Mixtures for protecting plants comprising limonene and fungicides

Abstract

The present invention relates to mixtures comprising limonene and fungicides and methods to protect plants using such mixtures.

Description

[0001] BASF SE 241435

[0002] 1

[0003] Mixtures for protecting plants comprising limonene and fungicides

[0004] Field of the Invention

[0005] The present invention relates to mixtures comprising limonene and fungicides and methods to protect plants using such mixtures.

[0006] Background of the Invention

[0007] Crop plants are under constant threat by plant pathogens and plant pests. Thus, there is a constant need to develop a broad toolkit of alternative pesticides to protect crop plants and to improve on the shortcomings of existing pesticides. In this context, it is of interest to develop pesticides comprising natural compounds, which show a similar performance and ease of application as comparable pesticides based on purely synthetic compounds.

[0008] D-limonene is a well-known cyclic monoterpene and has been shown to have insecticidal, miti- cidal and antimicrobial effects when applied to the respective organisms. It has been found in more than 300 plant essential oils from a diverse set of plant species. Limonene is currently mostly produced as a natural essential oil via extraction of citrus peels and can therefore be considered to be a side product of the citrus juice industry. In addition thereto it can also be produced via chemical synthesis or via biotechnological production in microorganisms.

[0009] The application of plant essential oils comprising limonene as pesticides has been described e.g. in W02022 / 101613 which describes a bio-fungicide composition comprising microencapsulated essential oils or isolated terpenes. WO2016 / 004326 discloses a seed, soil, or plant treatment composition, comprising one or more essential oils and one or more emulsifiers, wherein the one or more essential oils are present as an emulsion and the average particle size of the one or more essential oils in the emulsion is less than about 25 microns. WO2016 / 004326 also describes that this plant treatment composition can be combined with several pesticides, including fungicides. W02014 / 020109 describes a synthetic blend of three substantially pure terpenes a-terpinene, p-cymene and limonene to mimic the main components of essential oil extracts of Chenopodium ambrosioides. WO2014 / 020109 also describes that this synthetic blend can also be combined with synthetic fungicides and may even show synergistic effects in some of these combinations.

[0010] Description of the invention

[0011] Described herein are mixtures comprising as active components limonene and a fungicide selected from the group comprising ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, propamocarb, cymoxanil, dithianon, metalaxyl, metalaxyl-M, mancozeb, me- tiram, folpet, cyazofamid, fluopicolide, fosetyl-AI and a phosphite.

[0012] In one embodiment the fungicide is selected from ametoctradin, dimethomorph, mandipropamid, cymoxanil, metiram, folpet, cyazofamid, fluopicolide, oxathiapiprolin, fluoxapiprolin and BASF SE 241435

[0013] 2 dithianone, In another embodiment the fungicide is selected from oxathiapiprolin, fluoxapiprolin and dithianone. In a further embodiment the fungicide is ametoctradin.

[0014] Limonene is well known in the art and is commercially available. It exists in two enantiomeric forms, D- and L-limonene, which are both included in the invention, while D-limonene is preferred. Limonene can be provided via chemical synthesis, via biotechnological production in microorganisms or via extraction of essential oils of plants and fractionation of these oils. In many cases it is obtained by steam distillation after alkali treatment of citrus peels and pulp, and also by fractionation of citrus essential oils, preferably orange oil.

[0015] The limonene used in the mixtures can be present as a component of a plant essential oil, which is preferably orange oil. Accordingly, the mixtures may comprise further terpenes and other compounds present in the respective plant essential oil used in the mixture. Preferably, the limonene represents more than 90 % weight / weight of the combined amount of terpenes in the essential plant oil used. Preferably, a-terpinene and / or p-cymene are present only in minor amounts, like less than 5 % weight / weight, less than 3 % weight / weight or even more preferred less than 1 % weight / weight.

[0016] The fungicides used for the mixtures are commercially available. Their preparation and their activity against fungi is known (www.bcpcpesticidecompendium.bcpc.org / ).

[0017] Phosphites are phosphorous acid and its (alkali metal or alkaline earth metal) salts, such as potassium phosphites.

[0018] Preferred are phosphites having fungicidal activity, such as H3PO3, KH2PO3, K2HPO3, NaH2PO3, Na2HPO3, (NH4)2HPO3, (NH4)H2PO3, and mixtures of these compounds. More preferred are H3PO3, KH2PO3and K2HPO3.

[0019] Preferably the weight / weight ratio of limonene, preferably D-limonene, to the fungicide is between 70 to 1 and 1 to 10, or between 65 to 1 and 1 to 10, or between 50 to 1 and 1 to 10, or between 40 to 1 and 1 to 10, or between 30 to 1 and 1 to 10, or between 25 to 1 and 1 to 10, or between 24 to 1 and 2 to 10, or between 100 to 1 and 1 to 2, or between 70 to 1 and 1 to 2, or between 65 to 1 and 1 to 2, or between 50 to 1 and 1 to 2, or between 40 to 1 and 1 to 2, or be- tween 30 to 1 and 1 to 2, or between 25 to 1 and 1 to 2, or between 24 to 1 and 2 to 1 , or between 24 to 1 and 2.5 to 1 , or between 24 to 1 and 3 to 1 , or between 24 to 1 and 4 to 1 , or between 24 to 1 and 5 to 1 , or between 24 to 1 and 6 to 1 , or between 24 to 1 and 8 to 1 , or between 24 to 1 and 12 to 1 , or between 20 to 1 and 1 to 2, or between 15 to 1 and 1 to 2, or between 10 to 1 and 1 to 2, or between 20 to 1 and 5 to 1 , or between 20 to 1 and 10 to 1 , or between 20 to 1 and 12 to 1 , or between 20 to 1 and 6 to 1 , or between 8 to 1 and 1 to 2, or between 6 to 1 and 1 to 2, or between 6 to 1 and 2 to 2, or between 5 to 1 and 2 to 1 , or between

[0020] 20 to 1 and 1 to 20, or between 15 to 1 and 1 to 15, or between 10 to 1 and 1 to 10, or between 5 to 1 and 1 to 5, or between 15 to 1 and 1 to 5, or between 12 to 1 and 1 to 3, or between 10 to 1 and 1 to 2, or between 10 to 1 and 1 to 1 , or between 8 to 1 and 1 to 1 , or between 5 to 1 and 1 to 1 , or between 4 to 1 and 1 to 1 , or between 3 to 1 and 1 to 1 . or between 10 to 1 and 1 to BASF SE 241435

[0021] 3

[0022] 30, or between 10 to 1 and 1 to 25, or between 10 to 1 and 1 to 20, or between 5 to 1 and 1 to 30, or between 5 to 1 and 1 to 25, or between 5 to 1 and 1 to 20, or between 5 to 1 and 1 to 10, or between 1 to 1 and 1 to 30, or between 1 to 1 and 1 to 25 or between 1 to 1 and 1 to 20, or between 1 to 5 and 1 to 30 or between 1 to 5 and 1 to 25, or between 1 to 5 and 1 to 20.

