Bactericidal composition

Abstract

A fungicidal composition comprising a mixture of components (A) and (B), in which component (A) is an aureobasidin, and use of the composition in agriculture or horticulture for controlling or preventing infection of plants by phytopathogenic microorganisms, preferably fungi.

Description

[Technical field]

[0001] The present invention relates to novel fungicidal compositions for treating phytopathogenic diseases on useful plants, in particular caused by phytopathogenic fungi, and to a method for controlling such diseases and / or fungi on useful plants. [Background technology]

[0002] Although many fungicidal compounds belonging to various different chemical classes have been / are being developed for use as fungicides in crops of useful plants, the resistance and efficacy of the crops against certain phytopathogenic fungi do not always meet the requirements of agricultural practice in many respects. WO 2018 / 102345 discloses the use of Aureobasidin A as an agricultural fungicide for treating, preventing or controlling fungal infections in plants and seeds. Aureobasidin A is an antifungal cyclic depsipeptide antibacterial agent produced by Aureobasidium pullulans. See, for example, Takesako et al., The Journal of Antibiotics, 1991, 44, 919-924.

[0003] However, there continues to be a need to find new compositions with superior biological properties for use in controlling or preventing plant infestation by phytopathogenic fungi, such as compositions with a broader spectrum of activity, improved crop resistance, synergistic interactions or enhancing properties, or compositions that exhibit a more rapid onset of action or have longer lasting residual activity, or that allow for fewer applications and / or reduced rates of application of compounds and compositions required for effective control of plant pathogens, thereby allowing for beneficial resistance management practices, reduced environmental impact, and reduced worker exposure.

[0004] Compositions containing mixtures of different fungicidal compounds with different mechanisms of action can be used to meet some of these demands (eg, by combining fungicides with different spectra of activity). Summary of the Invention [Means for solving the problem]

[0005] According to the present invention, there is provided a fungicidal composition comprising as active ingredients a mixture of components (A) and (B), wherein component (A) is a cyclic depsipeptide of formula (I-A1): [ka] or its stereoisomers; and Ingredient (B) is a histone deacetylase inhibitor: Ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1, 2,4-Oxadiazol-3-yl]phenyl]methyl]propanamide, 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-Dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-Ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoro 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one n-propyl]-1,2,4-triazol-3-amine, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-Oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate, N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(E)- N-Methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-N-Methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoic acid, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate or ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, or a salt, enantiomer, tautomer or N-oxide thereof is selected from the group consisting of:

[0006] Preferably, the fungicidal composition comprises as active ingredients a mixture of components (A) and (B), where component (A) is a cyclic depsipeptide of formula (I-A1): [ka] or a stereoisomer thereof, Ingredient (B) is a histone deacetylase inhibitor: Ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy- 3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, or a salt, enantiomer, tautomer or N-oxide thereof.

[0007] Disclosed herein are compositions comprising a mixture of components (A) and (B), where component A is a cyclic depsipeptide of formula (I): [ka] (In the formula, R 1 is methyl, ethyl, 1-hydroxyethyl or 2-hydroxyethyl; A 1 is an α-amino acid residue selected from the group consisting of N-methyl-L-valine (L-MeVal) and L-valine (L-Val) residues; A 2is an α-amino acid residue selected from the group consisting of L-phenylalanine (L-Phe), ortho-fluoro-L-phenylalanine (Lo-FPhe), meta-fluoro-L-phenylalanine (Lm-FPhe), L-tyrosine (L-Tyr), L-cyclohexylalanine (L-Cha), O-acetyl-L-tyrosine [L-Tyr(Ac)], On-hexanoyl-L-tyrosine [L-Tyr(n-hexanoyl)], O-benzoyl-L-tyrosine [L-Tyr(Bzl)] and persephanine residues; A 3are N-methyl-L-phenylalanine (L-MePhe), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), ortho-fluoro-N-methyl-L-phenylalanine (LoF-MePhe), meta-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), para-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), meta-bromo-N-methyl-L-phenylalanine (Lm-Br-MePhe), para-bromo-N-methyl Br-MePhe, meta-iodo-N-methyl-L-phenylalanine (LmI-MePhe), para-iodo-N-methyl-L-phenylalanine (LpI-MePhe), 3-phenyl-N-methyl-L-phenylalanine, 4-phenyl-N-methyl-L-phenylalanine, 3-(4-fluorophenyl)-N-methyl-L-phenylalanine, 4-(4-fluorophenyl)-N-methyl-L-phenylalanine, 3-(4-pyridinyl)-N-methyl-L-phenylalanine, 4-( 4-pyridinyl)-N-methyl-L-phenylalanine, 3-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-4-pyridinyl)-N-methyl-L-phenylalanine, 3-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 3-[4-(piperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4-(piperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4-(4-methylpiperazin-1-yl)phen-1-yl]phenyl-N-methyl-L-phenylalanine, β-oxo-N-methyl-L-phenylalanine (L-β-oxo-MePhe), β-acetoxy-N-methyl-L-phenylalanine (L-β-AcO-MePhe), N-methyl-L-tyrosine (L-MeTyr),an α-amino acid residue selected from the group consisting of O-methyl-N-methyl-L-tyrosine [L-MeTyr(Me)], N-methyl-L-alanine (L-MeAla), N-methyl-L-serine (L-MeSer), N-methyl-D-phenylalanine (D-MePhe), N-methyl-D-alanine (D-MeAla), N-methyl-D-valine (D-MeVal), N-methyl-D-serine (D-MeSer), N-methyl-sarcosine (MeSar) and N-methyl-L-serine (L-MeSer) residues; A 4 is an α-amino acid residue selected from the group consisting of L-proline (L-Pro), L-thioproline (L-SPro) and 4-hydroxy-L-proline (L-4Hyp) residues; A 5 is an α-amino acid residue selected from the group consisting of L-allo-isoleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle), L-norvaline (L-Nva) and L-valine (L-Val) residues; A 6 is an α-amino acid residue selected from the group consisting of N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), N-methyl-L-allo-isoleucine (L-MeAIle) and L-valine (L-Val) residues; A 7 is an α-amino acid residue selected from the group consisting of L-leucine (L-Leu), L-allo-isoleucine (L-AIle) and L-norvaline (L-Nva) residues; and A 8 are β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), γ-hydroxy-N-methyl-L-valine (L-γ-OH-MeVal), N-methyl-L-valine (L-MeVal), L-valine (L-Val), and N-methyl-2,3-didehydro-L-valine (L-MeDH). 2,3 Val), N-methyl-3,4-didehydro-L-valine (L-MeDH 3,4Val), N-methyl-L-phenylalanine (L-MePhe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), N-methyl-L-threonine (L-MeThr), sarcosine (Sar) and N,β-dimethyl-L-aspartic acid (LN,β-MeAsp) residues. or its stereoisomers; and Ingredient (B) is a histone deacetylase inhibitor: Ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1, 2,4-Oxadiazol-3-yl]phenyl]methyl]propanamide, 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-Dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-Ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoro 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one n-propyl]-1,2,4-triazol-3-amine, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-Oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate, N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(E)-N -Methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoic acid, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, or ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, or a salt, enantiomer, tautomer or N-oxide thereof.

[0008] In general, the mass ratio of component (A) to component (B) can be from 100:1 to 1:1000, preferably from 100:1 to 1:500, more preferably from 50:1 to 1:200, even more preferably from 50:1 to 1:20, even more preferably from 30:1 to 1:1, and even more preferably from 10:1 to 3:1.

[0009] In some preferred embodiments of the present invention, the weight ratio of component (A) to component (B) may be 1:1, or 1:2, or 1:4, or 1:8, or 2:1, or 4:1, or 8:1, or 16:1, or 20:1, or 1:200, or 1:100, or 1:50, or 1:25, or 1:20, or 1:12.5, or 1:10, or 1:6.2, or 1:5, or 1:2.5, or 2:1, or 3:1, or 10:1, or 20:1, or 30:1.

[0010] According to a second aspect of the present invention, there is provided a method for controlling or preventing phytopathogenic diseases, in particular caused by phytopathogenic fungi, in useful plants or their propagation material, comprising applying a composition as defined in the present invention to a useful plant, its habitat or its propagation material. Preferred is a method comprising applying a composition according to the present invention to a useful plant or its habitat, more preferably to a useful plant. Further preferred is a method comprising applying a composition according to the present invention to propagation material of a useful plant.

[0011] According to a third aspect of the present invention there is provided the use of a composition comprising component (A) and component (B) as defined in the present invention as a fungicide.

[0012] It has been found that the use of the compound of formula (IA-1) in combination with the compound of component (B) and, optionally, with the compound of component (C) can unexpectedly and substantially increase the effectiveness of the compound of formula (IA-1) against fungi, and vice versa.Also, the use of the composition of the present invention can be effective against a broader range of such fungi than can be controlled by the individual active ingredients when used alone.

[0013] The benefits conferred by particular fungicidal compositions according to the invention may include, in particular, advantageous levels of biological activity for protecting plants against diseases caused by fungi, or superior properties for use as an active pesticide ingredient (e.g. high biological activity, advantageous activity spectrum, increased safety profile, improved physicochemical properties, or increased biodegradability). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] As used herein, the term "cyclic depsipeptide" refers to a peptide that is a peptide consisting of consecutive units derived from 2-hydroxy-3-methylalkanoic acid and the α-amino acid A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 and a unit derived from the α-amino acid residue A 8 is linked to 2-hydroxy-3-methylalkanoic acid via the ester group -OCH(CH(CH3)R 1 ) part to form -C(=O)OCH(CH(CH3)R 1 ) moiety, and α-amino acid residue A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 are linked to each other via a peptide bond. The 2-hydroxy-3-methylalkanoic acid can be 2(R)-hydroxy-3(R)-methylpentanoic acid or 2(R)-hydroxy-3-methylbutanoic acid.

