DK201400182U1 - Et kombinationsprodukt - Google Patents

Abstract

Et kombinationsprodukt til at opnå en udbytteforøgelse af afgrøder samt bekæmpelse af uønsket svampevækst.

Description

BACKGROUND OF THE INVENTION (1) Field of the Invention

The present invention relates to a fungicidal composition comprising prothioconazole and fluazinam as active ingredients. The combination shows a synergistic effect in the control of harmful fungi.

The present invention also relates to a method of improving the plant health, yield and vigor of plants, by applying the fungicidal composition to a plant or plant propagation material. (2) Background

The fungicidal active compound prothioconazole is a synthetic compound of the triazolinthione family of compounds. It is a compound known form United States patent no. US 5,789,430. It is a broad spectrum systemic fungicide, with curative, preventative and eradicative action, it can he used as both a seed treatment and a foliar treatment. After absorption it moves into cells of the target organisms, effecting sterol biosynthesis and thereby disrupting membrane structure. This ultimately effects hyphal growth and germ tube elongation. Fungi susceptible to prothioconazole include Early leaf spot (Mycosphaerella arachidis), eyes pot, Fusarium spp,, powdery mildew, net blotch, phoma leaf spot, Rhynehosporium secalis, Sclerotinia sclerotiorum, Sclerotium rolfsii, Septoria tritici, Septoria nodorum, rust and tan spot. However prothioconazole has not, previously, been reported to have a yield improving effect on the crops, when applied either to the plant or plant propagation material.

The fungicidal active compound fluazinam is a member of the dinitroaniline fungicides and is known from United States patent number US 4,331,670. Fluazinam is a broad spectrum contact fungicide that can be applied as a foliar spray or soil treatment. It is effective against a number of pathogenic fungi that cause the following diseases: gray mold and downy mildew in grapes; melanose and mites in citrus; scab and Alternaria blotch in apples; clubroot in crucifers; Sclerotinia blight in peanuts; white root rot and violet root rot on fruit trees. Its best known however due to the fact that it protects against Foliar blight , tuber blight and sclerotinia rot in potatoes caused by the fungus Phytophthora infestans. The effect on potatoes is unparalleled. Fluazinam is effective against both spore germination and spore growth, thereby giving it protective action with a good residual effect. It also has good rainfastness. The mode of action of fluazinam is due to the disruption of energy production in the fungus at multiple sites - therefore preventing resistance. However fluazinam has not reported to have effect on rust diseases found on soybean plants. Fluazinam has also not previously been reported to have a yield improving effect, when applied either to the plant or plant propagation material.

Mixtures of plant protection products have been proposed in the literature to control e.g. inhibit or destroy fungi. However, lower application doses of fungicides and greater control of fungi are required for safer handling as well as for environmental protection. This is achievable by applying combinations of fungicides, which do not only generate an additive enhancement, but also a synergistic effect.

It is impossible to predict if a combination of fungicides has a synergistic effect, and it is therefore of high importance to develop novel fungicidal combinations, which exhibit a synergistic effect. Surprisingly, it has now' been found that the combination of prothioconazole and fluazinam exhibit a synergistic effect against fungi, but also show's an improvement on the yield and vigor of plants, when applied to the plants or plant propagation material.

DESCRIPTION OF THE INVENTION

The present invention relates to a method for controlling harmful fungi using the combination prothioconazole and fluazinam. The invention further relates to a process for the preparation of the novel composition, and to the use thereof. Additionally, the present invention also comprises a method for the protection of the plant and plant propagation material from harmful fungi comprising contacting the plant and/or plant propagation materials with a combination according to the invention in pesticidally effective amounts. The term "combination" will be used to describe the mixture prothioconazole and fluazinam throughout this patent application.

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.

All fungicides have a limited activity and in particular the persistence and the spectrum of activity. It is an object of the present invention, with a view of reducing the application rates and broadening the activity spectrum of the known compounds, to provide a mixture which, at a reduced total amount of active compounds applied, have improved activity, in particular persistence, against the harmful fungi. It has now been found that this object is achieved by the combinations defined in this invention. Moreover, it has been found that applying prothioconazole in combination with fluazinam simultaneously, either together or separately, or applying the combination in succession provides better control of the harmful fungi than is possible with the individual compounds (synergistic mixtures).

The combination demonstrates excellent activity against a broad spectrum of phytopathogenic fungi, but also the soil-home fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.

The combination according to the invention and the compositions thereof, respectively, are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e.g. wheat, rye, barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fmits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citms fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; com; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e.g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.

