DESC:FIELD OF THE INVENTION:

The present invention relates to synergistic fungicidal compositions of bioactive amounts of Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin. The present invention also relates to process for preparing the said compositions comprising bioactive amounts of Metalaxyl M and one or more agrochemically active ingredients along with at least one inactive excipient.

BACKGROUND OF THE INVENTION

Fungi serve as the planet's decomposers by breaking down organic material in nature, while many form healthy symbiotic relationships with plants in the soil. Unfortunately some fungi develop parasitic relationships with plants where the plant is harmed making it important to have the proper fungicide to minimize those effects.

Fungi are plants which obtain their nutrition from an organic carbon source. The body of the fungus secretes enzymes which degrade the organic substrate on which they are growing and yield smaller entities. These in turn are absorbed into the body of the fungus and are metabolized and provide energy to carry on vital processes.

Fungicides can either be contact, translaminar or systemic. Contact fungicides are not taken up into the plant tissue, and protect only the plant where the spray is deposited; translaminar fungicides redistribute the fungicide from the upper, sprayed leaf surface to the lower, unsprayed surface; systemic fungicides are taken up and redistributed through the xylem vessels. Few fungicides move to all parts of a plant. Some are locally systemic, and some move upwardly.

Fungicides also can be classified based upon their chemical composition. Chemically, organic molecules are those that contain carbon atoms in their structure whereas inorganic molecules do not. Many of the first fungicides developed were inorganic compounds based on sulfur or metal ions such as copper, tin, cadmium and mercury that are toxic to fungi. Copper and sulfur are still widely used. Most other fungicides used today are organic compounds and thus contain carbon. The term "organic" as used here is based on chemistry terminology and differs from "organic" used to describe a system of agriculture that strives to be holistic and to enhance agro ecosystem health.

Fungicides kill fungi by damaging their cell membranes, inactivating critical enzymes or proteins, or by interfering with key processes such as energy production or respiration. Others impact specific metabolic pathways such as the production of sterols or chitin. In recent developments, the newly developed fungicides are unique in that they do not directly affect the pathogen itself. Many of new fungicides elicit a response from the host plant known as "systemic acquired resistance" (SAR). These SAR inducers basically mimic chemical signals in plants that activate plant defense mechanisms such as the production of thicker cell walls and anti-fungal proteins. The utility of SAR inducers, however, has been limited so far since many pathogens are capable of over-powering such defenses.

Fungicide resistance is a stable, heritable trait that results in a reduction in sensitivity to a fungicide by an individual fungus. This ability is obtained through evolutionary processes. Fungicides with single-site mode of action are at relatively high risk for resistance development compared to those with multi-side mode of action. Most fungicides being developed today have a single-site mode of action because this is associated with lower potential for negative impact on the environment, including non-target organisms.

When fungicide resistance results from modification of a single major gene, pathogen subpopulations are either sensitive or highly resistant to the pesticide. Resistance in this case is seen as complete loss of disease control that cannot be regained by using higher rates or more frequent fungicide applications. This type of resistance is commonly referred to as "qualitative resistance."

The control of phytopathogenic fungi is of great economic importance since fungal growth on plants or on parts of plants inhibits production of foliage, fruit or seed, and the overall quality of a cultivated crop.

Metalaxyl M is methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate and has the structure

Metalaxyl M is a phenylamide fungicide with systemic function. Its chemical name is methyl N-(methoxyacetyl)-N-(2,6-xylyl)-D-alaninate. It can be used to control Pythium in a number of vegetable crops, and Phytophthora in peas. Metalaxyl has been known to those skilled in the art that the R-enantiomer (Metalaxyl M) is far superior to the S-enantiomer in terms of fungicidal action and is in practice regarded as the actual mechanism of action. Commercial metalaxyl is available in the form of the racemate. Likewise, mixtures of metalaxylracemate with mancozeb, chlorothalonile, copper preparations, folpet, fluazinam or cymoxanil have become known commercially and otherwise.

Metalaxyl M is a fungicide, protective, can be absorbed by plant roots, stems, and subsequently within the body of water transport, and transferred to the various organs of the plant. Metalaxyl M is synthetic inhibitors of ribosomal RNA I mainly inhibit protein synthesis in vivo mycelial to nutritional deficiencies.

Coumethoxystrobin is first disclosed in US7642364B2. Coumethoxystrobin is chemically known as methyl (2E)-2-{2-[(3,4-dimethyl-2-oxo-2H-chromen-7-yl)oxymethyl]phenyl}-3-methoxyacrylate and having chemical structure as below;

Dimoxystrobin is first disclosed in US 5395854A, US5516804, US5523454, US5677347. Dimoxystrobin is chemically known as E)-2-(2,5-Dimethylphenoxymethyl)-alpha-methoxyimino-N-ethylphenylacetamid and having chemical structure as below;

Metominostrobin and its fungicidal activity were first disclosed in EP0398692. Metominostrobin is chemically known as (E)-a-(methoxyimino)-N-methyl-2-phenoxy-benzeneacetamide having chemical structure as below;

Metominostrobin is one of the broad-spectrum, systemic fungicides with preventative and curative activity. Metominostrobin is mainly potent on soybean rust, which can seriously damage soybeans.

Pyrametostrobin was disclosed in US7786045 B2. Pyrametostrobin is chemically known as methyl 2-[(1,4-dimethyl-3-phenylpyrazol-5-yl)oxymethyl]-N-methoxycarbanilate and having chemical structure as below;

Trifloxystrobin was first disclosed in US 5238956. Trifloxystrobin is chemically known as methyl (E)-methoxyimino-{(E)-a-[1-(a,a,a-trifluoro-m-tolyl)ethylideneaminooxy]-o-tolyl}acetate and having chemical structure as below;

Indian patent application 7325/DELNP/2011 describes compositions and uses thereof comprising a component (A) and a component (B), wherein components (A) and (B) are: (A) a carboxylic acid amide fungicide; and (B) a benzamide fungicide; with the proviso that the mixture does not comprise: 1).fluopicolide and mandipropamid and clothianidin; or 2).fluopicolide and mandipropamid and imidacloprid; or 3).fluopicolide and mandipropamid and thiamethoxam. The invention also relates to mixtures, compositions and uses thereof wherein component (A) is metalaxyl-M and component (B) is a benzamide fungicide.

Indian patent application no 7463/DELNP/2009 discloses combinations comprising the known fungicidally active compounds N-[2-(l,3-dimethylburyl) phenyl] -5-fluoro-l,3-dimethyl-lH- pyrazole-4-carboxamide, metalaxyl and strobilurin, which are highly suitable for controlling unwanted phytopathogenic fungi. Moreover, the invention relates to a method for the curative or preventive treatment of phytopathogenic fungi on plants or useful plants, in particular to the treatment of seed, for example seed of cereals, and not least to the treated seed itself.

