Method to for controlling soybean rust using compositions comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate)and other fungicides

Abstract

The present invention relates to a method for controlling soybean rust, comprising treating the plants or the soil with a fungicidally effective amount of a composition comprising: as active component 1) the compound (I) methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2- enoate) and as active component 2) compound (II) which is selected from the group consisting of azoxystrobin (II-1), picoxystrobin (II-2), trifloxystrobin (II-3), metominostrobin (II-4) and the ag- riculturally acceptable salts thereof.

Description

[0001] 240844

[0002] 1

[0003] Method to for controlling soybean rust using compositions comprising methyl (2Z)-3-methoxy-2- [(4-methylbiphenyl-3-yl)oxy]prop-2-enoate)and other fungicides

[0004] Description

[0005] The present invention relates A method for controlling soybean rust, comprising treating the plants or the soil with a fungicidally effective amount of a composition comprising: as active component 1) the compound (I) methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate and as active component 2) compound (II) which is selected from the group consisting of azoxystrobin (11-1), picoxystrobin (I I-2), trifloxystrobin (II-3), metominostrobin (I I-4) and the agriculturally acceptable salts thereof.

[0006] One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control. In regard to the present invention the term pests embrace harmful fungi and animal pests.

[0007] Another problem encountered concerns the need to have available pest control agents which are effective against a broad spectrum of harmful fungi and harmful animal pests.

[0008] There also exists the need for pest control agents that combine knock-down activity with prolonged control, that is, fast action with long lasting action.

[0009] Another difficulty in relation to the use of pesticides is that the repeated and exclusive application of an individual pesticidal compound leads in many cases to a rapid selection of pests, that means animal pests, and harmful fungi, which have developed natural or adapted resistance against the active compounds in question. Therefore, there is a need for pest control agents that help prevent or overcome resistance.

[0010] Especially controlling fungicidal diseases in soybeans is a challenge and already now, more than one active ingredient is needed to achieve sufficient activity. It is expected, that in future all products will consist of at least two active ingredients (binary compositions).

[0011] Therefore, it is an object of the present invention to provide, with a view to effective resistance management and effective control of phytopathogenic harmful fungi, at application rates which are as low as possible, method of use of compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful fungi (synergistic compositions) and a broadened activity spectrum.

[0012] We have accordingly found that this object is achieved by the compositions, defined herein, comprising the compound (I) and the compound (11-1) or (I I-2) or (I I-3) or (I I-4) as defined above.

[0013] The compound (I) and its mixture are known from e.g. US 20230130546 A1 , US 2023010754 A1 , US 20230069915 A1 , JP 2023064110 A, J P 2024009309 A. Further, the compound (II) is known from WO2014193974 and http: / / www.bcpcpesticidecompendium.org / . 240844

[0014] 2

[0015] Compounds (11-1) to (I I-4) as well as their pesticidal action and methods for producing them are generally known (cf.: http: / / www.alanwood.net / pesticides / ); these substances are commercially available.

[0016] The compounds (11-1) to (I I-4) as defined above for component 2) is herein collectively referred to as “compounds of the formula (II)” or “compounds (II)”.

[0017] Compound (I) and / or the compounds (II) can be present in different crystal modifications, which may differ in biological activity.

[0018] The scope of the present invention includes compositions of the (R)- and (S)-isomers and the racemates of compounds (I) and / or (II) having one or more chiral centers. As a result of hindered rotation of asymmetrically substituted groups, atrope isomers of active compounds (I) and / or (II) may be present. They also form part of the subject matter of the invention.

[0019] Agriculturally acceptable salts of the active compounds (I), (II) encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the active compounds. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry 1 to 4 Ci-C4-alkyl substituents and / or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds (I) with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

[0020] According to further embodiments, the compound (I) and the compounds (II) are usually present in the ratios from 10:1 to 1 :10, often from 9:1 to 1 :9, more often from 8:1 to 1 :8, even more often from 7:1 to 1 :7, regularly from 6:1 to 1 :6, preferably from 5:1 to 1 :5, more preferably from 4:1 to 1 :4, even more preferably from 3:1 to 1 :3, most preferably from 2:1 to 1 :2, specifically 1 :1.