[0023] In one embodiment the fungicide is selected from ametoctradin, oxathiopiprolin, mandipropamid and dithianone and the weight / weight ratio of limonene, preferably D-limonene, to the fungicide is between 10 to 1 and 1 to 10, or between 5 to 1 and 1 to 5, or between 4 to 1 and 1 to 4, or is 4 to 1.

[0024] The mixture may also comprise a second fungicide, with the proviso that the second fungicide is not identical with the fungicide, i.e. the first fungicide. The second fungicide is preferably selected from fungicides, which show an additional positive effect in the mixture, like synergistic effects with the first fungicide or the capability to control further fungal species. For example, EP1909579 discloses fungicides with additional positive effects when combined with ametoctra- din and which may preferably be selected as a second fungicide of the mixture.

[0025] In one embodiment the mixtures comprise ametoctradin as first fungicide and dimethomorph as second fungicide.

[0026] In one embodiment the mixtures comprise ametoctradin as first fungicide and propamocarb or propamocarb hydrochloride as second fungicide.

[0027] In one embodiment the mixtures comprise ametoctradin as first fungicide and cymoxanil as second fungicide.

[0028] In one embodiment the mixtures comprise ametoctradin as first fungicide and one or more phosphites as second fungicide.

[0029] In one embodiment the second fungicide is selected from the group comprising ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, propamocarb, cymoxanil, dithi- anon, metalaxyl, metalaxyl-M, mancozeb, metiram, folpet, cyazofamid, fluopicolide, fosetyl-AI and a phosphite, with the proviso that the second fungicide is not identical with the fungicide. Preferably the weight / weight ratio of the first fungicide to the second fungicide is between 5 to 1 and 1 to 5, or between 4 to 1 and 1 to 4, or between 5 to 1 and 1 to 1 , or between 4 to 1 and 1 to 1 , or between 1 to 1 and 1 to 4, or between 1 to 1 and 1 to 5.

[0030] Preferably the weight / weight ratio of limonene, preferably D-limonene, to the second fungicide is between 70 to 1 and 1 to 10, or between 65 to 1 and 1 to 10, or between 50 to 1 and 1 to 10, or between 40 to 1 and 1 to 10, or between 30 to 1 and 1 to 10, or between 25 to 1 and 1 to 10, or between 24 to 1 and 2 to 10, or between 100 to 1 and 1 to 2, or between 70 to 1 and 1 to 2, or between 65 to 1 and 1 to 2, or between 50 to 1 and 1 to 2, or between 40 to 1 and 1 to 2, or between 30 to 1 and 1 to 2, or between 25 to 1 and 1 to 2, or between 24 to 1 and 2 to 1 , or between 24 to 1 and 2.5 to 1 , or between 24 to 1 and 3 to 1 , or between 24 to 1 and 4 to 1 , or BASF SE 241435

[0031] 4 between 24 to 1 and 5 to 1 , or between 24 to 1 and 6 to 1 , or between 24 to 1 and 8 to 1 , or between 24 to 1 and 12 to 1 , or between 20 to 1 and 1 to 2, or between 15 to 1 and 1 to 2, or between 10 to 1 and 1 to 2, or between 20 to 1 and 5 to 1 , or between 20 to 1 and 10 to 1 , or between 20 to 1 and 12 to 1 , or between 20 to 1 and 6 to 1 , or between 8 to 1 and 1 to 2, or between 6 to 1 and 1 to 2, or between 6 to 1 and 2 to 2, or between 5 to 1 and 2 to 1 , or between 20 to 1 and 1 to 20, or between 15 to 1 and 1 to 15, or between 10 to 1 and 1 to 10, or between 5 to 1 and 1 to 5, or between 15 to 1 and 1 to 5, or between 12 to 1 and 1 to 3, or between 10 to 1 and 1 to 2, or between 10 to 1 and 1 to 1 , or between 8 to 1 and 1 to 1 , or between 5 to 1 and 1 to 1 , or between 4 to 1 and 1 to 1 , or between 3 to 1 and 1 to 1 , or between 10 to 1 and 1 to 30, or between 10 to 1 and 1 to 25, or between 10 to 1 and 1 to 20, or between 5 to 1 and 1 to 30, or between 5 to 1 and 1 to 25, or between 5 to 1 and 1 to 20, or between 1 to 1 and 1 to 30, or between 1 to 1 and 1 to 25 or between 1 to 1 and 1 to 20, or between 1 to 5 and 1 to 30 or between 1 to 5 and 1 to 25, or between 1 to 5 and 1 to 20.

[0032] Preferably the mixtures comprise limonene, preferably D-limonene, and the fungicide (first fungicide) in synergistically effective amounts.

[0033] Perferably, the mixtures comprise limonene, preferably D-limonene, and the fungicide (first fungicide) in synergistically effective amounts and show low phytotoxicity.

[0034] Preferably the mixtures comprise limonene, preferably D-limonene, and the second fungicide in synergistically effective amounts.

[0035] A "synergistically effective amount" in this context represents a quantity of a combination of limonene, preferably D-limonene and a fungicide that is more effective a phytopathogenic fungi than the limonene or the fungicide only.

[0036] The mixtures can be converted into customary types of agrochemical compositions, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types (see also “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 8thEd. May 2022, CropLife International) are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials, such as seeds (e.g. GF). The agrochemical compositions are prepared in a known manner (e.g. Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2000; Agrow Reports DS243, T&F Informa, London, 2005). The invention also relates to agrochemical compositions comprising the mixtures and at least one auxiliary.

[0037] Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, BASF SE 241435

[0038] 5 adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers, and binders.

[0039] Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, paraffin, tetrahydronaphthalene, and alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol, glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. / V-methyl pyrrolidone, fatty acid dimethyl amides; and mixtures thereof.

[0040] Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

[0041] Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1 : Emulsifiers & Detergents, MC Publishing, USA, 2020 (Int. Ed.; 978-0944254806).

[0042] Suitable anionic surfactants are alkali, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and of alkyl naphthalenes, sulfosuccinates, or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids, of oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

[0043] Suitable nonionic surfactants are alkoxylates, / V-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of / V-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters, or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters, or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinyl pyrrolidone, vinyl alcohols, or vinyl acetate. BASF SE 241435

[0044] 6

[0045] Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide, and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.

[0046] Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the mixture on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries, e.g. as listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter s. Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives, such as alkylisothiazolinones and benzisothiazoli- nones. Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea, and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

[0047] The agrochemical compositions generally comprise between 0.01 and 95 %, preferably between 0.1 and 90 %, more preferably between 1 and 70 %, and in particular between 10 and 60 %, by weight of active substances. The agrochemical compositions generally comprise between 5 and 99.9 %, preferably between 10 and 99.9 %, more preferably between 30 and 99 %, and in particular between 40 and 90 %, by weight of at least one auxiliary. The active substances are preferably employed in a purity of 90 % to 100 %, more preferred 95 % to 100 % (according to NMR spectrum).

