Fungicidal composition

Abstract

Disclosed is a composition suitable for controlling diseases caused by plant pathogens, comprising: (A) a compound of formula (I) wherein R1 is a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C3 alkoxy C1-C3 alkyl group, a C3-C5 cycloalkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group; r2 is hydrogen, a C1-C3 alkyl group, a C1-C3 alkoxy group, or a C3-C5 cycloalkyl group; r3 is a C1-C6 alkyl group; r4 is hydrogen or fluorine, and A is 1, 4-phenyl or 2, 5-thienyl; and (B) at least one compound selected from compounds of which their fungicidal activity is known; and to a method for controlling diseases on useful plants, in particular rust on soybeans or cereals. # imgabs0 #

Description

[0001] The present invention relates to novel fungicidal compositions suitable for controlling diseases caused by phytopathogenic fungi, especially Phakopsora pachyrhizi (the causative agent of Asian soybean rust), and to a method of controlling diseases on useful plants, especially soybeans.

[0002] It is known from WO 2019 / 131867 and WO 2020 / 256113 that certain oxadiazole derivatives and mixtures comprising the oxadiazole derivatives have biological activity against plant pathogenic fungi. On the other hand, various fungicidal compounds of different chemical classes are well known as plant fungicides for use in various cultivated plant crops. However, crop tolerance and activity against plant pathogenic plant fungi do not always meet the needs of agricultural practice in many cases and aspects. For example, Psora pachyrhizi (the pathogen of Asian soybean rust) has become an increasingly important problem in soybean production, resulting in considerable yield losses. Many conventional fungicides are not suitable for controlling Asian soybean rust, or their effects against Psora pachyrhizi are unsatisfactory.

[0003] Brief description of the invention

[0004] In view of the need for improved crop tolerance and / or improved activity against plant pathogenic fungi (such as Puccinia pachyrhizi) in the above-mentioned agricultural practice, a novel composition suitable for controlling diseases caused by plant pathogens is proposed according to the present invention, the composition comprising:

[0005] (A) a compound having formula I:

[0006]

[0007] Where R 1 is C1-C6 alkyl, C1-C6 haloalkyl, C1-C3 alkoxy-C1-C3 alkyl, C3-C5 cycloalkyl, C2-C4 alkenyl, C2-C4 alkynyl; R 2 is hydrogen, C1-C3 alkyl, C1-C3 alkoxy or C3-C5 cycloalkyl; R 3 is a C1-C6 alkyl group; R 4 is hydrogen or fluorine, and A is 1,4-phenyl or 2,5-thienyl; and

[0008] (B) at least one compound selected from the group consisting of flufenoxadiazam, inpyrfluxam, metaylpicoxamid, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate, methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate and methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate.

[0009] It has been found that the combined use of component (B) with component (A) unexpectedly and substantially enhances the effectiveness of the latter against fungi, and vice versa. In addition, the method of the present invention is effective against a wider spectrum of such fungi than those fungi that can be combated with the active ingredients of the method when used independently and alone.

[0010] Another aspect of the invention relates to a method for controlling diseases caused by plant pathogens on useful plants or on their propagation materials, which method comprises applying a composition according to the invention to these useful plants, their place or their propagation materials. Preferably, a method comprises applying a composition according to the invention to useful plants or their place, more preferably to useful plants. Further preferably, a method comprises applying a composition according to the invention to the propagation material of useful plants.

[0011] Another aspect of the present invention relates to a method of controlling leaf spot on plants, which method comprises applying to the plants, the locus thereof or their propagation material a composition according to the present invention comprising a compound of formula (I).

[0012] Detailed description of the invention

[0013] In each case, the compounds of formula I according to the invention are in free form, oxidized form (such as N-oxides), or salt form (for example agronomically usable salt forms).

[0014] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, by A. Albini and S. Pietra in 1991 in the book "Heterocyclic N-oxides", CRC Press, Boca Raton.

[0015] The compounds of the present invention may have asymmetric centers, chiral axes and chiral planes, as described, for example, in EL Elel and SH Wilen, Stereochemistry of Carbon Compounds, John Wiley & Sons, New York 1994, pp. 1119-1190, and may exist as racemates, racemic mixtures, and individual diastereomers, wherein all possible isomers and mixtures thereof (including optical isomers) are included in the present invention. In addition, the compounds disclosed herein may exist as tautomers, and both tautomeric forms are intended to be covered by the scope of the present invention, even if only one tautomeric structure is depicted.

