WO 2009/033582 PCT/EP2008/007139 Post-harvest treatment The present invention relates to methods for the protection of harvested fruit, cutflowers or vegeta bles against decay caused by certain storage diseases or disorders expressed in storage conditions. In 5 particular the invention relates to the application of certain fungicidal active compounds to protect harvested fruit, cutflowers or vegetables against phytopathogenic fungi. The purpose of any pre-harvest plant protection program for fruit, cutflowers and vegetables is to prevent the development of diseases that might impair the final quality of the fruit, cutflowers and 10 vegetables and to obtain adequate production yields. The system for post-harvest application of plant protection products on fruit, cutflowers and vegetables during packing aims to safeguard the health of the fruit and vegetables during the period of storage and transport to the final consumer in the coun tries in the northern hemisphere. 15 To date, for example, only few techniques have been used for preventing the disease Botrytis cinerea, and their common denominator is gassing with sulphur dioxide (SO 2 ). Gassing with SO 2 only con trols the disease Botrytis cinerea at the time of application - it does not have a residual effect. With this traditional treatment based on SO 2 gassing, e.g. grapes can be maintained in acceptable condi tions for a period of 30 days. However, fruit exporters are looking for alternatives to provide storage 20 in good conditions for a period of 45 to 90 days. This would enable them to plan exports with a broader time spread, making it possible to obtain better prices and greater trading profitability. It is already known that several fungicidal active compounds can be used to prevent post-harvest damages of fruit or vegetables. EP-A 0 972 4450 relates to a method for treatment of fruit and vege 25 tables in post-harvest conditions for the purpose of achieving their preservation; the method com prises cooling the fruit to the core and then treating it with a shower consisting of an aqueous compo sition for treatment by immersion, preliminary treatment of the aqueous composition with fungicide by means of thiabendazole, a terpene compound, 2-phenylphenol and its salts and enilconazole, at a temperature from 40 to 60*C. 30 Furthermore, the use of a new system of post-harvest application of plant protection products is known from WO 2007/009474, where post-harvest electrostatic spraying of fungicides, in particular of fenhexamid is disclosed.
H: xd\Interwoven\NRPortbl\DCC\SXD\6716483_1doc-8.092014 -2 Also imazalil, fludioxonil and pyrimethanil are already known for post-harvest treatment (cf. WO 2005/074684, Journal of Agricultural Food Chemistry 2007, 55, 825-831 and Postharvest Biology and Technology 2006, 42, 75-85). Since, moreover, the environmental and economic requirements imposed on modem-day fungicides are continually increasing, with regard, for example, to the spectrum of activity, toxicity, selectivity, application rate, formation of residues, and favorable preparation ability, and since, furthermore, there may be problems, for example, with resistances developing to known active compounds, a constant task is to develop new fungicide agents which in some areas at least have advantages over their known counterparts. Therefore, there is still a need to find and/or develop other fungicides for post-harvest treatment. It has now been found, surprisingly, that certain fungicides, in particular strobilurine or (tri)azole fungicides, may be used for post-harvest treatment of fruit and vegetables for the treatment of post harvest and/or storage diseases. The invention furthermore relates to a method of combating certain post-harvest and/or storage diseases by treatment of the crops infested with these diseases by certain fungicides or mixtures thereof The fungicides are highly active against a broad spectrum of storage diseases with low application rates reducing the risk for workers and meeting the demand for quality and safe food covering residues. The plant compatibility is very good that is no damage to the outer surface or soft tissue of fruit and vegetables have been observed under various storage conditions with different controlled atmosphere systems in respect to temperature and humidity. In