[0048] For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of 0.01 to 60 % by weight, preferably 0.1 to 40 %, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying the mixtures and agrochemical compositions thereof, respectively, onto plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, soaking, as well as in-furrow application. Preferably, the mixtures BASF SE 241435

[0049] 7 or the agrochemical compositions thereof, respectively, are applied onto plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating, and dusting.

[0050] Various types of oils, wetters, adjuvants, fertilizers, or micronutrients, and further pesticides (e.g. growth regulators, herbicides, insecticides, safeners) may be added to the mixtures or the agrochemical compositions thereof as premix, or, 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.

[0051] The mixtures and the agrochemical compositions thereof, respectively, are suitable as fungicides effective against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, in particular from Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomy- cetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi imper- fecti). They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides.

[0052] The mixtures and the agrochemical compositions thereof are preferably useful in the control of phytopathogenic fungi on various cultivated plants, such as cereals (e.g. wheat, rye, barley, triticale, oats, millet, corn [maize] or rice); beets (e.g. sugar or fodder beet); fruits, (e.g. pomes: apples, pears, etc.); stone fruits (e.g. plums, peaches, almonds, cherries), or soft fruits, also called berries (e.g. strawberries, raspberries, blackberries, gooseberries, etc.); leguminous plants (e.g. lentils, peas, alfalfa, or soybeans); oil plants (e.g. oilseed rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts, or soybeans); cucurbits (e.g. squashes, cucumber, or melons); fiber plants (e.g. cotton, flax, hemp, or jute); citrus fruits (e.g. oranges, lemons, grapefruits, or mandarins); vegetables (e.g. spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits, or paprika); lauraceous plants (e.g. avocados, cinnamon, or camphor); energy and raw material plants (e.g. corn [maize], soybean, oilseed rape, sugar cane, or oil palm); corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants; or ornamental and forestry plants, (e.g. flowers, shrubs, broad-leaved trees, or evergreens (conifers, eucalypts, etc.)); on the plant propagation material, such as seeds; and on the crop material of these plants.

[0053] More preferably, mixtures and the agrochemical compositions thereof, respectively are used for controlling fungi on field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn [maize], cotton, soybeans, oilseed rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

[0054] The term "plant propagation material" is to be understood to denote all the generative parts of the plant, such as seeds; and vegetative plant materials, such as cuttings and tubers (e.g. BASF SE 241435

[0055] 8 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 to be transplanted after germination or after emergence from soil.

[0056] Preferably, treatment of plant propagation materials with the mixtures and the agrochemical compositions thereof, respectively, is used for controlling fungi on fruits and vegetables.

[0057] According to the invention all of the above cultivated plants are understood to comprise all species, subspecies, variants, varieties and / or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc, further including dwarf, semi-dwarf and full-dwarf varieties and / or hybrids with reduced height and thicker and shorter stems, e.g. short stature corn (also called ‘smart corn’), semi-dwarf wheat and dwarf rice.

[0058] Corn (Zea mays) is also known as Indian corn or maize which comprises all kinds of corn such as field corn and sweet corn. According to the invention all maize or corn subspecies and / or varieties are comprised, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high amylose Zea mays varieties), pod corn or wild maize (Zea mays var. tunicata) and striped maize (Zea mays var. japonica).

[0059] Most soybean cultivars are classifiable into indeterminate and determinate growth habit, whereas Glycine soja, the wild progenitor of soybean, is indeterminate (PNAS 2010, 107 (19) 8563-8568). The indeterminate growth habit (Maturity Group, MG 00 to MG 4.9) is characterized by a continuation of vegetative growth after flowering begins whereas determinate soybean varieties (MG 5 to MG 8) characteristically have finished most of their vegetative growth when flowering begins. According to the invention all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.

[0060] The term "cultivated plants" is to be understood as including plants which have been modified by mutagenesis or genetic engineering to provide a new trait to a plant or to modify an already present trait. Mutagenesis includes random mutagenesis using X-rays or mutagenic chemicals, but also targeted mutagenesis to create mutations at a specific locus of a plant genome. Targeted mutagenesis frequently uses oligonucleotides or proteins like CRISPR / Cas, zinc-finger nucleases, TALENs or meganucleases. Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant to add a trait or improve or modify a trait. These integrated genes are also referred to as transgenes, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, which differ in the genomic locus in BASF SE 241435

[0061] 9 which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.

[0062] Herbicide tolerance has been created by using mutagenesis and genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by mutagenesis and breeding are e.g. available under the name Clearfield®. Herbicide tolerance to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitors and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione, has been created via the use of transgenes.

[0063] Transgenes to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601 , gat4621 , goxv247; for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 , aad-12; for tolerance to dicamba: dmo; for tolerance to oxynil herbicies: bxn; for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA; for tolerance to ALS inhibitors: csr1-2; and for tolerance to HPPD inhibitors: hppdPF, W336, avhppd-03.

[0064] Transgenic corn events comprising herbicide tolerance genes include, but are not limited to, DAS40278, MON801 , MON802, MON809, MON810, MON832, MON87411 , MON87419, MON87427, MON88017, MON89034, NK603, GA21 , MZHGOJG, HCEM485, VCO-01981-5, 676, 678, 680, 33121 , 4114, 59122, 98140, Bt10, Bt176, CBH-351 , DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275. Transgenic soybean events comprising herbicide tolerance genes include, but are not limited to, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21 , A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHT0H2, W62, W98, FG72 and CV127. Transgenic cotton events comprising herbicide tolerance genes include, but are not limited to, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211 , BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701 , MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40. Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1 , HCN10, HCN28, HCN92, MS1 , MS8, PHYU, PHY23, PHY35, PHY36, RF1 , RF2 and RF3.

[0065] Transgenes providing insect resistance include but are not limited to, toxin genes of Bacillus spp. and synthetic variants thereof (e.g. cry1A, crylAb, cry1Ab-Ac, crylAc, cry1A.1O5, cry1 F, cry1 Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1 , cry34Ab1 , cry35Ab1 , cry9C, vip3A(a), and vip3Aa20); transgenes of plant origin (e.g. coding for protease inhibitors, like CpTI and pinll); and transgenes producing double-stranded RNA (e.g. dvsnf7). Transgenic insect resistance corn events include, but are not limited to, Bt10, Bt11 , Bt176, MON801 , MON802, MON809, MON810, MON863, MON87411 , MON88017, MON89034, 33121 , 4114, 5307, BASF SE 241435

[0066] 10

[0067] 59122, TC1507, TC6275, CBH-351 , MIR162, DBT418 and MZIR098. Transgenic insect resistance soybean events include, but are not limited to, MON87701 , MON87751 and DAS- 81419. Transgenic cotton events comprising genes for insecticidal proteins include, but are not limited to, SGK321 , MON531 , MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601 , Eventl , COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.

[0068] Cultivated plants with increased yield have been created by using the transgene athb17 (e.g., corn event MON87403), or bbx32 (e.g. soybean event MON87712).