Preferably, combinations according to the invention and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

Preferably, treatment of plant propagation materials with combinations according to the invention and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats, rice, corn, cotton and soybeans.

The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agri."products,asp). Genetically modified plants are plants, which genetic material has been modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transitional modification of protein(s), oligo - or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylated or famesylated moieties or PEG moieties.

Plants that have been modified by breeding, mutagenesis or genetic engineering, e.g. have been rendered tolerant to applications of specific classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e.g. the following patent publications nos. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/026390, WO 97/41218, WO 98/002526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/014357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e.g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e.g. EP-A 242 236, EP-A 242 246) or oxynil herbicides (see e.g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering.

Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e.g. CryiA(b), CryiA(c), CryiF, CryiF(a2), CryiiA(b), CryiiiA, CryiiiB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e.g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-1 DP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e.g. biomass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.

Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e.g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera®rape, DOW Agro Sciences, Canada).

Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e.g. potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).

The combination according to the invention and compositions thereof, respectively, may be used for improving the health, the vigor and/or the yield of a plant. The combination can be applied by foliar application, treatment of the seed and/or the foliage of the plant and/or the locus where the plant is growing or is to grow with an effective amount of the combination, which has the capability of causing an improvement in the vigor and/or the yield of the plant whether or not the plant is under pest pressure from fungal pathogens. In particular, this effect is observed when the plant is not under pest pressure from fungal pathogens of the type fluazinam and prothioconazole are known to have activity against. In preferred embodiments, in fact, the increase in yield and/or vigor can be shown to take place even when the treated plant and/or seeds are under no pest pressure, for example, as in tests where germination, sprouting and plant growth take place under substantially sterile conditions.

The increase in yield and/or vigor is entirely unexpected because it is brought about by fungicides, but can occur even in the absence of pest pressure by fungal pathogens against which the fungicides are known to be active. By way of example, the method is useful to increase plant vigor and/or yield in geographic areas, or with cultivation practices, where the particular fungicide is not normally used, and even under conditions where the fungicide has no activity against the fungal pathogens that are known to be harmful to the plant.

It has also been observed that the combination is useful in situations where the treated seed or plant is subjected to some stress during or after germination. For example, such stress could be caused by environmental stress, such as drought, cold, cold and wet, and other such conditions.

The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e.g. increased biomass and/or increased content of valuable ingredients), plant vigor (e.g. improved plant growth and/or greener leaves ("greening effect")), quality (e.g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.

The term "increasing the yield" of a plant, is to be understood to denote that the yield of a product of the plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the subject method. It is preferred that the yield be increased by at least about 0.5%, more preferred that the increase be at least about 1%, even more preferred is about 2%, and yet more preferred is about 4%, or more. By way of example, if untreated soybeans yielded 2.20 kg/Ha, and if soybeans that received the subject treatment yielded 2.39 kg/Ha under the same growing conditions, then the yield of soybeans would be said to have been increased by ((2.39-2.20)/2.20) * 100=8.6%.

The term "increasing the vigor" of a plant, is to be understood that the vigor rating, or the plant weight, or the plant height, or the plant canopy, or the visual appearance, or any combination of these factors, is increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the subject method. It is preferred that such factor(s) is increased or improved by a significant amount.

As used herein the terms "fungal pest pressure", or "pest pressure by fungal plant pathogen", is to be understood as harm or damage to the plant or to its propagation material that is caused by fungal pathogens of the plant. Harm or damage is considered to be any such harm or damage that would normally be recognized as such by a skilled practitioner in the field of agriculture and farming. The terms "absence of pest pressure", or "lack of pest pressure", refer to the case where any harm or damage that is caused to the plant or its propagation material by the pest being described is either nonexistent, or is so minor that it would not normally be considered to be harm or damage by the skilled practitioner. In a preferred embodiment, a plant or seed that was sown, sprouted and/or grown in an environment having an absence of fungal pest pressure, or which was free of pest pressure due to fungal pathogens, would be rated as having the least, or lowest, amount of damage or harm due to fungal pests if analyzed by a test method wherein harm or damage to the plant or its propagation material is rated, by whatever scale that is used, from lowest to highest. One example of an environment that has an absence of fungal pest pressure is a sterile environment.

The term "an effective amount" of a fungicide or other active agent is to be understood as a sufficient amount of the fungicidal combination comprising prothioconazole and fluazinam is applied to the plant or its propagation material to achieve an increase in the plant health, yield and/or the vigor of the plant. The effective amount is also the amount, which is sufficient for controlling the harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal specie to be controlled, the treated cultivated plant or material, the climatic conditions and the specific combination used. An agrochemical composition comprises a fungicidally effective amount of a combination according to the invention.