Indian patent application 2343/CHENP/2004 describes fungicidal mixture that comprises (1) 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazolo-3-thion (prothioconazole) of the formala I or a salts or adducts thereof and at least one further fungicidal composition, selected from group consisting (2) boscalid of the formula II (3) carboxine of the formula III (4) metrafenone of the formula IV (5) a compound of the formula (V) (6) a compound of formula (VI) (7) quinoxyfen of formula (VII) (8) dithianon of the formula (VIII) (9) thiram of the formula (IX) (10) mepiquat chlorides of the formula X (11) cyazofamid of the formula XI (12) fenoxanil of the formula XII (13) a compound of the formula (XIII) (14) thiophanate methyl of the formula (XIV) (15) carbendazim of the formula (XV) (16) metalaxyl of the formula (XVI) (17) fludioxonil (18) thiabendazole of the formula (XVIII) (19) quintozene of the formula (XIX) (20) prochloraz of the formula (XX) (21) anthraquinone of the formula (XXI) in a synergistically effective amount, is described.

Indian patent application 10198/DELNP/2007 discloses a formulation mixture useful for treating plant propagation material comprising (A) Tebuconazole; and (B) one or more compounds selected from Carboxin, Chlorothalonil, Difenoconazole, Azoxystrobin, Fluquinconazole, Metalaxyl, Mefenoxam, Thiram, Abamectin, Lambda-cyhalothrin, Beta-cyflutrin, Tefluthrin, Thiamethoxam, Flubendamide and a compound of formula (A-1) and (C) one or more customary formulation adjuvants; with the proviso that the mixture excludes the mixtures consisting, as active ingredients, of (I) tebuconazole, carboxin and tridimenol and (II) tebuconazole, difenconazole and fludioxonil.

Indian patent application 515/MUMNP/2012 discloses synergistic mixtures comprising, as active components, chlorfenapyr as insecticidal compound I and a fungicidal compound Il selected from the group of azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, pico- xystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, trifloxysstrobin, 2-(ortho-((2,5-dimethylphenyl-oxymethylen)phenyl)-3-methoxy-acrylic acid methyl ester, 2-(2-(3- (2,6-dichlorophenyl) -1 – methyl -allylideneaminooxymethyl) -phenyl)-2- methoxy imino-N-methyl-acetamide.

Indian patent application 642/MUMNP/2012 describes synergistic mixtures comprising, as active components one insecticidal compound I selected from the group of acrinathrin, allethrin, alpha- cypermethrin, beta-cypermethrin, bifenthrin, cycloprothrin, cyfluthrin, cypermethrin, cyphenothrin, deltamethrin, dimefluthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, imiprothrin, permethrin, prallethrin, profluthrin, pyrethrin I, pyrethrin II, resmethrin, silafluofen, tau-fluvalinate, tetramethrin, theta-cypermethrin, tralomethrin, transfluthrin and zeta-cypermethrin; and one fungicidal compound Il selected from the group of azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, trifloxysstrobin, 2-(ortho- ((2,5-Dimethylphenyl-oxymethylen)phenyl)-3-methoxy-acrylic acid methyl ester, 2-(2- (3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino- N-methyl-acetamide in synergistic effective amounts.

Application of fungicides to plants may stimulate growth of plants by depressing growth of undesirable and/or pathogenic fungi, such as smuts, molds, rusts, and mildews. For example, a fungicide may be applied to suppress potato blight, wheat rust, wheat blight, wheat smut, or grape mildew.

One way that fungicide may be applied is as a seed treatment. This may be effective, for example, to suppress damage caused by seed decay, seedling blights, and root rots of certain seeds. Fungi that may cause this damage include, for example, species of the following genera: Pythium, Phytophthora, Rhizoctonia, Fusarium, Verticillium and Macrophomina.

Previously people have tried many alternatives and option to overcome the problem of low efficacy and development of resistance and to overcome it developed poly mixture of fungicide, use of non-toxic ingredients and developing novel compositions which provides effective amount of the pesticide, especially fungicide and at the required specific part only.

However the use of poly mixture containing large number of pesticides poses a problem in many was like preparing composition of multiple pesticides with different chemical properties and behavior and physical properties. It also creates challenge for formulator in term of compatibility and stability of all the pesticide along with used excipients in the composition.

However still there is a need for a fungicidal composition which overcomes some of the existing problems and can be prepared easily without much complex manufacturing process and exhibit synergistic effect.

Inventors of the present invention have surprisingly found that the synergistic fungicidal composition of Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin as described herein in can provide solution to the above mentioned problems.

SUMMARY OF THE INVENTION

Accordingly, in a first aspect, the present invention relates to synergistic fungicidal pesticidal compositions which comprise bioactive amounts of Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin with at least one inactive excipient.

Accordingly, in a second aspect, the present invention relates to process for preparing the synergistic fungicidal compositions comprising bioactive amounts of Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin.

Accordingly, in a third aspect, the present invention provides a method of protecting a plant propagation material, a plant, parts of a plant and/or plant organs that grow at a later point in time against pathogenic damage or pest damage by applying to the plant propagation material a composition comprising a formulated mixture defined in the first aspect.

Accordingly, in a fourth aspect the said composition is to be developed in suitable formulations selected from Flowable Slurry (FS) / Flowable Suspension(FS) / Suspension Concentrate (SC) and Water dispersible powder for slurry seed treatment (WS) comprising Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin and one or more customary formulation adjuvants such as a) dispersant b) wetting agent c) anti foaming agent d) biocides e) anti freezing agent f) suspending agent g)thickener h) coating agent and i) buffering agent.

According to another aspect of the present invention there is provided a stable formulation comprising from 1.0:20.0 Metalaxyl M and 10.0:1.0 and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin by weight of active ingredients, optional formulation also contains at least one Biocide, dispersant and thickener (or agent of suspension).

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides synergistic fungicidal compositions comprising bioactive amounts of Metalaxyl M and one more agrochemically active ingredient selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin with at least one inactive excipient.

A fungicidal effect may also be achieved by providing a seed that has been genetically engineered to produce a protein that is able to reduce the growth of undesirable and/or pathogenic fungi. Such genetically engineered organisms are reported, for example, in Herrera-Estrella, L. & Simpson, J., “Genetically Engineered Resistance to Bacterial and Fungal Pathogens” World J. of Micro. & Biotech. 11(4): 383-392 (2004) and in U.S. Pat. No. 7,098,378, to Sainz, et al.

Additionally, the present invention also comprises a method for protection of plant propagation material from phytopathogenic fungi and phytophagous insects comprising contacting the plant propagation materials with an inventive mixture in fungicidally and insecticidal effective amounts. The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring. In a particular preferred embodiment, the term propagation material denotes seeds. The present invention further relates to plant-protecting active ingredient mixtures having synergistically enhanced action of improving the health of plants and to a method of applying such inventive mixtures to the plants.