[0015] As used herein, the terms "hydroxyl" or "hydroxy" refer to an --OH group.

[0016] As used herein, the term "C1-C4 alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having 1-4 carbon atoms, and attached to the remainder of the molecule by a single bond. Examples of C1-C4 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1,1-dimethylethyl (t-butyl). A "C1-C4 alkylene" group refers to the corresponding definition of C1-C4 alkyl, except that such group is attached to the remainder of the molecule by two single bonds. Examples of C1-C4 alkylene groups are methylene (-CH2-) and hydroxymethylene (-CH(OH)-).

[0017] Disclosed in the present invention are one or more cyclic depsipeptides of formula (IA): [ka] (In the formula, R 1 is methyl or ethyl; X 1 , X 2 and X 3 Each of X is hydrogen or 1 , X 2 and X 3 is hydrogen, fluorine or hydroxyl, with the proviso that X 1 , X 2 and X 3 is fluorine or hydroxyl; X 4 is S, methylene, or hydroxymethylene; A 3are N-methyl-L-phenylalanine (L-MePhe), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), ortho-fluoro-N-methyl-L-phenylalanine (LoF-MePhe), meta-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), para-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), meta-bromo-N-methyl-L-phenylalanine (Lm-Br-MePhe), para-bromo-N-methyl Br-MePhe, meta-iodo-N-methyl-L-phenylalanine (LmI-MePhe), para-iodo-N-methyl-L-phenylalanine (LpI-MePhe), 3-phenyl-N-methyl-L-phenylalanine, 4-phenyl-N-methyl-L-phenylalanine, 3-(4-fluorophenyl)-N-methyl-L-phenylalanine, 4-(4-fluorophenyl)-N-methyl-L-phenylalanine, 3-(4-pyridinyl)-N-methyl-L-phenylalanine, 4-( 4-pyridinyl)-N-methyl-L-phenylalanine, 3-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-4-pyridinyl)-N-methyl-L-phenylalanine, 3-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 3-[4-(piperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4-(piperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4-(4-methylpiperazin-1-yl)phen-1-yl]phenyl-N-methyl-L-phenylalanine, β-oxo-N-methyl-L-phenylalanine (L-β-oxo-MePhe), β-acetoxy-N-methyl-L-phenylalanine (L-β-AcO-MePhe), N-methyl-L-tyrosine (L-MeTyr),an α-amino acid residue selected from the group consisting of O-methyl-N-methyl-L-tyrosine [L-MeTyr(Me)], N-methyl-L-alanine (L-MeAla), N-methyl-L-serine (L-MeSer), N-methyl-D-phenylalanine (D-MePhe), N-methyl-D-alanine (D-MeAla), N-methyl-D-valine (D-MeVal), N-methyl-D-serine (D-MeSer) and N-methyl-L-serine (L-MeSer) residues; A 5 is an α-amino acid residue selected from the group consisting of L-allo-isoleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle), L-norvaline (L-Nva) and L-valine (L-Val) residues; A 6 is an α-amino acid residue selected from the group consisting of N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), N-methyl-L-allo-isoleucine (L-MeAIle) and L-valine (L-Val) residues; A 7 is an α-amino acid residue selected from the group consisting of L-leucine (L-Leu), L-allo-isoleucine (L-AIle) and L-norvaline (L-Nva) residues; and A 8 are β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), γ-hydroxy-N-methyl-L-valine (L-γ-OH-MeVal), N-methyl-L-valine (L-MeVal), L-valine (L-Val), and N-methyl-2,3-didehydro-L-valine (L-MeDH). 2,3 Val), N-methyl-3,4-didehydro-L-valine (L-MeDH 3,4 Val), N-methyl-L-phenylalanine (L-MePhe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), N-methyl-L-threonine (L-MeThr), sarcosine (Sar) and N,β-dimethyl-L-aspartic acid (LN,β-MeAsp) residues. Compound (A) comprises:

[0018] The compound of formula (I) is selected from compounds 1.001 to 1.035 listed in Table A (below) or compounds 2.001 to 2.045 listed in Table B (below).

[0019] The following list includes substituents R for compounds of formula (I): 1 , A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 For any one of these substituents, any of the definitions given below may be combined with any of the definitions of any other substituents given below or elsewhere in this specification.

[0020] Table A: This table discloses 35 compounds of formula (I), wherein R 1 , A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 are as set forth in Table A below.

[0021] [Table 1] JPEG2024540501000006.jpg173170

[0022] Table B: This table discloses 45 compounds of formula (I), wherein R 1 is ethyl, and A 1 is L-MeVal, and A 4 is L-Pro, and A 6 is L-MeVal, and A 7 is L-Leu, and A 2 , A3 , A 5 and A 8 are as set forth in Table B below.

[0023] [Table 2] JPEG2024540501000008.jpg253170

[0024] In a first variant of this first embodiment of the invention, component (A) is a cyclic depsipeptide of formula (I-A1), hereinafter referred to as aureobasidin A: [ka] or a stereoisomer thereof.

[0025] As used herein, the term "aureobasidin A" refers to a cyclic depsipeptide of formula (I-A1) consisting of consecutive units derived from 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-phenylalanine (L-Phe), N-methyl-L-phenylalanine (L-MePhe), L-proline (L-Pro), L-allo-isoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu) and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), or a stereoisomer thereof.

[0026] Component (A) further comprises a cyclic depsipeptide of formula (I-A2), hereinafter referred to as aureobasidin E: [ka] or a stereoisomer thereof.

[0027] As used herein, the term "aureobasidin E" refers to a cyclic depsipeptide of formula (I-A2) consisting of consecutive units derived from 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), L-proline (L-Pro), L-allo-isoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu) and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), or a stereoisomer thereof.

[0028] Component (A) further comprises a cyclic depsipeptide of formula (I-A3), hereinafter referred to as aureobasidin G: [ka] or a stereoisomer thereof.

[0029] As used herein, the term "aureobasidin G" refers to a cyclic depsipeptide of formula (I-A3) consisting of consecutive units derived from 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-phenylalanine (L-Phe), N-methyl-L-phenylalanine (L-MePhe), L-proline (L-Pro), L-allo-isoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu) and N-methyl-L-valine (L-MeVal), or a stereoisomer thereof.

[0030] Component (A) may further comprise two or more cyclic depsipeptides of formula (IA) as defined above or stereoisomers thereof.

[0031] Component (A) may further comprise aureobasidin A and one or more other cyclic depsipeptides of formula (IA) as defined above or stereoisomers thereof.

[0032] Component (A) may further comprise aureobasidin E and one or more other cyclic depsipeptides of formula (IA) as defined above or stereoisomers thereof.

[0033] In a preferred embodiment of the present invention, component (A) comprises aureobasidin A and one or more cyclic depsipeptides of formula (I) or stereoisomers thereof selected from the group consisting of compounds 1.001-1.004 and 1.006-1.035 listed in Table A. Preferably, component (A) comprises aureobasidin A and at least one other cyclic depsipeptide of formula (IA) or stereoisomers thereof selected from the group consisting of aureobasidin E and aureobasidin G.

[0034] In an embodiment of the invention, component (A) comprises aureobasidin A and aureobasidin E. In another embodiment of the invention, component (A) comprises aureobasidin A and aureobasidin G. In another embodiment of the invention, component (A) comprises aureobasidin A, aureobasidin E and aureobasidin G.

[0035] In another preferred embodiment of the present invention, component (A) comprises aureobasidin A and one or more cyclic depsipeptides of formula (IA) or stereoisomers thereof selected from the group consisting of compounds 2.001 to 2.045 listed in Table B.

[0036] In embodiments in which component (A) comprises aureobasidin A and one or more other cyclic depsipeptides of formula (IA) or stereoisomers thereof, said component (A) is typically 10% to 99.9% by mass, preferably 20% to 99.9% by mass, more preferably 40% to 99.9% by mass of aureobasidin A; 0.1% to 90% by mass, preferably 0.1% to 80% by mass, more preferably 0.1% to 60% by mass of one or more other cyclic depsipeptides of formula (IA) or stereoisomers thereof; Includes.

[0037] In embodiments in which component (A) comprises aureobasidin E and one or more other cyclic depsipeptides of formula (IA) or stereoisomers thereof, said component (A) is typically 10% to 99.9% by mass, preferably 20% to 99.9% by mass, more preferably 40% to 99.9% by mass of aureobasidin E; 0.1% to 90% by mass, preferably 0.1% to 80% by mass, more preferably 0.1% to 60% by mass of one or more other cyclic depsipeptides of formula (IA) or stereoisomers thereof; Includes.

[0038] In one embodiment according to the invention, component (A) is typically 60% to 99.5% by mass of aureobasidin A; 0.05% to 5% by mass of aureobasidin E; Optionally, 0.1% to 30% by weight of aureobasidin G; Optionally, 0.1% to 10% by weight of one or more other cyclic depsipeptides of formula (IA) or stereoisomers thereof. Includes.