Additional fungicides or insecticides may also be added to the combination, preferably so selected that the additional pesticides do not interfere negatively, with the synergistic relationship between prothioconazole and fluazinam. The optional additional fungicides or insecticides can advantageously be included for example to widen the spectrum of action or to prevent the build-up of resistance.

Suitable examples of additional fungicides that may also be combined with the compositions as herein disclosed are e.g.: A) azoles, in particular: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, flutriafol, fenbuconazole, flusilazole, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, penconazole, propiconazole, pyrisoxazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole; prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid; benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole; B) strobilurins, in particular: azoxystrobin, benzothiostrobin, coumethoxystrobin, coumoxystrobin, enoxastrobin, dimoxystrobin, fenaminstrobin, flufenoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyriminostrobin, pyrametostrobin, trifloxystrobin, triclopyricarb, pyraoxystrobin, fenamidone, famoxadone, or pyribencarb; C) carboxamides, in particular: carboxin, benalaxyl, benodanil, boscalid, fenfuram, fenhexamid, fenpyrazamine, flutolanil, furalaxyl, furametpyr, isofetamid, isotranil, kiralaxyl, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, pyrimorph, thifluzamide, tiadinil, bixafen, dimethomorph, flumorph, flumetover, fluopicolide (picobenzamid), zoxamide, carpropamid, diclocymet, mandipropamid, isopyrazam, fluxapyroxad, sedaxane, penflufen, fluopyram; D) heterocylic compounds, in particular: benzovindiflupyr, isofetamid, pyrifenox, bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil, triforine, fenpiclonil, fludioxonil, aldimorph, chloozolinate, dimethirimol, dodemorph, ethirimol, fenpropimorph, tridemorph, fenpropidin, iprodione, piperalin. procymidone, vinclozolin, famoxadone, fenamidone, octhilinone, probenazole, pyrisoxazole, amisulbrom, anilazine, diclomezine, pyroquilon, proquinazid, tricyclazole, acibenzolar-S-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen; E) carbamates, in particular: mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram, benthiavalicarb, diethofencarb, iodocarb, iprovalicarb, flubenthiavalicarb, methasulfocarb, propamocarb, prothiocarb, pyributicarb , valifenalate; and F) other active compounds, selected from guanidines: dodine, iminoctadine, guazatine, antibiotics: blasticidin-S, kasugamycin, streptomycin, oxytetracycline, polyoxin, validamycin; nitrophenyl derivates: binapacryl, dinocap, dinobuton, meptyldinocap; sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane; organometal compounds: fentin salts, such as fentin-acetate, chloride or hydroxide; organophosphorus compounds: edifenphos, iprobenfos, fosetyl, fosetyl-AL, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; organochlorine compounds: biphenyl, chloroneb, dicloran, chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, tecnazene, thiophanate-methyl, tolylfluanid; inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, metrafenone, flutianil, pyriofenone, bupirimate, oxathiapiprolin, benzovindiflupyr and spiroxamine; G) Biological fungicides, in particular: Bacillus spp.: B. subtilis, B amyloliquefaciens\ plant extracts: Melaleuca alternifolia.

Suitable examples of insecticides that may also be combined with the composition are e.g. abamectin, acephate, acrinathrin, alanycarb, albendazole, aldicarb, alphamethrin, amitraz, azadirachtin, azinphos, azocyclotin, Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap, bephenium, betacyfluthrin, bifenazate, bifenthrin, bistrifluron, BPMC, brofenprox, bromophos, brotianide, bufencarb, buprofezin, butamisole, butocarboxin, butylpyridaben, cadusafos, cambendazole, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chloroethoxyfos, chlorfenapyr, chlorofenvinphos, chlorofluazuron, chloromephos, chlorpyrifos, chromafenozide, cis-resmethrin, clocythrin, clofentezine, clorsulon, closantel, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton, diamphenethide, dibromosalan, dichlorophen, difenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diethylcarbamazine, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton, emamectin(-benzoate), epsiprantel, esfenvalerate, ethiofencarb, ethion, ethiprole, ethofenprox, ethoprophos, etoxazole, etrimphos, febantel, fenamiphos, fenbendazole, fenzaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, flonicamid, fluazuron, flubendazole, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, gamma-cyhalothrin, haloxon, heptenophos, hexaflumuron, hexachlorophene, hexythiazox, imidacloprid, indoxacarb, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, levamisole, lufenuron, malathion, mebendazole, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, methoxyfenozide, methyridine, metolcarb, milbemectin, monocro tophos, morantel, naled, netobimin, niclopholan, niclosamide, nitroxynil, omethoate, oxamyl, oxfendazole, oxibendazole, oxyclozanide, oxydemethon M, oxydeprofos, parathion A, parathion M, parbendazol, permethrin, phenothiazine, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos, praziquantel, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyrantel, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, rafoxanide, rynaxypyr, salithion, sebufos, silafluofen, spinosad, spinetoram, spirodiclofen, spiromesifen, spirotetratmat, sulfotep, sulprofos, tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetra-chlorvinphos, tetramisole, thenium, thiabendazole, thiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, triclabendazole, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, zetamethrin.