Seed coating technology is an application developed soaking or dressing in traditional technology based on common seed treatment technology. The dry or wet seeds with pesticides or fertilizers containing such binder compositions package have a protective layer formed on the function and strength of the seed coating, the coating process in the seed, the seed package. The seed coating composition is called out, for a crop or other plant seed treated with film-forming properties of the pesticide homogeneous system. The seed coating composition forming film on seed is the biggest advantage the layer of relatively solid film can be formed on the outside of the seed. The seed swelling in the soil without being dissolved, allowing moisture and air required for seed germination .The slow release fertilizer and pesticides coating on seed and other substances are required for normal seed germination. So, Seed has to kill soil pests, seedling pests, control seedling diseases and systemic diseases, improve seed germination, and promote the healthy growth of seedlings, less the amount of seeds and other effects, and ultimately achieve pest and disease prevention, strong seedlings, the purpose of improving production. Pest prevention and control issues are most prone to drug resistance, followed by a single control spectrum, many times when farmers use pesticide, causing serious environmental pollution, large field crop pesticides on human health. Applicants different fungicides and insecticides mechanism complex to achieve the purpose of preventing a double-jet, effective prevention and treatment of various diseases of crops, prevention of the original single agent to expand the spectrum, does not directly act on the crop and the crop growing period decomposition of pesticide residues on crop residue or no residue, by the food safety, and significant synergistic effects, excellent environmental compatibility, greatly reducing the amount of pesticide treatment, reducing the cost of pesticide farmers.

The term "synergistic", as used herein, refers the combined action of two or more active agents blended together and administered conjointly that is greater than the sum of their individual effects.

"Bioactive amounts” as mentioned herein means that amount which, when applied treatment of crops, is sufficient to effect such treatment.

The term composition and formulation can be used interchangeably and represent the similar meaning.

The formulation can be in various physical forms, for example in the form of a dustable powder (DP), a gel, a wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), a water-dispersible tablet (WT), an emulsifiable concentrate (EC), Flowable Suspension (FS), a micro- emulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD), a suspo-emulsion (SE), a capsule suspension (CS), a soluble liquid, a water-soluble concentrate (with water or a water-miscible organic solvent as carrier), an impregnated polymer film, or jumbo formulation.

Preferably, the formulation is in the form of a jumbo formulation, wettable powder (WP), a granule (GR) (such as an emulsifiable granule (EG) or more particularly a water-dispersible granule (WG)), an emulsifiable concentrate (EC), Flowable Suspension (FS), a microemulsifiable concentrate, an oil-in-water emulsion (EW), an oil flowable (e.g. a spreading oil (SO)), an aqueous dispersion (e.g. aqueous suspension concentrate (SC)), an oily dispersion (OD), a soluble liquid, or a water-soluble concentrate (wherein the water-soluble concentrate is with water or a water-miscible organic solvent as carrier). More preferably, the formulation is in the form of an emulsifiable concentrate (EC).

As per one embodiment, the preferred fungicidal composition is selected from Suspension concentrate (SC), Flowable Suspension (FS) and Wettable Granules (WG).

The formulation of the present invention is to be considered for application by any means selected from foliar spray, seed treatment, soil application, drenching, through drip irrigation.

Formulation of the present invention can be in any of the form described above.

The present compositions comprises of Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin.

Further as per the embodiment of the present invention, the active ingredient Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin are present in the ratio of 1.0:20.0 to 10.0:1.0.

The synergistic fungicidal composition of the present invention exhibits Synergistic activity compared to individual fungicide activity.

Further synergistic fungicidal composition of the present invention exhibits preventive, curative and eradicative action against plant pathogenic fungus.

The synergistic fungicidal compositions of the present invention can be used to control fungal diseases in Cotton (Gossypium spp.), Jute (Corchorus oliotorus), Paddy (Oryza sativa), Wheat (Triticum aestavum), Rice, Barley (Hordeum vulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Ragi (Eleusine coracana), Pearl millet (Pennisetum glaucum), Sugarcane (Saccharum officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Castor (Ricinus communis), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Bean (Phaseolus vulgaris L.), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun), Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Pepper (Capsicum spp.), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Gerbera ( Gerbera jamesonii), Carnation (Dianthus caryophyllus), Pigeonpea, Sugarcane, Carrot, Cucurbits,. Further as per one ambodiment, the synergistic fungicidal composition of the present invention can also be used or effective aginst genetically modified crops listed above.
The synergistic fungicidal compositions of the present invention can be used to control fungal disease of different crops. The amount of combination of the invention to be applied, will depend on various factors such as the compound employed, the subject of the treatment (plant, soil, seed), the type of treatment (e.g. spraying, dusting, seed dressing, soil incorporation, stem painting, trunk injection), the purpose of the treatment (prophylactic or therapeutic), the type of fungi to be treated and the application time.
It has been found, that the use of combination Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin surprisingly and substantially enhances the effectiveness of the crop against fungi, and vice versa.

The fungicidal composition of the present invention is having curative, preventive and systemic fungicidal properties for protecting cultivated plants. As has been mentioned, said active ingredient mixtures can be used to inhibit or destroy the pathogens that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops or useful plants, while at the same time those parts of plants which grow later are also protected from attack by such pathogens. Active ingredient mixtures have the special advantage of being highly active against diseases in the soil that mostly occur in the early stages of plant development