[0039] In a second embodiment of the invention, component (A) further comprises one or more cyclic depsipeptides of formula (IB): [ka] (In the formula, R 1 is methyl or ethyl; X 4 is S, methylene, or hydroxymethylene; A 5 is an α-amino acid residue selected from the group consisting of L-allo-isoleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle) and L-valine (L-Val) residues; A 6is an α-amino acid residue selected from the group consisting of N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), L-allo-isoleucine (L-AIle) and N-methyl-L-allo-isoleucine (L-MeAIle) residues; A 7 is an α-amino acid residue selected from the group consisting of L-leucine (L-Leu), L-allo-isoleucine (L-AIle) and L-norvaline (L-Nva) residues; and A 8 are β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), γ-hydroxy-N-methyl-L-valine (L-γ-OH-MeVal), N-methyl-L-valine (L-MeVal), and N-methyl-2,3-didehydro-L-valine (L-MeDH). 2,3 Val), N-methyl-3,4-didehydro-L-valine (L-MeDH 3,4 Val), N-methyl-L-phenylalanine (L-MePhe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), N-methyl-L-threonine (L-MeThr), sarcosine (Sar) and N,β-dimethyl-L-aspartic acid (LN,β-MeAsp) residues. or its stereoisomers.

[0040] As used herein, the term "persephanine residue" refers to a compound having the formula: [ka] represents the α-amino acid residues of

[0041] For example, component (A) may further comprise a cyclic depsipeptide of formula (I-B1), hereinafter referred to as Persephacin A: [ka] or its stereoisomers.

[0042] As used herein, the term "Persephacin A" refers to a cyclic depsipeptide of formula (I-B1) consisting of consecutive units derived from 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-persephanine, sarcosine (Sar), L-proline (L-Pro), L-allo-isoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu) and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), or a stereoisomer thereof.

[0043] Component (A) is a cyclic depsipeptide of formula (I-B2), hereinafter referred to as Persephacin B: [ka] or a stereoisomer thereof.

[0044] As used herein, the term "Persephacin B" refers to a cyclic depsipeptide of formula (I-B2) consisting of consecutive units derived from 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-persephanine, sarcosine (Sar), L-proline (L-Pro), L-allo-isoleucine (L-AIle), L-allo-isoleucine (L-AIle), L-leucine (L-Leu) and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), or a stereoisomer thereof.

[0045] Component (A) is a cyclic depsipeptide of formula (I-B3), hereinafter referred to as Persephacin C: [ka] or a stereoisomer thereof.

[0046] As used herein, the term "Persephacin C" refers to a cyclic depsipeptide of formula (I-B3) consisting of consecutive units derived from 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-persephanine, sarcosine (Sar), L-proline (L-Pro), L-allo-isoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu) and N-methyl-L-valine (L-MeVal), or a stereoisomer thereof.

[0047] Disclosed herein is a component (A) which further comprises two or more cyclic depsipeptides of formula (IB) as defined above or stereoisomers thereof.

[0048] Further disclosed herein is a component (A) which further comprises Persephacin A and one or more other cyclic depsipeptides of formula (IB) as defined above or stereoisomers thereof.

[0049] In another embodiment of the present invention, component (A) comprises a cyclic depsipeptide of formula (I-A1) or a stereoisomer thereof and one or more cyclic depsipeptides of formula (IB) or stereoisomers thereof as defined above.

[0050] In a variant of this embodiment of the invention, component (A) comprises aureobasidin A and one or more cyclic depsipeptides of formula (IB) or stereoisomers thereof as defined above.

[0051] In another variant of this embodiment of the invention, component (A) comprises aureobasidin A, one or more other cyclic depsipeptides of formula (IA) as defined above or stereoisomers thereof, and one or more cyclic depsipeptides of formula (IB) as defined above or stereoisomers thereof.

[0052] In another variant of this embodiment of the invention, component (A) comprises aureobasidin A, at least one other cyclic depsipeptide of formula (IA) or a stereoisomer thereof selected from the group consisting of aureobasidin E and aureobasidin G, and one or more cyclic depsipeptides of formula (IB) or a stereoisomer thereof as defined above.

[0053] Disclosed herein is a component (A) further comprising a strain of Aureobasidium pullulans, generally the strain of Aureobasidium pullulans R106 deposited at the International Patent Organisms Depositary under accession number FERM BP-1938, or the strain of Aureobasidium pullulans deposited at the China General Microbiological Culture Collection Center under accession number CGMCC No. 20887.

[0054] It is understood, without limiting the scope of the present invention, that one or more cyclic depsipeptides of formula (IA) or stereoisomers thereof as defined above can be obtained from the fermentation broth of a strain of Aureobasidium pullulans, generally the strain Aureobasidium pullulans R106 deposited at the International Patent Organisms Depositary under accession number FERM BP-1938, or the strain Aureobasidium pullulans deposited at the China General Microbiological Culture Collection Center under accession number CGMCC No. 20887.

[0055] In another embodiment of the invention, component (A) further comprises a strain or a genetically engineered strain of Sphaceloma coryli.

[0056] Without limiting the scope of the present invention, it is understood that one or more cyclic depsipeptides of formula (IB) or stereoisomers thereof as defined above are obtainable from the fermentation broth of a strain or a genetically engineered strain of Sphaceloma coryli.

[0057] As used herein, the term "fermentation broth" refers to the composition obtained from the fermentation process of a bacterial strain.

[0058] In another embodiment of the present invention, component (A) further comprises a fermentation broth comprising two or more cyclic depsipeptides of formula (I) or stereoisomers thereof as defined above.

[0059] In a first variant of this embodiment of the invention, component (A) further comprises a fermentation broth comprising two or more cyclic depsipeptides of formula (IA) or stereoisomers thereof as defined above.

[0060] In one embodiment according to the invention, component (A) further comprises a fermentation broth comprising aureobasidin A and one or more other cyclic depsipeptides of formula (IA) as defined above or stereoisomers thereof.

[0061] In another embodiment of the present invention, component (A) further comprises a fermentation broth comprising aureobasidin E and one or more other cyclic depsipeptides of formula (IA) as defined above or stereoisomers thereof.

[0062] The compounds of component (B) are known and commercially available, and / or can be prepared using techniques known in the art and / or reported in the literature.

[0063] The possible presence of one or more asymmetric carbon atoms in component (B) means that the compound can occur in optically isomeric forms, i.e. enantiomeric or diastereomeric forms. Atropisomers can also occur as a result of restricted rotation about a single bond. The present invention includes all of these possible isomeric forms (e.g. geometric isomers) of component (B) and mixtures thereof. The present invention also includes all of the possible tautomeric forms of component (B) and racemates, i.e. mixtures of at least two enantiomers in a substantially 50:50 ratio.

[0064] In each case, component (B) according to the invention is in free form, in oxidized form as an N-oxide, or in salt form, for example an agriculturally acceptable salt form.

[0065] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds, as described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0066] Component (B) comprises a compound selected from compounds B.01, B.02, B.03, B.04, B.05, B.06, B.07, B.08, B.09, B.10, B.11, B.12, B.13, B.14, B.15, B.16, B.17, B.18, B.19, B.20, B.21, B.22, B.23, B.24 or B.25 as defined in Table C below. More preferably, component (B) is a compound selected from compounds B.01, B.02, B.03, B.04, B.05, B.06, B.07 or B.08 as defined in Table C below. Even more preferably, component (B) is a compound selected from compounds B.01, B.02, B.03, B.04, B.05, B.06 or B.07 as defined in Table C below.

[0067] [Table 3] JPEG2024540501000018.jpg243170 JPEG2024540501000019.jpg251164 JPEG2024540501000020.jpg125169

[0068] The presence of an asymmetric carbon atom in any of compounds B.01, B.02, B.03, B.04, B.05, B.06, B.07, B.08, B.09, B.10, B.11, B.12, B.13, B.14, B.15, B.16, B.17, B.18, B.19, B.20, B.21, B.22, B.23, B.24 or B.25 as defined in Table C above means that these compounds may occur in chiral enantiomeric form, i.e., in (R)- and (S)-enantiomers.

[0069] Enantiomerically pure final compounds may be obtained from appropriate racemic starting materials via standard physical separation techniques such as reverse phase chiral chromatography, or by stereoselective synthesis techniques, for example by using chiral starting materials.

[0070] In a preferred composition according to the invention, component (A) comprises one or more cyclic depsipeptides of formula (I-A1) as defined above or stereoisomers thereof, and component (B) comprises one or more cyclic depsipeptides of formula (I-A1) as defined above or stereoisomers thereof, such as ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl ]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 100:1 to 1:1000, preferably 100:1 to 1:500, more preferably 50:1 to 1:200, even more preferably 50:1 to 1:20, even more preferably 30:1 to 1:1, and even more preferably 10:1 to 3:1.

[0071] In another preferred composition according to the invention, component (A) is aureobasidin A and component (B) is ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarbox ...pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N-ethyl- a compound selected from the group consisting of 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 50:1 to 1:200.

[0072] In another preferred composition according to the invention, component (A) is aureobasidin A and component (B) is ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarbox ...pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N-ethyl- a compound selected from the group consisting of 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 50:1 to 1:20.

[0073] In another preferred composition according to the invention, component (A) is aureobasidin A and component (B) is ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoro and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 30:1 to 1:1.

[0074] In another preferred composition according to the invention, component (A) is aureobasidin A and component (B) is ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoro and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 10:1 to 3:1.