The combination according to the invention are employed as such or in form of compositions by treating the fungi, their habitat or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal or insect attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi. Prothioconazole in combination with fluazinam can be applied simultaneously jointly, simultaneously separately or in succession.

Plant propagation materials may be treated with combinations according to the invention as such or a composition thereof either at or before planting or transplanting. Plants may also be treated with the combination after or before planting by foliar application.

The invention also relates to agrochemical compositions comprising a solvent or solid carrier and a combination according to the invention and to the use for controlling the harmful fungi.

The invention also relates to the use of the prothioconazole and fluazinam for preparing a composition comprising said combination suitable for controlling the harmful fungi.

The combinations can be converted into customary types of agrochemical compositions, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The composition type depend on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention. Examples for composition types are suspensions, pastes, pastilles, wettable powders or dusts or granules, which can be water-soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds.

The compositions are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Oec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 and ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701, US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001).

The agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions. The auxiliaries used depends on the particular application form and active substance, respectively.

Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and an organic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations).

Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and vegetable oils or epoxidised vegetable oils such as rape oil, castor oil, coconut oil, or soybean oil, and silicone oils or animal oils, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, diethylene glycol or 2-methoxyethanol or 2-ethoxyethanol, ketones such as cyclohexanone, gamma-butyrolactone, isophorone or diacetone alcohol; fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, such as dimethyl sulfoxide, N-methylpyrrolidone or N,N-dimethylformamide.

Solid carriers typically used for dusts, granules and dispersible powders are usually mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., 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.

Suitable surfactants (adjuvants, wetters, tackifiers, dispersants or emulsifiers) compounds are nonionic, cationic and for anionic surfactants or mixtures of surfactants having good emulsifying, stability, spreading, dispersibility, wetting, or other surface-modifying properties. The surfactants listed below shall be regarded merely as exemplary; many more surfactants customarily employed in formulation technology and suitable for use in the practice of the invention are described in the relevant literature.

Nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable nonionic surfactants are water-soluble poly-adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Representative examples of nonionic surfactants are nonylphenol polyethoxyethanols, polyethoxylated eastor oil, polyadducts of polypropylene and polyethylene oxide, tributylphenol polyethoxylate, polyethylene glycol and octylphenol polyethoxylate. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable nonionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts carrying, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates orethyl sulfates. Examples are stearyltrimethylammonium chloride and benzyl bis(2-chloroethyl)ethylammonium bromide.

Suitable anionic surfactants may be water-soluble soaps as well as water-soluble synthetic surface-active compounds. Suitable soaps are the alkali metal salts, alkaline earth metal salts and unsubstituted or substituted ammonium salts of higher fatty acids (Cio -C22), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures, which can be obtained e.g. from coconut oil or tall oil. Further suitable soaps are also the fatty acid methyl taurin salts.

More frequently, however, synthetic surfactants are used, preferably fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and usually contain a C8-C22 alkyl radical, which also includes the alkyl moiety of acyl radicals. Typical examples are the sodium or calcium salt of ligninsulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Typical examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde. Corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids, are also suitable.

Examples for thickeners (i.e. compounds that impart a modified flowability to compositions, i.e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).

Bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide ® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie).

Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Examples for anti-foaming agents are silicone emulsions (such as e.g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.

Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples to be mentioned and the designations rhodamin B, C. 1. pigment red 112, C. 1. solvent red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

Examples for tackifiers or binders are polyvinylpyrrolidons, poly vinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).

Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding combination and, if appropriate, further active substances, with at least one solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talcm kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea's, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal, and nutshell meal, cellulose powders and other solid carriers.