contrast, the visual appeal of the fruit was enhanced. The fungicidal properties of the compounds enable their use in different application systems like dipping, drenching, dump tank, spraying, fogging, brushing, packaging and coatings like wax and electrostatic and other targeted applications. Another advantage is that while using the fungicides the control of post-harvest and/or storage diseases is achieved for a longer period to allow transport of the harvested fruit or vegetables over long distances. Accordingly, in one aspect the present invention provides use of fluopyram [(N-{2-[3-chloro-5-(tri fluoromethyl)pyridin-2-yl]ethyl }-2-(trifluoromethyl)benzamide)] and salts thereof, for post-harvest treatment of fruit, cutflowers or vegetables to protect harvested fruit, cutflowers or vegetables against post-harvest and/or storage diseases.
H: xd\Interwoven\NRPortbl\DCC\SXD\6716483_1doc-8.092014 - 2a In a further aspect, the present invention provides a method of combating post-harvest and/or storage diseases by treating harvested fruit, cutflowers or vegetables with fluopyram [(N-{2-[3-chloro-5 (trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamide)], or a salt thereof, after the fruit, cutflowers or vegetables have been harvested. In other aspects, the present invention relates to the use of at least one fungicide, selected from the group consisting of (a) trifloxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, enestrobin and fenamidone, and salts thereof, (b) bitertanol, bromuconazole, cyproconazole, difenoconazole, epoxiconazole, fenbuconazole, fenpropidin, fenpropimorph, fluquinconazole, flusilazole, flutriafol, metconazole, penconazole, WO 2009/033582 PCT/EP2008/007139 -3 propiconazole, prothioconazole, spiroxamine, tebuconazole, triadimefon, triadimenol, and salts thereof, (c) bixafen [N-(3',4'-dichloro-5-fluoro-1,1'-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyra zole-4-carboxamide], carboxin, 3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro-9-(1-me 5 thylethyl)-1,4-methanonaphthalen-5-yl]-1H-pyrazole-4-carboxamide (isopyrazam), fluopico lide, fluopyram [(N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl) benzamide)], flutolanil, furametpyr, penthiopyrad, thifluzamide, N-[2-(1,3-dimethylbutyl) phenyl]-5-fluoro-1,3-dimethyl-lH-pyrazole-4-carboxamide, N-{2-[1,1'-bi(cyclopropyl)-2-yl] phenyl}-3-(difluoromethyl)-1-methyl-lH-pyrazole-4-carboxamide, 1-methyl-N-[2-(1,1,2,2-te 10 trafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, 2-chloro-N-[4'-(3,3 dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide, 3-(difluoromethyl)-1-methyl N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N [(9R)-9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-1-methyl-iH-pyrazole-4 carboxamide, 3-(difluoromethyl)-N-[(9S)-9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaph 15 thalen-5-yl]-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-[4'-(3,3-dimethyl but-i -yn- 1 -yl)biphenyl-2-yl]-1 -methyl- 1H-pyrazole-4-carboxamide and salts thereof, (d) cyprodinil, mepanipyrim, fluazinam, and salts thereof, (e) fosetyl-Al, iprodione, propineb, tolylfluanid and salts thereof, to protect harvested fruit, cutflowers or vegetables against phytopathogenic fungi. 20 The invention furthermore relates to a method of combating post-harvest and/or storage diseases by treating the fruit, cutflowers or vegetables with at least one fungicide selected from the group consist ing of (a) trifloxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, enestrobin and 25 fenamidone, and salts thereof, (b) bitertanol, bromuconazole, cyproconazole, difenoconazole, epoxiconazole, fenbuconazole, fen propidin, fenpropimorph, fluquinconazole, flusilazole, flutriafol, metconazole, penconazole, propiconazole, prothioconazole, spiroxamine, tebuconazole, triadimefon, triadimenol, and salts thereof, 30 (c) bixafen [N-(3',4'-dichloro-5-fluoro-1,1'-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyr azole-4-carboxamide], carboxin, 3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro-9-(1-me thylethyl)-1,4-methanonaphthalen-5-yl]-1H-pyrazole-4-carboxamide (isopyrazam), fluopico lide, fluopyram [(N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl) benzamide)], flutolanil, furametpyr, penthiopyrad, thifluzamide, N-[2-(1,3-dimethylbutyl) 35 phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, N-{2-[1,1'-bi(cyclopropyl)-2-yl] phenyl}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 1-methyl-N-[2-(1,1,2,2-te- WO 2009/033582 PCT/EP2008/007139 -4 trafluoroethoxy)phenyl]-3-(trifluoromethyl)-iH-pyrazole-4-carboxamide, 2-chloro-N-[4'-(3,3 dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide, 3-(difluoromethyl)-1-methyl N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-iH-pyrazole-4-carboxamide, 3-(difluoromethyl)-N [(9R)-9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-1-methyl-iH-pyrazole-4 5 carboxamide, 3-(difluoromethyl)-N-[(9S)-9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaph thalen-5-yl]-1-methyl-lH-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-[4'-(3,3-dimethyl but-i -yn-i -yl)biphenyl-2-yl]- 1-methyl-i H-pyrazole-4-carboxamide and salts thereof, (d) cyprodinil, mepanipyrim, fluazinam, and salts thereof. (e) fosetyl-Al, iprodione, propineb, tolylfluanid and salts thereof. 10 Within this application "post-harvest treatment" is to be understood in a very broad sense. On the one hand it means literally the treatment of fruit or vegetables after the fruit and vegetables have been harvested. For post-harvest treatment the fruit or vegetable is treated with (e.g. with using the method and apparatus disclosed in WO 2005/009474), dipped or tank dumped or drenched into a liquid, 15 brushed with, fumigated, painted, fogged (warm or cold), or the fruit may be coated with a waxy or other composition. According to the invention, post-harvest and storage diseases may be caused for example by the fol lowing fungi: 20 Colletotrichum spp., e.g. Colletotrichum musae, Colletotrichum gloeosporioides, Colletotrichum coc codes; Fusarium spp., e.g. Fusarium semitectum, Fusarium moniliforme, Fusarium solani, Fusarium oxysporum; Verticillium spp., e.g. Verticillium theobromae; Nigrospora spp.; Botrytis spp., e.g. Bo trytis cinerea; Geotrichum spp., e.g. Geotrichum candidum; Phomopsis spp., Phomopsis natalensis; Diplodia spp., e.g. Diplodia citri; Altemaria spp., e.g. Alternaria citri, Alternaria alternata; Phy 25 tophthora spp., e.g. Phytophthora citrophthora, Phytophthora fragariae, Phytophthora cactorum, Phy tophthora parasitica; Septoria spp., e.g. Septoria depressa; Mucor spp., e.g. Mucor piriformis; Monili nia spp., e.g. Monilinia fructigena, Monilinia laxa; Venturia spp., e.g. Venturia inaequalis, Venturia pyrina; Rhizopus spp., e.g. Rhizopus stolonifer, Rhizopus oryzae; Glomerella spp., e.g. Glomerella cingulata; Sclerotinia spp., e.g. Sclerotinia fruiticola; Ceratocystis spp., e.g. Ceratocystis paradoxa; 30 Penicillium spp., e.g. Penicillium funiculosum, Penicillium expansum, Penicillium digitatum, Penicil lium italicum; Gloeosporium spp., e.g. Gloeosporium album, Gloeosporium perennans, Gloeospo rium fructigenum, Gloeosporium singulata; Phlyctaena spp., e.g. Phlyctaena vagabunda; Cylindro carpon spp., e.g. Cylindrocarpon mali; Stemphyllium spp., e.g. Stemphyllium vesicarium; Phacy diopycnis spp., e.g. Phacydiopycnis malirum; Thielaviopsis spp., e.g. Thielaviopsis paradoxy; Asper 35 gillus spp., e.g. Aspergillus niger, Aspergillus carbonarius; Nectria spp., e.g. Nectria galligena; Pezi cula spp.
WO 2009/033582 PCT/EP2008/007139 -5 According to the invention, post-harvest storage disorders are for example scald, scorch, softening, senescent breakdown, lenticel spots, bitter pit, browning, water core, vascular breakdown, CO 2 in jury, CO 2 deficiency and 02 deficiency. 5 Fruit, cutflower and vegetables to be treated according to the invention are particularly selected from cereals, e.g. wheat, barley, rye, oats, rice, sorghum and the like; beets, e.g. sugar beet and fodder beet; pome and stone fruit and berries, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries; leguminous plants, e.g. beans, lentils, peas, soy beans; oleaginous plants, e.g. rape, mustard, poppy, olive, sunflower, coconut, castor-oil plant, cocoa, ground-nuts; cu 10 curbitaceae, e.g. pumpkins, gherkins, melons, cucumbers, squashes; fibrous plants, e.g. cotton, flax, hemp, jute; citrus fruit, e.g. orange, lemon, grapefruit, mandarin; tropical fruit, e.g. papaya, passion fruit, mango, carambola, pineapple, banana; vegetables, e.g. spinach, lettuce, asparagus, brassicaceae such as cabbages and