[0016] In the case of the presence of asymmetric carbon atoms in compounds of formula I, the compounds may exist in the form of optical isomers (i.e., enantiomers or diastereomers). As a result of restricted rotation around a single bond, atropisomers may also exist. The present invention includes all those possible isomeric forms of compounds of formula I and mixtures thereof. Likewise, formula I is intended to include all possible tautomers. The present invention includes all possible tautomeric forms of compounds of formula I, and also includes racemic compounds, i.e., mixtures of at least two enantiomers in a substantially 50:50 ratio.

[0017] When any variable or substituent (such as R 1 ) occurs more than one time in any constituent, its definition on each occurrence is independent of its definition at every other occurrence. Also, combinations of substituents and variables are permissible only if such combinations result in stable compounds.

[0018] A line drawn from a substituent into a ring system indicates that the indicated bond may be attached to any of the substitutable ring carbon atoms or heteroatoms (including a carbon atom or heteroatom as the point of attachment). If the ring system is polycyclic, it is intended that the bond may be attached to any of the suitable carbon atoms or heteroatoms of any ring.

[0019] It should be understood that one of ordinary skill in the art can select substituents and substitution patterns on the compounds of the present invention to provide compounds that are chemically stable and can be easily synthesized from readily available starting materials by techniques known in the art and those described below. If a substituent itself is substituted with more than one group, it should be understood that these multiple groups can be on the same carbon or on different carbons, as long as a stable structure is produced. The phrase "optionally substituted with one or more substituents" should be considered equivalent to the phrase "optionally substituted with at least one substituent", and in such cases, preferred embodiments will have zero to three substituents.

[0020] As used herein, "alkyl" is intended to include both branched and straight-chain aliphatic hydrocarbon groups with a specified number of carbon atoms. For example, C1-C6 as in "C1-C6" is defined to include groups having 1, 2, 3, 4, 5 or 6 carbons arranged in a straight or branched chain. For example, "C1-C6 alkyl" specifically includes methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, and stereoisomers thereof. As used herein, the terms "C1-C6 alkyl" and "C1-C3 alkoxy" are intended to include branched or straight-chain alkyl groups with a specified number of carbon atoms.

[0021] As used herein, "cycloalkyl" is intended to include non-aromatic cyclic hydrocarbon groups having a specified number of carbon atoms, which may or may not be bridged or structurally restricted. Examples of "C3-C5 cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, and cyclopentyl.

[0022] As used herein, the term "alkoxy" refers to an alkyl group with the indicated number of carbon atoms attached through an oxygen bridge. As used herein, the term C1-C3 alkoxy-C1-C3 alkyl refers to an ether group, where, for example, C1 alkoxy-C1 alkyl refers to a methoxymethyl ether group having the formula -CH2-O-CH3.

[0023] The term "alkenyl" refers to a straight, branched or cyclic non-aromatic hydrocarbon group containing 2 to 10 carbon atoms and at least one carbon-carbon double bond. Preferably there is one carbon-carbon double bond, and up to 4 non-aromatic carbon-carbon double bonds may be present. Thus, "C2-C4 alkenyl" means an alkenyl group having 2 to 4 carbon atoms. Alkenyl groups include vinyl, propenyl and butenyl. As described above for allyl, the straight, branched or cyclic portion of the alkenyl group may contain double bonds and may be substituted if a substituted alkenyl group is indicated.

[0024] The term "alkynyl" refers to a straight or branched hydrocarbon group containing 2 to 4 carbon atoms and at least one carbon-carbon triple bond. There may be up to 2 carbon-carbon triple bonds. Thus, "C2-C4 alkynyl" means an alkynyl group having 2 to 4 carbon atoms. Alkynyl groups include ethynyl, propynyl and butynyl. As described above with respect to alkyl, if a substituted alkynyl group is indicated, the straight or branched portion of the alkynyl group may be substituted.

[0025] As will be appreciated by those skilled in the art, "halo" or "halogen" as used herein is intended to include chloro, fluoro, bromo, and iodo.

