OA16327A - Synergistic fungicidal composition. - Google Patents

Description

SYNERGISTIC FUNGICEDAL COMPOSITION

FIELD OF THE INVENTION [0001] The présent invention relates to a composition comprising a combination of a morpholine fongicide; a phthalimide fongicide; and a phosphorus containing fongicide, wherein the composition has a synergistically enhanced activity. The invention further relates to a method for controlling phytopathogenic fungi by applying to a plant, a locus thereof or propagation material thereof a combination of a morpholine fongicide; a phthalimide fungicide; and a phosphorus containing fongicide, wherein the composition has a synergistically enhanced activity.

BACKGROUND OF THE INVENTION [0002] Phytopathogenic fongi may cause a substantial réduction in expected crop yields quality and profit; further losses can resuit during storage of harvested crops. For those fungi that can seriously affect economically important plants, means hâve been sought to control these infections by a treatment of plants using agricultural fongicides. Generally, agricultural fongicides are chemical compounds used to kill or inhibit fongi or fungal spores. Agricultural fongicides can be used to protect seed grain during storage, shipment and germination and to protect mature crops, bernes, seedlîngs, flowers and grasses in the field, in storage and during shipment. They can be applied to the soil to control fungi that are résident there, to the seed or foliage of the plant to be protected, or to harvested produce to prevent storage losses.

[0003] Combinations of agricultural fongicides are typically used to broaden the spectrum of control, to minimize the doses of chemicals used and to reduce the cost of the treatment through additive effect. Combinations of agricultural fongicides can be also used to avoid or [0004] Synergism has been defined as the simultaneous action of two or more compounds in which the total response of an organism to the pesticide combination is greater than the sum of the individual components. Although many combinations of fongicides hâve been studied, a synergistic effect is rarely revealed and the global use of fungicide combinations with synergistically enhanced activity is rather limited.

[0005] Therefore, there is still a need for novel fungicide compositions that demonstrates synergistically enhanced and broader scope of activity.

SUMMARY OF THE INVENTION [0006] The invention relates to a novel synergistic fungicidal composition that comprises a combination of a morpholine fungicide: a phthalimide fungicide; and a phosphores containing fungicide.

[0007] In an embodîment of the invention there is provided a fungicidal combination comprising a morpholine fungicide; a phthalimide fungicide; and a phosphores containing fungicide, in a synergistically effective amount.

[0008] In an embodîment of the invention, there is provided a fungicidal composition comprising a morpholine fungicide; a phthalimide fungicide; and a phosphores containing fungicide, in a synergistically effective amount.

[0009] In some embodiments of the invention, the morpholine fungicide is dimethomorph. [00010] In some embodiments of the invention, the phthalimide fungicide is folpet.

[00011] In some embodiments, the phosphores containing fongicide is fosetyl-Al.

[00012] In another embodîment of the invention, there is provided a method of controlling diseases caused by phytopathogenic fungi in plants or on propagation material thereof which comprises contacting the plants, the locus thereof or propagation material thereof with a synergistically effective amount of a combination of a morpholine fungicide; a phthalimide fungicide; and a phosphores containing fungicide. The morpholine fungicide, phthalimide fungicide; and the phosphores containing fungicide, may be applied simultaneously, or in succession.

[00013] The présent invention also relates to a method for controlling and/or preventing a disease caused by phytopathogenic fungi in plants that are agriculturally important or in propagation material thereof, such as seeds, by contacting the plants, the locus thereof or propagation material thereof, with a synergisticaily effective amount of a morpholine fungicide; a phthalimide fungicide; and a phosphores containing fungicide; and an agriculturally acceptable carrier.

[00014] Furthermore, the invention also relates to a process for preparing a temary synergistic fungicidal composition that comprises a combination of a morpholine fungicide; a phthalimide fungicide; and a phosphores containing fungicide.

DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION [00015] It has been surprisingly found that by combîning fungicides of three different chemical groups characterized by different modes of action, i.e. a morpholine fungicide, a phthalimide fungicide and a phosphores containing fungicide, a fungicidal composition that :[ ί

î i

i î

I î

i i

î has a considérable synergistic enhanced actîvity is obtained. The composition provides a higher fungicidal activîty than that envisaged on the basis of the sum of activities of each of the fungicides found therein. Such a combination has a wider spectrum of fungi control, and allows the reduced dosages of the single fungicides, thereby allowing effective control of numerous diseases caused by phytopathogenic fungi, which can damage agriculturally important plants.

[00016] In an embodiment of the invention, the combination is temary synergistic fungicidal composition that comprises a combination of a morpholine fùngicide; a phthalimide fungicide; and a phosphorus containing fùngicide.

[00017] In an embodiment of the invention, there is provided a composition consisting of a combination of a morpholine fungicide; a phthalimide fungicide; a phosphorus containing fùngicide and an agriculturally acceptable carrier.

[00018] In yet another embodiment, the morpholine fungicides include compounds such as aldimoiph, benzamorf, carbamorph, dimethomorph, dodemorph and salts thereof, fenpropimorph, flumorph, and tridemorph or a combination comprising at least one of the foregoing. In one représentative embodiment, the morpholine fungicide is dimethomorph.

[00019] In another embodiment, the phthalimide fungicides include compounds such as captafol, captan, ditalimfos, folpet, and thiochlorfenphim or a combination comprising at least one of the foregoing. In an embodiment of the invention, the phthalimide fungicide is folpet.