The novel compositions of combination Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin is effective for management of mixed infestation of fungal diseases.
The compositions according to the invention have very good fungicidal properties and can be employed for controlling phytopathogenic fungi such as Ascomycetes, Basidiomycetes, Chytridiomycetes, Deuteromycetes, Oomycetes, Plasmodiophoromycetes, Zygomycetes, and the like. Examples which may be mentioned, but not by limitation, are some pathogens of fungal diseases which come under the above generic terms: Diseases caused by pathogens causing powdery mildew such as, for example, Blumeria species such as, for example, Blumeria graminis; Podosphaera species such as, for example, Podosphaera leucotricha; Sphaerotheca species such as, for example, Sphaerotheca fuliginea; Uncinula species such as, for example, Uncinula necator; Leveillula species such as, for example Leveillula taurica, Erysiphe species such as for example Erysiphe polygoni, diseases caused by pathogens of rust diseases such as, for example, Gymnosporangium species such as, for example, Gymnosporangium sabinae, Hemileia species such as, for example, Hemileia vastatrix; Phakopsora species such as, for example, Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species such as, for example, Puccinia graminis, Puccinia recondita or Puccinia triticina, Puccinia striiformis; Uromyces species such as, for example, Uromyces phaseoli; diseases caused by pathogens of smut diseases such as, for example, Sporisorium species such as , for example, Sporisorium scitamineum; Ustilago species such as, for example Ustilago maydis, Tilletia species such as for example Tilletia tritici, Ustilaginoidea species such as , for example Ustilaginoidea virens, diseases caused by pathogens of ergot diseases such as, for example Claviceps species, Claviceps purpurea; diseases caused by pathogens from the group of the Oomycetes such as, for example, Bremia species such as, for example, Bremia lactucae; Peronospora species such as, for example, Peronospora pisi or P. brassicae; Phytophthora species such as, for example, Phytophthora infestans; Plasmopara species such as, for example, Plasmopara viticola; Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species such as, for example, Pythium ultimum; leaf spot diseases and leaf wilt caused by, for example, Alternaria species such as, for example, Alternaria solani; Cercospora species such as, for example, Cercospora beticola; Cladiosporum species such as, for example, Cladiosporium cucumerinum; Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium); Colletotrichum species such as, for example, Colletotrichum lindemuthanium; Cycloconium species such as, for example, Cycloconium oleaginum; Diaporthe species such as, for example, Diaporthe citri; Elsinoe species such as, for example, Elsinoe fawcettii; Gloeosporium species such as, for example, Gloeosporium laeticolor; Glomerella species such as, for example, Glomerella cingulata; Guignardia species such as, for example, Guignardia bidwelli; Leptosphaeria species such as, for example, Leptosphaeria maculans; Magnaporthe species such as, for example, Magnaporthe grisea; Mycosphaerella species such as, for example, Mycosphaerella graminicola; Phaeosphaeria species such as, for example, Phaeosphaeria nodorum; Pyrenophora species such as, for example, Pyrenophora teres; Ramularia species such as, for example, Ramularia collo-cygni; Rhynchosporium species such as, for example, Rhynchosporium secalis; Septoria species such as, for example, Septoria apii; Typhula species such as, for example, Typhula incarnata; Venturia species such as, for example, Venturia inaequalis; root and stalk diseases, caused by, for example, Corticium species such as, for example, Corticium graminearum; Fusarium species such as, for example, Fusarium oxysporum; Gaeumannomyces species such as, for example, Gaeumannomyces graminis; Rhizoctonia species such as, for example, Rhizoctonia solani; Tapesia species such as, for example, Tapesia acuformis; Thielaviopsis species such as, for example, Thielaviopsis basicola; ear and panicle diseases (including maize cobs), caused by, for example, Alternaria species such as, for example, Alternaria spp.;
Aspergillus species such as, for example, Aspergillus flavus; Cladosporium species such as, for example, Cladosporium spp.; Claviceps species such as, for example, Claviceps purpurea; Fusarium species such as, for example, Fusarium culmorum; Gibberella species such as, for example, Gibberella zeae; Monographella species such as, for example, Monographella nivalis; diseases caused by smuts such as, for example, Sphacelotheca species such as, for example, Sphacelotheca reiliana; Tilletia species such as, for example, Tilletia caries; Urocystis species such as, for example, Urocystis occulta; Ustilago species such as, for example, Ustilago nuda; fruit rot caused by, for example, Aspergillus species such as, for example, Aspergillus flavus; Botrytis species such as, for example, Botrytis cinerea; Penicillium species such as, for example, Penicillium expansum; Sclerotinia species such as, for example, Sclerotinia sclerotiorum; Verticilium species such as, for example, Verticilium alboatrum; seed- and soil-borne rots and wilts, and seedling diseases, caused by, for example, Fusarium species such as, for example, Fusarium culmorum; Phytophthora species such as, for example, Phytophthora cactorum; Pythium species such as, for example, Pythium ultimum; Rhizoctonia species such as, for example, Rhizoctonia solani; Sclerotium species such as, for example, Sclerotium rolfsii; cankers, galls and witches' broom diseases, caused by, for example, Nectria species such as, for example, Nectria galligena; wilts caused by, for example, Monilinia species such as, for example, Monilinia laxa; deformations of leaves, flowers and fruits, caused by, for example, Taphrina species such as, for example, Taphrina deformans; degenerative diseases of woody species, caused by, for example, Esca species such as, for example, Phaemoniella clamydospora; flower and seed diseases, caused by, for example, Botrytis species such as, for example, Botrytis cinerea; diseases of plant tubers caused by, for example, Rhizoctonia species such as, for example, Rhizoctonia solani; diseases caused by bacterial pathogens such as, for example, Xanthomonas species such as, for example, Xanthomonas campestris pv. oryzae; Pseudomonas species such as, for example, Pseudomonas syringae pv. lachrymans; Erwinia species such as, for example, Erwinia amylovora; by preference, the following diseases of soya beans can be controlled: fungal diseases on leaves, stems, pods and seeds caused by, for example, alternaria leaf spot (Alternaria spec, atrans tenuissima), anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cercospora leaf spot and blight (Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospora manshurica), drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi), scab(Sphaceloma glycines), stemphylium leaf blight (Stemphylium botryosum), target spot (Corynespora cassiicola) fungal diseases on roots and the stem base caused by, for example, black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmopspora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

The synergistic fungicidal compositions of the present invention comprising of Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin in addition further comprises of at least one inactive excipient including but not limited to dispersant, anti-freezing agent, anti-foam agent,wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents (also referred to as “stickers” or “binders”) and buffering agent.

A dispersant is a substance which adsorbs onto the surface of particles and helps to preserve the state of dispersion of the particles and prevents them from re-aggregating. Dispersants are added to agrochemical formulations to facilitate dispersion and suspension during manufacture, and to ensure the particles re-disperse into water in a spray tank. They are widely used in wettable powders, suspension concentrates and water-dispersible granules. Surfactants that are used as dispersants have the ability to adsorb strongly onto a particle surface and provide a charged or steric barrier to re-aggregation of particles. The most commonly used surfactants are anionic, non-ionic, or mixtures of the two types. For wettable powder formulations, the most common dispersants are sodium lignosulphonates. For suspension concentrates, very good adsorption and stabilization are obtained using polyelectrolytes, such as sodium naphthalene sulphonate formaldehyde condensates. Tristyrylphenolethoxylate phosphate esters are also used. Nonionics such as alkylarylethylene oxide condensates and EO-PO block copolymers are sometimes combined with anionics as dispersants for suspension concentrates. In recent years, new types of very high molecular weight polymeric surfactants have been developed as dispersants. These have very long hydrophobic ‘backbones’ and a large number of ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These high molecular weight polymers can give very good long-term stability to suspension concentrates because the hydrophobic backbones have many anchoring points onto the particle surfaces. Examples of dispersants used herein include but not limited to sodium lignosulphonates; sodium naphthalene sulphonate formaldehyde condensates; tristyrylphenolethoxylate phosphate esters; aliphatic alcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graft copolymers or mixtures thereof.

Anti-freezing agent as used herein can be selected from the group consisting of polyethylene glycols, methoxypolyethylene glycols, polypropylene glycols, polybutylene glycols, glycerin and ethylene glycol.