[0026] The salts of the compounds of formula I of the present invention advantageously include those compounds which can be prepared using a pK a Conventional salts formed from inorganic and organic acids with an A / D content of less than about 4. For example, these salts include those derived from inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, sulfamic acid, phosphoric acid, nitric acid, hexafluorophosphate, perchlorate, tetrafluoroborate, hexafluoroantimonate, tetraarylborate, and the like; and salts prepared from organic acids such as acetic acid, propionic acid, succinic acid, glycolic acid, stearic acid, lactic acid, malic acid, tartaric acid, citric acid, ascorbic acid, maleic acid, hydroxymaleic acid, phenylacetic acid, glutamic acid, benzoic acid, salicylic acid, sulfanilic acid, 2-acetoxy-benzoic acid, fumaric acid, toluenesulfonic acid, methanesulfonic acid, ethanedisulfonic acid, oxalic acid, isethionic acid, trifluoroacetic acid, and the like. Agrochemically acceptable salts of the compounds of the present invention include conventional non-toxic salts of the compounds of the present invention such as those formed from inorganic or organic acids. For example, conventional non-toxic salts include those derived from inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, sulfamic acid, phosphoric acid, nitric acid and the like; and salts prepared from organic acids such as acetic acid, propionic acid, succinic acid, glycolic acid, stearic acid, lactic acid, malic acid, tartaric acid, citric acid, ascorbic acid, pamoic acid, maleic acid, hydroxymaleic acid, phenylacetic acid, glutamic acid, benzoic acid, salicylic acid, sulfanilic acid, 2-acetoxy-benzoic acid, fumaric acid, toluenesulfonic acid, methanesulfonic acid, ethanedisulfonic acid, oxalic acid, isethionic acid, trifluoroacetic acid and the like.

[0027] The agrochemically acceptable salt of the compound of the present invention can be synthesized from the compound of the present invention containing alkaline or acidic parts by conventional chemical methods. Usually, the salt of the basic compound is prepared by ion exchange chromatography or by reacting the free alkali with a stoichiometric amount or an excessive amount of the desired salified inorganic or organic acid in a suitable solvent or various combinations of solvents. Similarly, the salt of the acidic compound is formed by reaction with a suitable inorganic or organic base.

[0028] Preferred compositions are those comprising:

[0029] (A) Compounds having formula I

[0030]

[0031] Where R 1 is C1-C4 alkyl, C1-C2 alkoxy-C1-C2 alkyl, C3-C5 cycloalkyl; R 2 is hydrogen or C3-C5 cycloalkyl; R 3 is a C1-C4 alkyl group; R 4 is hydrogen or fluorine, and A is 1,4-phenyl or 2,5-thienyl; and

[0032] (B) at least one compound selected from the group consisting of fluopicolide, pyraclostrobin, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate, methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate and methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate.

[0033] Preferred embodiments of the present invention are represented by those compositions comprising as component A) a compound of formula (I) wherein R 1 is C1-C3 alkyl or C1-C2 alkoxy C1-C2 alkyl; R 2 is hydrogen; R 3 is methyl; R 4 is fluorine; and A is 2,5-thienyl. The composition according to the invention also comprises all stereoisomers and mixtures thereof in any ratio.

[0034] Preferred compounds of formula (I) are:

[0035] N-[Methoxy-[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]butanamide (Compound A-1.1) according to structure Ia:

[0036]

[0037] 2-Methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]acetamide according to structure Ib (Compound A-1.2):

[0038]

[0039] N-[Methoxy-[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]-2-methyl-propionamide (Compound A-1.3) according to structure Ic:

[0040]

[0041] According to a preferred embodiment, the present invention relates to those compositions comprising as component (B) a fungicide selected from the group consisting of fluopicolide, pyraclostrobin, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionate, methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate and methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate. Advantageously, the composition comprises fungicidally effective amounts of components (A) and (B).

[0042] Particularly preferred compositions according to the invention comprise as component (A) a compound selected from the group consisting of N-[methoxy-[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]butanamide (compound A-1.1), 2-methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]acetamide (compound A-1.2) and N-[methoxy-[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]acetamide (compound A-1.3). 2-Methyl-propionamide (compound A-1.3); and as component (B) a compound selected from the group consisting of fluopicolide, pyraclostrobin, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionic acid methyl ester, N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester and N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester.

[0043] Compound A-1.1, Compound A-1.2 and Compound A-1.3 can advantageously be prepared in a similar manner to that outlined in WO 2020 / 256113.

[0044] Component (B) is known and is referred to above by its so-called ISO common name or its IUPAC name.

[0045] The following preferred components (B) are included in the UK Crop Production Council's Pesticide Manual Online ("E-pesticide Manual") and Alan Wood's Compendium of Pesticide Common Names: trifloxystrobin, fluopyram and pyraclostrobin.

[0046] Methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate is disclosed in WO 2019 / 093522 and WO 2020 / 213739;

[0047] Methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate and methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate are disclosed in WO 2020 / 097012 and WO 2021 / 226234.

[0048] Examples of particularly suitable compounds as component (B) are compounds selected from the following group P: fluazifop, fluopicolide, pyraclostrobin, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate, methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate and methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate.