[00020] In an embodiment, the phosphorus containing fungicides includes organophosphorus fungicides such as ampropylfos, ditalimfos, edifenphos, fosetyl and salts thereof, hexylthiofos, iprobenfos, phosdiphen, pyrazophos, tolclofos-methyl, and triamiphos and inorganic phosphorus fungicides such as phosphonic acid, potassium phosphonate and dipotassium phosphonate or a combination comprising at least one of the foregoing. In an embodiment of the invention, the phosphorus containing fungicide is fosetyl and salts thereof. In yet another embodiment, the phosphorous containing fungicide is fosetyl-Al.

[00021] In some embodiments, the fungicidal compositions comprise a combination of dimethomorph; a phthalimide fungicide; and a phosphorus containing fungicide. Altematively, the fungicidal composition can comprise a combination of a morpholine fungicide; folpet and a phosphorus containing fungicide. The fungicidal composition can altematively comprise a combination of a morpholine fungicide; a phthalimide fungicide and fosetyl-Al. The fungicidal composition can altematively comprise a combination of dimethomorph; folpet and a phosphorus containing fungicide. In yet another embodiment, the fungicidal composition comprises a combination of dimethomorph; a phthalimide fungicide and fosetyl-Al. In yet another embodiment, the fungicidal composition comprises a combination of a morpholine fimgicide; folpet and fosetyl-Al. In yet another embodiment, the fungicidal composition comprises a combination of dimethomorph, folpet and fosetyl-Al.

[00022] In another embodiment, the ratio (by weight) of the morpholine fungicide to the phthalimide fungicide is from 1:100 to 100:1. In another embodiment the ratio is from 1:25 to 25:1 and in another embodiment from 1:10 to 10:1.

[00023] In yet another embodiment, the ratio (by weight) of dimethomorph to folpet is from 1:100 to 100:1. In another embodiment the ratio is from 1:25 to 25:1 and in another embodimentfrom l:10to 10:1.

[00024] In an embodiment of the invention, the ratio of the amount of dimethomorph to the amount of folpet îs about 1:5.

[00025] In another embodiment, the ratio (by weight) of the morpholine fungicide to the phosphorus contaîning fungicide is from 1:100 to 100:1. In another embodiment, the ratio is from 1:50 to 50:1 and in another embodiment, the ratio is from 1:25 to 25:1.

[00026] In yet another embodiment, the ratio (by weight) of dimethomorph to fosetyl-Al is from 1:100 to 100:1. In another embodiment the ratio is from 1:50 to 50:1 and in another embodiment the ratio is from 1:25 to 25:1.

[00027] In an embodiment of the invention, the ratio of the amount of dimethomorph to the amount of fosetyl-Al îs about 1:10.

[00028] In an embodiment of the invention, the weight ratio between the morpholine fimgicide, the phthalimide fimgicide and the phosphorus contaîning fungicide is 0.5 - 10 : 2 50 : 4 - 100, respectively.

[00029] In another embodiment of the invention, the weight ratio between morpholine fungicide, phthalimide fungicide and phosphorus contaîning fungicide is 1:5:10, respectively. [00030] In an embodiment of the invention, the ratio by weight of dimethomorph, folpet and fosetyl-Al is in the range of between 0.5 - 10 : 2 - 50 : 4 - 100 , respectively.

[00031] In an embodiment of the invention, the ratio by weight between dimethomorph, folpet and fosetyl-AI is 1:5:10, respectively.

[00032] In another embodiment, a method for controlling and/or preventing a disease caused by phytopathogenîc fungi in plants that are agriculturally important or in propagation material thereof, by contacting the plants, the locus thereof or propagation material thereof, such as seeds, with a synergistically effective amount of a morpholine fungicide; a phthalimide fungicide; and a phosphorus contaîning fungicide, is provided.

^:ι ί

I j j ï

[00033] The term contacting, as used herein, refers to applying the compounds and compositions of the invention to the plant, to a site of infestation by fungi, to a potential site of infestation by the fungi, which may require protection from infestation, or the environment around the habitat or potential habitat of the fungi. The application may be by methods described in the présent invention such as by sprayîng, dipping, etc.

[00034] For example, a method for controlling and/or preventing a disease caused by phytopathogenic fungi in a plant by contacting the useful plants, the locus thereof or propagation material thereof, such as seeds, with a synergistically effective amount of dimethomorph; a folpet; and fosetyl-AI is provided.

[00035] As used herein the term plant includes reference to whole plants, plant organs (e.g.

leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), or plant cells. This term also encompasses plant crops such as fruits.

[00036] In yet another embodiment, the plants include vegetables, such as tomatoes, peppers, cabbage, broccoli, asparagus, squash, lettuce, spinach, cauliflower, melon, watermelon, 15 cucumbers, carrots, onions, cucurbits and potatoes, tobacco, pome and stone fruits and berries, such as walnuts, kiwi, banana, avocado, olives, pasionfiruit, almonds, pineapples, apples, pears, plums, peaches, and cherries, table and wine grapes, citrus fruit, such as oranges, Iemons, grapefruits and limes, cotton, soybean, oil seed râpe, wheat, barley, rye, triticale, oats, maïze, sorghum, sunflower, peanuts, rice, sugar beet, fodder beet, coffee, 20 beans, peas, yucca, sugar cane, clover, turf and omamentals such as roses.

[00037] In still another embodiment, plants that tolerate the action of herbicides, fungicides or insecticides as a resuit of breeding, mutagenesîs or genetic engineering methods are also included.

[00038] In yet another embodiment, the propagation material includes seeds and spores, 25 végétative structures such as bulbs, corms, tubers, rhizomes, roots stems, basal shoots, stolons, and buds.