[0075] In another preferred composition according to the present invention, component (A) is aureobasidin E, and component (B) is ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarbox ...pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N- a compound selected from the group consisting of 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 50:1 to 1:200.

[0076] In another preferred composition according to the present invention, component (A) is aureobasidin E, and component (B) is ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarbox ...pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N- a compound selected from the group consisting of 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 50:1 to 1:20.

[0077] In another preferred composition according to the present invention, component (A) is aureobasidin E, and component (B) is ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoro and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 30:1 to 1:1.

[0078] In another preferred composition according to the present invention, component (A) is aureobasidin E, and component (B) is ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoro and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 10:1 to 3:1.

[0079] In another preferred composition according to the present invention, component (A) comprises aureobasidin A and one or more cyclic depsipeptides of formula (I) selected from the group consisting of compounds 1.001 to 1.004 and 1.006 to 1.035 in Table A, or stereoisomers thereof. Preferably, component (A) comprises aureobasidin A and at least one other cyclic depsipeptide of formula (IA) selected from the group consisting of aureobasidin E and aureobasidin G, or stereoisomers thereof, and component (B) comprises ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N -[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl a compound selected from the group consisting of 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 50:1 to 1:200.

[0080] In the composition disclosed herein, component (A) comprises aureobasidin A and one or more cyclic depsipeptides of formula (I) selected from the group consisting of compounds 1.001 to 1.004 and 1.006 to 1.035 listed in Table A, or stereoisomers thereof. Preferably, component (A) comprises aureobasidin A and at least one other cyclic depsipeptide of formula (IA) selected from the group consisting of aureobasidin E and aureobasidin G, or stereoisomers thereof, and component (B) comprises ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[ The compound is selected from the group consisting of [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 50:1 to 1:20.

[0081] In the composition disclosed herein, component (A) includes aureobasidin A and one or more cyclic depsipeptides of formula (I) selected from the group consisting of compounds 1.001 to 1.004 and 1.006 to 1.035 listed in Table A, or stereoisomers thereof. Preferably, component (A) includes aureobasidin A and at least one other cyclic depsipeptide of formula (IA) selected from the group consisting of aureobasidin E and aureobasidin G, or stereoisomers thereof. And component (B) includes ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N- The compound is selected from the group consisting of [[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 30:1 to 1:1.

[0082] In the composition disclosed herein, component (A) comprises aureobasidin A and one or more cyclic depsipeptides of formula (I) selected from the group consisting of compounds 1.001-1.004 and 1.006-1.035 listed in Table A, or stereoisomers thereof. Preferably, component (A) comprises aureobasidin A and at least one other cyclic depsipeptide of formula (IA) selected from the group consisting of aureobasidin E and aureobasidin G, or stereoisomers thereof; and component (B) comprises ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy- The compound is selected from the group consisting of N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 10:1 to 3:1.

[0083] The compositions disclosed herein are derived from a strain of Aureobasidium pullulans, generally Aureobasidium pullulans. pullulans R106, and component (B) may further comprise ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1 -[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 100:1 to 1:1000, preferably 100:1 to 1:500, more preferably 50:1 to 1:200, even more preferably 50:1 to 1:20, even more preferably 30:1 to 1:1, and even more preferably 10:1 to 3:1.

[0084] The composition disclosed herein may further comprise a fermentation liquid medium comprising a cyclic depsipeptide of formula (I-A1) as defined above or a stereoisomer thereof, and component (B) is selected from the group consisting of ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarbox ... A compound selected from the group consisting of panamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 100:1 to 1:1000, preferably 100:1 to 1:500, more preferably 50:1 to 1:200, even more preferably 50:1 to 1:20, even more preferably 30:1 to 1:1, and even more preferably 10:1 to 3:1.

[0085] In another preferred composition according to the present invention, component (A) is a fermentation liquid medium containing aureobasidin A or a stereoisomer thereof as defined above, and component (B) is selected from the group consisting of ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl] propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea and 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, wherein the mass ratio of component (A) to component (B) is 100:1 to 1:1000, preferably 100:1 to 1:500, more preferably 50:1 to 1:200, even more preferably 50:1 to 1:20, even more preferably 30:1 to 1:1, and even more preferably 10:1 to 3:1.

[0086] The compositions disclosed herein may, under certain circumstances, comprise an additional active ingredient, component (C), different from component (B), where component (C) is selected from the list of components (B) defined in accordance with the present invention.

[0087] When the composition contains components (A), (B) and (C), the mass ratio of component (A) to the sum of components (B) and (C) can be 100:1 to 1:1000, preferably 100:1 to 1:500, more preferably 50:1 to 1:200, even more preferably 50:1 to 1:20, even more preferably 30:1 to 1:1, and even more preferably 10:1 to 3:1.

[0088] The weight ratio of component (A) to the sum of components (B) and (C) can be 1:1, or 1:2, or 1:4, or 1:8, or 2:1, or 4:1, or 8:1, or 16:1, or 20:1, or 1:200, or 1:100, or 1:50, or 1:25, or 1:20, or 1:12.5, or 1:10, or 1:6.2, or 1:5, or 1:2.5, or 2:1, or 3:1, or 10:1, or 20:1, or 30:1.

[0089] The compound of formula (I) or its stereoisomers can be prepared by methods known to those skilled in the art. The compound of formula (I) can be purchased or prepared using synthetic or semi-synthetic chemistry or fermentation processes. For example, the compound of formula (IA) or its stereoisomers can be prepared by methods known in Takesako et al., The Journal of Antibiotics, 1991, 44, 919-924; Takesako et al., Tetrahedron, 1996, 52, 4327-4346; and Maharani et al. Tetrahedron, 2014, 70, 2351-2358. The fermentation broth containing one or more compounds of formula (IA) or their stereoisomers can be obtained from the fermentation process of a strain of Aureobasidium pullulans, generally the strain Aureobasidium pullulans R106. A fermentation broth containing one or more compounds of formula (IB) or stereoisomers thereof is obtainable from the fermentation process of a strain of Sphaceloma coryli. The fermentation broth may not require purification. Alternatively, one or more compounds of formula (I) can be isolated and purified from the fermentation broth by, for example, chromatography using adsorbents (e.g., silica and reverse-phase silica gel, optically active adsorbents, resins) or one or more solvents (e.g., partitioning, countercurrent separation, mixtures of multi-phase solvents) or other chemical means (e.g., crystallization, recrystallization, salt formation and precipitation) to achieve final purity. The purity of the compound of formula (I) or its stereoisomers can include, but is not limited to, 10% to 20%, 20% to 30%, 30% to 40%, 40% to 50%, 50% to 60%, 60% to 70%, 70% to 80%, 80% to 90%, or 90% to 100%. The purity of the compound of formula (I) or its stereoisomers can be measured by any technique known to one of skill in the art, including NMR, mass spectrometry, liquid chromatography mass spectrometry (LCMS), high performance liquid chromatography (HPLC), and other analytical means.

[0090] The term "fungicide" as used herein means a compound that controls, modifies, or prevents fungal growth. The term "fungicidally effective amount" means an amount of such a compound or combination of such compounds that is capable of producing an effect on fungal growth. A controlling or modifier effect includes any deviation from natural development, such as killing, retardation, etc., and prevention includes the formation of a barrier or other defense in the plant to prevent infection by the fungus.

[0091] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage and fruits.

[0092] The term "plant propagation material" means all reproductive parts of a plant, for example seeds or growing parts of a plant such as cuttings or tubers, including not only seeds in the strict sense, but also roots, fruits, tubers, bulbs, rhizomes and plant parts.

[0093] As used herein, the term "habitat" refers to the field in which the plant is growing or in which the seeds of the cultivated plant are sown or in which the seeds will be planted in the soil, including the soil, the seeds and seedlings, and established vegetation.

[0094] Throughout this specification, the expression "composition" refers to various mixtures or combinations of components (A) and (B) (including the embodiments defined above), such as single "premixed" forms, multiple spray mixtures such as "tank mixes" made up of individual combinations of single active ingredient components, and combinations of single active ingredients when applied sequentially (i.e., one after the other within a reasonably short time, such as hours or days). The order in which components (A) and (B) are applied is not critical to the working of the invention.

[0095] The compositions of the present invention are effective against harmful microorganisms, such as those causing phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria.