[0049] Throughout this document, the expression "composition" represents various mixtures or combinations of components (A) and (B), for example in a single "ready-to-use" form, in a combined spray mixture (which mixture consists of separate formulations of the individual active ingredient components) (such as a "tank mix"), and in a combination of individual active ingredients when applied in a sequential manner (i.e., one after the other within a reasonably short period of time, such as a few hours or days). For the practice of the present invention, the order in which components (A) and (B) are applied is not important.

[0050] Further examples of compositions according to the invention comprising three active ingredients are defined as in Examples E1, E2 and E3:

[0051] Preferred embodiment E1:

[0052] The term "TX1" means in this article: "Compound A-1.1 + a compound selected from group P". Preferred examples include the following compositions: flubendiamide + TX1, fluopicolide + TX1, pyraclostrobin + TX1, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionic acid methyl ester + TX1, N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX1 and N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX1.

[0053] Preferred embodiment E2:

[0054] The term "TX2" means in this article: "Compound A-1.2 + a compound selected from group P". Preferred examples include the following compositions: flubendiamide + TX2, fluopyram + TX2, pyraclostrobin + TX2, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionic acid methyl ester + TX2, N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX2 and N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX2.

[0055] Preferred embodiment E3:

[0056] The term "TX3" means in this article: "Compound A-1.3 + a compound selected from group P". Preferred examples include the following compositions: flubendiamide + TX3, fluopicolide + TX3, pyraclostrobin + TX3, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionic acid methyl ester + TX3, N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX3 and N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX3.

[0057] Embodiments E1, E2 and E3 define compositions according to the invention comprising three active ingredients. In the embodiments, the mixed partners selected from group P must be different from the other described mixed partners. For example, the composition "flufenoxazole + TX1" means a composition comprising flufenoxazole, compound A-1.1 + a compound selected from group P as active ingredients. In the composition, the compound selected from group P is different from flufenoxazole.

[0058] The compositions according to the invention are effective against unwanted microorganisms, such as microorganisms which cause phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria.

[0059] The compositions according to the invention are particularly effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Psoralea, Erysiphe, Mycosporium, Mycosphaeria, Uncinaria, Pyrocoel); Basidiomycetes (e.g. Hemileia, Rhizoctonia, Puccinia, Puccinia, Ustilago, Tilletia); Imperfect Fungi (also known as Deuteromycetes; e.g. Botrytis, Helminthosporium, Rhizoctonia, Fusarium, Zymoseptoria, Cercosporium, Alternaria, Pyrosporum and Pseudocercosporium); Oomycetes (e.g. Phytophthora, Peronospora, Pseudocercospora, Albugo, Discoideum, Pythium, Pseudocercoideum, Monoparaceta).

[0060] According to the invention, "useful plants" typically include the following plant species: grapevines; cereals, such as wheat, barley, rye or oats; beets, such as sugar beets or fodder beets; fruits, such as pome, stone or soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oil crops, such as rapeseed, mustard, poppy, olives, sunflowers, coconuts, castor oil plants, cocoa beans or peanuts; cucumber plants, such as apples, gourds, cucumbers or melons; fiber plants such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapefruits or mandarins; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, melons or peppers; lauraceae such as avocado, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar cane; tea; vines; hops; durian; bananas; natural rubber plants; turf or ornamental plants such as flowers, shrubs, broadleaf trees or evergreens such as pines and cypresses. This list does not represent a limitation.

[0061] The term "useful plants" is to be understood as also including useful plants which have been rendered tolerant to herbicides such as bromoxynil or classes of herbicides such as, for example, HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyruvyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors as a result of conventional methods of breeding or genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones such as imazamox by conventional methods of breeding (mutagenesis) are Summer rapeseed (Canola). Clearfield is a registered trademark of BASF Agrochemical Products B.V.

[0062] Examples of crops that have been rendered tolerant to herbicides or herbicides by genetic engineering methods include glyphosate-resistant and glufosinate-resistant maize varieties sold under the trade names Roundup and Herculex and Commercially available. RoundupReady is a registered trademark of Monsanto Technology LLC; Herculex is a registered trademark of Corteva Agriscience LLC; and LibertyLink is a registered trademark of BASF Agricultural Solutions Seed US LLC.

[0063] The term "useful plants" is to be understood as also including useful plants which have been transformed by the use of recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular from the genus Bacillus.