The composition will usually comprise 0.1 to 99%, preferably 0.1 to 95%, of a combination of prothioconazole and fluazinam, and 1 to 99.9%, preferably 5 to 99.9%, of at least one solid or liquid carrier; usually they will contain 0 to 50%, preferably 0.1 to 20%, of surfactants (in each case percentages are by weight). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations having a substantially lower concentration of active ingredient. Particularly preferred formulations will be made up as follows: (throughout, percentages are by weight):

Depending on the intended objectives and the prevailing circumstances, the combination according to the invention may be employed in any conventional form, for example, in the form of a twin pack, or ready-to-use solutions, emulsifiable concentrates, emulsions, dilute emulsions, suspensions, wettable powders, soluble powders, dispersible powders, dusts, granules, soluble granules, dispersible granules, microemulsions, microcapsule suspensions e.g. capsules comprising both active ingredients or present within separate capsules, and mixtures thereof. Such compositions can be formulated using diluents and formulation techniques that are known in the art for individually formulating the pesticides. For example, the pesticides may be mixed together, optionally with other formulating ingredients.

The compositions of this invention are prepared by a known process in the absence of diluents, typically by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a specific particle size, and in the presence of at least one diluent, for example by mixing and grinding the active ingredient or mixture of active ingredients with the diluent(s) and/or surfactant(s). The invention also relates to the preparation of the compositions. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The composition may be applied in various combinations of the two or three active compounds. For example, they may be applied as a single "ready-mix" form, or in a combined spray mixture composed from separate formulations of the active compounds, e.g. a "tank-mix" form. Thus, to be used in combination, it is not necessary that the two or three pesticides are applied in a physically combined form, or even at the same time, i.e. the components may be applied in a separately and/or sequentially application, provided that the application of the second active compound occurs within a reasonable period of time from the application of the first active compound. The combination effect results as long as the two pesticides are present at the same time, regardless of when they were applied. The order of applying the individual actives prothioconazole and fluazinam is not essential.

The methods of applying the composition, i.e. the methods of controlling fungi and/or insects, typically spraying, atomising, dusting, coating, dressing, scattering or pouring, selected in accordance with the intended objectives and prevailing circumstances, and the use of the compositions for controlling pests of the indicated type, are further objects of the invention. A preferred method of application in the field of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depend on the risk of infestation by the particular pests.

Water-soluble concentrates, flowable concentrates, powders for dry treatment, water-dispersible powders for slurry treatment, water-soluble powders, emulsions, emulsifiable concentrates, and gels are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.

Application can be carried out before or during sowing. Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting. The treatment of plants and parts of plants according to the invention may be carried out directly or by action on their environment (e.g. soil application), habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multilayer coating. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active substances according to the invention.

The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1% by weight of active substance.

The active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.

When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 50 to 2500 g/ha, preferably from 50 to 2000 g/ha, more preferably from 100 to 1500 g/ha, in particular from 200 to 1200 g/ha, and even more particular from 200 to 1100 g/ha and utmost particular between 250 to 1000 g/ha. In treatment of plant propagation materials such as seeds, e.g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.

Thus, the invention also relates to plant propagation materials, preferably seeds, comprising the combination according to the invention or a composition thereof in an amount as used for treatment thereof.

When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect.

Amounts customarily applied in the protection of materials are, e.g., 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Rates of application of the composition will vary according to prevailing conditions such as degree of infestation, weather conditions, crop species, method of application, and application timing. Compositions containing prothioconazole and fluazinam may be applied in the manner, in which they are formulated, as discussed above.

Various types of oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions comprising them, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, e.g. Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates such as Lutensol XP 80®; and dioctyl sulfosuccinate sodium such as Leophen RA®.

According to this invention, applying prothioconazole together with fluazinam is to be understood to denote that fluazinam and prothioconazole occur simultaneously at the site of action (i.e. the harmful fungi to be controlled or their habitats such as infected plants, plant propagation materials, particularly seeds, surfaces, materials or the soil as well as plants, plant propagation materials, particularly seeds, soil, surfaces, materials or rooms to be protected from fungal attack) in a fungicidally effective amount. This can be obtained by applying fluazinam in combination with prothioconazole simultaneously, that is jointly (e.g. as tank-mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for obtaining the claimed effect of the present invention.