[00039] In another embodiment, the phytopathogenic fungi are one or more of the classes Ascomycètes, Basidiomycetes, Deuteromycetes and Oomycetes, such as Achlya conspicua (Water-mold), Achlya klebsiana (Water-mold), Aecidium cantensis (Deforming rust), 30 Akaropeltopsis sp. (Sooty blotch), Albugo tragopogonis (White rust), Altemaria alternate (Altemaria rot, Black mold rot, Black shoulder, Brown spot and Black pit, Altemaria leaf spot, Altemaria leaf blight, stem spot and head rot, Albinism), Altemaria altemata f.sp, Lycopersici (Altemaria stem canker), Altemaria brassicae (Altemaria leaf spot), Altemaria brassïcicola (Altemaria leaf spot), Altemaria citri (Altemaria leaf spot of rough lemon,

Altemaria stem-end rot, Black rot), Altemaria helîanthi (Altemaria leaf blight, stem spot and head rot), Altemaria helianthicola (Altemaria leaf blight, stem spot and head rot), Alternai·™ leucanthemi (Altemaria leaf blight, stem spot and head rot), Altemaria limicola (Mancha foliar de los citricos), Altemaria padwickii (Stackbum), Altemaria solani (Early blight), Altemaria spp. (Kernel blight = black point), Altemaria tenuissima (Altemaria leaf blight, stem spot and head rot), Altemaria zinnia (Altemaria leaf blight, stem spot and head rot), Angiosorus solani (Thecaphora smut), Annillaria mellea (Aimillaria root rot, Mushroom root rot = shoestring root rot or oak root fungi), Armillaria tabescens (Clitocybe root rot), Arthrinium arundinis (Kernel blight = black point), Ascochyta graminea (Ascochyta leaf spot), Ascochyta hordei (Ascochyta leaf spot), Ascochyta sorghi (Ascochyta leaf spot), Ascochyta triticî (Ascochyta leaf spot), Ashbya gossypii (Dry rot (fruit)), Aspergillus flavus (Albinism), Aspergillus niger (Aspergillus rot, Black mold rot), Asteridiella perseae (Black mildew), Bipolaris sorokiniana (feaf spots), Botryodiplodia spp. (Fruit rot), Botryosphaeria dîsrupta (Branch canker), Botryosphaeria dothidea (Cane blight canker), Botryosphaeria obtuse (Branch canker, Fruit rot), Botryosphaeria quercuum (Branch canker, Fruit rot), Botryosphaeria rhodina (Branch canker, Fruit rot), Botryosphaeria ribis (Cane blight canker, Dothiorella gummosis and rot), Botrytis cinerea (Fruit rot, Gray Mold, Botrytis blight, Botrytis head rot, Botrytis blossom and twig blight, gummosis, Gray mold), Ceratobasidium oryzae-sativae (Aggregate sheath spot), Cercospora janseana (Narrow brown leaf spot), Cercospora rosicola (Cercospora leaf spot), Chalara thielavioides (Black mold), Choanephora cucurbitarum (Choanephora blight), Claviceps purpurea (Ergot), Cochliobolus miyabeanus (Brown spot), Cochliobolus sativus (Common root rot, crown rot and seedling blight, Kernel blight = black point, Spot blotch), Coleosporium helîanthi (Yellow rust), Coleosporium pacificum (Yellow rust), Colletotrichum acutatum (Post bloom fiuit drop), Colletotrichum cereale Manns (Anthracnose), Colletotrichum coccodes (Anthracnose, Black dot), Colletotrichum dematium (Anthracnose), Colletotrichum gloeosporioides (Anthracnose, Fruit rot, Rusty blight), Coniothyrium rosarum (Graft canker), Coniothyrium wemsdorffiae (Brand canker), Corticium stevensii (Thread blight), Corynespora cassücola (Target spot), Cryptosporella umbrina (Brown canker), Cryptosporium minimum (Fungal canker), Curvularia lunata (Black kernel), Cylindrocladium scoparium (Fruit rot, Crown canker), Dematophora necatrix Dematophora (Root rot), Diapleella coniothyrium (Common stem canker), Diaporthe citri (Melanose), Diaporthe eres (Fungal canker), Didymella lycopersicî Didymella (Stem rot), Diplocarpon rosae (Black spot), Diplodia cacaoicola (Dieback), Diplodia sp. (Fungal canker), Discostroma corticola (Cane blight canker), Dothiorella