turnips, carrots, onions, tomatoes, potatoes, hot and sweet peppers; laurel-like plants, e.g. avocado, cinnamon, camphor tree; or plants such as maize, tobacco, nuts, coffee, sugar 15 cane, tea, grapevines, hops, rubber plants, as well as ornamental plants, e.g. cutflowers, roses, gerbera and flower bulbs, shrubs, deciduous trees and evergreen trees such as conifers. This enumeration of culture plants is given with the purpose of illustrating the invention and not to delimiting it thereto. Particularly preferred is the treatment of pome and stone fruit and berries, in particular apples, pears, 20 plums, peaches, almonds, cherries, strawberries, raspberries and blackberries. Particularly preferred is the treatment of citrus fruit, in particular orange, lemon, grapefruit, mandarin. Particularly preferred is the treatment of tropical fruit, in particular papaya, passion fruit, mango, carambola, pineapple, banana. Particularly preferred is the treatment of grapevines. 25 The fungicides mentioned above are all known compounds (cf. e.g. The Pesticide Manual, 13th Edi tion, British Crop Protection Council, 2003). According to the invention the fungicides are preferably selected from the group consisting of 30 (a) trifloxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, enestrobin, and salts thereof, (b) bitertanol, cyproconazole, difenoconazole, epoxiconazole, fenbuconazole, fenpropidin, fen propimorph, fluquinconazole, flusilazole, penconazole, propiconazole, prothioconazole, spi roxamine, tebuconazole, triadimefon, triadimenol, and salts thereof, 35 (c) bixafen [N-(3',4'-dichloro-5-fluoro-1,1 '-biphenyl-2-yl)-3-(difluoromethyl)-l-methyl-lH-pyra zole-4-carboxamide], 3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4- WO 2009/033582 PCT/EP2008/007139 -6 methanonaphthalen-5-yl]-IH-pyrazole-4-carboxamide (isopyrazam), fluopicolide, fluopyram [(N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamide)], pen thiopyrad, 1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-lH-pyrazole-4 carboxamide, 2-chloro-N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide, 5 3-(difluoromethyl)-l-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carbox amide, 3-(difluoromethyl)-N-[(9R)-9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5 yl]-l-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-[(9S)-9-isopropyl-1,2,3,4-tetra hydro-1,4-methanonaphthalen-5-yl]-1-methyl-lH-pyrazole-4-carboxamide, 3-(difluoromethyl) N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide, 10 (d) cyprodinil, and salts thereof, (e) fosetyl-Al, iprodione, propineb, tolylfluanid and salts thereof. According to the invention the fungicides are particularly preferably selected from the group consist ing of 15 (a) trifloxystrobin, fluoxastrobin, and salts thereof, (b) cyproconazole, difenoconazole, prothioconazole, spiroxamine, tebuconazole, triadimenol, and salts thereof, (c) bixafen [N-(3',4'-dichloro-5-fluoro-1,1'-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-iH-pyr azole-4-carboxamide], fluopyram [(N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2 20 (trifluoromethyl)benzamide)], 1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoro methyl)-lH-pyrazole-4-carboxamide, 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoro ethoxy)phenyl]-1H-pyrazole-4-carboxamide, (d) cyprodinil, and salts thereof, (e) fosetyl-Al, iprodione, tolylfluanid, and salts thereof. 25 The fungicides used according to the invention are generally applied in form of a composition com prising at least one fungicide as mentioned above. Preferably the fungicidal composition comprises agriculturally acceptable additives, solvents, carriers, surfactants, or extenders. 30 According to the invention, the term "carrier" denotes a natural or synthetic, organic or inorganic compound with which the active compounds are combined or associated to make it easier to apply, notably to the fruit and vegetables treated according to the invention. This support is thus preferably inert and should be at least agriculturally acceptable. The support may be a solid or a liquid. 