[0096] The compositions of the present invention may be used to control plant diseases caused by a wide range of fungal plant pathogens in the Basidiomycota, Ascomycota, Oomycota and / or Fungi Imperfecti, Blasocladiomycete, Chrytidiomycete, Glomeromycete and / or Mucoromycete classes: Oomycete, including: Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium aphanidermatum; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; Peronospora destructor, Peronospora parasitica, Peronospora manshurica, Peronospora tabacina, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora diseases caused by Peronosporales such as C. cubensis, C. albugo, C. sclerophthora macrospora and C. bremia lactucae;and others such as Aphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghi and Sclerospora graminicola; Ascomycetes, such as Stemphylium solani, Stagonospora tainanensis, Spirocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solanisolani and Alternaria tomatophila; Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora beticola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella herpotrichoides; Cladosporium carpophyllum carpophilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Gaeumannomyces graminisMagnaporthales such as Magnaporthe grisea, Magnaporthe oryzae; Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-Juglandacearum. clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma, etc.; as well as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp.spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora spp. blotch, spot, blast or blight and / or rot diseases such as those caused by others such as those caused by Gloeotinia sorghi, Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale, Monilinia fructicola, Monilinia laxa, Monilinia fructigena, Monographella albescens, Monosporascus cannonballuscannonballus, Naemacyclus spp., Ophiostomanovo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, Petriellidium spp., Pezicula spp., Phialophora gregata, Phialophora tetraspora, Phyllachora pomigena, Phymatotrichum omnivora, omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi pomi, Sclerotinia sclerotiorum, Sclerotinia minor, Sclerotium spp, Typhula ishikariensis, Seimatosporium mariae, Lepteutypacupressi), Septocyta ruborum, Sphaceloma perseae, Sporone Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; e.g. Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis; powdery mildew diseases, such as those caused by Erysiphales, such as Podosphaera pannosa, Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis;For example, Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botrytis tracheiphila, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta fungi, such as those caused by the Botryosphaeriales, for example Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata and Colletotrichum graminicola; anthracnose, for example those caused by the Glommerelales, for example Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata and Colletotrichum graminicola;As well as, for example, Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium brasiliense, Fusarium tucumaniae, Fusarium cuneirostrum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp.cubense, Gerlachia wilt or blight diseases such as those caused by Hypocreales such as Gibberella nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum and Verticillium theobromae; Basidiomycete including smut fungi such as those caused by the Ustilaginales, e.g. Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, e.g. Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis ... graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp.Hordei, Puccinia striiformis f.sp.the Pucciniales, such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phakopsora meibomiae, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces visciae-fabie. Rust fungi, such as those caused by Uredinales such as Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp.), Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia haperplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia Other decays and diseases such as those caused by caries;. Blastocladiomycetes, such as Physoderma maydis; and Diseases caused by Choanephora cucurbitarum; Mucor spp.; Mucoromycetes such as Rhizopus arrhizus, Rhizopus oryzae, Rhizopus stolonifera, Rhizopus nigricans, and other species and genera closely related to those listed above.

[0097] In addition to its fungicidal activity, the composition may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Streptomyces scabies and other related species, as well as certain protozoa.

[0098] The composition of the present invention may be selected from the group consisting of fungi from the class Ascomycetes (e.g. Venturia, Alternaria, Podosphaera, Erysiphe, Magnaporthe, Monilinia, Mycosphaerella, Uncinula); fungi from the class Basidiomycetes (e.g. Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); fungi from the class Fungi Imperfecti (e.g. Fungi spp., ... imperfecti (also known as Deuteromycetes; e.g. Botrytis, Colletotrichum, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Penicillium, Pyricularia, and and Pseudocercosporella; Oomycetes (e.g. Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara).

[0099] Preferably, the composition according to the invention is selected from the group consisting of Alternaria, Ascochyta, Botrytis, Cercospora, Cochliobolus sativus, Colletotrichum, Colletotrichum lagenarium, Corynespora, Erysiphe, Erysiphe cichoracearum, Sphaerotheca fuliginea, Fusarium, Fusarium oxysporum, Gaeumannomyces graminis, graminis, Guignardia, Helminthosporium, Hemileia vastatrix, Magnaporthe, Magnaporthe oryzae, Monilinia, Mycosphaerella, Mycosphaerella arachidis, Phakopsora, Phoma, Phomopsis, Puccinia, Pseudocercosporella, Pseudopezicula, Phragmidium mucronatum mucronatum, Podosphaera, Pyrenophora, Pyrenophora teres, Pyricularia, Pyricularia oryzae, Ramularia, Ramularia collo-cygni, Rhizoctonia, Rhizoctoniasolani, Rhynchosporium secalis, Sclerotinia, Septoria, Septoria tritici, Sphacelotheca reilliana, Tilletia, Urocystis occulta, Uncinula, Ustilago, Venturia, Monilia and Penicillium.

[0100] The compositions of the present invention may be particularly effective against plant pathogenic fungi selected from the group consisting of Alternaria, Botrytis, Cercospora, Colletotrichum, Corynespora, Guignardia, Mycosphaerella, Monilinia, Penicillium, Phakopsora, Phomopsis, Podosphaera, Pseudopezicula, Septoria, Uncinula, and Venturia.

[0101] The composition of the present invention is effective against Alternaria solani, Alternaria alternata, Alternaria porri, Botrytis cinerea, Botrytis allii, Botrytis squamosa, Cercospora capsici, Colletotrichum lagenarium, Corynespora cassiicola, Guignardia bidwellii, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Penicillium It may be particularly effective against plant pathogenic fungi selected from the group consisting of Penicillium digitatum, Penicillium italicum, Penicillium expansum, Phomopsis viticola, Podosphaera leucotricha, Podosphaera xanthii, Pseudopezicula tracheiphila, Septoria tritici, Uncinula necator and Venturia inaequalis.

[0102] According to the invention, "useful plants" typically include the following perennial or annual plants: Cereals, such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale, tritordeum and grains such as wheat, amaranth, buckwheat, chia, quinoa and canuera; fruits and nuts such as grapes (table and wine grapes), almonds, apples, apricots, avocados, bananas, blackberries, blueberries, breadfruit, cocoa, cashews, cherimoya, cherry, chestnuts (nuts), amplexicaule, citrus fruits (including grapefruit, lime, lemon, orange, calamansi), coconut, coffee, cranberries, currants, dates, feijoa, figs, hazels (hazelnuts), gooseberries, guavas, kiwi, lychees, macadamia, mangoes, nectarines, olives, papayas, passion fruit, peaches, pears, pecans, persimmons, pineapples, pistachios, plums (including prunes), pomegranates, quince, raspberries, strawberries, Suriname cherries, and walnuts; Artichoke, asparagus, beans (snap beans, green beans, dry beans, edible beans), beets (table), broccoli / Italian turnip, Brussels sprouts, cabbage (including Chinese cabbage), carrots, cauliflower, celeriac, celery, chickpeas, chives, chili peppers (including kale), cucumber, edamame, eggplant, endive, peas (garden peas) vegetables such as peas, dried peas, edible peas, garlic, horseradish, turnip cabbage, leeks, lentils, lettuce, melons, mushrooms (cultivated), mustard and other leafy greens, okra, onion, parsley, parsley, pepper, potato, prickly pear, pumpkin, radish, rhubarb, rutabaga, burdock, spinach, squash (summer and winter squash), sweet corn, sweet potato, Swiss chard, taro, tomato / grape gooseberry, turnip and watermelon; agricultural crops such as sugar beets, sugar cane, tobacco, peanuts, and soybeans; Oilseed crops such as rapeseed (canola), mustard, camelina, crambe, sunflower, poppy, sesame and safflower; Forage crops such as alfalfa, clover, cowpea, vetch, sainfoin, lupine, fodder beet, ryegrass, Kentucky bluegrass, fescue, and orchard grass; Fiber crops such as cotton, flax, hemp, jute and sisal; forest vegetation, including coniferous species such as larch, fir or pine, temperate and tropical hardwoods (e.g. oak, birch, beech, teak or mahogany), as well as tree species in dry zones, such as eucalyptus; horticultural crops such as hops, maple (maple syrup), tea, rubber plants and turfgrasses (e.g., bentgrass, Kentucky bluegrass, barley, fescue, turfgrass, centipedegrass, crested hairgrass, Japanese larkspur, St. Augustine grass, Japanese lawn grass, timothy grass, and broad-leaved grass; Examples include begonias, dahlias, geraniums, balsam, petunias, coleus, marigolds, pansies, snapdragons, saintpaulia, azaleas, chrysanthemums, flower bulbs, hydrangeas, lilies, orchids, poinsettias, roses, astilbes, goldenrods, delphiniums, dianthus, heucheras, hostas, phlox, rudbeckias, salvias, vincas, columbines, large-leaved hostas, and chrysanthemums (garden floriculture, greenhouse and nursery plants including flowers, broad-leaved or evergreen trees such as chrysanthemum, ivy, ornamental grasses, peonies, delphiniums, gladioli, irises, snapdragons, tulips, eucalyptus, pittosporum, ferns, anthuriums, dieffenbachia, dracaena, figs, philodendrons, spathiphyllum, bromeliads, cacti, palms, balsam firs, spruces, American pines, Fraser fir, noble firs, Scots pine, white pine, magnolia, ash, elms, ornamental cherry, ornamental plum, hawthorn, redbud and rowan berry; Propagation material such as bare seedlings, cuttings, liners, plugs, seeds, tissue culture plantlets and prefinished plants; For example, allspice, Angelica spp., anise, annatto, yellow laurel, basil (all species), bay leaf (cultivated species), bladderwrack (seaweed), Bolivian coriander, borage, calendula (herbal use), candlenut, capers, caraway, cardamom, cassia spice, cinnamon, clary sage, cloves, catnip, chamomile, chervil, chicory, cicely, cilantro, comfrey, coriander, mustard, cumin, curry, dill, fennel, fenugreek, Culinary herbs and spices such as fillet (cultivated species), fingerroot, galangal, ginger, hops, horehound, hyssop, lavender, lemon balm, lemon thyme, lovage, mace, mahaleb, marabourtrum, marjoram, mint (all species), mugwort, nutmeg, oregano, orris root, paprika, parsley, pepper, rosemary, rue, saffron, sage (all species), savory (all species), wood sorrel, tarragon, thyme, turmeric, vanilla, horseradish, and watercress; and Medicinal herbs such as arum, Artemisia spp., astragalus, Bordeaux, comfrey, coneflower, fenugreek, feverfew, foxglove, ginkgo, ginseng, goat's root, hydrangea, gypsywort, horehound, horsetail, lavender, licorice, marshmallow, mullein, nettle, passionflower, patchouli, peony, pokeweed, skullcap, wood sorrel, Hypericum perforatum, senna, sowberry, stevia, mugwort, witch hazel, caterpillar, wormwood, yarrow, yerba buena and ylang-ylang.