I

I aromatic (Fruit rot), Dothiorella gregaria (Fruit rot), Drechslera gigantean (Eyespot), Drechslera teres (Net blotch), Drechslera teres f. maculate (Net blotch (spot form)), Drechslera wirreganensis (Wirrega blotch), Elsinoë ampelina (Anthracnose and bird's-eve rot), Elsinoë australis (Sweet orange scab), Elsinoë fawcettîi (Scab), Elsinoë rosarum (Spot anthracnose), Entyloma oryzae (Leaf smut), Erysiphe cichoracearum (Powdery mildew), Erysiphe graminis f.sp. hordeî (Powdery mildew), Erythricium salmonicolor (Pink disease), Fomitella supine (Wood rots), Fulvia fiilva (Leaf mold), Fusarium culmorum (Common root rot, crown rot and seedling blight), Fusarium decemcellulare (Fruit rot), Fusarium equiseti (Fusarium stalk rot), Fusarium graminearum (Common root rot, crown rot and seedling blight), Fusarium graminearum (Scab = head blight), Fusarium moniliforme (Fusarium wilt), Fusarium oxysporum (Fusarium wilt), Fusarium oxysporum f.sp. citri (Fusarium wilt), Fusarium oxysporum f.sp. lycopersici (Fusarium wilt), Fusarium oxysporum f.sp. radicislycopersici (Fusarium crown and root rot), Fusarium solani (Fusarium stalk rot), Fusarium spp. (Fusarium dry rot, Fusarium wilt, Kernel blight = black point, Root and bark rot, Scab = head blight, Fusarium rot (fruit)), Gaeumannomyces graminis (Crown sheath rot), Gaeumannomyces graminis var tritici (Takc-all). Galactomyces candidum (Sour rot), Ganodenna applanatum (Heart rot), Ganoderma brownie (Heart rot), Ganoderma lucidum (Heart rot), Ganoderma zonatum (Butt rot), Geotrichum candidum (Sour rot), Geotrichum citri-aurantii (Sour rot), Geotrichum klebahnii (Sour rot), Gliocladium roseum (Pink mold), Gloeodes pomigena (Sooty blotch), Glomerella cingulata (Anthracnose = wither-tip), Guignardia citricarpa (Black spot), Helminthosporium solani (Silver scurf), Helminthosporium spp. (Smudgy spot), Hendersonula toruloidea (Hendersomila branch wilt, Rio Grande gummosis), Hymenula cerealis (Cephalosporium stripe), Laetiporus sulphureus (Wood rots), Lasiodiplodia theobromae (Fruit rot, Diplodia gummosis and stem-end rot), Leptosphaeria lindquistii (Phoma black stem), Leveillula compositarum f. helianthi (Powdery mildew), Leveillula taurica (Powdery mildew), Macrophomina phaseolina (Charcoal rot), Magnaporthe salvînii (Stem rot), Microdochium nivale (Pink snow mold = Fusarium patch), Microdochium oryzae (Leaf scald), Microdochium tabacinum (Fusarium stalk rot), Mucor paronychia (Mucor fruit rot), Mucor racemosus (Mucor fruit rot), Mycosphaerella angulata (Angular leaf spot), Mycosphaerella citri (Greasy spot and greasy spot rind blotch), Mycosphaerella horii (Leaf spot), Mycosphaerella lageniformis (Leaf spot), Mycovellosiella concors (Cercospora leaf blotch), Myriosclerotinia borealis (Snow scald = Sclerotinia snow mold), Myrothecîum roridum (Myrothecium leaf and stem spot), Myrothecium verrucaria (Myrothecium leaf and stem spot), Nectria cinnabarina (Fungal canker), Nectria c

haematococca (Dry root rot complex), Nectria pseudotrichia (Fruit rot), Nematospora coryli (Dry rot (fruit)), Oidiopsis sicula (Powdery mildew), Oïdium spp. (Powdery mildew), Oïdium tingitaninum (Powdery mildew),* Oxyporus latemarginatus (Heart rot, Poria root rot), Pellicularia koleroga (Thread blight), Pénicillium digitatum (Green mold), Pénicillium italicum (Blue mold), Pénicillium ulaiense (Whisker mold), Peronospora sparsa (Downy mildew), Pestalotia adusta (Leaf spots), Pestalotia spp. (Fruit rot, Leaf spots), Pestalotia versicolor (Fruit rot), Phaeoramularia angolensis (Phaeoramularia leaf and fruit spot), Phialophora asteris (Phialophora yellows), Phoma andigena var. andina (Phoma leaf spot), Phoma destructive (Phoma rot), Phoma macdonaldii (Phoma black stem), Phoma solanîcola f. foveata (Gangrené), Phoma tracheiphila (Mal secco), Phomopsis citri (Phomopsis stem-end rot), Phomopsis helianthi (Phomopsis brown stem canker), Phomopsis perseae (Fruit rot), Phomopsis spp. (Dieback, Phomopsis spot, Phomopsis brown stem canker), Phragmidium mucronatum (Rust), Phragmidium rosae-pîmpinellïfoliae (Rust), Phyllachora gratissima (Leaf spots, Tar spot), Phyllosticta micropuncta (Leaf spots), Phymatotrichopsis omnivore (Phymatotrichum root rot (cotton root rot)), Physalospora abdita (Branch canker), Physalospora perseae (Physalospora canker), Phytophthora capsici (Buckeye fruit and root rot), Phytophthora cinnamomi (Phytophthora crown rot, Phytophthora root rot, Phytophthora trunk canker), Phytophthora citricola (Phytophthora crown rot, Phytophthora trunk canker, Brown rot (fruit)), Phytophthora citrophthora (Brown rot (fruit), Phytophthora foot rot, gummosis and root rot), Phytophthora drechsleri (Buckeye fruit and root rot, Phytophthora stem rot), Phytophthora heveae (Phytophthora trunk canker), Phytophthora hibemalis (Brown rot (fruit), Phytophthora foot rot, gummosis and root rot), Phytophthora infestans (Laie blight), Phytophthora nicotianae var. parasitica (Buckeye fruit and root rot, Brown rot (fruit), Phytophthora foot rot, gummosis and root rot), Phytophthora palmivora (Seedling blight, Brown rot (fruit), Phytophthora foot rot, gummosis and root rot), Phytophthora spp. (Pink rot, Phytophthora stem rot), Phytophthora syringae (Brown rot (fruit), Phytophthora foot rot, gummosis and root rot), Plasmopara halstediî (Downy mildew), Plasmopara helianthi f. helianthi (Downy mildew), Plasmopara vîticola (Downy mildew), Pleospora herbarum (Pleospora rot), Polyscytalum pustulans (Skin spot), Pseudocercosoporella herpotrichoides (Eyespot), Pseudocercospora fuligena (Cercospora leaf mold), Pseudocercospora puderi (Cercospora leaf spot), Pseudocercospora purpurea (Cercospora spot (blotch)), Pseudoperonospora cubensis (Downy mildew), Pseudopezicula tetraspora (Angular leaf scorch), Pseudoseptoria donacis (Halo spot), Puccinia coronata var. hordei (Crown rust), Puccinia gramims f.sp. secalis (Stem rust), Puccinia graminis f.sp. tritici (Stem rust), Puccinia helianthi (Rust), Puccinie hordei (Leaf rust), Puccinia pittieriana (Common rust), Puccinia striifonnis f. sp. Hordei (Stripe rust = yellow rust), Puccinia xanthii (Rust), Pyrenochaeta lycopersici (Corky root rot), Pyrenophora graminea (Barley stripe), Pyrenophora triticirepentis (Tan spot), Pyricularia grisea (Blast), Pythium aphanidermatum (Pythium damping5 off and fruit rot, Pythium seedling blight and root rot, Damping-off), Pythium arrhenomanes (Pythium damping-off and fruit rot, Pythium root rot), Pythium debaryanum (Pythium damping-off and fruit rot, Pythium seedling blight and root rot, Damping-off), Pythium graminicola (Pythium root rot), Pythium irregular (Pythium seedling blight and root rot), Pythium iwayamae (Snow rot), Pythium myriotylum (Pythium damping-off and fruit rot), 1D Pythium okanoganense (Snow rot), Pythium paddicum (Snow rot), Pythium rostratum (Damping-off, Rootlet rot), Pythium spp. (Damping-off, Leak, Pythium root rot, Pythium seedling blight and root rot), Pythium tardicrescens (Pythium root rot), Pythium ultimum (Pythium damping-off and fruit rot, Rootlet rot), Pythium vexans (Damping-off), Rhizoctonia cerealis (Sharp eyespot), Rhizoctonia oryzae (Sheath spot), Rhizoctonia solani (Canker and 15 black scurf, Damping-off and fruit τοζ Root rot, Seedling blight), Rhizopus arrhizus (Rhizopus head rot), Rhizopus microspores (Rhizopus head rot), Rhizopus stolonifer (Fruit rot, Rhizopus rot, Rhizopus head rot), Rhynchosporium secalis (Scald), Rhytidhysteron rufulum (Twig blight), Rigidoporus ulmarius (Wood rots), Rosellinia bunodes (Rosellinia root rot), Rosellinia necatrix (White root rot), Rosellinia spp. (Rosellinia root rot, White root 20 rot, Rosellinia black rot), Rosellinia subiculata (White root rot), Sarocladium oryzae (Sheath rot), Schizothyrium pomi (Fly speck), Sclerophthora macrospora (Downy mildew), Sclerophthora rayssiae (Downy mildew), Sclerotinia minor (White mold, Sclerotinia basal stalk rot and wilt), Sclerotinia sclerotiorum (Collar rot, Fruit rot, White mold, Sclerotinia basal stalk rot and wilt, mid-stalk rot, head rot, Sclerotinia twig blight, fruit rot and root rot), 25 Sclerotium rolfsii (Seedling blight, Southem blight, Stem rot), Septoria citri (Septoria spot),