In the combination according to the invention and compositions thereof comprising fluazinam and prothioconazole, the weight ratio of fluazinam(A):prothioconazole(B) generally depends on the properties of the active substances used, usually it is in the range from 1:100 to 100:1, preferred in the range from 1:50 to 50:1, more preferred in the range from 1:20 to 20:1, particular preferred in the range of from 1:10 to 10:1 and very particular preferred in the range of from 1:5 to 5:1. In some embodiments the weight ratio is least 1:70 (e.g., at least 1:60. at least 1:50 at least 1:40, at least 1:30, at least 1:25, at least 1:20, at least 1:15, at least 1:12, at least 1:10, at least 1:8, at least 1:6, at least 1:5, at least 1 :4, at least 1 :3, at least 1 :2, at least 1:1 , at least 2:1 ,at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 8:1, at least 10:1, at least 15:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, at least 60:1, or at least 70:1). In some embodiments, the weight ratio of (A) to (B) that is sufficient to induce a synergistic fungicidal effect is 80:1 or less (e.g., 50:1 or less, 45:1 or less, 40:1 or less, 35:1 or less, 30:1 or less, 25:1 or less, 20:1 or less, 15:1 or less, 10:1 or less, 5:1 or less, 4:1 or less, 3:1 or less, 2:1 or less, 1:1 or less, 1:2 or less, 1:3 or less, 1:4 or less, 1:5 or less, 1:10 or less, 1:15 or less, 1:20 or less, 1:25 or less, 1:30 or less, 1:35 or less, 1 :40 or less, or 1 :50 or less). In some embodiments, the weight ratio of (A) to (B) is from 1:30 to 30:1 (e.g., from 1:25 to 30:1, from 1:20 to 30:1, from 1:20 to 25:1, from 1:20 to 20:1, from 1:16 to 20:1, from 1:15 to 15:1, from 1:10 to 15:1, from 1:10 to 10:1, from 1:8 to 10:1, from 1:8 to 8:1, from 1:7 to 7:1, from 1:6 to 6:1, from 1:5 to 5:1, from 1:4 to 4:1, from 1:3 to 3:1, from 2:1 to 2:1, from 1.5:1 to 1.5:1). The weight ratio of fhiazinam:prothioconazole will depend on various factors such as the mode of application, the harmful pests to be controlled, the useful plant to be protected, the application time, etc.

The components of the compositions according to the invention can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used later in time as a composition such as a kit of parts.

In one embodiment of the invention, the kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition. E.g., kits may include one or more fungicide component(s) and/or an adjuvant component and/or a insecticide component and/or a growth regulator component and/or a herbicide. One or more of the components may already be combined together or pre-formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister. In other embodiments, two or more components of a kit may be packaged separately, i.e. not pre-formulated. As such, kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination according to the invention for preparing the composition according to the invention.

The user applies the composition according to the invention usually from a pre-dosage device, a knapsack sprayer, a spray tank or a spray plane. Here, the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 100 to 400 liters.

According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a combination may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e.g. components comprising a combination according to the invention, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix).

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e.g. components comprising a combination according to the invention, can be applied jointly (e.g. after tank-mix) or consecutively.

The compositions according to the invention can, in the use form as fungicides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immediately prior to use (tank mix).

In a further aspect, the invention provides a method for obtaining regulatory approval for the use of a composition comprising prothioconazole and fluazinam as active ingredients to control a fungi comprising at least one step of referring to, submitting or relying on biological data showing that said active combination composition reduces fungi pressure, e.g. on a crop.

Biological efficacy

The weight ratio of fluazinam (component A) to prothioconazole (component B) is selected to provide a synergistic pesticidal action, i.e. prothioconazole is present in an activity enhancing amount with respect to fluazinam or vice versa. A synergistic effect exists whenever the action of a combination of two chemicals is greater than the sum of the action of each of the chemicals alone. Therefore, a synergistic combination is a combination of chemical components having an action that is greater than the sum of the action of each chemical component alone, and a synergistically effective amount is an effective amount of a synergistic combination. Synergism can involve either 2 pesticides, or one pesticide plus a substance that is not by itself toxic to the pest, and such a substance is termed a synergist, i.e. a chemical that enhances the toxicity of a pesticide to a pest.

Well-known methods for determining whether synergy exists include the Colby method, the Tammes method and the Wadley method, all of which are described below. Any one of these methods may be used to determine if synergy exists between the compounds A and B.

In the Colby method, also referred to as the Limpels method, the action to be expected E for a given active ingredient combination obeys the so-called Colby formula. According to Colby, the expected action of ingredients A+B using p+q ppm of active ingredient is:

where ppm=milligrams of active ingredient (=a.i.) per liter of spray mixture X=% action by component A using p ppm of active ingredient Y=% action by component B using q ppm of active ingredient. If the ratio R defined as the action actually observed (0) divided by the expected action (E) is >1 then the action of the combination is super additive, i.e. there is a synergistic effect. For a more detailed description of the Colby formula, see Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide combination," Weeds, Vol. 15, pages 20-22; 1967; see also Limpel et al., Proc. NEWCC 16: 48-53 (1962).