[0021] The compound (I) and the compounds (II) can be also present in the ratios from 10:1 to 1 :1 , often from 9:1 to 1 :1 , more often from 8:1 to 1 :1 , even more often from 7:1 to 1 :1 , regularly from 6:1 to 1 :1 , preferably from 5:1 to 1 :1 , more preferably from 4:1 to 1 :1 , even more preferably from 4:1 to 1 :1 , most preferably from 3:1 to 1 :1 , especially preferably from 2:1 to 1 :1.

[0022] The compound (I) and the compounds (II) can be further present in the ratios from 1 :1 to 1 :10, often from 1 :1 to 1 :9, more often from 1 :1 to 1 :8, even more often from 1 :1 to 1 :7, regularly from 1 :1 to 1 :6, preferably from 1 :1 to 1 :5, more preferably from 1 :1 to 1 :4, even more preferably from 1 :1 to 1 :3, most preferably from 1 :1 to 1 :2.

[0023] In a preferred aspect the present invention relates to fungicidal compositions M.1 to M.224 that are each identified in one row of table M below, wherein component 1) and component 2) are identified together with their relative amounts (weight ratio).

[0024] Compound (I) and / or the compounds (II) can be present in different crystal modifications, which 240844

[0025] 3 may differ in biological activity.

[0026] The scope of the present invention includes compositions of the (R)- and (S)-isomers and the racemates of compounds (I) and / or (II) having one or more chiral centers. As a result of hindered rotation of asymmetrically substituted groups, atrope isomers of active compounds (I) and / or (II) may be present. They also form part of the subject matter of the invention.

[0027] Agriculturally acceptable salts of the active compounds (I), (II) encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the active compounds. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry 1 to 4 Ci-C4-alkyl substituents and / or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds (I) with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

[0028] According to further embodiments, the compound (I) and the compounds (II) are usually present in the ratios from 10:1 to 1 :10, often from 9:1 to 1 :9, more often from 8:1 to 1 :8, even more often from 7:1 to 1 :7, regularly from 6:1 to 1:6, preferably from 5:1 to 1:5, more preferably from 4:1 to 1:4, even more preferably from 3:1 to 1:3, most preferably from 2:1 to 1 :2, specifically 1:1.

[0029] The compound (I) and the compounds (II) can be also present in the ratios from 10:1 to 1:1 , often from 9:1 to 1:1, more often from 8:1 to 1:1, even more often from 7:1 to 1 :1 , regularly from 6:1 to 1:1 , preferably from 5:1 to 1 :1 , more preferably from 4:1 to 1:1 , even more preferably from 4:1 to 1:1 , most preferably from 3:1 to 1:1, especially preferably from 2:1 to 1 :1.

[0030] The compound (I) and the compounds (II) can be further present in the ratios from 1 :1 to 1:10, often from 1:1 to 1:9, more often from 1 :1 to 1:8, even more often from 1 :1 to 1:7, regularly from 1:1 to 1:6, preferably from 1:1 to 1 :5, more preferably from 1 :1 to 1:4, even more preferably from 1:1 to 1:3, most preferably from 1 :1 to 1:2.

[0031] In a preferred aspect the present invention relates to fungicidal compositions M.1 to M.224 that are each identified in one row of table M below, wherein component 1) and component 2) are identified together with their relative amounts (weight ratio).

[0032] Table M 240844

[0033] 4 240844

[0034] 5 240844

[0035] 6 240844

[0036] 7

[0037] The term "plant propagation material" is to be understood to denote all the generative parts of the plant in particular seeds.

[0038] Plants and as well as the propagation material of said plants, which can be treated with fungi- cidally effective amount of a composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbi- phenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and / or the generation of mutants, or by recombinant procedures. 240844

[0039] 8

[0040] For example, mixtures according to the present invention can be applied (as seed treatment, spray treatment, in furrow or by any other means) also to plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http: / / www.bio.org / speeches / pubs / er / agri_prod- ucts.asp). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transitional modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.

[0041] For use according to the present invention, a composition comprising methyl (2Z)-3-methoxy-2- [(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the mixtures according to the present invention. The formulations are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: ’’Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91 / 13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001).

[0042] The agrochemical formulations may also comprise auxiliaries which are customary in agrochemical formulations. The auxiliaries used depend on the particular application form and active substance, respectively.

[0043] Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and inorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations).

[0044] Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gammabutyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e. g. amines such as N-methylpyrrolidone.

[0045] Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers. 240844

[0046] 9

[0047] Suitable surfactants (adjuvants, wetters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Mor- wet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid (Nekal® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl-arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearyl phenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.

