) nodorum ) on wheat, septrotia leaf and glume blotch on rye; Stemphyllium spp. e.g. stemphy Ilium leaf spot on cotton, Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fmits, vegetables, soybeans and cotton, e.g. T. basicola (syn. Chalara elegansf Tilletia spp. (common bunt or stinking smut) on cereals, such as e.g. T. tritici (syn. T. caries , wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e.g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e.g. U. appendiculatus, syn. U. phaseoli ) and sugar beets (e.g. U. betae ); Ustilago spp. (loose smut) on cereals (e.g. U. nuda and U. avaenae ), com (e.g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e.g. V. inaequalis ) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e.g. V. dahliae on strawberries, rape, potatoes and tomatoes.
In another embodiment, the fungicidal composition or combination according to the present invention is distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-bome fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
In another preferred embodiment, the combination or composition of the present invention provides a non-agronomic (other than field crops) application such as application on horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.).
In yet another embodiment, the combination or the composition of the present invention is particularly important for controlling a multitude of undesired pathogenic microorganisms, on various cultivated plants or plant parts, such as cereals, e.g. wheat, rye, barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as com, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e.g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
In one embodiment, the rate of application amount varies depending on, for example, the blending ratio of an active ingredient, a metrological condition, a dosage form, an application time, an application method, an application place, a pest to be controlled, and a target crop, in ordinary cases.
In another embodiment, a method of combating pathogenic microorganism depending on the type of compound and the desired effect, the application rates of the active ingredients in the mixture according to the invention are preferably from 5000 to 2500g/l/ha, more preferably from 3000 to 1500g/l/ha, most preferably from 2500 to lOOOg/l/ha.
In a further embodiment, the present invention provides a method for improving crop health (phyto-tonic effect), comprising treating a plant with an effective amount of composition of propineb and metominostrobin.
The present invention is further illustrated by the following examples. These examples describe possible preferred embodiments for illustrative purposes only, but they do not limit the scope of the invention. These laboratory scale experiments can be scaled up to industrial/ commercial scale.
Example 1: Water Dispersible Granule (WDG)
Figure imgf000021_0001
Example 2: Water Dispersible Granule (WDG)
Figure imgf000022_0001
Example 3: Water Dispersible Granule (WDG)
Figure imgf000022_0002
Example 4: Wettable Powder (WP)
Figure imgf000022_0003
Figure imgf000023_0004
Example 5: Wettable Powder (WP)
Figure imgf000023_0001
Example 6: Wettable Powder (WP)
Figure imgf000023_0002
Example 7: Suspension Concentrate (SC)
Figure imgf000023_0003
Figure imgf000024_0001
Example 8: Suspension Concentrate (SC)
Figure imgf000024_0002
Example 9: Oil Dispersion (OD)
Figure imgf000024_0003
Example 10: Oil Dispersion (OD)
Figure imgf000024_0004
Figure imgf000025_0001
Example 11: Oil Dispersion (OD)
Figure imgf000025_0002
Example 12: Oil Dispersion (OD)
Figure imgf000025_0003
Biological Examples:
Experiments were carried out to study synergies if any in terms of disease, pest control, crop vigour, and yield with the combinations of the present invention. Bio-efficacy assessments were done for the control of leaf spots, blast disease, late blight disease in rice, fruits and vegetable pathogens and its indirect influence on vigor and yield.
Figure imgf000025_0004
Figure imgf000026_0001
Combinations are tank mix
Field Trials
Trials were conducted in the field to test the efficacy of the combination of propineb and metominostrobin for controlling leaf spots, blast, late blight in rice and fruits and vegetable pathogens at different test concentrations.
Disease severity was recorded one day before application and 3, 7 and 10 days post application. Crop vigour was recorded at 30 days after application.
At the time of application the crop (rice, potato) indicated 5-10% disease severity. The composition comprising the compound of component (1) and the component (2) may show a synergistic effect. According to the present invention, a synergistic effect of the combination is always present when the pesticidal activity of the active compound combinations exceeds the total of the activities of the individual combining partners when applied individually. The expected activity for a given combination of two active compounds (binary mixture) can be calculated by using the Colby’s formulas (COLBY, S.R. "Calculating synergistic and antagonistic responses of herbicide combination", Weeds, Vol. 15, pages 20-22; 1967).