[0103] This list does not represent any limitation, however, preferably, the useful plants may be selected from the group consisting of wheat, barley, rice, soybean, apple, almond, cherry, raspberry, grape, cucumber, peanut, tomato, strawberry, citrus and banana.

[0104] The term "useful plants" should also be understood to include useful plants that have been rendered resistant to herbicides such as bromoxynil or to a class of herbicides (e.g., HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyroyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors, etc.) by conventional breeding or genetic engineering methods. An example of a crop that has been rendered resistant to imidazolinones, such as imazamox, by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops that have been rendered resistant to herbicides or to a class of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant corn varieties available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

[0105] The term "useful plants" should also be understood to include useful plants that have been transformed using recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known from toxin-producing bacteria. Examples of toxins that may be expressed include delta-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of nematode symbiotic bacteria, and toxins produced by scorpions, arachnids, wasps and fungi.

[0106] An example of a crop modified to express Bacillus thuringiensis toxins is Bt corn KnockOut® (Syngenta Seeds). An example of a crop containing more than one gene encoding insecticide resistance and therefore expressing more than one toxin is VipCot® (Syngenta Seeds). Crops or their seed material can also be resistant to multiple pests (so-called overlapping transgenic events when formed by genetic modification). For example, plants can be herbicide resistant and at the same time capable of expressing insecticidal proteins, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0107] Toxins which can be expressed by such genetically modified plants include, for example, insecticidal proteins, such as those from Bacillus cereus or Bacillus popliae; or from Bacillus thuringiensis, such as the δ-endotoxins, e.g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidal proteins (VIPs), e.g. VIP1, VIP2, VIP3 or VIP3A; or from Photorhabdus species, such as Photorhabdus luminescens, Xenorhabdus nematophilus, insecticidal proteins of nematode symbiotic bacteria such as Xenorhabdus spp. or Xenorhabdus spp.; toxins produced by animals such as scorpion toxins, spider toxins, wasp toxins and other insect specific neurotoxins; toxins produced by fungi such as Streptomycete toxins, plant lectins such as pea lectin, barley lectin or snowdrop lectin; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ricin, Ribosome-inactivating proteins (RIPs) such as maize-RIP, abrin, rufin, saporin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0108] In the context of the present invention, delta-endotoxins, such as CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or trophic insecticidal proteins (VIP), such as VIP1, VIP2, VIP3 or VIP3A, are to be understood as being in particular also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of these proteins (see, for example, WO 02 / 15701). An example of a truncated toxin is the truncated CryIA(b) expressed in Bt11 maize from Syngenta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the natural toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of CryIIIA055, a cathepsin D-recognition sequence is inserted into the CryIIIA toxin (see WO 03 / 018810).

[0109] Examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0110] The processes for the preparation of such transgenic plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90 / 13651.

[0111] The toxins contained in the genetically modified plants confer resistance to harmful insects on the plants, which can be from any of the insect taxa, but are most commonly found among beetles (Coleoptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

[0112] Transgenic plants that contain one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some are commercially available. Examples of such plants are: YieldGard® (a corn variety expressing a CryIA(b) toxin); YieldGard Rootworm® (a corn variety expressing a CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (a corn variety expressing a Cry9(c) toxin); Herculex I® (a corn variety expressing a CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing a CryIA(c) toxin); Bollgard I® (a cotton variety expressing a CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxin); NewLeaf® (a potato variety expressing CryIIIA toxin); NatureGard® and Protecta®.

[0113] Further examples of such genetically modified crops are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seed SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. A genetically engineered maize (Zea mays) that is resistant to the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CryIA(b) toxin. Bt11 maize also achieves tolerance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.

[0114] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seed SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. A genetically engineered maize (Zea mays) that is resistant to the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of the CryIA(b) toxin. Bt176 maize also achieves tolerance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.

[0115] 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seed SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Maize with insect resistance conferred by transgenic expression of a modified CryIIIA toxin. This toxin is Cry3A055 modified by the insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0116] 4. MON863 maize, registration number C / DE / 02 / 9, from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON863 expresses the CryIIIB(b1) toxin and confers resistance to certain coleopteran insects.

[0117] 5. IPC531 Cotton made by Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0118] 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Maize genetically engineered for expression of the protein Cry1F to achieve resistance to certain lepidopteran insects, and for expression of the PAT protein to achieve resistance to the herbicide glufosinate ammonium.

[0119] 7. NK603 x MON810 maize, registration number C / GB / 02 / M3 / 03, from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. It consists of a conventional hybrid maize variety by crossing the genetically engineered varieties NK603 and MON810. NK603 x MON810 maize transgenic expresses the protein CP4 EPSPS from the strain CP4 of Agrobacterium sp., which confers resistance to the herbicide Roundup® (containing glyphosate), and the CryIA(b) toxin from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European corn borer.

[0120] The term "useful plants" should also be understood to include useful plants that have been genetically modified using DNA recombinant techniques so as to be able to synthesize antipathogenic substances with selective action, such as, for example, so-called "infection-specific proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and genetically modified plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818 and EP-A-0 353 191. Methods for generating such genetically modified plants are generally known to the skilled person and are described, for example, in the abovementioned publications.

[0121] Anti-pathogenic substances which can be expressed by such genetically modified plants include, for example, ion channel blockers, such as sodium and calcium channel blockers, e.g. the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "infection specific proteins" (PRPs; see, for example, EP-A-0 392 225); anti-pathogenic substances produced by microorganisms, such as, for example, peptide or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors involved in plant pathogen defence (the so-called "plant disease resistance genes" described in WO 03 / 000906).

[0122] The compositions according to the invention are particularly effective in controlling or preventing phytopathogenic diseases caused by certain phytopathogenic fungi, in particular powdery mildew, rust, leaf spot, summer blight or mould, in cereal grains, fruits and tree nuts, vegetables, field crops, oilseed crops, fodder crops, forest plants, horticultural crops, floriculture, greenhouse and nursery plants, propagation material, culinary herbs and spices, and medicinal plants, as follows: Alternaria solani, preferably in tomato.

[0123] Alternaria alternata, preferably in eggplant.

[0124] Alternaria porri, preferably in onion.

[0125] Botrytis cinerea, preferably in tomatoes, peppers, onions, pome fruits, stone fruits, kiwi, blueberries, sugar beets or grapes.

[0126] Botrytis allii, preferably in onions.

[0127] Botrytis squamosa, preferably in onions.

[0128] Cercospora capsici, preferably in pepper.

[0129] Corynespora cassiicola, preferably in tomato.

[0130] Guignardia bidwellii, preferably in grapes.

[0131] Monilinia fructicola, preferably in cherries, peaches, plums, prunes, nectarines or almonds.

[0132] Monilinia fructigena, preferably in cherries, peaches, plums, prunes, nectarines or almonds.

[0133] Monilinia laxa, preferably in cherries, peaches, plums, prunes, nectarines or almonds.

[0134] Phomopsis viticola, preferably in grapes.

[0135] Preferably in apples, Podosphaera leucotricha.

[0136] Preferably in the Cucurbitaceae family, Podosphaera xanthii.

[0137] Pseudopezicula tracheiphila, preferably in grapes.

[0138] Uncinula necator, preferably in grapes.

[0139] Preferably in apples, Venturia inaequalis.

[0140] Furthermore, the composition according to the present invention is effective in preventing and / or preventing the growth of Alternaria spp., Ascochyta spp., Botrytis cinerea, Cercospora spp., Claviceps purpurea, Gramineae leaf spot fungus, Colletotrichum spp., Epicoccum spp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusarium subglutinans, Fusarium spp. ... subglutinans, Gaeumannomyces graminis, Helminthosporium spp., Microdochium nivale, Phoma spp., Pyrenophora graminea, Pyricularia oryzae, Rhizoctonia solani, Rhizoctonia cerealis, Sclerotinia spp., Septoria spp., Sphacelotheca reilliana, Tilletia spp., Typhula incarnata incarnata, Urocystis occulta, Ustilago spp. or Verticillium spp.) and soil-borne diseases; in particular against pathogens of cereals such as wheat, barley, rye or oats; maize; rice; cotton; soybean; turf; sugar beet; oilseed rape; potato; cereal crops such as peas, lentils or chickpeas; and sunflower.

[0141] Furthermore, the composition according to the present invention is preferably used in the treatment of diseases caused by Botrytis cinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotrichum candidum, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Mucor piriformis, Penicillium italicum, Penicillium solitum, Penicillium digitatum or Penicillium expansum. expansum), especially against post-harvest diseases of pome fruits, e.g. apple and pear, stone fruits, e.g. peaches and plums, citrus fruits, melons, papayas, kiwi, mango, berries, e.g. strawberries, avocados, pomegranates and bananas, and against fruit pathogens such as nuts.

[0142] The compositions of the present invention can also be used in crop enhancement, where "crop enhancement" in the present invention means improved plant vigor, improved plant quality, improved resistance to stress factors, and / or improved input use efficiency.

[0143] In the present invention, "improved plant vigor" means that a particular trait is qualitatively or quantitatively improved when compared to the same trait in a control plant grown under the same conditions in the absence of the method of the present invention.