Septoria helianthi (Septoria leaf spot), Septoria lycopersici (Septoria leaf spot), Septoria passerinii (Septoria speckled leaf blotch), Septoria rosae (Septoria leaf spot), Sphaceloma perseae (Scab (fruit & leaf)), Sphaeropsis tumefaciens (Branch knot), Sphaerotheca fuliginea (Powdery mildew), Sphaerotheca pannosa var. rosae (Powdery mildew), Spongospora 3q subterranea f.sp. Subterranea (Powdery scab), Stagonospora avenae f.sp. triticae (Septoria speckled leaf blotch), Stagonospora avenae f.sp. triticae (Stagonospora blotch), Stagonospora nodorum (Stagonospora blotch), Stemphylium botryosum (Black mold rot), Stemphylium botryosum f.sp. lycopersici (Gray leaf spot), Stemphylium lycopersici (Gray leaf spot), Stemphylium solani (Gray leaf spot), Synchytrium endobioticum (Wart), Thanatephorus

cucumeris (Sheath blight, Areolate leaf spot), Thielaviopsis basicola (Black root rot), Tilletia barclayana (Kernel smut), Tilletia controverse (Dwarf bunt), Trametes hirsute (Wood rots), Trichodcnna viride (Trichoderma rot), Trichothecium roseum (Pink rot), Typhula idahoensis (Speckled snow mold), Typhula incarnate (Gray snow mold = Typhula blight), Typhula ishikariensis (Gray snow mold = Typhula blight), Ulocladium atrum (Ulocladium blight), Uromyces junci (Rust), Ustilagînoidea virens (False smut), Ustilago hordei (Covered smut), Ustilago nigra (False loose smut), Ustilago nuda (Loose smut), Ustulina deusta (Ustulina root rot), Verticillium albo-atrum (Verticillium wilt), Verticillium dahlia (Verticillium wilt). [00040] In another embodiment, the morpholine fungicide, the phthalimide fongicide and the phosphorus containing fongicide can be applied simultaneously, that is jointly or separately, or in succession. In the case of separate application, the order of applying the fongicides has no effect on the activity of the combination.

[00041] For example, dimethomorph, folpet and fosetyl-Al can be applied simultaneously, jointly or separately, or in succession. In the case of separate application, the order of applying the fongicides has no effect on the activity of the combination.

[00042] The application rates of the combination may vary, depending on the desired effect. In an embodiment, depending on the desired effect, the application rates of the mixtures according to the invention are from 10 g/ha to 2500 g/ha, particularly from 100 to 2000 g/ha, more particularly from 500 to 1500 g/ha.

[00043] The application rates of the combination when used for treating seeds are from 0.1 to 50 g a.î./kg, and preferably from 1 to 15 g a.i./kg.