Colby's formula:
The expected activity for a given combination of two active compounds (binary composition) can be calculated as follows:
XY
E - X + y - -
100
In which E represents the expected percentage of inhibition of the disease for the combination of two pesticides at defined doses (for example equal to x and y respectively), x is the percentage of inhibition observed for the disease by the compound (1) at a given dose (equal to x), y is the percentage of inhibition observed for the disease by the compound (2) at a defined dose (equal to y). When the percentage of inhibition observed for the combination is greater than E, there is a synergistic effect. Here the efficacy is determined in %. 0 % means an efficacy which corresponds to that of control, whereas 100 % means that no infection is observed.
If an actual combination exceeds the calculated value, the action of the combination is super additive i.e., synergistic effect is present, in this case the actually observed efficacy must exceed the value calculated using the above formula for expected efficacy (E). In case of purely complementary addition of activities (expected activity), said difference (O-E) is zero. A negative value of said difference (O-E) signals a loss of activity compared to the expected activity. However, besides the actual synergistic action with respect to fungicidal activity, the composition according to the invention can also have further surprising advantageous properties. Examples of such advantageous properties that may be mentioned are: more advantageous degradability; improved toxicological and ecotoxicological behaviours; or improved characteristics of plants including, emergence, higher yields, better developed root system, tillering increases, increase in plant height, bigger blades, stronger tillers, greener leaf colour, early flowering, early maturity, increased shoot growth, increased plant vigour and early germination.
In vitro test for combinations were conducted using food poison method to observe synergy.
Example 1: Pyricularia oryzae (Rice blast):
Compounds (A and B, A+B) were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 ml medium with the compound in the desired concentration was dispensed into 60 mm sterile petri -plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and then the radial growth of the combination and the single compounds was measured in comparison to the one in the respective untreated controls to evaluate the efficacy. A synergistic effect was found when the activity of the mixture was exceeding the one of the individual compounds combined.
Example 2: Rhizoctonia solani (Rice sheath blight/ Potato black scurf):
Compounds (A and B, A+B) were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 ml medium with the compound in the desired concentration was dispensed into 60 mm sterile petri -plates. After solidification each plate was seeded with a 5mm size mycelial disc taken from the periphery of an actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and then the radial growth of the combination and its single components was compared to the one in their respective untreated control. A synergistic effect was seen when the efficacy of the combination was higher than the combined activity of the single compounds.
Example 3: Alternaria solani (Early blight of tomato/potato):
Compounds (A and B, A+B) were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 ml medium with the compound in the desired concentration was dispensed into 60 mm sterile petri -plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and then the radial growth of the combination and the single compounds was measured and compared to the one of the respective individual control. Combinations showed synergistic effects when the efficacy of the combination was higher when compared to the combined activity of the single compounds.
Example 4: Corynespora cassucola (CORYCA)
Compounds (A and B, A+B) were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into Petri dishes. 5 ml medium with the compound in the desired concentration was dispensed into 60 mm sterile petri -plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 70% relative humidity for seven days and then the radial growth was measured and compared to that of the respective individual control. A synergistic effect was found when the activity of the combination was higher than the ones of the single compounds combined.
Example 5: Phytophthora infestans (Late blight of potato & tomato):
Compounds (A and B, A+B) were dissolved in 0.3% dimethyl sulfoxide and then added to rye agar medium just prior to dispensing it into petri dishes. 5 ml medium with the compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate. Plates were incubated in growth chambers at 18 °C temperature and 95% relative humidity for seven days and radial growth was measured and compared to that of the respective individual control. A synergistic effect was found when the efficacy of the combination was higher than the activity of the single compounds combined.
Greenhouse trials:
Example 1: Pyricularia oryzae test in Rice
Compounds (A and B and A+B) were dissolved in 2% dimethyl sulfoxide/ acetone and then mixed with water containing emulsifier to the calibrated spray volume of 50 ml. This 50 ml spray solution was poured into the spray bottles for further applications.