[0144] In the present invention, "improved plant quality" means that a particular trait is qualitatively or quantitatively improved when compared to the same trait in a control plant grown under the same conditions in the absence of the method of the present invention. In the present invention, "improved resistance to stress factors" means that a particular trait is qualitatively or quantitatively improved when compared to the same trait in a control plant grown under the same conditions in the absence of the method of the present invention. In the present invention, "improved input use efficiency" means that a plant can be grown more efficiently using a given input level compared to the growth of a control plant grown under the same conditions in the absence of the method of the present invention.

[0145] Other crop enhancements of the present invention include reduced plant height, or reduced tillering, which are beneficial traits in crops or conditions where it is desirable to have less biomass and fewer tillers.

[0146] Some compositions according to the invention are systemically active and can be used as foliar, soil and seed treatment fungicides.

[0147] The compositions according to the invention make it possible to inhibit or eliminate phytopathogenic microorganisms occurring in plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plants, while at the same time also protecting subsequently growing plant parts from attack by phytopathogenic microorganisms.

[0148] The compositions according to the invention can be applied to phytopathogenic microorganisms, to useful plants threatened by microbial attack, their habitats, their propagation material, storage articles or technical material.

[0149] The compositions according to the invention can be applied before or after the infection of useful plants, their propagation material, storage items or technical material by microorganisms.

[0150] Compositions comprising component (A) in combination with component (B) may be applied, for example, in a single "premixed" form, in multiple spray mixtures such as "tank mixes" composed of individual formulations of the single active ingredients, and sequentially, i.e., in combination with the single active ingredients when applied one after the other within a reasonably short time, such as a few hours or days. The order in which the compounds of component (A) and the active ingredients of component (B) are applied is not critical to the operation of the invention.

[0151] The compositions according to the invention are active ingredients which are prophylactically and / or therapeutically useful in the field of pest control, even at low application rates.

[0152] When applied to useful plants, component (A) is applied in an amount of 25 g ai / ha to 500 g ai / ha, accompanied by component (B) at 10 g ai / ha to 500 g ai / ha. In another embodiment of the invention, when applied to useful plants, component (A) is applied in an amount of 25 g ai / ha to 500 g ai / ha, accompanied by component (B) at 25 g ai / ha to 500 g ai / ha. In another embodiment of the invention, when applied to useful plants, component (A) is applied in an amount of 25 g ai / ha to 250 g ai / ha, accompanied by component (B) at 25 g ai / ha to 250 g ai / ha.

[0153] In a preferred embodiment of the present invention, the method for controlling or preventing phytopathogenic diseases, in particular by phytopathogenic fungi, in useful plants or their propagation material comprises applying to a useful plant, its habitat or its propagation material a composition as defined in the present invention, in which component (A) is applied in an amount of 25 g ai / ha to 500 g ai / ha, together with component (B) at 10 g ai / ha to 500 g ai / ha.

[0154] In another embodiment of the present invention, a method for controlling or preventing phytopathogenic diseases, in particular phytopathogenic fungi, in useful plants or their propagation material comprises the step of applying to a useful plant, its habitat or its propagation material a composition according to the present invention, wherein component (A) is applied in an amount of 25 g ai / ha to 500 g ai / ha, together with 25 g ai / ha to 500 g ai / ha of component (B).

[0155] In another embodiment of the present invention, a method for controlling or preventing phytopathogenic diseases, in particular by phytopathogenic fungi, in useful plants or their propagation material comprises applying a composition as defined in the present invention to a useful plant, its habitat or its propagation material, wherein component (A) is applied in an amount of 25 g ai / ha to 250 g ai / ha, together with 25 g ai / ha to 250 g ai / ha of component (B).

[0156] The method for controlling or preventing plant pathogenic diseases according to the present invention may be particularly effective against plant pathogenic fungi selected from the group consisting of Alternaria, Botrytis, Cercospora, Colletotrichum, Corynespora, Guignardia, Mycosphaerella, Monilinia, Penicillium, Phakopsora, Phomopsis, Podosphaera, Pseudopezicula, Septoria, Uncinula, and Venturia.

[0157] The method for controlling or preventing plant pathogenic diseases according to the present invention includes the steps of: controlling or preventing plant pathogenic diseases by using Alternaria solani, Alternaria alternata, Alternaria porri, Botrytis cinerea, Botrytis allii, Botrytis squamosa, Cercospora capsici, Colletotrichum lagenarium, Corynespora cassiicola, Guignardia bidwellii, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Monilinia arginata ... laxa, Penicillium digitatum, Penicillium italicum, Penicillium expansum, Phomopsis viticola, Podosphaera leucotricha, Podosphaera xanthii, Pseudopezicula tracheiphila, Septoria tritici, Uncinula necator and Venturia inaequalis.

[0158] Preferred is a method for controlling or preventing phytopathogenic diseases, especially caused by phytopathogenic fungi, which comprises applying a composition according to the invention to useful plants selected from the group consisting of cereal grains, fruits and nuts, vegetables, field crops, oilseed crops, fodder crops, forest plants, horticultural crops, floriculture, greenhouse and nursery plants, propagation material, culinary herbs and spices, and medicinal plants.

[0159] Further preferred is a method for controlling or preventing phytopathogenic diseases, especially caused by phytopathogenic fungi, which comprises applying the composition according to the present invention to useful plants selected from the group consisting of wheat, barley, rice, soybean, apple, almond, cherry, raspberry, grape, cucumber, peanut, tomato, strawberry, citrus fruits and banana.

[0160] In an embodiment of the present invention, the method of controlling or preventing phytopathogenic diseases according to the present invention may be particularly effective against phytopathogenic fungi selected from the group consisting of Alternaria, Cercospora, Colletotrichum, Corynespora, Mycosphaerella, Phakopsora, Phomopsis and Septoria in soybean plants.

[0161] In an embodiment of the present invention, the method of controlling or preventing phytopathogenic diseases according to the present invention may be particularly effective against phytopathogenic fungi selected from the group consisting of Alternaria spp., Cercospora kikuchii, Cercospora sojina, Phakopsora pachyrhizi and Septoria glycines in soybean plants.

[0162] The present invention also provides a fungicidal composition comprising a synergistically effective amount of a combination of components (A) and (B) as described above, together with an agriculturally acceptable carrier and, optionally, a surfactant, in which the weight ratio of (A) to (B) is preferably from 100:1 to 1:1000, preferably from 100:1 to 1:500, more preferably from 50:1 to 1:200, even more preferably from 50:1 to 1:20, even more preferably from 30:1 to 1:1, even more preferably from 10:1 to 3:1, as described herein above.

[0163] Surprisingly, it has been found that a certain mass ratio of component (A) to component (B) can result in synergistic activity. Thus, a further aspect of the present invention is a composition in which component (A) and component (B) are present in the composition in an amount that results in a synergistic effect. This synergistic activity is evident from the fact that the fungicidal activity of a 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 extends the range of action of component (A) and component (B) in two ways. Firstly, the application rates of component (A) and component (B) are reduced while the action remains equally good, which means that even in the low application rate range where the two individual components are completely ineffective, the active ingredient mixture still achieves a high level of control of plant pathogens. Secondly, the range of plant pathogens that can be controlled is substantially expanded.

[0164] A synergistic effect exists whenever the action of a combination of active ingredients is greater than the sum of the actions of the individual ingredients. The expected activity E for a given combination of active ingredients can be calculated according to the so-called COLBY formula as follows (COLBY, SR "Calculating synergistic and antagonistic responses of herbicide combination". Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (=ai) per litre of spray mixture X=% effect of active ingredient (A) using p ppm of active ingredient Y = % effect due to active ingredient (B) using q ppm of active ingredient.

[0165] According to COLBY, the expected (active) effect of active ingredients (A)+(B) using p+q ppm of active ingredients is:

number

[0166] When the actual observed effect (O) is greater than the expected effect (E), the effect of the combination is superadditive, i.e. synergism exists. In mathematical terms, synergy corresponds to a positive value of the difference (OE). In the case of a pure complementary addition of activities (expected activity), said difference (OE) is zero. A negative value of said difference (OE) indicates a loss of activity compared to the expected activity.

[0167] However, apart from the actual synergistic action with respect to the fungicidal activity, the compositions of the invention may also have further surprising advantageous properties.Examples of such advantageous properties that may be mentioned are: more advantageous degradability; improved toxicological and / or biotoxicological behavior; or improved properties of useful plants (germination, crop yield, more developed root system, increased tillers, increased plant height, larger leaf blades, less basal leaves, stronger tillers, greener leaf color, less fertilizer required, less seeds required, more productive tillers, earlier flowering, earlier grain, less plant verse (lodging), increased shoot growth, improved plant vigor, and earlier germination, etc.).

[0168] The following examples are intended to illustrate the present invention and are not meant to limit the invention in any way. EXAMPLES

[0169] Biological Examples The compositions according to the invention are tested for their biological (fungicidal) activity using application rates in which component (A) is applied in an amount of 25 g ai / ha to 500 g ai / ha, with component (B) at 10 g ai / ha to 500 g ai / ha.

[0170] Compositions according to the invention are tested for their biological (bactericidal) activity as solutions in dimethylsulfoxide (DMSO) using one or more of the protocols described in the following examples. A standard description of the liquid culture test is given in Example 1.