[0064] The term "useful plants" is to be understood as also including useful plants which have been transformed by the use of recombinant DNA techniques so that they can synthesize selectively acting antipathogenic substances, such as, for example, so-called "pathogenesis-related proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants which can synthesize such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818 and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

[0065] The term "location" of useful plants as used herein is intended to include places where useful plants grow, where plant propagation material of useful plants is sown or where plant propagation material of useful plants will be placed in the soil. Examples of such locations are fields where crop plants grow.

[0066] The term "plant propagation material" should be understood to mean the reproductive parts of plants, such as seeds, which can be used for the propagation of plants, and vegetative materials, such as cuttings or tubers (e.g., potatoes). For example, seeds (in the strict sense), roots, fruits, tubers, corms, rhizomes and parts of plants can be mentioned. Germinated plants and young plants that will be transplanted after germination or after emergence can also be mentioned. These young plants can be protected before transplanting by being treated completely or partially via dipping. Preferably, "plant propagation material" should be understood to mean seeds.

[0067] In another aspect, the present application also relates to plant propagation material coated with the composition according to the invention.

[0068] Composition of the present invention can also be used in the field of protecting storage goods from fungal attack. According to the present invention, term "storage goods" should be understood as natural substances and processed forms thereof representing plants and / or animal origin, which are taken from natural life cycle and wish to be protected for a long time. Storage goods of plant origin (such as plants or parts thereof (such as, stalks, leaves, tubers, seeds, fruits or grains)) can be protected in the state of fresh harvest or in processed forms (such as pre-dried, moistened, crushed, ground, pressed or baked). Also falling under the definition of storage goods is wood, whether it is wood in the form of logs, such as building timber, transmission towers and fences, or wood in the form of finished products, such as wooden furniture or objects. Storage goods of animal origin are raw hides, leather, fur, hair etc. Unfavorable effects can be prevented according to composition of the present invention, such as corruption, fading or mildew. Preferably, "storage goods" should be understood as natural substances and / or processed forms thereof representing plants origin, more preferably fruits and processed forms thereof (such as pears, drupes, berries and citrus fruits and processed forms thereof). In another preferred embodiment of the present invention, "stored goods" is understood to mean wood.

[0069] Therefore, another aspect of the present invention is a method for protecting stored goods, which method comprises applying a composition according to the present invention to the stored goods.

[0070] The composition according to the invention can also be used in the field of protecting technical materials from fungal attack. According to the invention, the term "technical material" includes paper; carpets; buildings; cooling and heating systems; wallboards; ventilation and air conditioning systems, etc.; preferably, "technical material" is understood to mean wallboards. The composition according to the invention can prevent adverse effects such as decay, discoloration or mold.

[0071] Furthermore, the compositions according to the invention are particularly effective against seedborne and soilborne diseases, such as Alternaria spp., Ascochyta spp., Botrytis cinerea, Cercospora spp., Claviceps purpurogenum, Cochliobolus graminearum, Colletotrichum spp., Epicoccum spp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusarium gloeosporium, Fusarium graminearum ... graminis, Helminthosporium spp., Pyrenophora graminea, Pyrithosporium spp., Rhizoctonia cerealis, Sclerotinia spp., Zymoseptoria spp., Tilletia spp., Typhula incarnata, Ustilago spp., Ustilago spp., or Verticillium spp.); in particular against pathogens of cereals, such as wheat, barley, rye or oats; maize; rice; cotton; soybeans; turf; sugar beet; rapeseed; potatoes; pulse crops (pulsecrop), such as peas, lentils or chickpeas; and sunflower.

[0072] Furthermore, the compositions according to the invention are particularly effective against post-harvest diseases such as Botrytis cinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotrichum candidum, Psoralea corylifolia, Sclerotinia sclerotiorum, Mucor piriformis, Penicilium italicum, Penicilium solitum, Penicillium digitatum or Penicillium expansum, in particular against pathogens of fruits such as pome fruits (e.g. apples and pears), stone fruits (e.g. peaches and plums), citrus, melon, papaya, kiwi, mango, berries (e.g. strawberries), avocados, pomegranates and bananas, and nuts.

[0073] The compositions according to the invention are particularly useful for controlling the following diseases on the following crops: Blumeria graminis in cereals; Uncinula necator in grapes, Sphaerotheca fuliginea in cucurbits, Puccinia species in cereals, Phakopsora pachyrhizi in soybeans.

[0074] However, in addition to the actual synergistic effect with respect to the fungicidal activity, the compositions according to the invention may also have further unexpected advantageous properties. Examples of such advantageous properties that may be mentioned are: more favorable degradability; improved toxicological and / or ecotoxicological behavior; or improved characteristics of useful plants, including: emergence, crop yield, more developed root system, increased tillering, increased plant height, larger leaves, less basal leaf death, stronger tillering, greener leaf color, less fertilizer required, less seed required, more productive tillering, earlier flowering, earlier grain maturity, less plant lodging (lodging), enhanced shoot growth, improved plant vigor and early germination.