[0069] Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1 , Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A (e.g. soybean events 260-05, MON87705 and MON87769).

[0070] Tolerance to abiotic conditions, such as drought, has been created by using the transgene cspB (corn event MON87460) and Hahb-4 (soybean event IND-00410-5).

[0071] Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process resulting in a cultivated plant with stacked traits. Preferred combinations of traits are combinations of herbicide tolerance traits to different groups of herbicides, combinations of insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, combinations of herbicide tolerance with one or several types of insect resistance, combinations of herbicide tolerance with increased yield as well as combinations of herbicide tolerance and tolerance to abiotic conditions.

[0072] Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art: information to the mutagenized or integrated genes and the respective events are available from websites of the “International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http: / / www.isaaa.org / gmapprovaldatabase) and the “Center for Environmental Risk Assessment (CERA)” (http: / / cera-gmc.org / GMCropDatabase). Further information can be found for canola events MS1 , MS8, RF3, GT73, MON88302, KK179 in W001 / 031042, W001 / 041558, W001 / 041558, W002 / 036831 , WO11 / 153186, WO13 / 003558; for cotton events MON1445, MON15985, MON531 (MON15985), LLCotton25, MON88913, COT102, 281-24-236, 3006-210-23, COT67B, GHB614, T304-40, GHB119, MON88701 , 81910 in WO02 / 034946, W002 / 100163, W002 / 100163, W003 / 013224, WO04 / 072235, WO04 / 039986, WO05 / 103266, WO05 / 103266, WO06 / 128573, W007 / 017186, WO08 / 122406, W008 / 151780, WO12 / 134808, WO13 / 112527; for corn events GA21 , MON810, DLL25, TC1507, MON863, MIR604, LY038, MON88017, 3272, 59122, NK603, MIR162, MON89034, 98140, 32138, MON87460, 5307, 4114, MON87427, DAS40278, MON87411 , 33121 , MON87403, MON87419 in W098 / 044140, US02 / 102582, US03 / 126634, WO04 / 099447, W004 / 011601 , WO05 / 103301 , W005 / 061720, W005 / 059103, WO06 / 098952, WO06 / 039376, US2007 / 292854, W007 / 142840, W007 / 140256, WO08 / 112019, W009 / 103049,

[0073] WO09 / 111263, W010 / 077816, W011 / 084621 , W011 / 062904, WO11 / 022469, WO13 / 169923, BASF SE 241435

[0074] 11

[0075] WO14 / 116854, WO15 / 053998, WO15 / 142571 ; for potato events E12, F10, J3, J55, V11 , X17, Y9 in WO14 / 178910, WO14 / 178913, WO14 / 178941 , WO14 / 179276, WO16 / 183445, W0 17 / 062831 , W017 / 062825; for rice events LLRICE06, LLRICE601 , LLRICE62 in WO00 / 026345, WO00 / 026356, WO00 / 026345; and for soybean events H7-1 , MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701 , MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712, SYHT0H2, DAS81419, DAS81419 x DAS44406-6, MON87751 in WO04 / 074492, WO06 / 130436, WO06 / 108674, WO06 / 108675, WO08 / 054747, W008 / 002872, WO09 / 064652, W009 / 102873, W010 / 080829, W010 / 037016, WO11 / 066384, W0 11 / 034704, W012 / 051199, W012 / 082548, W013 / 016527, W013 / 016516, W014 / 201235.

[0076] The use of the mixtures and the agrochemical thereof, respectively, on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain transgene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors (e.g. enhanced yield, early vigour, early or delayed ripening, changed amino acid or fatty acid spectrum or content; enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens; or cold or heat tolerance).

[0077] The mixtures and the agrochemical compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. Candida) and sunflowers (e.g. A. tragopogonisy, Alternaria spp. (Alternaria leaf spot) on vegetables (e.g. A. dauci or A. porri), oilseed rape (A. brassicicola or brassicae), sugar beets (A. tenuis), fruits (A. grandis), rice, soybeans, potatoes and tomatoes (A. solani, A. grandis or A. alternata), tomatoes (A. solani or alternata) and wheat (A. triticina)- Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on vegetables and cereals (A. tritici on wheat; A. hordei on barley); Aureobasidium zeae (syn. Kapatiella zeae) on corn; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e.g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn; spot blotch (B. sorokiniana) on cereals and B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. wheat or barley); Botrytis spp. e.g. B. cinerea (teleomorph: Botryotinia fuckeliana'. grey mold) on fruits and berries (e.g. strawberries), vegetables (e.g. lettuce, carrots, celery and cabbages); B. squamosa or B. allii on onions, oilseed rape, ornamentals (B eliptica), vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens (C. ulmi on elm); Cercospora spp. (Cer- cospora leaf spots) on corn (C. zeae-maydis), rice, sugar beets (C. beticola), sugar cane, vegetables, coffee, soybeans (C. sojina or kikuchii) and rice; Cladobotryum (syn. Dactylium) spp. (C. mycophilum (teleomorph: Nectria albertinii, Nectria rosella syn. Hypomyces rosellus) on mushrooms; Cladosporium spp. on tomatoes (C. fulvunr. leaf mold) and cereals (C. herbarum (black ear) on wheat); Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helmin- thosporium or Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (C. sativus, anamorph: BASF SE 241435

[0078] 12

[0079] B. sorokiniana) and rice (C. miyabeanus, anamorph: H. oryzaey, Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (C. gossypli), corn (C. graminicola: stalk rot), soft fruits, potatoes (C. coccodes black dot), beans (C. lindemuthianum), soybeans (C. truncatum or gloeosporioides), vegetables (C. lagenarium or capslci), fruits (e.g. C. acutatum), coffee (C. ka- hawae or coffeanum) and C. gloeosporioides on various crops; Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans, cotton and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (C. lirioden- dri, teleomorph: Neonectria liriodendrr'. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyr- enophora) spp. on corn, cereals (D. teres net blotch on barley; D. tritici-repentis’. tan spot on wheat), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora, Phaeoacremonium aleophilum and / or Botryosphaeria obtusa- Elsinoe spp. (anthracnose) on pome fruits (E pyri), soft fruits (E. veneta) and vines (E. ampelina); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e.g. E. pisi), such as cucurbits (E. cichoracearum), cabbages, oilseed rape (e.g. E. cruciferarumy Eu- typa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (E. turcicumy Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) e.g. on cereals (F. gra- minearum or culmorunr. root rot, scab or head blight), tomatoes (F. oxysporum), soybeans (F. virguliforme, cuneirostruum, tucumaniae and brasiliense-. sudden death syndrome), and corn (F. verticillioides); Gaeumannomyces graminis (take-all) on cereals (wheat, barley corn); Gibberella spp. on cereals (G. zeae) and rice (G. fujikuror'. Bakanae disease); Glomerella cingulata on vines, pome fruits and cotton (G. gossypii)- Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants (pears rust: G. sabinae) and junipers; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals, potatoes and rice; Hemileia spp., e.g. on coffee (H. vastatrix'. leaf rust); Isariopsis clavispora (syn. Pseudocercospora vitis) on vines; Macrophomina phaseolina (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e.g. M. laxa, fructi- cola and fructigena (bloom and twig blight, brown rot) on rosaceous plants (stone fruits); Myco- sphaerella spp. on cereals ( / W. graminicola [anamorph: Zymoseptoria tritici formerly Septoria trifid . Septoria blotch on wheat), bananas (M. fijiensis [syn. Pseudocercospora fijiensis]: black Sigatoka disease; M. musicola), soft fruits, ground nuts (M arachidis [anamorph: Cercospora arachidicola] or M. berkeleyi on peanuts), peas ( / W. pisi), and brassicas ( / W. brassiciolay Perono- spora spp. (downy mildew) on cabbage (P. brassicae), oilseed rape (P. parasitica), onions (P. BASF SE 241435