[0171] Aureobasidin A and its synthesis are known from Takesako et al., The Journal of Antibiotics, 1991, 44, 919-924. Aureobasidin A is isolated from the fermentation broth by extraction with ethyl acetate, followed by extraction of the ethyl acetate concentrate with a mixture of MeOH:H2O (80% by volume) and cyclohexane (20% by volume), and purification by silica gel column chromatography (silica gel, elution with hexane:ethyl acetate), followed by reversed-phase column chromatography (RP18, elution with acetonitrile:H2O). As mentioned, component (B) of the composition is known, commercially available, and / or can be prepared using techniques known in the art and / or reported in the literature.

[0172] Example 1: Liquid medium test in well plates Compounds to be tested were prepared as solutions in DMSO (up to 10 mg / mL) and diluted to the appropriate concentration with 0.025% TWEEN 20® surfactant just prior to spraying. Soybean leaf disks were placed on agar in a multi-well plate (24-well format) and sprayed with the test solution. After drying for 24 hours, the disks were inoculated with a fungal spore suspension. Disease severity for the compound or mixture was evaluated 12 days after inoculation and reported as percent efficacy relative to untreated control disks.

[0173] result The results of the tests outlined above are shown below in Tables 1-8. These data show that synergistic fungicidal activity is observed in combination with Aureobasidin A and other active ingredients of component (B) at certain mass ratios against soybean rust caused by Phakopsora pachyrhizi in soybeans.

[0174] According to COLBY, mathematically, the synergy factor (SF) corresponds to O / E. In practical agriculture, a SF above 1.0 indicates a significant improvement over the purely complementary addition of activity (the assumed activity), whereas a SF below 0.9 in practical application routine indicates a loss of activity compared to the assumed activity.

[0175] [Table 4]

[0176] [Table 5]

[0177] [Table 6]

[0178] [Table 7]

[0179] [Table 8]

[0180] [Table 9]

[0181] [Table 10]

[0182]

Table 11

Claims

1. A fungicidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a cyclic depsipeptide of formula (I-A1): 【Chemistry 1】 or a stereoisomer thereof; and Component (B) is a histone deacetylase inhibitor: Ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1, 2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one N-propyl]-1,2,4-triazol-3-amine, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate, N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(E)- N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoic acid, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate or ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, or a salt, enantiomer, tautomer or N-oxide thereof A composition selected from the group consisting of:

2. 2. The composition of claim 1, wherein the weight ratio of (A) to (B) is from 100:1 to 1:1000, preferably from 100:1 to 1:500, more preferably from 50:1 to 1:200, even more preferably from 50:1 to 1:20, even more preferably from 30:1 to 1:1, and even more preferably from 10:1 to 3:

1.

3. Component (A) is one or more other cyclic depsipeptides of formula (IA) different from aureobasidin A: 【Chemistry 2】 (In the formula, R 1 is methyl or ethyl; X 1 , X 2 and X 3 are each hydrogen, or X 1 , X 2 and X 3 is hydrogen, fluorine or hydroxyl, provided that X 1 , X 2 and X 3 is fluorine or hydroxyl; X 4 is S, methylene or hydroxymethylene; A 3 are N-methyl-L-phenylalanine (L-MePhe), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), ortho-fluoro-N-methyl-L-phenylalanine (L-o-F-MePhe), meta-fluoro-N-methyl-L-phenylalanine (L-m-F-MePhe), para-fluoro-N-methyl-L-phenylalanine (L-p-F-MePhe), meta-bromo-N-methyl-L-phenylalanine (L-m-Br-MePhe), and para-bromo -N-methyl-L-phenylalanine (L-p-Br-MePhe), meta-iodo-N-methyl-L-phenylalanine (L-m-I-MePhe), para-iodo-N-methyl-L-phenylalanine (L-p-I-MePhe), 3-phenyl-N-methyl-L-phenylalanine, 4-phenyl-N-methyl-L-phenylalanine, 3-(4-fluorophenyl)-N-methyl-L-phenylalanine, 4-(4-fluorophenyl)-N-methyl-L-phenylalanine, 3-(4-pyridinyl)-N-methyl-L-phenylalanine 4-(4-pyridinyl)-N-methyl-L-phenylalanine, 3-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-4-pyridinyl)-N-methyl-L-phenylalanine, 3-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 3-[4-(piperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4- (piperazin-1-yl)phen-1-yl]phenyl-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4-(4-methylpiperazin-1-yl)phen-1-yl]phenyl-N-methyl-L-phenylalanine, β-oxo-N-methyl-L-phenylalanine (L-β-oxo-MePhe), β-acetoxy-N-methyl-L-phenylalanine (L-β-AcO-MePhe), N-methyl-L-tyrosine (L-MeTyr),an α-amino acid residue selected from the group consisting of O-methyl-N-methyl-L-tyrosine [L-MeTyr(Me)], N-methyl-L-alanine (L-MeAla), N-methyl-L-serine (L-MeSer), N-methyl-D-phenylalanine (D-MePhe), N-methyl-D-alanine (D-MeAla), N-methyl-D-valine (D-MeVal), N-methyl-D-serine (D-MeSer) and N-methyl-L-serine (L-MeSer) residues; A 5 is an α-amino acid residue selected from the group consisting of L-allo-isoleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle), L-norvaline (L-Nva), and L-valine (L-Val) residues; A 6 is an α-amino acid residue selected from the group consisting of N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), N-methyl-L-allo-isoleucine (L-MeAIle) and L-valine (L-Val) residues; A 7 is an α-amino acid residue selected from the group consisting of L-leucine (L-Leu), L-allo-isoleucine (L-AIle), and L-norvaline (L-Nva) residues; and A 8 β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), γ-hydroxy-N-methyl-L-valine (L-γ-OH-MeVal), N-methyl-L-valine (L-MeVal), L-valine (L-Val), N-methyl-2,3-didehydro-L-valine (L-MeDH), 2,3 Val), N-methyl-3,4-didehydro-L-valine (L-MeDH 3,4 and N,β-dimethyl-L-aspartic acid (L-N,β-MeAsp) residues). Or the composition of claim 1 further comprising a stereoisomer thereof.

4. The composition of claim 1 , wherein component (A) further comprises aureobasidin E and / or aureobasidin G.

5. Component (A) is: 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight of the cyclic depsipeptide of formula (I-A1) or a stereoisomer thereof; and 0.1% to 90% by weight, preferably 0.1% to 80% by weight, more preferably 0.1% to 60% by weight of one or more other cyclic depsipeptides of formula (IA) or stereoisomers thereof different from aureobasidin A The composition of claim 1 comprising:

6. Component (A) is one or more cyclic depsipeptides of formula (IB): 【Transformation 3】 (In the formula, R 1 is methyl or ethyl; X 4 is S, methylene, or hydroxymethylene; A 5 is an α-amino acid residue selected from the group consisting of L-allo-isoleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle), and L-valine (L-Val) residues; A 6 is an α-amino acid residue selected from the group consisting of N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), L-allo-isoleucine (L-AIle) and N-methyl-L-allo-isoleucine (L-MeAIle) residues; A 7 is an α-amino acid residue selected from the group consisting of L-leucine (L-Leu), L-allo-isoleucine (L-AIle), and L-norvaline (L-Nva) residues; and A 8 β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), γ-hydroxy-N-methyl-L-valine (L-γ-OH-MeVal), N-methyl-L-valine (L-MeVal), N-methyl-2,3-didehydro-L-valine (L-MeDH), 2,3 Val), N-methyl-3,4-didehydro-L-valine (L-MeDH 3,4 and N,β-dimethyl-L-aspartic acid (L-N,β-MeAsp) residues). or a stereoisomer thereof.

7. 10. The composition of claim 1, further comprising an agriculturally acceptable carrier and / or formulation adjuvant, and optionally a surfactant.

8. 10. A method for controlling or preventing phytopathogenic diseases, in particular caused by phytopathogenic fungi, in useful plants or their propagation material, which method comprises applying to said useful plants, their habitat or their propagation material a composition according to any one of claims 1 to 7.

9. 9. The method of claim 8, wherein component (A) is applied in an amount of 25 g a.i. / ha to 500 g a.i. / ha, with component (B) at 10 g a.i. / ha to 500 g a.i. / ha.

10. The plant pathogenic fungi include Alternaria, Botrytis, Cercospora, Colletotrichum, Corynespora, Guignardia, Mycosphaerella, Monilinia, 9. The method of claim 8, wherein the fungus is selected from the group consisting of Penicillium, Phakopsora, Phomopsis, Podosphaera, Pseudopezicula, Septoria, Uncinula, and Venturia.

11. 9. The method according to claim 8, wherein the useful plants are selected from cereal grains, fruits and nuts, vegetables, field crops, oilseed crops, fodder crops, forest plants, horticultural crops, floriculture, greenhouse and nursery plants, propagation material, culinary herbs and spices, and medicinal plants.

12. 9. The method according to claim 8, wherein the useful plants are selected from the group consisting of wheat, barley, rice, soybean, apple, almond, cherry, raspberry, grape, cucumber, peanut, tomato, strawberry, citrus fruits and banana.

13. 9. The method of claim 8, wherein the method controls or prevents plant pathogenic fungi selected from the group consisting of Alternaria, Cercospora, Colletotrichum, Corynespora, Mycosphaerella, Phakopsora, Phomopsis and Septoria in soybean plants.

14. 9. The method of claim 8, wherein components (A) and (B) as defined in any one of claims 1 to 7 are applied sequentially.

15. Use of a composition comprising component (A) and component (B) according to any one of claims 1 to 7 as a disinfectant.

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