[0075] Some of the compositions according to the invention have systemic action and can be used as foliar, soil and seed treatment fungicides.

[0076] With the compositions according to the invention it is possible to inhibit or destroy phytopathogenic microorganisms which are present on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of various useful plants, while also protecting later growing plant parts from attack by phytopathogenic microorganisms.

[0077] The compositions according to the invention can be applied to phytopathogenic microorganisms, to useful plants threatened by attack by microorganisms, to the locus thereof, to their propagation material, to stored goods or to technological material.

[0078] The compositions according to the invention can be applied before or after the useful plants, their propagation material, stored goods or technical material have been infected with the microorganisms.

[0079] The amount of the composition according to the invention to be applied will depend on various factors, such as the compound used; the object of treatment, such as, for example, plants, soil or seeds; the type of treatment, such as, for example, spraying, dusting or seed dressing; the purpose of the treatment, such as, for example, prevention or treatment; the type of fungus to be controlled or the time of application.

[0080] When applied to useful plants, component (A) is typically applied at a rate of 5 to 2000 g ai / ha, especially 10 to 1000 g ai / ha, for example 50, 75, 100 or 200 g ai / ha, typically in combination with 1 to 5000 g ai / ha, especially 2 to 2000 g ai / ha, for example 100, 250, 500, 800, 1000, 1500 g ai / ha of component (B).

[0081] In agricultural practice, the application rates of the compositions according to the invention depend on the type of action desired and typically range from 20 to 4000 g of total composition per hectare.

[0082] When the composition according to the invention is used to treat seed, a ratio of 0.001 to 50 g of compound of component (A) per kg of seed, preferably 0.01 to 10 g / kg of seed, and 0.001 to 50 g of compound of component (B) per kg of seed, preferably 0.01 to 10 g / kg of seed is generally sufficient.

[0083] The composition of the present invention can be used in any conventional form, for example, in the form of a twin pack, a dry powder for seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water-dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), a water-dispersible granule (WG), an emulsifiable granule (EG), an oil-in-water emulsion (EO), an oil-in-water emulsion (EW), a microemulsion (ME), a dispersible oil suspension (OD), an oil suspension (OF), an oil-soluble liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a master batch (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with an agriculturally acceptable adjuvant.

[0084] Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with at least one suitable inert formulation adjuvant (for example, diluent, solvent, filler and optionally other formulation ingredients, such as surfactant, biocide, antifreeze agent, adhesive, thickener and compound providing auxiliary effect). Conventional slow-release formulations intended to last for a long time can also be used. In particular, formulations to be used in the form of sprays, such as water-dispersible concentrates (for example EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders and granules, can contain surfactants such as wetting agents and dispersants and other compounds providing auxiliary effects, such as condensation products of formaldehyde and naphthalene sulfonates, alkyl aryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0085] The compositions according to the invention may also comprise additional pesticides, such as, for example, fungicides, insecticides or herbicides.

[0086] The seed dressing formulation is applied to the seed in a manner known per se using the composition according to the invention and a diluent in the form of a suitable seed dressing formulation, for example as an aqueous suspension or in the form of a dry powder with good adhesion to the seed. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example as slow-release capsules or microcapsules.

[0087] Typically, the formulation comprises 0.01% to 90% by weight of an active agent, 0 to 20% of an agriculturally acceptable surfactant, and 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants, the active agent being composed of at least a compound of component (A) together with a compound of component (B), and optionally other active agents (particularly microbicides or preservatives, etc.). The concentrated form of the composition typically contains between about 2% and 80% by weight, preferably between about 5% and 70% of the active agent. The application form of the formulation may, for example, contain 0.01% to 20% by weight, preferably 0.01% to 5% by weight of the active agent. However, commercial products will preferably be formulated as concentrates, and end users will typically use diluted formulations. The additional features of the composition comprising a compound of formula (I), the method of applying it to plants, and its use ratio are as described for the composition comprising a compound of formula (I) and additionally at least one component (B) as described above. Their application can be before and after these plants or their parts are infected by fungi. Preferably, treatment is carried out before infection. When the compound with formula (I) is used by itself, the application rate in the method according to the present invention is as described above, for example, typically 5 to 2000 g ai. / ha, particularly 10 to 1000 g ai / ha, for example a ratio of 50, 75, 100 or 200 g ai / ha. During the growing season, the compound with formula (I) can be applied to these plants once or more than once. In order to use in the method according to the present invention, the compound with formula (I) can be converted into the conventional formulation described above, such as solution, emulsion, suspension, dust, powder, paste and granule. The use form will depend on the specific intended purpose; in each case, it should ensure the fine and uniform distribution of the compound with formula (I).