To test the preventive activity of compounds, healthy young rice seedlings/ plants raised in the greenhouse were sprayed with active compound preparation at the stated application rates inside the generation-3 spray cabinets using hallow cone nozzles. One day after the treatment, the plants were inoculated with a spore suspension (2% malt solution) containing 1.4 x 106 Pyricularia oryzae inoculum and then an equal amount/ quantity of infected sorghum grain powder containing the pathogen was added. The inoculated plants were kept in the greenhouse chamber at 28 °C temperature and 95% relative humidity for disease expression.
A visual assessment of the compound performance was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7 and 10 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with the one in the untreated control. The treated plants were also assessed for phytotoxic effects by recording symptoms like necrosis, chlorosis & stunting. The percentage efficacy of Compound A, Compound B and mixtures thereof were calculated against Pyricularia oryzae. The results were tabulated as hereunder:
Table 1
Figure imgf000030_0001
Example 2: Alternaria solani & Phytopthora infestans test in Tomato
Compounds (A and B, A+B) were dissolved in 2% dimethyl sulfoxide/ acetone and then mixed with water containing emulsifier to a calibrated spray volume of 50 ml. This 50 ml spray solution was poured into the spray bottles for further applications.
To test the preventive activity of compounds, healthy young tomato plants raised in the greenhouse were sprayed with active compound preparation at the stated application rates inside spray cabinets using hallow cone nozzles. One day after treatment, the plants were inoculated with a spore suspension (2% malt) containing 0.24 x 106 Alternaria solani inoculum, and additionally with a spore suspension (tween 20 water solution) containing 2.6 x 106 Corynespora cassiicola inoculum and with a sporangial suspension (sterile water) containing 0.24 x 106 Phytopthora infestans inoculum. After inoculation the plants were kept in darkness at 20 °C during 24 hours. Then they were transferred to a greenhouse chamber with 22 °C temperature and 95-100 % relative humidity for disease expression.
A visual assessment of the performance of the compounds was carried out by rating the disease severity (0-100% scale) on treated plants 3, 7 and 10 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatments with the one of the untreated control. The treated plants were also assessed for plant compatibility by recording symptoms like necrosis, chlorosis & stunting. The percentage efficacy of Compound A, Compound B and mixtures thereof were calculated 5 against Alt e maria solani and Phytopthora infestans. The results were tabulated as hereunder:
Table 2a:
Figure imgf000031_0001
Table 2b:
Figure imgf000031_0002
Figure imgf000032_0001
Example 3: Rhizoctonia solani test in Rice
Compounds (A & B combination ratio) were dissolved in 2% DMSO/ acetone and then mixed with water to a calibrated spray volume of 50 ml. This 50 ml spray solution was 5 poured into the spray bottles for further applications.
To test the preventive activity of compounds, healthy young rice seedling/ plants raised in the greenhouse were sprayed with active compound preparation at the stated application rates inside the spray cabinets using hallowcone nozzles. One day after treatment, the plants were 10 inoculated with equal quantity of infected rice bran containing Rhizoctonia solani. The inoculated plants were then kept in greenhouse chamber at 24-25 °C temperature and 90-95 % relative humidity for disease expression.
A visual assessment of compound’s performance was carried by rating the disease severity 15 (0-100% scale) on treated plants on 3, 7, 10 and 15 days after application. Efficacy (% control) of the compounds was calculated by comparing the disease rating in the treatment with untreated control. The sprayed plants were also assessed for compound’s phytotoxic effects by recording symptoms like necrosis, chlorosis and stunting. The percentage efficacy of Compound A, Compound B and mixtures thereof were calculated against Rhizoctonia 20 solani. The results were tabulated as hereunder:
Table 3:
Figure imgf000032_0002
Figure imgf000033_0001
The novel agrochemical composition of the invention also exhibits vigorous growth in crop. Vigour, here refers to early leaf area development and growth rate of the crop, has often been associated with improved competitive ability. Rapid canopy closure allows crops to quickly shade the ground and competing plants. Vigorous early growth may also promote greater root growth and improve WUE (Siddique el ah, 1990; Richards el ah, 2007; Richards, 2008), which may contribute to higher yields in water and nutrient-limited environments overall a potent strengthening effect in plants is observed. Accordingly, they can be used for mobilizing the defenses of the plant against the attack by undesirable microorganisms. Increased plant vigor, comprising plant health / plant quality and seed vigor, reduced stand failure, improved appearance, increased recovery after periods of stress, improved pigmentation (e.g. chlorophyll content, stay-green effects, etc.) and improved photo synthetic efficiency. Table 4: Vigour index followed
Figure imgf000033_0002
Additive effects and antagonist ones are presented in percentage of disease control, vigour and yield in the table. Conclusion:
From the above results, it is concluded that the combination of propineb and metominostrobin is showing synergy against Pyricularia oryzae, Rhizoctonia solani in rice and Phytopthora infestans, Alternaria solani in tomato. Thus, from the foregoing description, it will be apparent to a person skilled in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth in the description. Accordingly, it is not intended that the scope of the foregoing description be limited to the description set forth above, but rather that such description be construed as encompassing such features that reside in the present invention, including all the features and embodiments that would be treated as equivalents thereof by those skilled in the relevant art.