[0080] 13 destructor), tobacco (P. tabacina) and soybeans (P. manshuricay, Phakopsora pachyrhizi and meibomiae (soybean rust) on soybeans; Phialophora spp. e.g. on vines (P tracheiphila and tet- raspora) and soybeans (P gregata: stem rot); Phoma spp. on oilseed rape and cabbage (P lingam syn. Leptosphaeria maculans and biglobosa: Phoma stem canker), sugar beet (P betae: root rot, leaf spot and damping-off) and corn (P zeae-maydis, syn. Phyllostica zeae) Phomopsis spp. on sunflowers, vines (P. viticola: cane and leaf spot) and soybeans (stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum) Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) e.g. on paprika and cucurbits (P. capsici), soybeans (P. megasperma, syn. P. sq / ae), potatoes and tomatoes (P. infestans: late blight), and broad-leaved trees (P. ramorunr. sudden oak death); Plasmodiophora brassicae (club root) e.g. on cabbage, oilseed rape, radish; Plasmopara spp., on vines (P. viticola: downy mildew) and sunflowers (P. halstedii Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pomes (P. leucotricha on apples), soft fruits and curcurbits (P. xanthii Polymyxa spp. on cereals (P. graminis on wheat and barley) and sugar beets (P. betae) including thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (syn. Oculimacula yallundae, O. acuformis: eyespot, teleomorph: Tapesia yallundae) on cereals, e.g. wheat or barley; Pseudoperonospora (downy mildew) e.g. on cucurbits (P. cubensis) and hop (P. humili); Pseudopezicula tracheiphila (red fire disease or ,rotbrenner’, anamorph: Phialophora) on vines; Puccinia spp. (rusts) e.g. on cereals (wheat, barley or rye: P. triticina: brown or leaf rust, P. striiformis: stripe or yellow rust, P. horde!: dwarf rust, P. graminis-. stem or black rust, P. recondlta: brown or leaf rust), sugar cane (P. kuehnii: orange rust) and aspargus (P. asparagi): Pyrenopeziza spp. e.g. on oilseed rape (P. brassicae): Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea: rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) e.g. on turf, rice, corn, wheat, cotton, oilseed rape, sunflower, soybeans, sugar beets, vegetables (e.g. P. ultimum or aphanidermatum) and mushrums (P. oligandrum)- Ramularia spp., e.g. R. collo- cygni (Ramularia leaf spots) on barley, R. areola (teleomorph: Mycosphaerella areola) on cotton and R. beticola on sugar beets; Rhizoctonia spp. e.g. on cotton, rice, potatoes, turf, corn, oilseed rape, potatoes, sugar beets, vegetables, soybeans (R. solani: root and stem rot), rice (R. solani: sheath blight) and wheat and barley (R. cerealis: spring blight); Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis and commune (scald) on barley, rye and triticale; Sarocladium oryzae and attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables (S. minor and S. sclerotiorum) and field crops, such as oilseed rape, sunflowers (S. sclerotiorum) and soybeans (S. sclerotiorum and rolfsii), peanut, vegetables, corn, cereals and ornamentals; Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (syn. Zymoseptoria tritici, Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; BASF SE 241435

[0081] 14

[0082] Setosphaeria spp. (leaf blight) on corn (S. turcicum, syn. Helminthosporium) and turf; Sphace- lotheca spp. (smut) on corn, (S. reiliana, syn. Ustilaga. head smut), sorghum und sugar cane; Sphaerotheca fuliginea (syn. Podosphaera xanthii: powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals (wheat: S. nodorurrr. Stagonospora blotch, teleomorph: Leptosphaeria , Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e.g. T. basicola (syn.

[0083] Chalara elegans) Tilletia spp. (common bunt or stinking smut) on cereals (wheat: T. tritici: wheat bunt, T. controversa: dwarf bunt); Trichoderma harzianum on mushrooms; Typhula incar- nata (grey snow mold) on barley or wheat; Urocystis spp., e.g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables (beans: U. appendiculatus, syn. phaseoli), sugar beets (U. betae or beticola) and on pulses (U. vignae, pisi, viciae-fabae and fabae): Ustilago spp. (loose smut) on cereals (U. nuda and avaenae), corn (U. maydis corn smut) and sugar cane; Venturia spp. (scab) on apples (V. inaequalis) and pears; and Verticillium spp. (wilt) e.g. on fruits (strawberry: V. dahliae), ornamentals, vines, soft fruits, vegetables and field crops (oilseed rape: V. longisporum), and mushrooms (V. fungicola) Zymoseptoria tritici on cereals.

[0084] The mixtures and agrochemical compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g. Phakopsora pachyrhizi and P. meibomiae on soy; Puccinia tritici and P. striiformis on wheat); molds on specialty crops, soybean, oil seed rape and sunflowers (e.g. Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, S. minor and S. rolfsii on oil seed rape, sunflowers and soybean); Fusarium diseases on cereals (e.g. Fusarium culmorum and F. graminearum on wheat); downy mildews on specialty crops (e.g. Plasmopara viticola on vines, Phytophthora in- festans on potatoes or tomatoes, Pseudoperonospora cubensis on cucrbits, Peronospora de- tructor on onions); powdery mildews on specialty crops and cereals (e.g. Uncinula necator on vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); and leaf spots on cereals, soybean and corn (e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean).

[0085] It has been observed that populations of phytopathogenic fungi apparently consisting of non- resistant strains can readily develop resistance. The compounds can be applied under such conditions, too, to prevent the formation of resistance and the spread of resistant strains altogether. In this regard it is useful that they have strong activity also against non-resistant phytopathogenic fungi.