[0088] The term "plants" as used herein includes seedlings, shrubs and crops of fruits and vegetables.

[0089] The following examples are used to illustrate the present invention, "active ingredient" means a mixture of component (A) and component (B) in a specific mixing ratio. The same formulation can be used in a composition containing only the compound of formula (I) as the active ingredient.

[0090] Preparation Examples

[0091]

[0092] The active ingredient is mixed thoroughly with the other formulation components and the mixture is thoroughly ground in a suitable grinder to give wettable powders which can be diluted with water to provide a suspension having the desired concentration.

[0093]

[0094] The active ingredient is thoroughly mixed with other formulation components and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.

[0095] Emulsifiable concentrates

[0096]

[0097] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0098]

[0099] Ready-to-use dusts are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing of seeds.

[0100]

[0101] The active ingredient is mixed and ground with the other formulation components, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0102] Suspension concentrates

[0103]

[0104] The finely ground active ingredient is thoroughly mixed with the other formulation components to give a suspension concentrate which can be diluted in water in any desired ratio. Using such a dilution, living plants and plant propagation materials can be treated and protected from microbial infestation by spraying, pouring or immersion.

[0105] Flowable concentrate for seed treatment

[0106]

[0107]

[0108] The finely ground active ingredient is thoroughly mixed with other formulation components to obtain a suspension concentrate which can be further diluted in water for application to seeds. Using such a dilution, the propagation material can be treated and protected from microbial infestation by spraying, pouring or dipping.

[0109] Therefore, another aspect of the invention is a method of controlling leaf spot on plants, which method comprises applying to the plants, the locus thereof or their propagation material a composition comprising a compound of formula (I).

[0110] Preferred is the method wherein the plant pathogen is Phakopsora pachyrhizi.

[0111] Preference is given to a method which comprises applying a composition comprising a compound of formula (I) to plants or the locus thereof, preferably to these plants.

[0112] Further preferred is a method which comprises applying a composition comprising a compound of formula (I) to propagation material of a plant.

[0113] The method according to the invention, in particular when a compound of formula (I) is used in combination with at least one compound (B) as described above, also allows good control of other frequently encountered harmful fungi in plants.

[0114] Preference is given to a method of controlling diseases on soybeans, especially caused by rust, which method comprises applying to these useful plants, their locus or their propagation material a composition comprising a compound of formula (I)

[0115]

[0116] Where R 1 is C1-C6 alkyl, C1-C6 haloalkyl, C1-C3 alkoxy-C1-C3 alkyl, C3-C5 cycloalkyl, C2-C4 alkenyl, C2-C4 alkynyl; R 2 is hydrogen, C1-C3 alkyl, C1-C3 alkoxy or C3-C5 cycloalkyl; R 3 is a C1-C6 alkyl group; R 4 is hydrogen or fluorine, and A is 1,4-phenyl or 2,5-thienyl.

[0117] Typically, the weight ratio of component (A) to component (B) is in the range of 2000:1 to 1:1000. The weight ratio of component (A) to component (B) is preferably 100:1 to 1:100; more preferably 20:1 to 1:50, still more preferably 12:1 to 1:25; still more preferably 10:1 to 1:10, again more preferably 5:1 to 1:15; and most preferably 2:1 to 1:5.

[0118] It has been found that, unexpectedly, certain weight ratios of component (A) to component (B) can produce synergistic activity. Therefore, another aspect of the present invention is such a composition, wherein component (A) and component (B) are present in the composition in an amount that produces a synergistic effect. This synergistic activity is apparent from the fact that the fungicidal activity of the composition comprising component (A) and component (B) is greater than the sum of the fungicidal activities of component (A) and component (B). This synergistic activity expands the scope of action of component (A) and component (B) in two ways. First, the application rate of component (A) and component (B) is reduced, but the effect remains equally good, which means that even if the two individual components have become completely ineffective within such a low application rate range, the active ingredient mixture still achieves a high degree of plant pathogen control. Second, the spectrum of plant pathogens that can be controlled is greatly widened.