35 Suitable solid carriers are the following: e.g. ammonium salts and natural rock powders, such as kao lins, clays, talcum, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic WO 2009/033582 PCT/EP2008/007139 -7 rock powders such as highly disperse silica, aluminium oxide and silicates, oil waxes, solid fertilizers, water, alcohols, preferably butanol, organic solvents, mineral and vegetable oils and essential oils and derivatives thereof, mixtures of such carriers may also be used; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, 5 dolomite and synthetic granules of inorganic and organic powders and granules of organic materials such as paper, sawdust, coconut shells, corn stalks and tobacco stalks; suitable emulsifiers and/or foam-forming agents are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, suitable dispersants are non-ionic and/or ionic substances, for example from the classes comprising alcohol POE and/or POP ethers, acid and/or 10 POP or POE esters, alkyl-aryl and/or POP or POE ethers, fatty and/or POP-POE adducts, POE and/or POP polyol derivatives, POE and/or POP/sorbitan or sugar adducts, alkyl or aryl sulphates, sulpho nates and phosphates or the corresponding PO ether adducts. Furthermore, suitable oligomers or polymers, for example based on vinyl monomers, acrylic acid, EO and/or PO alone or in combination with for example (poly-)alcohols or (poly-)amines. Use can also be made of acetic acid, peracetic 15 acid, salicylic acid, acetaldehyde, phosphorous acid, lignin and sulphonic acid derivatives thereof, simple and modified celluloses, aromatic and/or aliphatic sulphonic acids, aromatic and/or aliphatic salicylic acids and adducts thereof with formaldehyde. Suitable as dispersants are for example ligno sulphite waste liquors and methylcellulose. 20 By liquefied gaseous diluents or supports are meant such liquids that are gaseous at normal tempera ture and under normal pressure, for example, aerosol propellants such as halo hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. It is possible to use in the formulations adhesives such as carboxymethylcellulose, natural and syn 25 thetic powdered, granular or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids. Fur ther additives can be mineral or vegetable oils and waxes, optionally modified. Suitable extenders are, for example, water, polar and non-polar organic chemical liquids, for example 30 from the classes of the aromatic and non-aromatic hydrocarbons (such as paraffms, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which, if appropriate, may also be sub stituted, etherified and/or esterified), the ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, aides, lactams (such as N alkylpyrrolidones) and lactones, the sulphones and sulphoxides (such as dimethyl sulphoxide). 35 WO 2009/033582 PCT/EP2008/007139 -8 If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for 5 example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and also their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo hexanone, strongly polar solvents such as dimethyl sulphoxide, and also water. The composition according to the invention may also comprise additional components. In particular, the 10 composition may further comprise a surfactant. The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants. Mention may be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, 15 taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phe nols, fatty acid esters of polyols, and derivatives of the present compounds containing sulphate, sulpho nate and phosphate functions, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sul phates, aryl sulphonates, protein hydrolyzates, lignosulphite waste liquors and methyl cellulose. The presence of at least one surfactant is generally essential when the active compound and / or the inert 20 support are water-insoluble and when the vector agent for the application is water. Preferably, surfactant content may be comprised from 5% to 40% by weight of the composition. Colouring agents such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyanblue, and organic pigments such as alizarin, azo and metallophthalocyanine dyes, and trace elements such as iron, 25 manganese, calcium, magnesium, boron, copper, cobalt, molybdenum and zinc salts can be used. Optionally, other additional components may also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active compounds can be combined with any solid or liquid additive, which complies with the usual 30 formulation techniques. In general, the composition used according to the invention may contain from 0.05 to 99% by weight of active compounds, preferably from 1 to 70% by weight, particularly preferably from 10 to 50 % by weight. 