[0086] Fungicide-resistant strains of various phytopathogenic fungi have been reported, with strains resistant to one or more fungicides from various mode of action classes being observed by tar- get-site mutations in the genes of the respective proteins (e.g. Qol (C3, according to FRAC convention, for details www.frac.info), quinone outside stigmatellin binding subsite inhibitors (QoSI; BASF SE 241435

[0087] 15

[0088] C8), and quinone inside inhibitors (Qil; C4): CytB target protein; sterol demethylation (DMI, G1): Cyp51 [Erg11]; carboxylic acid amides (CAA, H5): CesA3; SDHI (C2): SdhB, SdhC and SdhD; dicarboximides (E3): Os-1 (including Bos1 , Daf1 etc.); keto reductase inhibitors (KRI; Class III SBIs; G3): Erg27; and oxysterol binding protein inhibitors (OSBPI; F9): 0RP1. Examples of mutation sites of genes encoding such target proteins resulting in the listed single amino acid exchanges, deletions or insertions in the respective target protein sequences conferring resistance against certain fungicides in phytopathogenic fungi are indicated in Table M (see also Pest Manag Sci 72(8) 2016: 1449-1459). Table M: BASF SE 241435

[0089] 16 BASF SE 241435

[0090] 17 BASF SE 241435

[0091] 18

[0092] * based on alignment to reference sequence from Phytophthora infestans ** G54E / K / R / V / W indicates the possibility of five different amino acid changes at position 54; A indicates a deletion of an amino acid; # refers to an amino acid insertion.

[0093] Thus, the mixtures and the agrochemical compositions thereof are particularly useful to control such fungicide-resistant strains of phytopathogenic fungi described in Table M. Such strains may have one or more resistances derived from one or more mutations of one or more genes encoding target proteins of various kinds of the fungicides including, but not limited to, the mutations listed in Table M and / or a resistance derived from an overexpression of the respective target protein.

[0094] In addition, certain strains of fungi may have developed so-called multidrug resistance eventually leading to a broad cross resistance to many structurally and functionally unrelated compounds. "Multidrug resistance” (MDR) also called “pleiotropic drug resistance” (PDR) describes a resistance phenomenon usually caused by overexpression of certain membrane transporters, leading to an increased activity of efflux pump which export certain substrates, e.g., fungal toxins but also fungicidal compounds. Examples of such membrane transporters include ATP-bind- ing cassette (ABC) transporters and Major Facilitator Superfamily (MFS) transporters. Overexpression of membrane transporters can be confirmed, e.g., by measuring an amount of the transporter protein or of the corresponding mRNA. The measured amount of mRNA may be, e.g., 2-fold, 5-fold, 20-fold, up to 100-fold or more, relative to the mRNA amount of the corresponding fungicide-sensitive wild-type fungus.

[0095] The mixtures and the agrochemical compositions thereof can be applied to control a plant disease that is caused by a multidrug-resistant (MDR) fungus. The multidrug-resistant fungus may have in addition one or more resistances derived from one or more mutations of one or more genes encoding target proteins of various kinds of the fungicides including but not limited to the mutations listed in Table M and / or a resistance derived from an overexpression of the target protein. Thus, the mixtures and the agrochemical compositions thereof are also particularly useful to control such multidrug-resistant fungi.

[0096] The mixtures and the agrochemical compositions thereof, respectively, are also suitable for controlling harmful microorganisms in the protection of stored products or harvest, and in the protection of materials.

[0097] The term "stored products or harvest" is understood to denote natural substances of plant or animal origin and their processed forms for which long-term protection is desired. Stored products of plant origin, for example stalks, leaves, tubers, seeds, fruits or grains, can be protected BASF SE 241435

[0098] 19 in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Stored products of animal origin are hides, leather, furs, hairs and alike. Preferably, "stored products" is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms, where application of mixtures and agrochemical compositions thereof can also prevent disadvantageous effects such as decay, discoloration or mold.

[0099] The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper, paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber, or fabrics against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.

[0100] 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 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active substance per cubic meter of treated material.

[0101] The mixtures and agrochemical compositions thereof, respectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material, and / or the locus where the plant is growing or is to grow with an effective amount of the mixtures and the agrochemical compositions thereof, respectively.

[0102] 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.

[0103] The mixtures are employed as such or in form of compositions by treating the fungi, the plants, plant propagation materials, such as seeds; soil, surfaces, materials, or rooms to be protected from fungal 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.

[0104] An agrochemical composition comprises a fungicidally effective amount of a mixture. The term "fungicidally effective amount" denotes an amount of the composition or of the mixture, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of stored BASF SE 241435

[0105] 20 products or harvest or of materials and which does not result in a substantial damage to the treated plants, the treated stored products or harvest, or to the treated materials. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant, stored product, harvest or material, the climatic conditions, and the specific mixture used.

[0106] Plant propagation materials may be treated with the mixtures as such or an agrochemical composition comprising at least one mixture prophylactically either at or before planting or transplanting.

[0107] When employed in plant protection, the amounts per active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

[0108] In treatment of plant propagation materials such as seeds, e.g. by dusting, coating, or drenching, amounts of active substance of generally 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 kg of plant propagation material (preferably seeds) are required.

[0109] The user applies the agrochemical composition usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, drones, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and / or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area. The ready-to- use spray liquor may preferably comprise the fungicide in an amount of 300 to 1500 ppm in a volume 50 to 1500 liters per hectare. Higher amounts of the fungicide in the ready-to-use spray liquor are usually used when the volume of the ready-to-use spray liquor is low. Low volumes of the ready-to-use spray liquor are preferably used in cases where the ready-to-use spray liquor is applied via drones or air planes. For example, a fungicide may be applied in an amount of 300 to 600 ppm in a volume of 100 to 200 liters per hectare, preferably in an amount of 500 ppm in a volume of 150 liters per hectare. In one embodiment, the fungicide may be applied in an amount of 750 to 1500 ppm in a volume of 50 to 100 liters per hectare. Accordingly, another embodiment of the invention is a method of controlling or suppressing plant pathogens or preventing plant pathogen infection, wherein the plant pathogens, their habitat or the materials or plants to be protected against plant pathogen attack, or the soil or the plant propagation material are treated with an effective amount of a mixture comprising limonene and a fungicide selected from the group comprising ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, propamocarb, cymoxanil, dithianon, metalaxyl, metalaxyl-M, mancozeb, me- tiram, folpet, cyazofamid, fluopicolide, fosetyl-AI and a phosphite, or treated with an effective amount of an agrochemical composition comprising such mixture. These methods exclude the treatment of the human or animal body by surgery or therapy and diagnostic methods practised BASF SE 241435

[0110] 21 on the human or animal body. Preferably the pathogens are oomycetes. More preferred the pathogens are selected from the genera Plasmopara, Phytophthora, Peronspora, Bremia, Pseu- doperonospora, Albugo, Aphanomyces, or Pythium.