[00044] In yet another embodiment, the synergistic composition may be applied in various mixtures or combinations of the morpholine fungicide, the phthalimide fongicide and the phosphorus containing fungicide, for example in a single “ready-for-use” form, or in a combined spray mixture composed from separate formulations of the single active ingrédients, such as a “tank-mix” form.

[00045] In yet another embodiment, the combination is applied in the form of a ready-for-use formulation comprising the morpholine fungicide, the phthalimide fungicide and the phosphorus containing fongicide. This formulation can be obtained by combining the three active ingrédients with an agriculturally acceptable carrier, a surfactant or other applicationpromoting adjuvant customarily employed in formulation technology.

[00046] The term surfactant, as used herein, means an agriculturally acceptable material which imparts emulsifîability, stability, spreading, wetting, dispersibility or other surfacemodifying properties. Examples of suitable surfactants include non-ionic, anionic, cationic i 11 i

s

J j and ampholytic types such as lignin sulfonates, fatty acid sulfonates (e.g. lauryl sulfonate), j phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styrylphenol ethoxylatcs, condensâtes of sulfonated naphthalene and naphthalene dérivatives with formaldéhyde, condensâtes of 5 naphthalene or of naphthalenesulfonic acid with phénol and formaldéhyde, alkylarylsulfonates, ethoxylated alkylphenols and aiyl phénols, polyalkylene glycols and ethoxylated fatty alcohols.

[00047] Other ingrédients, such as wetting agents, adhesives, thickeners, binders, fertilizers or anti-freeze agents, may also be added to the composition including the combination of the 10 fimgicides in order to increase the stabiiity, density and viscosity of the composition.

[00048] For example, the composition of the présent invention is applied in the fonn of a i

ready-for-use formulation comprising dimethomorph, folpet and fosetyl-Al, obtained by

I combining the three active ingrédients with agriculturally acceptable carriers, a surfactant or any other application-promoting adjuvant customarily employed in formulation technology.

[00049] Ready-for-use compositions containing the morpholine fungicide, the phthalimide fungicide and the phosphorus containing fungicide may be employed in any conventional J fonn, for example, in the form of a twin pack, or as an emulsifiable concentrate, an oil-inwater émulsion, soluble concentrate, suspension concentrate, microemulsion, wettable powder, ready-to-spray solution, soluble granule and water-dispersible granule. Such 20 compositions can be formulated usîng with agriculturally acceptable carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology and formulation techniques that are known in the art.

[00050] In yet another embodiment, the composition is applied in the form of émulsion ί concentrâtes (EC), suspension concentrâtes (SC), suspoemulsion (SE), oil dispersion (OD), water dispersîble granules (WDG) and wettable powders (WP). In an embodiment of the | invention the formulation is in the form of water dispersîble granules.

[00051] In another embodiment, the combined amount of the morpholine fungicide, the phthalimide fungicide and the phosphorus containing fungicide together in the ready-to-use water dispersîble granules formulations is 1-95 wt.%. In an embodiment ofthe invention the combined amount of the morpholine fungicide, the phthalimide fungicide and the phosphorus containing fungicide together in the ready-to-use water dispersîble granules formulations is 50-90 wt.%, based on the total weight of the formulation. In another embodiment, the combined amount is 75-85 wt.%, based on the total weight ofthe formulation.

[00052] For example, the combined amount of dimethomorph, folpet and fosetyl-Al in the ready-to-use water dispersible granules formulations according to the invention is 1 -95 wt. %.

In another embodiment the combined amount is 50-90 wL%. In another embodiment, the combined amount is 75-85 wt.%, based on the total weight of the formulation.

[00053] In another embodiment, the water dispersible granules are prepared by mixing the components of the synergîstic combination with sodium sulfate, fatty alcohol ethoxylate and magnésium silicate, milling the premix followed by the addition of water, methyl méthacrylate graft copolymer, polyalkoxylated alkyl ether and ammonium sait of polyarylphenyl ether phosphate. The water dispersible granules are finally obtained by 10 extrusion granulation and drying in fluidized bed dryer.

[00054] Examples of suitable solid carriers include minerai earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnésium sulfate, magnésium oxide, sodium carbonate and bicarbonate, and sodium sulfate, ground synthetic materials, fertilizers, such as, for 15 example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

[00055] Examples of suitable liquid carriers include water, alcohols such as methanol, cyclohexanol and decanol, ethylene glycol and polypropylene glycol, N,N20 dimethylformamide, dimethylsulfoxide, N-alkylpyrrolidone, aromatic hydrocarbons such as alkylbenzenes and alkylnaphthalenes, paraffins, oils of olive, castor, linseed, tung, sesame, com, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, îsophorone and 4-hydroxy-4-methyl-2-pentanone and the like.

[00056] In another embodiment, the présent invention provides a kit comprising a temary 25 synergîstic fungicidal composition as described herein, or components thereof. Such kits may comprise, in addition to the aforementioned active components, one or more additional active and/or inactive ingrédients, either within the provided fungicidal composition or separately. Certain kits comprise a morpholine fongicide, a phthalimide fongicide and a phosphorus containing fongicide, each in a separate container, and each optionally combined with a 30 carrier.

[00057] As noted above, the compositions, kits and methods described herein exhibit a synergîstic effect. A synergîstic effect existe wherever the action of a combination of active components is greater than the sum of the action of each of the components alone. Therefore, a synergistically effective amount (or an effective amount of a synergîstic composition or

combination) is an amount that exhibits greater insecticidal activity than the sum of the fiingicidal activîties of the individual components.

[00058] The following examples illustrate the practice of the présent invention în some of its embodiments, but should not be construed as limîting the scope of the invention. Other embodiments will be apparent to one skilled in the art from considération of the spécification and examples. It is intended that the spécification, including the examples, îs considered exemplary only without limiting the scope and spirit of the invention.