The Tammes method uses a graphic representation to determine whether a synergistic effect exists. See "Isoboles, a graphic representation of synergism in pesticides," Netherlands Journal of Plant Pathology, 70 (1964) p. 73-80.

The Wadley method is based on comparison of an observed ED50 value (i.e. dose of a given compound or combination of compounds providing 50% pest control) obtained from experimental data using the dose response curves and an expected ED50 calculated theoretically from the formula:

wherein a and b are the weight ratios of component A and B in the mixture and ED50obs is the experimentally determined ED50 value obtained using the dose response curves for the individual compounds. The ratio ED50(A+B)expected/ED50(A+B)observed expresses the factor of interaction (F) (synergy factor). In case of synergism, F is >1. The same formula applies when LD50 values are used, i.e. lethal dose, as well as EC50 values, i.e. effective concentration, and LC50 values, i.e. lethal concentration. For a more detailed description of the Wadley method, see Fevi et al., EPPO-Bulletin 16, 1986, 651-657. ED90 values (i.e. dose of a given compound (component) or combination of compounds providing 90% pest control) are often also used when calculating synergism.

An alternative approach as mentioned by D.F. Richer (Pesticide Science, 1987, 19, 309-315, especially p. 313) to determine synergy is based on purely observed values rather than observed and theoretical calculated values as used in the previously mentioned methods. In this alternative method the effect of a given rate of the mixture A and B is compared with the effect of the same rate of each of A and B used alone. If synergism exists, the observed effect of the mixture will be greater than the observed effect of either component used alone: Eobs(xA + yB)>Eobs(x + y)A, and > Eobs(x + y)B wherein x and y are the quantities of A and B in the mixture.

Examples

The active substances were formulated separately or together as a stock solution comprising 25 mg of active substance which was made up to 10 ml using a mixture of acetone and/or dimethyl sulfoxide (DMSO) and the emulsifier Wettol EM 31 (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) in a volume ratio of solvent/emulsifier of 99 to 1. This solution was then made up to 100 ml using water. This stock solution was diluted with the solvent/emulsifier/water mixture described to the active substance concentration given below.

Activity against early blight on tomatoes caused by Phytophthora in-festans with protective application Young seedlings of tomato plants were grown in pots. The plants were sprayed to runoff with an aqueous suspension containing the concentration of active substance stated below. The next day, the treated plants were inoculated with an aqueous suspension of sporangia of Phytophthora infestans. After inoculation, the trial plants were immediately transferred to a humid chamber. After 6 days at 18 to 200C and a relative humidity close to 100%, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

Curative action against Puccinia recondita on wheat (brown rust of wheat) Leaves of potted wheat seedlings of the cultivar "Kanzler" were dusted with a suspension of spores of brown rust of wheat (Puccinia recondita). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%), at 20-220C, for 24 hours. During this time, the spores germinated and the germinal tubes penetrated into the leaf tissue. The next day, the infected plants were sprayed to runoff point with an aqueous suspension having the concentration of active substance stated below. After drying of the sprayed suspension, the test plants were returned into the greenhouse and culti-vated at temperatures between 20 and 22°C and at 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust development on the leaves was then determined visually.

Protective action against Puccinia recondita on wheat (brown rust of wheat):

Leaves of potted wheat seedlings of the cultivar "Kanzler" were sprayed to runoff point with an aqueous suspension having the concentration of active substance stated below. The next day, the treated plants were dusted with a suspension of spores of brown rust of wheat (Puccinia recondita). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%), at 20-220C, for 24 hours. During this time, the spores germinated and the germinal tubes penetrated into the leaf tissue. The next day, the test plants were returned into the greenhouse and cultivated at temperatures between 20 and 22°C and at 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust development on the leaves was then determined visually.

Protective action against Blumeria graminis tritici on wheat (mildew of wheat):

Leaves of potted wheat seedlings of the cultivar "Kanzler" were sprayed to runoff point with an aqueous suspension having the concentration of active substance stated below. The next day, the treated plants were dusted with a suspension of spores of mildew of wheat (Blumeria graminis tritici). The plants were then returned into the greenhouse and cultivated at temperatures between 20 and 24°C and at 60 to 90% relative atmospheric humidity for a further 7 days. The extent of the mildew development on the leaves was then determined visually.