Water-based formulations often cause foam during mixing operations in production. In order to reduce the tendency to foam, anti-foam agents are often added either during the production stage or before filling into bottles. Generally, there are two types of anti-foam agents, namely silicones and non-silicones. Silicones are usually aqueous emulsions of dimethyl polysiloxane while the non-silicone anti-foam agents are water-insoluble oils, such as octanol and nonanol, or silica. In both cases, the function of the anti-foam agent is to displace the surfactant from the air-water interface.

A wetting agent is a substance that when added to a liquid increases the spreading or penetration power of the liquid by reducing the interfacial tension between the liquid and the surface on which it is spreading. Wetting agents are used for two main functions in agrochemical formulations: during processing and manufacture to increase the rate of wetting of powders in water to make concentrates for soluble liquids or suspension concentrates; and during mixing of a product with water in a spray tank or other vessel to reduce the wetting time of wettable powders and to improve the penetration of water into water-dispersible granules. Examples of wetting agents used in wettable powder, suspension concentrate, and water-dispersible granule formulations include but not limited to sodium lauryl sulphate; sodium dioctylsulphosuccinate; alkyl phenol ethoxylates; and aliphatic alcohol ethoxylates or mixtures thereof.

Suspension aid in the present description denotes a natural or synthetic, organic or inorganic material with which the active substance is combined in order to facilitate its application to the plant, to the seeds or to the soil. This carrier is hence generally inert, and it must be agriculturally acceptable, in particular to the plant being treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, and the like or mixtures thereof) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, and the like or mixtures thereof).

Biocides / Microorganisms cause spoilage of formulated products. Therefore anti-microbial agents are used to eliminate or reduce their effect. Examples of such agents include, but are not limited to: propionic acid and its sodium salt; sorbic acid and its sodium or potassium salts; benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt; methyl p-hydroxy benzoate; and biocide such as sodium benzoate, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, potassium sorbate, parahydroxy benzoates or mixtures thereof.

Thickeners or gelling agents are used mainly in the formulation of suspension concentrates, emulsions and suspoemulsions to modify the rheology or flow properties of the liquid and to prevent separation and settling of the dispersed particles or droplets. Thickening, gelling, and anti-settling agents generally fall into two categories, namely water-insoluble particulates and water-soluble polymers. It is possible to produce suspension concentrate formulations using clays and silicas. Examples of these types of materials, include, but are limited to, montmorillonite, e.g. bentonite; magnesium aluminum silicate; and attapulgite. Water-soluble polysaccharides have been used as thickening-gelling agents for many years. The types of polysaccharides most commonly used are natural extracts of seeds and seaweeds are synthetic derivatives of cellulose or mixtures thereof. Examples of these types of materials include, but are not limited to, guar gum; locust bean gum; carrageenam; xanthan gum; alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC) or mixtures thereof. Other types of anti-settling agents are based on modified starches, polyacrylates, polyvinyl alcohol and polyethylene oxide or mixtures.

The quick coating agentcan be a conventionally available sticker, for example polyesters, polyamides, poly- carbonates, polyurea and polyurethanes, acrylate polymers and copolymers, styrene copolymers, butadiene copolymers, polysaccharides such as starch and cellulose derivatives, vinylalcohol, vinylacetate and vinylpyrrolidone polymers and copolymers, polyethers, epoxy, phenolic and melamine resins, polyolefins and define copolymersand mixtures thereof. Examples of preferred polymers are acrylate polymers such as poly(methacrylate), poly(ethyl methacrylate), poly(methylmethacrylate), acrylate copoylmers and styrene-acrylic copolymers as defined herein below, poly(styrene-co maleic anhydride), cellulosic polymers such as ethyl cellulose, cellulose acetate, cellulose acetatebutyrate, acetylated mono, di, and triglycerides, poly(vinylpyrrolidone), vinyl acetate polymers and copolymers, poly(alkylene glycol), styrene butadiene copolymers, poly(orthoesters), alkyd resins, and mixtures of two or more of these. Polymers that are biodegradable are also useful in the present invention. As used herein, a polymer is biodegradable if is not water soluble, but is degraded over a period of several weeks when placed in an application environment. Examples of biodegradable polymers that are useful in the present invention include biodegradable polyesters, starch, polylactic acid starch blends, polylactic acid, poly(lactic acid-glycolic acid) copolymers, polydioxanone, cellulose esters, ethyl cellulose, cellulose acetate butyrate, starch esters, starch esteraliphatic polyester blends, modified corn starch, polycaprolactone, poly(namylmethacrylate), wood rosin, polyanhydrides, polyvinylalcohol, polyhydroxybutyratevalerate, biodegradable aliphatic polyesters, and polyhydroxybutyrate or mixtures thereof.

Buffering agent as used herein is selected from group consisting of calcium hydroxyapatite, Pottasium Dihydrogen Phosphate, Sodium Hydroxide, carbonated apatite, calcium carbonate, sodium bicarbonate, tricalcium phosphate, calcium phosphates, carbonated calcium phosphates, amine monomers, lactate dehydrogenase and magnesium hydroxide.

The solvent for the formulation of the present invention may include water, water-soluble alcohols and dihydroxy alcohol ethers. The water-soluble alcohol which can be used in the present invention may be lower alcohols or water-soluble macromolecular alcohols. The term "lower alcohol", as used herein, represents an alcohol having 1-4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. Macromolecular alcohol is not limited, as long as it may be dissolved in water in a suitable amount range, e.g., polyethylene glycol, sorbitol, glucitol, etc. The examples of suitable dihydroxy alcohol ethers used in the present invention may be dihydroxy alcohol alkyl ethers or dihydroxy alcohol aryl ethers. The examples of dihydroxy alcohol alkyl ether include ethylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, dipropylene glycol ethyl ether, etc. The examples of dihydroxy alcohol aryl ethers include ethylene glycol phenyl ether, diethylene glycol phenyl ether, propylene glycol phenyl ether, dipropylene glycol phenyl ether, and the like. Any of the above mentioned solvent can be used either alone or in combination thereof.

The synergistic fungicidal compositions of present invention are to be applied through Foliar spray, seed treatment, soil application, drenching, through drip irrigation.

The synergistic fungicidal compositions of present invention can be applied as Preventive or Curative, in case of foliar spray.

The process for preparing the present synergistic fungicidal compositions can be modified accordingly by any person skilled in the art based on the knowledge of the manufacturing the formulation. However all such variation and modification is still covered by the scope of present invention.