[0111] In one embodiment the pathogens belong to a species selected from the group comprising Plasmopara viticola, Plasmopara halstedii, Plasmopara obducens, Phytophthora capsici, Phytophthora sojae, Phytophthora litchi, Peronspora destructor, Phytophthora porri, Phytophthora infestans, Phytophthora erythroseptica, Phytophthora melonis, Phytophthora megasperma, Phytophthora brassicae, Phytophthora parasitica, Peronospora vicia, Bremia lactucae, Pseu- doperonospora cubensis, Peronospora sparsa, Aphanomyces euteiches, Phytophthora nicoti- anae, Phytophthora sojae and Phytophthora megasperma. Preferably the genus is selected from Plasmopara, Phytophthora, Pseudoperonospora, Alternaria, Septoria and Venturia. Preferably the species Plasmopara viticola, Phytophthora infestans, Pseudoperonospora cubensis, Alternatira solani, Septoria tritici or Venturia inequalis. Preferably the species is selected from Plasmopara viticola, Phytophthora infestans and Pseudoperonospora cubensis.

[0112] In one embodiment the mixture comprises limonene, preferably D-limonene, and ametoctradin and the pathogen belongs to the genus Phytophthora or Pseudoperonospora, preferably, the pathogen belongs to the species Phytophthora infestans or Pseudoperonospora cubensis. Preferably the weight / weight ratio of limonene, preferably D-limonene, to ametoctradin is between 10 to 1 and 1 to 10, or between 5 to 1 and 1 to 5.

[0113] In one embodiment the mixture comprises limonene, preferably D-limonene, and oxathiopipro- lin, mandipropamid or dithianone and the pathogen belongs to the genus Alternatria or Septoria, preferably, the pathogen belongs to the species Alternatira solani or Septoria tritici. Preferably the weight / weight ratio of limonene, preferably D-limonene, to oxathiopiprolin, mandipropamid or dithianone is between 10 to 1 and 1 to 10, or between 5 to 1 and 1 to 5, or between 4 to 1 and 1 to 1 , or is 4 to 1 or is 1 to 1 .

[0114] Preferably the methods of controlling, suppressing pathogens or preventing pathogen infection are used to control, suppress or preventing infection of Plasmopara viticola on grape; or Plasmopara halstedii on sunflower; or Plasmopara obducens on impatiens; or Phytophthora capsici on cucurbits, pepper, tomato, eggplant, snap or lima beans; or Peronspora destructor and Phytophthora porri on onions, or Phytophthora infestans on potato or tomato; or Phytophthora erythroseptica on potato; or Phytophthora melonis on melon; or Phytophthora megasperma on asparagus; or Phytophthora brassicae on cabbages; or Phytophthora parasitica on brassicas or solanaceous crops; or Peronospora vicia on legume crops, or Bremia lactucae on lettuce; or Pseudoperonospora cubensis on cucumber, cucurbits; squash, luffa or melon; or Peronospora sparsa in roses; or Albugo spp on spinach and beets; or Aphanomyces euteiches on beets or legume crops, or Pythium spp on potato or vegetable or ornamental crops, or Phytophthora ni- cotianae on tobacco, or Phytophthora sojae on soybean, or Phytophthora megasperma on soybean. BASF SE 241435

[0115] 22

[0116] The invention comprises also the use of a mixture comprising limonene and a fungicide selected from the group comprising ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, propamocarb, cymoxanil, dithianon, metalaxyl, metalaxyl-M, mancozeb, me- tiram, folpet, cyazofamid, fluopicolide, fosetyl-AI and a phosphite, or an agrochemical composition comprising such a mixture for controlling or suppressing plant pathogens or preventing plant pathogen infection or for protection of materials against infestation or destruction by harmful microorganisms.

[0117] In one embodiment the pathogens are selected from the genera Plasmopara, Phytophthora, Peronspora, Bremia, Pseudoperonospora, Albugo, Aphanomyces, or Pythium.

[0118] In one embodiment the pathogens belong to a species selected from the group comprising Plasmopara viticola, Plasmopara halstedii, Plasmopara obducens, Phytophthora capsici, Phytophthora sojae, Phytophthora litchi, Peronspora destructor, Phytophthora porri, Phytophthora infestans, Phytophthora erythroseptica, Phytophthora melonis, Phytophthora megasperma, Phytophthora brassicae, Phytophthora parasitica, Peronospora vicia, Bremia lactucae, Pseudoperonospora cubensis, Peronospora sparsa, Aphanomyces euteiches, Phytophthora nicoti- anae, Phytophthora sojae and Phytophthora megasperma. Preferably the species is selected from Plasmopara viticola, Phytophthora infestans or Pseudoperonospora cubensis.

[0119] In one embodiment the use is to control, suppress or preventing infection of Plasmopara viticola on grape; or Plasmopara halstedii on sunflower; or Plasmopara obducens on impatiens; or Phytophthora capsici on cucurbits, pepper, tomato, eggplant, snap or lima beans; or Peronspora destructor and Phytophthora porri on onions, or Phytophthora infestans on potato or tomato; or Phytophthora erythroseptica on potato; or Phytophthora melonis on melon; or Phytophthora megasperma on asparagus; or Phytophthora brassicae on cabbages; or Phytophthora parasitica on brassicas or solanaceous crops; or Peronospora vicia on legume crops, or Bremia lactucae on lettuce; or Pseudoperonospora cubensis on cucumber, cucurbits; squash, luffa or melon; or Peronospora sparsa in roses; or Albugo spp on spinach and beets; or Aphanomyces euteiches on beets or legume crops, or Pythium spp on potato or vegetable or ornamental crops, or Phytophthora nicotianae on tobacco, or Phytophthora sojae on soybean, or Phytophthora megasperma on soybean.

[0120] A further part of the invention is a kit of at least two parts comprising: a. a part comprising limonene in a concentrated form b. a part comprising a fungicide selected from the group comprising ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, propamocarb, cymoxanil, dithianon, metalaxyl, metalaxyl-M, mancozeb, metiram, folpet, cyazofamid, fluopicolide, fosetyl-AI and a phosphite and c. a part comprising instructions how to combine part a) and part b) to prepare the mixture comprising limonene and a fungicide selected from the group comprising ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, propamocarb, cymoxanil, BASF SE 241435

[0121] 23 dithianon, metalaxyl, metalaxyl-M, mancozeb, metiram, folpet, cyazofamid, fluopicolide, fosetyl-AI and a phosphite.

[0122] Preferably the instructions of part c) comprise also instructions on how to apply the mixtures in methods of controlling, suppressing pathogens or preventing pathogen infection of plants. In some embodiments part b) comprises more than one fungicide, wherein at least one is selected from ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, pro- pamocarb, cymoxanil, dithianon, metalaxyl, metalaxyl-M, mancozeb, metiram, folpet, cyazofamid, fluopicolide, fosetyl-AI and a phosphite

[0123] In one embodiment part b) comprises ametoctradin and one selected from the group comprising dimethomorph, propamocarb, propamocarb hydrochloride, cymoxanil and a phosphite.

[0124] Example 1 :

[0125] Late Blight (Phytophthora infestans, PHYTIN) at tomato plants

[0126] Seedlings of tomato plants were sprayed from top close to the point of run-off with a solution of the products, 1 day after application the plants were inoculated with a spore suspension of Phytophthora infestans (3x103spores / ml), and kept in high humidity conditions for 4 days and then assessed. Seedlings of tomato (Lycoperisicon esculentum ‘Goldene Kbnigin’) were potted 2 weeks before the start of trial. Ametoctratin was used as a formulated product with 200g / l as SC, Limonen in a 90% EC preparation. Assessment was done visually as percentage leaf damage, efficacy calculated according the Abbott formula. Synergism was calculated according to Colby.