EXAMPLES

FORMULATION EXAMPLE [00059] The formulation of the synergistic fungicidal water-dispersible granule (WDG) formulation used in the below described experiments is set forth in Table 1 below:

TABLE 1

water-dispersible granule
Ingrédient	Weight percent
Dimethomorph	5.0%
Folpet	25.0%
Fosetyl-Al	50.0%
Surfactant	9%
Canier	11.0%

Measurement of the Synergistic Factor [00060] A synergistic effect exists whenever the action of an active ingrédient combination is greater than the sum of the actions of the individual components. The Wadley Method is well-known method for determîning whether synergy exists. In the Wadley Method, synergistic activity is determined from dose response curvcs. With this method, the efficacy of the active ingrédient (“a.i”) is determined by comparing the degree of fungal attack on treated plants with that on untreated, similarly inoculated and incubated check plants. Each a.i. is generally tested at multiple (e.g., six) concentrations and dose response curves are generated. The dose response curves are used to establish the ED90 (i.e., estimated concentration required to produce 90% killing of fungi) of the individual compounds as well as of the combinations (ED90observed). The experimentally found values of the mixture at a given weight ratio are compared with the values that would hâve been found where only a complementary efficacy of the components was présent (ED90 (A+B) expected). The ED90

t (A+B) expected is generally calculated according to Wadley (Levi et al., EPPO- Bulletin 16, 1986, 651 657) or (Wadley, F.M., U.S. Dep. Agric., Agric. Res. Adm., But. Entomol. And Plant Quar. ET-223, 1945,8) as follows:

ED9O(/1 + B)expecteà =—--------------------[^£7290(/1 Joôserved ) + \ED9O(B)observed /] [00061] wherein a and b are the weight ratios of the compounds A and B in the mixture and the indexes (A), (B) and (À+B) refer to the observed ED^ovalues of the compounds A, B or the A+B mixture thereof. The ratio ED90 (A+B) expected/ ED^q (A+B) observed expresses the level of the synergistic fector (SF).

[00062] The nature of the synergistic factor (SF) existing between fongicides used in the combination obtaîned fiom the Wadley Formula is presented in the following Table 2 (Ulrich Gisi, Phytopathology, 86, 1996, 1273-1279).

TABLE 2

Synergy Factor (SF)	Mathematical définition	Biological response
<1.0	Antagonistic effect
1.0	Additive effect
> 1.0	Synergistic effect
<0.5		Antagonistic effect
0.5 - 1.5		Additive effect
> 1.5		Synergistic effect

EXAMPLE 1 [00063] A trial was conducted to in order to estimate the synergistic interaction between three fongicides in controlling the oomycete, Plasmopara viticola, the downy mildew causal agent, in grapevines.

[00064] Commercially available compositions of dimethomorph (Sphinx 50 SC), folpet (Folpan 80 WDG) and fosetyl-Al (Aliette 80 WDG), as well as 80 wt. %, WDG composition comprising a combination of dimethomorph, folpet and fosetyl-Al (mixed at a weight ratio of 1:5:10) were suspended in water, diluted to a sériés of concentrations in water and sprayed onto the lower leaf surface of detached grape leaves to initial run off.

[00065] Two cultivars of grapevines (Kiris viniferd) were used: Carinian and Merlo, both susceptible to P.viticola. Grafted Carinian plants were grown in pots in the greenhouse whereas Merlo vines were grown in the field. Plants were regularly sprayed with appropriate fongicides to protect them against powdery mildew (Uncinulla necator). In total, five

experiments were conducted, three with Carinian and two with Merlo. The results are presented in Table 3.

[00066] The 3^rd and the 4^Ih leaf from top of a branch were detached, sprayed on lower leaf surface with a fungicide, three leaves per fungicide per concentration per cultîvar, and placed lower surface uppermost on moisi fîlter paper in a plastic tray (70x50x5 cm). Normally, one tray served for one cultîvar and one fungicide and contained 27 leaves (21 leaves treated with 7 doses of a fungicide + 6 control untreated leaves).

[00067] Trays with the sprayed leaves were placed in a ventilated hood for about one hour until the spray droplets dried off and thereafter were inoculated with the pathogen.

[00068] An isolate of P.viticola was propagated on detached leaves of Carinian by repeated inoculations. Sporangia were harvested from freshly sporulating leaves into ice-cold distilled water, their concentration adjusted to lxl O⁵ sporangia/ml. Sporangîal suspension was sprayed onto the lower surface of the treated and control leaves laying in the trays. Trays were thereafter wrapped with cellophane bags, kept at 15°C in the dark for 20h and then at 20°C under 14h Iight photoperiod. At 7-10 days after inoculation, disease development was recorded by visual estimation of the leaf area occupied with sporophores and spores of P.viticola.

[00069] Mean sporulating leaf area was then calculated for each treatment (n=3, n for control=6). A mean value was calculated for ail four controls in an experiment. Percent control of the disease was calculated by using the formula 100(l-x/y), where x= mean sporulating leaf area in a treatment and y= grand mean of sporulating leaf area in the controls. [00070] The SPSS 15.0 software was used to calculate the ED$q value for each fungicide by Probit Analysis. An ED9Q value represents the dose, in pg/ml, required to reduce disease development by 90% relative to control. Four EDpo values were obtained in each experiment, one for each fungicide and one for the combination. The ED90 values of the single fungicides were placed into the Wadley Formula to calculate the expected ED90 of the 1:5:10 fungîcidal mixture. SF stands for Synergistic Factor.