EXAMPLES
Example 1: Metalaxyl-M 10% + Metominostrobin 25% SC (Suspension Concentrate)
Composition Percent (w/w)
Metalaxyl-M (95% purity) 10.74
Metominostrobin ( 97 % purity) 25.98
Ethoxylated Fatty Alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated naphtalene sulfonate, sodium salt 0.50
Silicone antifoam 0.50
1,2-benzisothiazolin-3-one 0.20
Mono Ethylene Glycol 5.00
Polysaccharides 0.20
Water 51.88
Total 100.00
Procedure:
Step 1 Gum Solution should be made 12-18 hour prior to use. Take required quantity of water, biocide, and defoamer and homogenise, then slowly add gum powder to it and stir till complete dissolution.
Step 2 Charge required quantity of DM water need to be taken in designated vessel for Suspension concentrate production.
Step 3 Add required quantity of Wetting agent, anti-freezing agent, dispersing agent & suspending agents and homogenise the contents for 45 – 60 minutes using high shear homogeniser.
Step 4 Then add technical and other remaining adjuvants excluding ‘thickener’ are added to it and homogenised to get uniform slurry ready for grinding.
Step 5 Before grinding half the quantity of antifoam was added and then material was subjected to grinding in Dyno mill till desired particle size is achieved.
Step 6 Half quantity of the antifoam was added after grinding process completes and before sampling for in process analysis.
Step 7 Finally add gum solution to this formulation and send to QC for quality check.

Example 2: Metalaxyl-M 10% + Trifloxystrobin 25% SC (Suspension Concentrate)

Composition Percent (w/w)
Metalaxyl-M (95% purity) 10.74
Trifloxystrobin (95% purity) 26.53
Ethoxylated Fatty Alcohol 2.00
Acrylic graft copolymer 3.00
Alkylated naphtalene sulfonate, sodium salt 0.50
Silicone antifoam 0.50
1,2-benzisothiazolin-3-one 0.20
Mono Ethylene Glycol 5.00
Polysaccharides 0.20
Water 51.33
Total 100.00

Procedure: As per Example 1

Example 3: Metalaxyl-M 7%+Metominostrobin 10% WG (Water Dispersible Granules)

Compositions Percent (w/w)
Metalaxyl-M (95% purity) 7.58
Metominostrobin ( 95% purity) 10.74
Alkylated naphtalene sulfonate, sodium salt 5.00
PPT Silica 4.00
Sodium Lauryl Sulfate 3.00
Silicone antifoam 0.50
Lactose 30.00
Corn starch 30.50
China Clay 8.68
TOTAL 100.00

Procedure:
Step 1 Charge the required quantity of filler, wetting agent, dispersing agent, and suspending agent, & technical in premixing blender for homogenization for 30 minutes.
Step 2 Pre-blended material is than grinded through Jet mill/ air classifier mills. Finely grinded material is blended in post blender till it becomes homogeneous. (for approx 1.5 hr)
Step 3 grinded powder is mixed with required quantity of water to form extrudable dough.
Step 4 Dough is passed through extruder to get granules of required size.
Step 5 Wet granuleas are passed through Fluidised bed drier and further graded using vibrating screens.
Step 6 Final product is sent for QC approval.
Step 7 After approval material is packed in requied pack sizes.

Exampple 4: Metalaxyl-M 7%+Trifloxystrobin 10% WG (Water Dispersible Granules)
Compositions Percent (w/w)
Metalaxyl-M (95% purity) 7.58
Trifloxystrobin (95% purity) 10.75
Alkylated naphtalene sulfonate, sodium salt 4.00
Polyacrylate co-polymer 2.00
Sodium alkyl naphthalene sulfonate blend 2.00
PPT silica 3.00
Silicone antifoam 0.50
Lactose 25.00
Corn Starch 30.00
Sodium SulfateAnhydrous 7.00
China Clay 8.17
TOTAL 100.00

Procedure: As per Example 3

Example 5: Storage Stability data

Storage stability data of all above formulations has been performed as per below condition and time points.
1) Heat stability at 54±2 0C for 14 days
2) Cold storage stability at 0±2 0C for 14 days
3) Room Temperature for 24 montths

Specifications for Metalaxyl-M 10% + Trifloxystrobin 25% SC (Suspension Concentrate)

Specification
Parameters In House
Description Off-white liquid
Metalaxyl-M content 9.5-10.5
Trifloxystrobin content 23.75-26.25
Metalaxyl-M suspensibility Mini 80%
Trifloxystrobin suspensibility Mini 80%
pH 5.5 to7.5
Particle size D50 <3, D90 <10
Pourability 95 % min
Specific gravity 1.05 – 1.15
Viscosity 300 -800 cps

Specification for Metalaxyl-M 7%+Metominostrobin 10% Water Dispersible Granuels (WG)
Parameters Specification
Description off-white granules
Metalaxyl-M content 6.65-7.35
Metominostorbin content 9.5-10.5
Metalaxyl-M suspensibility Mini.70%
Metominostrobin suspensibility Mini.70%
pH (1% in DM Water) 5.5-7.5
Wettability Max 60 sec
Wet Sieve(45 micron) Mini 98.5%
Bulk Density 0.35-0.45
Moisture Content Max 2%

Result: All the compositons/formulation complied with the specification as mentioned above and have found to be stable.

Example 6: Bio Efficacy Trials

Laboratory screening of mixtures of Metalaxyl-M and one more fungicide selected from the group of Dimoxystrobin, Metominostrobin and Trifloxystrobin were carried out to evaluate their efficacy against various fungi causing fungal diseases in crop plants.

Trial 1
In Vitro Chemical screening: The synergistic effect of compositions of Metalaxyl-M + Dimoxystrobin, Metalaxyl-M + Metominostrobin and Metalaxyl-M + Trifloxystrobin on growth of the pathogen in vitro was studied by poison food technique. Different concentrations of active ingredient were prepared by dissolving the requisite quantity of each active ingredient in warm potato dextrose agar medium before autoclaving. After autoclaving the medium was then dispensed uniformly into 90 mm diameter petriplate and inoculated at the 2 mm mycelial discs of pathogen taken from 7 day old culture. Pathogen inoculated in unamended medium served as control. Each treatment was maintained in four replications. The inoculated plates were incubated at 28 +/- 2 C for 3 days and the diameter of the fungal colony was measured by measuring the two opposite circumference of the colony growth at 3 days interval for 15 days. The growth of fungus was monitored by measuring the radial growth (in mm) every 72 h till the fungus covers the plate completely in control plates. The percent inhibition (PI) of the fungus over the control was calculated using the following formula:
PI = A-B X 100/A
Where A= Colony diameter of fungus in control plates (mm)
B= Colony diameter of fungus in treated plates (mm)

The synergistic pesticidal action of the inventive mixtures calculated as follows :
For mixture of two active ingredients,
E = [ A + B] – [AB/ 100]
in which,
E = Expected percentage of Insecticidal or fungicidal control for the combination of three active ingredient,
A is the percentage of insecticidal or fungicidal control observed by active ingredient I at defined dose,
B is the percentage of insecticidal or fungicidal control observed by Active Ingredient II at defined dose,

When the percentage of fungicidal control observed for the combination is greater than the expected percentage, there is a synergistic effect. (Ratio of O/E > 1, means synergism observed.)