[0048] Examples for thickeners (i. e. compounds that impart a modified flowability to formulations, i. e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and inorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).

[0049] Bactericides may be added for preservation and stabilization of the formulation. Examples for suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothia- zolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie).

[0050] Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

[0051] Examples for anti-foaming agents are silicone emulsions (such as e. g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.

[0052] Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples are rhodamin B, C. I. pigment red 112, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1 , pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

[0053] Examples for tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).

[0054] Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate 240844

[0055] 10

[0056] (I) and at least one compound (II) as described herein and, if appropriate, further active substances, with at least one solid carrier.

[0057] Granules, e. g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nut-shell meal, cellulose powders and other solid carriers.

[0058] Examples of formulation types are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water-soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF), herein further below exemplified in detail:

[0059] 1. Composition types for dilution with water i) Water-soluble concentrates (SL, LS)

[0060] 10 parts by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a formulation having a content of 10% by weight of active substance is obtained. ii) Dispersible concentrates (DC)

[0061] 20 parts by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e. g. polyvinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight. iii) Emulsifiable concentrates (EC)

[0062] 15 parts by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The composition has an active substance content of 15% by weight. iv) Emulsions (EW, EO, ES)

[0063] 25 parts by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous 240844

[0064] 11 emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight. v) Suspensions (SC, OD, FS)

[0065] In an agitated ball mill, 20 parts by weight of composition comprising methyl (2Z)-3-methoxy-2- [(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight. vi) Water-dispersible granules and water-soluble granules (WG, SG)

[0066] 50 parts by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. The composition has an active substance content of 50% by weight. vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)

[0067] 75 parts by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance. The active substance content of the composition is 75% by weight. viii) Gel (GF)

[0068] In an agitated ball mill, 20 parts by weight of composition comprising methyl (2Z)-3-methoxy-2- [(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w / w) of active substance is obtained.

[0069] 2. Composition types to be applied undiluted ix) Dustable powders (DP, DS)

[0070] 5 parts by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight. x) Granules (GR, FG, GG, MG)

[0071] 0.5 parts by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or 240844

[0072] 12 the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by weight. xi) ULV solutions (UL)

[0073] 10 parts by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are dissolved in 90 parts by weight of an organic solvent, e. g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight.

[0074] The agrochemical formulations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substances. composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein can be used as such or in the form of their compositions, e. g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the compounds present in composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein.

[0075] Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

[0076] The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1% by weight of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2- enoate (I) and at least one compound (II) as described herein.

[0077] Composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein may also be used successfully in the ultra- low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.

[0078] Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds present in the composition comprising methyl (2Z)-3- methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0079] Compositions of this invention may also contain fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators and safeners. These may be used sequentially or in combination with the above-described compositions, if appropriate 240844

[0080] 13 also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with the fertilizers.

[0081] Compositions are applied by treating the fungi or the plants, materials or soil to be protected from fungal attack with a pesticidally effective amount of composition comprising methyl (2Z)-3- methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein. The application can be carried out both before and after the infection of the materials, plants or the soil by the pests.

[0082] In general, "pesticidally effective amount" means the amount of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein or of compositions comprising composition comprising methyl (2Z)-3-meth- oxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary. A pesticidally effective amount will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

[0083] When preparing the compositions comprising composition comprising methyl (2Z)-3-methoxy-2- [(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein, it is preferred to employ the pure active compound, to which optionally further active compounds against pests, such as insecticides, herbicides, fungicides or else herbicidal or growth-regulating active compounds or fertilizers can be added as further active components according to need.

[0084] Preferably, composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-

[0085] 2-enoate (I) and at least one compound (II) as described herein is employed by treating the fungi or the plants or soil to be protected from pesticidal attack via foliar application with a pesticidally effective amount of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-

[0086] 3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein. Also herein, the application can be carried out both before and after the infection of the plants by the pests.

[0087] In the method of combating harmful fungi depending on the type of compound and the desired effect, the application rates of composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbi- phenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are from 0,1 g / ha to 10000 g / ha, preferably 2 g / ha to 2500 g / ha, more preferably from 5 to 1000 g / ha, most preferably from 50 to 100 g / ha, in particular from 75 to 100 g / ha.