TABLE 3

Control of Plasmopara vüicola in grapevines (pg/ml)

	Dimethomorph	Folpet	FosetylAl	Dimethomorph + Folpet + Fosetyl-Al
ED90 observed Trial l	2.42	65.8	936	12.92
ED90 expected Trial l				32.06
SF Trial 1				2.48
ED90 observed Trial 2	1.81	30.6	1522	8.59
ED90 expected Trial 2				22.16
SF Trial 2				2.57
ED90 observed Triai 3	0.91	57.1	611	13.1
ED90 expected Trial 3				13.3
SF Trial 3				1.02
ED90 observed Trial 4	3.95	61.8	274	21.2
ED90 expected Trial 4				43.2
SF Trial 4				2.04
ED90 observed Trial 5	2.25	39.8	297	17.64
ED90 expected Triai 5				26.4
SF Triai 5				1.49

[00071] Based on the results presented hereinabove, the temary fungicidal composition was found to exhibit a strong synergistic effect against phytopathogenic fimgi.

EXAMPLE 2 [00072] A trial was conducted to estimate the synergistic interaction between three 5 fungicides in controlling DMM-resistant isolâtes of P.cubensis, the causal agent of downy mildew in cucurbits.

[00073] Commercîally avaîlable compositions of dimethomorph (Sphinx 50 SC), folpet (Folpan 80 WDG) and fosetyl-AI (Aliette 80 WDG), as well as 80 wt. %, WDG composition comprising a combination of dimethomorph, folpet and fosetyl-Al (mixed at a weight ratio of 10 1:5:10) were suspended in water, diluted to a sériés of concentrations in water, and sprayed initial run off.

[00074] Two isolâtes of P. cubensis were used. Intact, two-true leaf cucumber plants (n-2) were used for inoculation. Inoculation and incubation were conducted according to the description in example 1, except that sporangial concentration was adjusted to 2x103 15 sporangia/ml. Disease records were taken by counting the number of downy mildew lésions per leaf (n4). Data analysis was done as described in Example 1. The results are presented in Table 4.

TABLE 4

Control of DMM-resistant isolâtes of Pseudoperonospora cubensis in cucumber (pg/ml)

Dirnethomorph

	Dirnethomorph	Folpet	Fosetyl-Al	+ Folpet + Fosetyl-Al
ED90 observed Trial 1	701	254	2088	190.6
ED90 expected Trial 1				620
SF Trial 1				3.25
ED90 observed Trial 2	424	81	508	62.7
ED90 expected Trial 2				191
SF Trial 2				3.0S

[00075] Based on the results presented hereinabove, the temary fungicidal composition was found to exhibit a strong synergistic effect against phytopathogenic fungi.

[00076] The results show that a synergistic combination of a morpholine fongicide, a phthalimide fungicide and a phosphorus containing fimgicide is suitable for controlling and/or preventing diseases in agriculturally important plants or propagation material thereof caused by phytopathogenic fiingi.

Claims (5)

What is claimed is;

1. A fungicidal composition comprising a morpholine fongicide; a phthalimîde fongicide; and a phosphores containing fungicide, in a synergistically effective amount.

2. The composition of claîm I, wherein said morpholine fungicide is aldimorph, benzamorf, carbamorph, dimethomorph, dodemorph and salts thereof, fenpropimorph, flumorph, tridemorph or any combination thereof.

3. The composition of claim 2, wherein said morpholine fongicide is dimethomorph.

4. The composition of claim 1, wherein said phthalimîde fongicide is captafol, captan, ditalimfos, folpet, thiochlorfenphim or any combination thereof.

5. The composition of claim 4, wherein said phthalimîde fungicide is folpet.

6. The composition of claim 1, wherein said phosphores containing fongicide is an organophosphorus fongicides or inorganic phosphores fungicides.

7. The composition of claim 6, wherein said organophosphorus fungicide is ampropylfos, ditalimfos, edifenphos, fosetyl and salts thereof, hexylthiofos, iprobenfos, phosdiphen, pyrazophos, tolclofos-methyl, triamiphos or any combination thereof.

8. The composition of claîm 6, wherein said inorganic phosphores fungicides is phosphonic acid, potassium phosphonate, dipotassium phosphonate or any combination thereof.

9. The composition of claim 6, wherein said phosphores containing fungicide is fosetyl-Al.

10. The composition of daim 1, comprising the morpholine fongicide and the phthalimîde fungicide in a weight ratio of from 1:100 to 100:1.

11. The composition of claim 1, comprising the morpholine fungicide and the phosphores containing fungicide in a weight ratio of from 1:100 to 100:1.

12. The composition of claim 1, wherein the morpholine fongicide, the phthalimîde fungicide and the phosphores containing fungicide are présent in a combined amount ranging from 50% to 90% by weight.

13. The composition of claim 1, further comprises an agriculturally acceptable carrier.

14. A method of controlling diseases caused by phytopathogenic fungi in plants or on propagation material thereof which comprises contacting the plants, the locus thereof or propagation material thereof with a synergistically effective amount of a combination of a morpholine fungicide; a phthalimîde fungicide; and a phosphores containing fungicide.

15. The method of claim 14, wherein the morpholine fongicide is dimethomorph; the phthalimîde fungicide is folpet; and the phosphores containing fungicide is fosetyl-Al.

16. The method of claim 14, wherein said combination is applied in an amount of from 10 g/ha to 2500 g/ha.

17. The method of claim 14, wherein said phytopathogenic fungi are of the class Ascomycètes, Basîdiomycetes, Deuteromycetes or Oomycetes or combination thereof.

5 18. The method of claim 14, wherein said morpholine fungicide; said phthalimide fungicide;

and said phosphores containing fungicide, are applied simultaneously, or in succession.