Table 1: Effect on mycelial growth of Pythium aphanidermatum
Concentrations Pythium aphanidermatum
Mycelial growth (mm) % Inhibition over control
Metalaxyl-M 5 ppm + Dimoxystrobin 5 ppm 0.0 100
Metalaxyl-M 5 ppm + Metominostrobin 5 ppm 0.0 100
Metalaxyl-M 5 ppm + Trifloxystrobin 5 ppm 0.0 100
Metalaxyl-M 5 ppm 42.7 48
Dimoxystrobin 5 ppm 37.7 54
Metominostrobin 5 ppm 40.3 51
Trifloxystrobin 5 ppm 18.5 78
Untreated 82.34 0

Table 2: Synergistic activity on mycelial growth of Pythium aphanidermatum
Compositions % Growth Inhibition of Pythium aphanidermatum
Obs.Value Cal.Value Ratio
Metalaxyl-M 5 ppm + Dimoxystrobin 5 ppm 100 76.25 1.31
Metalaxyl-M 5 ppm + Metominostrobin 5 ppm 100 74.64 1.34
Metalaxyl-M 5 ppm +
Trifloxystrobin 5 ppm 100 88.38 1.13
Metalaxyl-M 5 ppm 48
Dimoxystrobin 5 ppm 54
Metominostrobin 5 ppm 51
Trifloxystrobin 5 ppm 78
In vitro studies indicated the suppressive effect of Metalaxyl-M + Strobilurin fungicides on the radial growth of the mycelium of Pythium aphanidermatum (Table 1). It can be seen that the synergism was observed between Metalaxyl-M + Dimoxystrobin, Metalaxyl-M + Metominostrobin and Metalaxyl-M + Trifloxystrobin in terms of excellent suppressive effect on radial growth of Pythium aphanidermatum. (Table 2).
,CLAIMS:CLAIMS

We Claim;

[CLAIM 1]. A synergistic fungicidal composition comprising bioactive amounts of Metalaxyl M and one more agrochemically active ingredient selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin with at least one inactive excipient.
[CLAIM 2]. The synergistic fungicidal composition as claimed in claim 1 wherein the ratio of Metalaxyl M and one more agrochemically active ingredient selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and Trifloxystrobin is 1.0:20.0 to 10.0:1.0.
[CLAIM 3]. The synergistic fungicidal composition according to claim 1 or 2, wherein inactive excipients can be selected from the group consisting of dispersant, anti-freezing agent, anti-foam agent, wetting agent, suspension aid, anti-microbial agent, thickener, quick coating agent or sticking agents and buffering agent.
[CLAIM 4]. The synergistic fungicidal composition as claimed in claim 1-3, wherein the composition are selected from Flowable Suspension (FS), Suspo Emulsion (SE), Suspension Concentrate (SC), Wettable powder (WP) and Wettable Granuels (WG).
[CLAIM 5]. The synergistic fungicidal composition as claimed in any of the preceding claims, wherein the said composition is used for control of fungal diseases in Cotton (Gossypium spp.), Jute (Corchorus oliotorus), Paddy (Oryza sativa), Wheat (Triticum aestavum), Rice, Barley (Hordeum vulgare), Maize (Zea mays), Sorghum (Sorghum bicolor), Ragi (Eleusine coracana), Pearl millet (Pennisetum glaucum), Sugarcane (Saccharum officinarum) , Sugarbeet (Beta vulgaris), Soybean (Glycin max), Peanut (Arachis hypogaea), Sunflower (Helianthus annuus) , Mustard (Brassica juncea), Rape seed (Brassica napus), Linseed (Linum usitatissimum), Sesame (Sesamum indicum), Castor (Ricinus communis), Green gram (Vigna radiate), Black gram (Vigna mungo), Chickpea (Cicer aritinum), Cowpea (Vigna unguiculata), Redgram (Cajanus cajan), Frenchbean (Phaseolus vulgaris), Indian bean (Lablab purpureus), Horse gram (Macrotyloma uniflorum), Field pea (Pisum sativum), Cluster bean (Cyamopsis tetragonoloba), Bean (Phaseolus vulgaris L.), Lentils (Lens culinaris), Brinjal (Solanum melongena), Cabbage (Brassica oleracea var. capitata), Cauliflower (Brassica oleracea var. botrytis), Okra (Abelmoschus esculentus) , Onion (Allium cepa L.), Tomato (Solanum lycopersicun), Potato (Solanum tuberosum) , Sweet potato (Ipomoea batatas), Chilly (Capsicum annum), Garlic (Allium sativum), Cucumber (Cucumis sativus), Muskmelons (Cucumis melo), Watermelon (Citrullus lanatus), Bottle gourd (Lagenaria siceraria), Bitter gourd (Momordica charantia), Radish (Raphanus sativus), Carrot (Dacus carota subsp. sativus), Turnip (Brassica rapa subsp rapa), Apple (Melus domestica), Banana (Musa spp.), Citrus groups (Citrus spp.), Grape (Vitis vinifera), Guava (Psidium guajava), Litchi (Litchi chinensis), Mango (Mangifera indica), Papaya (Carica papaya), Pineapple (Ananas comosus), Pomegranate (Punica granatum) , Sapota (Manilkara zapota), Tea (Camellia sinensis), Coffea (Coffea Arabica), Turmeric (Curcuma longa), Ginger (Zingiber officinale), Cumin (Cuminum cyminum), Fenugreek (Trigonella foenum-graecum), Fennel (Foeniculum vulgare), Coriander (Coriandrum sativum), Ajwain (Trachyspermum ammi), Psyllium (Plantago ovate), Black Pepper (Piper nigrum), Pepper (Capsicum spp.), Stevia (Stevia rebaudiana), Safed musli (Chlorophytum tuberosum), Drum stick (Moringa oleifera), Coconut (Coco nucifera), Mentha ( Mentha spp.), Rose (Rosa spp.), Jasmine (Jasminum spp.), Marigold ( Tagetes spp.), Common daisy (Bellis perennis), Dahlia (Dahlia hortnesis), Gerbera ( Gerbera jamesonii), Carnation (Dianthus caryophyllus), Pigeonpea, Sugarcane, Carrot, Cucurbits,. Further as per one ambodiment, the synergistic fungicidal composition of the present invention can also be used or effective aginst genetically modified crops listed above.