35 WO 2009/033582 PCT/EP2008/007139 -9 The compositions used according to the invention can be used as such, in form of their formulations or as the use forms prepared therefrom, such as aerosol dispenser, capsule suspension, cold fogging concentrate, hot fogging concentrate, encapsulated granule, fine granule, flowable concentrate for seed treatment, ready-to-use solutions, dustable powder, emulsifiable concentrate, emulsion oil in wa 5 ter, emulsion water in oil, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, froths, paste, seed coated with a pesticide, suspension concentrate (flowable concentrate), suspensions-emulsions-concentrates, soluble concentrate, suspensions, solu ble powder, granule, water soluble granules or tablets, water soluble powder for seed treatment, wet table powder, natural and synthetic materials impregnated with active compound, micro 10 encapsulation in polymeric materials and in jackets for seed, as well as ULV- cold and hot fogging formulations, gas (under pressure), gas generating product, plant rodlet, powder for dry seed treat ment, solution for seed treatment, ultra low volume (ULV) liquid, ultra low volume (ULV) suspen sion, water dispersible granules or tablets, water dispersible powder for slurry treatment. 15 These formulations are prepared in a known manner by mixing the active compounds or active com pound combinations with customary additives, such as, for example, customary extenders and also solvents or diluents, emulsifiers, dispersants, and/or bonding or fixing agent, wetting agents, water repellents, if appropiate siccatives and UV stabilisers, colorants, pigments, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and water as well further processing auxiliaries. 20 These compositions include not only compositions which are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also concen trated commercial compositions which must be diluted before application to the crop. 25 The active compounds used according to the invention can be used in its commercially available for mulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals. 30 The treatment of plants and plant parts with the active compound according to the invention is carried out directly or by action on their environment, habitat or storage area by means of the normal treat ment methods, for example by watering (drenching), drip irrigation, spraying, vaporizing, atomizing, broadcasting, dusting, foaming, spreading-on, and as a powder. It is furthermore possible to apply the active compounds by the ultra-low volume method, or to inject the active compound preparation or 35 the active compound itself into the soil.
WO 2009/033582 PCT/EP2008/007139 -10 As already mentioned above, all plants and their parts can be treated in accordance with the inven tion. In a preferred embodiment, plant species and plant varieties which are found in the wild or are obtained by traditional biological breeding methods, such as hybridization or protoplast fusion, and parts of the former are treated. In a further preferred embodiment, transgenic plants and plant varie 5 ties which have been obtained by recombinant methods, if appropriate in combination with traditional methods (genetically modified organisms) and their parts are treated. The term "parts" or "parts of plants" or "plant parts" has been illustrated above. Particularly preferably, plants of the plant cultivars which are in each case commercially available or 10 in use are treated according to the invention. Plant cultivars are understood as meaning plants with new properties ("traits") which have been obtained by conventional cultivation, by mutagenesis or else by recombinant DNA techniques. These may be cultivars, breeds, biotypes or genotypes. Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, 15 vegetation period, nutrition), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or extensions of the activity spectrum and/or an increase in the activity of the substances and compositions that can be used accord ing to the invention, better plant growth, more developed root system, higher resistance of the plant vari ety or plant cultivar, increased growth of shoots, higher plant vitality, increased tolerance to high or low 20 temperatures, increased tolerance to drought or to water or soil salinity, increased flowering perform ance, easier harvesting, accelerated maturation, higher harvest yields, larger fruit, increased plant size, greener leaf colour, earlier blossoming, better quality and/or a higher nutritional value of the harvested products, higher sugar concentration in the fruits, better storage stability and/or processability of the har vested products which exceed the effects which were actually to be expected are possible. 25 The preferred transgenic plants or plant cultivars (i.e. those obtained by genetic engineering) which are to be treated according to the invention include all plants which, as a result of the recombinant modification, received genetic material which imparted particularly advantageous useful properties ("traits") to these plants. Examples of such properties are better plant growth, increased tolerance to 30 high or low temperatures, increased tolerance to drought or to water or soil salinity, increased flower ing performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such properties are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopatho 35 genic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop WO 2009/033582 PCT/EP2008/007139 - 11 plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape. Traits that are emphasized in particular are increased defence of the plants against insects, arachnids, nematodes, slugs and snails 5 as the result of toxins formed in the plants, in particular those formed in the plants by the genetic ma terial from Bacillus thuringiensis (for example by the genes CryLA(a), CryIA(b), CryLA(c), CrylIA, CryIUA, CryIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (hereinbelow referred to as "Bt plants"). Traits which are also particularly emphasized are the increased defence of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalex 10 ins, elicitors and resistance genes and the correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbi cidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphi nothricin (for example the "PAT" gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of "Bt plants" 15 which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD@ (for example maize, cotton, soya beans), KnockOut@ (for example maize), StarLink® (for example maize), Bollgard@ (cotton), Nucoton® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names 20 Roundup Ready@ (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link@ (tolerance to phosphinothricin, for example oilseed rape), IMI@ (tolerance to imidazolinones) and STS@ (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned also include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant cul 25 tivars having these genetic traits or genetic traits still to be developed, which cultivars will be devel oped and/or marketed in the future. The dose of active compound/application rate usually applied in the method of treatment according to the invention is generally and advantageously from 0,005 to 70 % by weight, preferably from 0,01 to 30 20 % by weight, more preferably from 0,05 to 10 % by weight, depending on the type of formulation to be selected for specific application purposes. The doses herein indicated are given as illustrative examples of the method according to the inven tion. A person skilled in the art will know how to adapt the application doses, notably according to 35 the nature of the plant or crop to be treated.
WO 2009/033582 PCT/EP2008/007139 - 12 The combination according to the invention can be used in order to protect plants within a certain time range after the treatment against pests and/or phytopathogenic fungi and/or microorganisms. The time range, in which protection is effected, spans in general one to 28 days, preferably one to 14 days after the treatment. 