[0088] In an alternative embodiment of the invention, the composition comprising methyl (2Z)-3-meth- oxy-2-[(4-methylbiphenyl-3-yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein are used for the protection of the the seedlings' roots and shoots.

[0089] Compositions, which are especially useful for seed treatment are e.g.:

[0090] A Soluble concentrates (SL, LS)

[0091] D Emulsions (EW, EO, ES)

[0092] E Suspensions (SC, OD, FS)

[0093] F Water-dispersible granules and water-soluble granules (WG, SG) 240844

[0094] 14

[0095] G Water-dispersible powders and water-soluble powders (WP, SP, WS)

[0096] H Gel-Formulations (GF)

[0097] I Dustable powders (DP, DS)

[0098] These compositions can be applied to plant propagation materials diluted or undiluted. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propagation material (and also in furrow treatment). In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by pelleting, coating and dusting.

[0099] In the treatment of plant propagation material (preferably seed), the application rates of the inventive mixture are generally for the formulated product (which usually comprises frornlO to 750 g / l of the active(s)).

[0100] The invention also relates to the propagation products of plants comprising a mixture as defined above or a composition containing the mixture of two or more active ingredients or a mixture of two or more compositions each providing one of the active ingredients. The plant propagation material comprises composition comprising methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate (I) and at least one compound (II) as described herein in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material, preferably 0.1 g to 1 kg per 100 kg of plant propagation mate rial.

[0101] The invention is further illustrated, but not limited by the following practical examples:

[0102] Biological Tests

[0103] Microtest

[0104] The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

[0105] The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.

[0106] Example 1 - Activity against the Alternaria solani in the microtiterplate test

[0107] A spore suspension of Alternaria solani in an aqueous biomalt or yeast-bactopeptone-sodi- umacetate solution was then added.

[0108] 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.

[0109] 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 240844

[0110] 15 pathogens in the respective active compounds.

[0111] These percentages were converted into efficacies.

[0112] 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.

[0113] 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. 240844

[0114] 16

[0115] Green House

[0116] The compound was dissolved in a mixture of acetone and / or dimethylsulfoxide and the wetting agent / emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a ratio (volume) solventemulsifier of 99 to 1 to give a total volume of 5 ml. Subsequently, water was added to total volume of 100 ml.

[0117] This stock solution was then diluted with the described solvent-emulsifier-water mixture to the final concentration given in the table below.

[0118] Example 1 - Protective control of soybean rust on soybeans caused by Phakopsora pachyrhizi

[0119] Leaves of potted soybean seedlings were sprayed to run-off with the previously described spray solution, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 1 day in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80 %. Then the plants were inoculated with spores of Phakopsora pachyrhizi. T o ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24 C for 24 h. The trial plants were cultivated for ten days in a greenhouse chamber at 23-27°C and a relative humidity between 60 and 80 %. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

[0120] The disease ratings (or diseased leaf area) were converted into efficacies.

[0121] An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.

[0122] 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. 240844

[0123] 17

Claims

24084418Claims1. A method for controlling soybean rust, comprising treating the plants or the soil with a fun- gicidally effective amount of a composition comprising: as active component 1) the compound (I) methyl (2Z)-3-methoxy-2-[(4-methylbiphenyl-3- yl)oxy]prop-2-enoate and as active component 2) compound (II) which is selected from the group consisting of azoxystrobin (11-1), picoxystrobin (I I-2), trifloxystrobin (I I-3), metominostrobin (II-4) and the agriculturally acceptable salts thereof.

2. The method according to claim 1, wherein the composition comprises as compound (II) azoxystrobin (11-1).

3. The method according to claim 1, wherein the composition comprises as compound (II) picoxystrobin (II-2).

4. The method according to claim 1, wherein the composition comprises as compound (II) trifloxystrobin (II-3).

5. The method according to claim 1, wherein the composition comprises as compound (II) metominostrobin (II-4).

6. The method according to any of claims 1 to 5, wherein the weight ratio of the compound (I) to compound (I I) is from 15: 1 to 1 : 15.

7. The method according to any of claims 1 to 6, wherein the weight ratio of the compound (I) to compound (I I) is from 10: 1 to 1 : 10.

8. The method according to any of claims 1 to 7, wherein the weight ratio of the compound (I) to compound (II) is from 8:1 to 1:8.

9. The method according to any of claims 1 to 8, wherein the weight ratio of the compound(I) to compound (II) is from 4:1 to 1:4.

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