Protective action against Sphaerotheca fuliginea on cucumber (mildew of cucumber) Leaves of potted cucumber seedlings (in the germ layer stage) were sprayed to runoff point with an aqueous suspension having the concentration of active substance stated below. The next day, the treated plants were dusted with a suspension of spores of mildew of cucumber {Sphaerotheca fuliginea). The plants were then returned into the greenhouse and cultivated at temperatures between 20 and 24°C and at 60 to 80% relative atmospheric humidity for a further 7 days. The extent of the mildew develop-ment on the seed leaves was then determined visually.

Pythium ultimum (Damping off): Mycelial fragments of the fungus, prepared from a fresh liquid culture, are directly mixed into nutrient broth (potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores are added. The test plates are incubated at 24°C and the inhibition of growth determined photometrically after 48 hours.

Rhizoctonia solanv. (foot rot, damping-off): Mycelial fragments of the fungus from cryogenic storage are directly mixed into nutrient broth (potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically after 48 hours.

Gaeumannomyces graminis'. Mycelial fragments of the fungus from cryogenic storage are directly mixed into nutrient broth (potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically after 48 hours at 620nm.

Monographella nivalis (syn. Microdochium nivale, Fusarium nivale), snow mould, foot rot: Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically after 72 hours at 620nm.

Botrytis cinerea (Gray mould): Conidia of the fungus from cryogenic storage aredirectly mixed into nutrient broth (potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth determined photometrically after 72 hours.

Glomerella lagenarium (syn. Colletotrichum lagenarium), Anthracnose of cucurbits: Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically after 72 hours at 620nm.

Septoria tritici (leaf blotch): Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically after 72 hours.

Mycosphaerella arachidis (syn. Cercospora arachidicola). Brown leaf spot of groundnut (peanut): Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically after approximately 5-6 days at 620nm.

Fusarium culmorum (root rot): Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically after 48 hrs.

The skilled person will understand that a variety of organisms and test methods (in vivo or in vitro) can be used to demonstrate synergy.

Greenhouse example

At treatment application, the first trifoliate was fully developed. Eleven leaflet replicates from greenhouse-grown soya plants were treated (protective treatment). After treatment, soya leaves were transferred to the climate chamber and maintained under appropriate conditions for 24 hours, after which treated and control leaves were inoculated with Asian Soybean Rust.

Inoculated leaflets were transferred to individual petri dishes and incubated in the dark for 24 hours (20°C, 100%RH) and subsequently maintained in climate chambers (20°C, 12h L/D) for two weeks prior to rating (% PESINC).

At treatment application, fifteen leaf disc replicates (35mm diameter) from greenhouse-grown cucumber plants were transferred to filter paper and treated (protective treatment). After treatment, cucumber leaf discs were transferred to petri dishes (3 discs per dish) maintained at room temperature for 24 hours, after which treated and control leaves were inoculated with 5μ1 of a BOTRCI spore suspension (500.000 spores/mL in 25% sterile grape juice).

Inoculated leaf discs were subsequently maintained in climate chambers (18°C, 12h L/D) for five days prior to rating (DIAMET; SPORUL).

Assessments:

Details of assessment dates and assessment types, PHAKPA.

Details of assessment dates and assessment types, BOTRCI.

Data analysis:

One-way analysis of variance (ANOVA); Tukey post-ANOVA comparison-of-means and/or Graphical display of averages ±95% Confidence Intervals, as appropriate. Calculation of synergy according to Colby's formula, revised for fungicidal effect.

Treatment details:

Formulation details:

Product and application

Details of used products and rates of application, ED30 determination.

Details of used products and rates of application, synergy determination (BOTRCI).

Details of used products and rates of application, synergy determination (PHAKPA).

Results:

Results. PHAKPA

Claims (2)

1. En komposition indeholdende stoffet 3-chloro-N-(3-chloro-2,6-dinitro-4- trifluoromethylphenyl)-5-trifluoromethyl-2-pyridinamin og stoffet 2-[2-(l- chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-3H-l,2,4-triazole-3-thione til kontrol af skadelige svampe.

2. Brugen af en komposition indeholdende stoffet 3-chloro-N-(3-chloro-2,6-dinitro-4- trifhioromethylphenyl)-5-trifhioromethyl-2-pyridinamin og stoffet 2-[2-(l- chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-3H-l,2,4-triazole-3-thione til at forbedre planters vækst og styrke samt til udbytteforøgelse af afgrøder.