5 Furthermore combinations and compositions according to the invention may also be used to reduce the contents of mycotoxins in plants and the harvested plant material and therefore in foods and animal feed stuff made therefrom. Especially but not exclusively the following mycotoxins can be specified: De oxynivalenole (DON), Nivalenole, 15-Ac-DON, 3-Ac-DON, T2- und HT2- Toxins, Fumonisines, 10 Zearalenone Moniliformine, Fusarine, Diaceotoxyscirpenole (DAS), Beauvericine, Enniatine, Fusaroproliferine, Fusarenole, Ochratoxines, Patuline, Ergotalkaloides und Aflatoxines, which are caused for example by the following fungal diseases: Fusarium spec., like Fusarium acuminatum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F scirpi, 15 F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F tricinctum, F. verticil lioides and others but also by Aspergillus spec., Penicillium spec. like P. expansum, P. digitatum, P. italicum, Clavicepspurpurea, Stachybotrys spec., Geotrichum candidum and others. Examples 20 In Example 1 and Example 2 all compounds except fluopyram were applied as commercially available. 1 weight proportion of fluopyram, however, was mixed with solvents (24.5 w/w acetone, 24.5 w/w dimethylacetamid) and emulsifier (1 w/w), respectively. Afterwards, the product was diluted in water. The concentration used is indicated below. 25 Example 1 Apples were dipped in a fungicidal solution and kept in plastic boxes for drying. Afterwards 10 pl of a spore solution of Penicillium expansum has been applied to injuries of the cuticle of the fruits. The trial has been assessed at different time intervals after inoculation. The efficacy of the products has been calculated based on the fungal growth of the treated apples with reference to the inoculated 30 untreated control. The efficacy is shown as % Abbott. Table la) Compound Dosage % Efficacy [Abbott] at 6d 10d 14d Teolc EW250] 100g a.i./1000 ltr. 100 100 100 untreated control [% infestation] [17] [37] [53] WO 2009/033582 PCT/EP2008/007139 - 13 Table lb) Compound Dosage % Efficacy [Abbott] at 6d 10d 15d Trifloxystrobin 50g a.i./1000 ltr. 50 63 52 [Flint WG5O]_______________ Fluopyram 100g a.i./1000 ltr. 93 90 70 TolylarenuaMWG5] 750g a.i./1000 ltr. 64 60 60 untreated control [% infestation] [23] [50] [83] Example 2 5 Apples were dipped in a fungicidal solution and kept in plastic boxes for drying. Afterwards 1 Opil of a spore solution of Botrytis cinerea has been applied to injuries of the cuticle of the fruits. The trial has been assessed at 6d and 10d after inoculation. The efficacy of the products has been calculated based on the fungal growth of the treated apples with reference to the inoculated untreated control. The efficacy is shown as % Abbott. 10 Table 2 Compound Dosage % Efficacy [Abbott] at 6d 10d Fluopyram 100g a.i./1000 ltr 98 96 untreated control [% infestation] [70] [90] Example 3: In vitro Test for the ED 0 determination of microorganisms Cavities of a 96-hole microtiter plates are filled with 10 pil of a solution of test compounds in 15 methanol together with the emulsifier tris (1-phenylethyl)phenol-16-ethoxylate ("PSI 6"). At the next step, into each cavity 200 p of liquid potato dextrose medium is pipetted amended with an appropriate concentration of spores or mycelial suspension of the test fungus. The resulting concentrations of the test compounds in the microtiter cavity are ranging from 50, 5, 0.5 and 0.05 ppm. 20 The extinction in all cavities is measured by a spectral photometer. The microtiter plates are then transferred for 3-5 days (depending on the fungal growth) onto a shaker at 20*C and 80 % relative humidity. At the end of the incubation time the growth of the test organisms is measured again photometrically to determine the fungal growth. From the resulting dose-response curves the ED 50 will be taken. The concentration that is necessary to give 50 % growth inhibition is defined and 25 reported as ED 50 value (= Effective Dose that causes 50 % growth inhibition) in ppm (= mg/l).
WO 2009/033582 PCT/EP2008/007139 -14 Table 3: In vitro Test for the ED5 0 determination of microorganisms Microorganism Active compound ED 5 0 Trifloxystrobin < 0,1 ppm Aspergillus carbonarius Pyrimethanil < 0,1 ppm Tebuconazole < 0,1 ppm Aspergillus ochraceus Trifloxystrobin <0,1 ppm Trifloxystrobin <0,1 ppm Aspergillus niger Fluopyram <0,1 ppm Bixafen <0,1 ppm 0,4 ppm Botrytis cinerea Trifloxystrobin <0,1 ppm Bixafen <0,1 ppm < 0,1 ppm Monilia spp. Trifloxystrobin 0,72 ppm Trifloxystrobin < 0,! ppm Kresoxim methyl 1,5 ppm Penicilliun verrucosum Bixafen <0,1 ppm Fluopyram <0,1 ppm Pyrimethanil 0,13 ppm Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.