[0119] A synergistic effect exists whenever the effect of the active ingredient combination is greater than the sum of the effects of the individual components. For a given active ingredient combination, the expected effect E obeys the so-called COLBY formula and can be calculated as follows (COLBY, SR "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pp. 20-22; 1967):

[0120] ppm = milligrams of active ingredient (=ai) per liter of spray mixture

[0121] X = effect of active ingredient A) in %, p ppm of active ingredient used

[0122] Y = action in % of active ingredient B), q ppm of active ingredient used.

[0123] According to Kolby, using p+q ppm of active ingredient, the expected (additive) effect of active ingredient A) + B) is

[0124] If the effect actually observed (O) is greater than the expected effect (E), then the effect of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms, synergy corresponds to a positive value of the difference (OE). In the case of a superposition of completely complementary activities (expected activity), the difference (OE) is zero. A negative value of the difference (OE) indicates a loss of activity compared to the expected activity.

Claims

1. A composition suitable for controlling diseases caused by plant pathogens, comprising: (A) at least one compound having formula I or an agrochemically acceptable salt or N-oxide thereof: Where R 1 It is C1-C6 alkyl, C1-C6 halogenated alkyl, C1-C3 alkoxy-C1-C3 alkyl, C3-C5 cycloalkyl, C2-C4 alkenyl, C2-C4 alkynyl; R 2 is hydrogen, C1-C3 alkyl, C1-C3 alkoxy or C3-C5 cycloalkyl; R 3 is a C1-C6 alkyl group; R 4 is hydrogen or fluorine, and A is 1,4-phenyl or 2,5-thienyl; and (B) at least one compound selected from the group consisting of fluopicolide, fluopicolide, pyraclostrobin, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionic acid methyl ester, N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester and N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester; or a combination thereof.

2. The composition according to claim 1, wherein In compound (A), R 1 is C1-C4 alkyl, C1-C2 alkoxy, C1-C2 alkyl, or C3-C5 cycloalkyl; R 2 is hydrogen or C3-C5 cycloalkyl; R 3 is C1-C4 alkyl; R 4 is hydrogen or fluorine, and A is 1,4-phenyl or 2,5-thienyl.

3. The composition according to any one of claims 1 to 2, wherein (A) comprising a compound selected from the group consisting of: N-[methoxy-[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]butanamide according to structure Ia (Compound A-1.1): 2-Methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]acetamide (Compound A-1.2) according to structure Ib: N-[Methoxy-[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]-2-methyl-propionamide (Compound A-1.3) according to structure Ic: or an agrochemically acceptable salt or N-oxide thereof, or a mixture of any one of compounds A-1.1, A-1.2 and A-1.3, or a plurality of agrochemically acceptable salts or N-oxides thereof.

4. The composition according to any one of claims 1 to 3, comprising as component (B) a fungicidally effective amount of a compound selected from the group consisting of fluazifop, fluopyram, pyraclostrobin, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate, methyl N-[[5-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate and methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate, or a combination thereof.

5. The composition according to any one of claims 1 to 4, wherein The weight ratio of component (A) to component (B) is in the range of 2000:1 to 1:1000.

6. The composition according to any one of claims 1 to 5, comprising one or more additional pesticides, preferably one or more additional fungicides, insecticides or herbicides.

7. A method for controlling diseases on useful plants or on their propagation material caused by phytopathogens, which method comprises applying a composition according to any one of claims 1 to 6 to the useful plants, their locus or their propagation material.

8. The method according to claim 7, which comprises applying a fungicidally effective amount of a composition according to any one of claims 1 to 6 to the useful plants, their locus or their propagation material.

9. The method according to claim 7 or 8, wherein: The plant pathogen attacks plants and causes disease, preferably wherein the plant pathogen is rust.

10. The method according to claim 9, wherein: The plants include soybeans and / or corn.

11. A method according to any one of claims 7 to 10 comprising applying component (A) at a rate of 5 to 2000 g ai / ha in conjunction with 1 to 5000 g ai / ha of component (B).

12. A method according to any one of claims 7 to 10, comprising applying 0.001 to 50 g of at least one compound of component (A) per kg of plant propagation material, in particular seeds, and 0.001 to 50 g of at least one compound of component (B) per kg of plant propagation material, in particular seeds.

13. The method according to claim 12, wherein: The components (A) and (B) are applied simultaneously or sequentially.

14. A coated plant propagation material, in particular seeds, comprising a coating comprising a composition according to any one of claims 1 to 6.

15. Use of a composition according to any one of claims 1 to 6 for controlling diseases caused by phytopathogens, in particular rusts, on useful plants, more particularly including soybeans and / or cereals, and / or for enhancing the growth of such useful plants.

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