Claims

CLAIMS:
1. A synergistic combination comprising: a) propineb, or its acceptable salt(s) thereof; b) metominostrobin, or its acceptable salt(s) thereof and optionally comprises one or more insecticide(s), fungicide(s), acaricide(s), nematicide(s), safener(s), herbicide(s) or any combination thereof.
2. The synergistic combination as claimed in claim 1, wherein the ratio of propineb and metominostrobin is from 20:1 to 1:20, preferably from 12:1 to 4:1, more preferably 10:1 to 7:1.
3. A synergistic composition comprising: a) propineb, or its acceptable salt(s) thereof; b) metominostrobin, or its acceptable salt(s) thereof; and optionally comprises one or more insecticide(s), fungicide(s), acaricide(s), nematicide(s), safener(s), herbicide(s) or any combination thereof; and c) agrochemically acceptable additives.
4. The synergistic composition as claimed in claim 3, wherein the ratio of propineb and metominostrobin is from 20:1 to 1:20, preferably from 12:1 to 4:1, more preferably 10:1 to 7:1.
5. The synergistic combination as claimed in claim 1 or the synergistic composition as claimed in claim 3, wherein the propineb and metominostrobin having a particle size of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
6. The synergistic combination as claimed in claim 1 or the synergistic composition as claimed in claim 3, wherein the propineb and metominostrobin having a particle size (d50, determined after dispersion in the water phase by laser diffraction) of 2 to 80 pm, more preferably 5 to 30 pm, most preferably 5 to 10 pm.
7. The synergistic composition as claimed in claim 3, wherein agrochemically acceptable additives are selected from the group comprising of solid carrier(s), liquid carrier(s), gaseous carrier(s), surfactant(s), binder(s), disintegrating agent(s), pH adjuster(s), thickener(s), preservative(s), anti-caking agent(s), anti-freezing agent(s), defoaming agent(s), extender(s), stabilizer(s) and/or coloring agent(s) or a combination thereof.
8. The synergistic composition as claimed in claim 3, wherein said composition is selected from a suspension concentrate (SC), a wettable powder (WP), a water dispersible granule (WDG), a water dispersible tablet (WT), an ultra-low volume (ULV) liquid (UL), an ultra-low volume (ULV) suspension (SU), a water soluble powder (SP), a soluble concentrate (SL), a water soluble granule (SG), a suspo- emulsion (SE), granule (GR), an emulsifiable granule (EG), an oil-in-water or water- in-oil emulsion (EW), an emulsifiable concentrate (EC), a micro-emulsion (ME), an oil dispersion (OD), a capsule suspension (CS), an aerosol (AE) or a mixed formulation of CS and SC (ZC).
9. The synergistic composition as claimed in claim 3, wherein said composition preferably is a suspension concentrate (SC), a water dispersible granule (WDG), a wettable powder (WP) or an oil dispersion (OD).
10. A method for preparation of the synergistic composition as claimed in claims 8-9, comprising steps of: a) addition of propineb, or its acceptable salt(s) thereof, and metominostrobin, or its acceptable salt(s) thereof; b) addition of agrochemically acceptable additives selected from surfactant(s), carrier(s) and other additive(s) uniformly in a mixer; and c) optionally milling by a mill.
11. A method for the management of the undesired phytopathogenic fungi and/or microorganisms, said method comprising applying to the phytopathogenic fungi and/or microorganisms the combination as claimed in claim 1 or the composition as claimed in claim 3.
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