[0127] Table 1 BASF SE 241435

[0128] 24

[0129] Example 2: Downy Mildew (Pseudoperonospora cubensis, PSPECU) at cucumber plants

[0130] Seedlings of tomato plants were sprayed from top close to the point of run-off with a solution of the products, 1 day after application the plants were inoculated with a spore suspension of Pseu- doperonospora cubensis (1x104spores / ml), and kept in high humidity conditions for 2 days, followed by dry conditions for 5 days, and then assessed. Seedlings of cucumber plants (Cucumis sativus ‘Chinese Slang’) were potted 3 weeks before the start of trial. Ametoctratin was used as a formulated product with 200g / l as SC, Limonen in a 90% EC preparation. Assessment was done visually as percentage leaf damage, efficacy calculated according to the Abbott formula. Synergism was calculated according to Colby. Table 2 BASF SE 241435

[0131] 25

[0132] Example 3:

[0133] Microtest

[0134] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

[0135] The product limonene was used as a formulation (90% EC preparation) and diluted with water to the stated concentration of the active compound.

[0136] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate and diluted with water to the stated concentrations.

[0137] - Spores in aqueous biomalt solutions were then added, containing:

[0138] 1. Alternaria solani (ALTESO)

[0139] 2. Septoria tritici (SEPTTR)

[0140] - Spores in Henninger media, containing Phytophthora infestans (PHYTIN), were then added.

[0141] The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

[0142] The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies.

[0143] An efficacy of 0 means that the growth level of the pathogens corresponds to that of the untreated control; an efficacy of 100 means that the pathogens were not growing. BASF SE 241435

[0144] 26

[0145] The expected efficacies of active compound mixtures were determined using Colby's formula [R.S. Colby, “Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies. Table 3: ALTESO

[0146] Table 4: SEPTTR BASF SE 241435 able 5: PHYTIN

[0147] The Limonene used in Examples 1 to 3 was a synthetic limonene.

Claims

BASF SE 24143528Claims1 A mixture comprising as active components, a. limonene and b. a fungicide selected from the group comprising ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, propamocarb, cymoxanil, dithi- anon, metalaxyl, metalaxyl-M, mancozeb, metiram, folpet, cyazofamid, fluopico- lide, fosetyl-AI and a phosphite having fungicidal activity2 The mixture of claim 1 , wherein the mixture comprises ametoctradin, oxathiapiprolin, mandipropamid or dithianon.3 The mixture of claim 1 or 2, wherein the weight / weight ratio between limonene and the fungicide is between 10 to 1 and 1 to 10.4 The mixture of any one of claims 1 to 3, comprising in addition to the fungicide a second fungicide, with the proviso that the second fungicide is not identical with the fungicide.5 The mixture of claim 4, wherein the second fungicide is selected from the group comprising ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, propamocarb, cymoxanil, dithianon, metalaxyl, metalaxyl-M, mancozeb, metiram, folpet, cyazofamid, fluopicolide, fosetyl-AI, and a phosphite, with the proviso that the second fungicide is not identical with the fungicide.6 The mixture of claim 5, wherein the weight / weight ratio between limonene and the second fungicide is between 10 to 1 and 1 to 10.7 The mixture of any one of claims 1 to 6, comprising limonene and the fungicide in synergistically effective amounts.8 The mixture of any one of claims 4 to 7, comprising limonene and the second fungicide in synergistically effective amounts.9 An agrochemical composition comprising a mixture as defined in any of the claims 1 to 8 and an auxiliary.BASF SE 2414352910 A method of controlling or suppressing plant pathogens or preventing plant pathogen infection, wherein the plant pathogens, their habitat or the materials or plants to be protected against plant pathogen attack, or the soil or the plant propagation material are treated with an effective amount of a mixture as defined in any of the claims 1 to 8 or with an effective amount of an agrochemical composition as defined in claim 9.11 The method of claim 10, wherein the pathogen is a member of the genera Plasmo- para, Phytophthora, Peronspora, Bremia, Pseudoperonospora, Albugo, Aphano- myces, or Pythium.12 The method of claim 10 or 11 , wherein the pathogen species is selected from the group comprising Plasmopara viticola, Plasmopara halstedii, Plasmopara obducens, Phytophthora capsici, Phytophthora sojae, Phytophthora litchi, Peronspora destructor, Phytophthora porri, Phytophthora infestans, Phytophthora erythroseptica, Phytophthora melonis, Phytophthora megasperma, Phytophthora brassicae, Phytophthora parasitica, Peronospora vicia, Bremia lactucae, Pseudoperonospora cubensis, Peronospora sparsa, Aphanomyces euteiches, Phytophthora nicotianae, Phytophthora sojae and Phytophthora megasperma.13 The use of a mixture as defined in any of the claims 1 to 8 or an agrochemical composition as defined in claim 9 for controlling or suppressing plant pathogens or preventing plant pathogen infection or for protection of materials against infestation or destruction by harmful microorganisms.14 The use of a mixture as defined in any of the claims 1 to 8 or an agrochemical composition as defined in claim 9 to control, suppress or preventing infection of Plasmopara viticola on grape; or Plasmopara halstedii on sunflower; or Plasmopara obducens on impatiens; or Phytophthora capsici on cucurbits, pepper, tomato, eggplant, snap or lima beans; or Peronspora destructor and Phytophthora porri on onions, or Phytophthora infestans on potato or tomato; or Phytophthora erythroseptica on potato; or Phytophthora melonis on melon; or Phytophthora megasperma on asparagus; or Phytophthora brassicae on cabbages; or Phytophthora parasitica on brassicas or solana- ceous crops; or Peronospora vicia on legume crops, or Bremia lactucae on lettuce; or Pseudoperonospora cubensis on cucumber, cucurbits; squash, luffa or melon; or Peronospora sparsa in roses; or Albugo spp on spinach and beets; or Aphanomyces euteiches on beets or legume crops, or Pythium spp on potato or vegetable or ornamental crops, or Phytophthora nicotianae on tobacco, or Phytophthora sojae on soybean, or Phytophthora megasperma on soybean.BASF SE 2414353015 A kit of at least two parts comprising: a. a part comprising limonene in a concentrated form b. a part comprising a fungicide selected from the group comprising ametoctradin, oxathiapiprolin, fluoxapiprolin, dimethomorph, mandipropamid, propamocarb, cy- moxanil, dithianon, metalaxyl, metalaxyl-M, mancozeb, metiram, folpet, cyazofamid, fluopicolide, fosetyl-AI and a phosphite and c. a part comprising instructions how to combine part a) and part b) to prepare a mixture as described in any one of claims 1 to 8.

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