[CLAIM 6]. The synergistic fungicidal composition as claimed in any of the preceding claims, wherein the said composition is used for controlling phytopathogenic fungi such as Ascomycetes, Basidiomycetes, Chytridiomycetes, Deuteromycetes, Oomycetes, Plasmodiophoromycetes, Zygomycetes, and the like. Examples which may be mentioned, but not by limitation, are some pathogens of fungal diseases which come under the above generic terms: Diseases caused by pathogens causing powdery mildew such as, for example, Blumeria species such as, for example, Blumeria graminis; Podosphaera species such as, for example, Podosphaera leucotricha; Sphaerotheca species such as, for example, Sphaerotheca fuliginea; Uncinula species such as, for example, Uncinula necator; Leveillula species such as, for example Leveillula taurica, Erysiphe species such as for example Erysiphe polygoni, diseases caused by pathogens of rust diseases such as, for example, Gymnosporangium species such as, for example, Gymnosporangium sabinae, Hemileia species such as, for example, Hemileia vastatrix; Phakopsora species such as, for example, Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species such as, for example, Puccinia graminis, Puccinia recondita or Puccinia triticina, Puccinia striiformis; Uromyces species such as, for example, Uromyces phaseoli; diseases caused by pathogens of smut diseases such as, for example, Sporisorium species such as , for example, Sporisorium scitamineum; Ustilago species such as, for example Ustilago maydis, Tilletia species such as for example Tilletia tritici, Ustilaginoidea species such as , for example Ustilaginoidea virens, diseases caused by pathogens of ergot diseases such as, for example Claviceps species, Claviceps purpurea; diseases caused by pathogens from the group of the Oomycetes such as, for example, Bremia species such as, for example, Bremia lactucae; Peronospora species such as, for example, Peronospora pisi or P. brassicae; Phytophthora species such as, for example, Phytophthora infestans; Plasmopara species such as, for example, Plasmopara viticola; Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species such as, for example, Pythium ultimum; leaf spot diseases and leaf wilt caused by, for example, Alternaria species such as, for example, Alternaria solani; Cercospora species such as, for example, Cercospora beticola; Cladiosporum species such as, for example, Cladiosporium cucumerinum; Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, syn: Helminthosporium); Colletotrichum species such as, for example, Colletotrichum lindemuthanium; Cycloconium species such as, for example, Cycloconium oleaginum; Diaporthe species such as, for example, Diaporthe citri; Elsinoe species such as, for example, Elsinoe fawcettii; Gloeosporium species such as, for example, Gloeosporium laeticolor; Glomerella species such as, for example, Glomerella cingulata; Guignardia species such as, for example, Guignardia bidwelli; Leptosphaeria species such as, for example, Leptosphaeria maculans; Magnaporthe species such as, for example, Magnaporthe grisea; Mycosphaerella species such as, for example, Mycosphaerella graminicola; Phaeosphaeria species such as, for example, Phaeosphaeria nodorum; Pyrenophora species such as, for example, Pyrenophora teres; Ramularia species such as, for example, Ramularia collo-cygni; Rhynchosporium species such as, for example, Rhynchosporium secalis; Septoria species such as, for example, Septoria apii; Typhula species such as, for example, Typhula incarnata; Venturia species such as, for example, Venturia inaequalis; root and stalk diseases, caused by, for example, Corticium species such as, for example, Corticium graminearum; Fusarium species such as, for example, Fusarium oxysporum; Gaeumannomyces species such as, for example, Gaeumannomyces graminis; Rhizoctonia species such as, for example, Rhizoctonia solani; Tapesia species such as, for example, Tapesia acuformis; Thielaviopsis species such as, for example, Thielaviopsis basicola; ear and panicle diseases (including maize cobs), caused by, for example, Alternaria species such as, for example, Alternaria spp.; Aspergillus species such as, for example, Aspergillus flavus; Cladosporium species such as, for example, Cladosporium spp.; Claviceps species such as, for example, Claviceps purpurea; Fusarium species such as, for example, Fusarium culmorum; Gibberella species such as, for example, Gibberella zeae; Monographella species such as, for example, Monographella nivalis; diseases caused by smuts such as, for example, Sphacelotheca species such as, for example, Sphacelotheca reiliana; Tilletia species such as, for example, Tilletia caries; Urocystis species such as, for example, Urocystis occulta; Ustilago species such as, for example, Ustilago nuda; fruit rot caused by, for example, Aspergillus species such as, for example, Aspergillus flavus; Botrytis species such as, for example, Botrytis cinerea; Penicillium species such as, for example, Penicillium expansum; Sclerotinia species such as, for example, Sclerotinia sclerotiorum; Verticilium species such as, for example, Verticilium alboatrum; seed- and soil-borne rots and wilts, and seedling diseases, caused by, for example, Fusarium species such as, for example, Fusarium culmorum; Phytophthora species such as, for example, Phytophthora cactorum; Pythium species such as, for example, Pythium ultimum; Rhizoctonia species such as, for example, Rhizoctonia solani; Sclerotium species such as, for example, Sclerotium rolfsii; cankers, galls and witches' broom diseases, caused by, for example, Nectria species such as, for example, Nectria galligena; wilts caused by, for example, Monilinia species such as, for example, Monilinia laxa; deformations of leaves, flowers and fruits, caused by, for example, Taphrina species such as, for example, Taphrina deformans; degenerative diseases of woody species, caused by, for example, Esca species such as, for example, Phaemoniella clamydospora; flower and seed diseases, caused by, for example, Botrytis species such as, for example, Botrytis cinerea; diseases of plant tubers caused by, for example, Rhizoctonia species such as, for example, Rhizoctonia solani; diseases caused by bacterial pathogens such as, for example, Xanthomonas species such as, for example, Xanthomonas campestris pv. oryzae; Pseudomonas species such as, for example, Pseudomonas syringae pv. lachrymans; Erwinia species such as, for example, Erwinia amylovora; by preference, the following diseases of soya beans can be controlled: fungal diseases on leaves, stems, pods and seeds caused by, for example, alternaria leaf spot (Alternaria spec, atrans tenuissima), anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), cercospora leaf spot and blight (Cercospora kikuchii), choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew (Peronospora manshurica), drechslera blight (Drechslera glycini), frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot (Leptosphaerulina trifolii), phyllostica leaf spot (Phyllosticta sojaecola), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi), scab(Sphaceloma glycines), stemphylium leaf blight (Stemphylium botryosum), target spot (Corynespora cassiicola) fungal diseases on roots and the stem base caused by, for example, black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmopspora vasinfecta), pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

[CLAIM 7]. The synergistic fungicidal compositions as per any preceeding claim wherein the said composition is to be applied through Foliar spray, seed treatment, soil application, drenching, through drip irrigation.

[CLAIM 8]. The synergistic fungicidal compositions of Metalaxyl M and one more agrochemically active ingredients selected from Coumethoxystrobin, Dimoxystrobin, Metominostrobin, Pyrametostrobin and as claimed in any of the preceding claims and exemplified with working examples as disclosed.