Fungicidal composition

Abstract

A fungicidal composition, the fungicidal composition comprising a component A, the component A comprising a cyclic ester peptide gold basidiosin A or a stereoisomer thereof; and a component B, wherein the component B comprises spring daily mycin or natamycin. A method of controlling or preventing a phytopathogenic disease or a phytopathogenic fungus on a plant or on propagation material thereof, the method comprising applying the composition to the plant, locus or propagation material thereof. The invention also relates to the use of the composition as a fungicide.

Description

[0001] This invention relates to novel fungicidal compositions for controlling fungi. Methods for controlling or preventing plant pathogenic diseases or plant pathogenic fungi on plants or their propagation material are also disclosed. Background Technology

[0002] Aureobasidium pullulans is a group of antifungal cyclic ester peptides first isolated from the filamentous fungus *Aureobasidium pullulans* R106 (EP 352092 A2; Takesako et al., 1991, *J. Antibiot.* 44, 919-924, doi: 10.7164 / antibiotics.44.919; Yoshikawa et al., 1993, *J. Antibiot.* 46, 1347-1354, doi: 10.7164 / antibiotics.46.1347; and Awazu et al., 1995, *J. Antibiot.* 48, 525-527, doi: 10.7164 / antibiotics.48.525). Aureobasidium pullulans exhibits broad-spectrum antifungal activity. In addition, the use of basidiosin for controlling various plant pathogenic fungi on plants and seeds has been disclosed (EP 0500264 A1, WO 2018102345). Combinations of basidiosin for controlling plant pathogenic fungi with one or more other active ingredients with different modes of action have also been disclosed (WO 2021245102 A1, WO 2021245103 A1, WO 2021245104 A1, WO 2021245105 A1, WO2021245106 A1).

[0003] However, the aforementioned fungicides and combinations may not be sufficiently effective and carry the risk of developing resistance. Therefore, there remains a need for improved antifungal compositions for controlling plant pathogenic fungi. Summary of the Invention

[0004] This invention discloses the unexpected synergistic antifungal activity of compositions comprising a cyclic ester peptide represented by formula (I), particularly aurabasidin A (AbA) and natamycin or kasugamycin. Both natamycin and kasugamycin are naturally produced by Streptomyces bacteria.

[0005] According to another aspect of the invention, a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi on plants or their propagation material is provided, the method comprising applying a composition as defined according to the invention to the plant, its location, or its propagation material. Preferably, the method comprises applying a composition according to the invention to a plant or its location, more preferably to a plant. Preferably, the method comprises applying a composition according to the invention to the propagation material of the plant.

[0006] According to another aspect of the invention, the use of a composition comprising components A and B as defined according to the invention is provided as a fungicide.

[0007] It has been found that the combination of natamycin or kasugamycin with a compound of formula (I) of component A (preferably including amberrin A) can unexpectedly and significantly enhance the latter's effectiveness against fungi, and vice versa. Furthermore, the compositions of the present invention can effectively combat a broader spectrum of these fungi than when the individual active ingredients are used alone.

[0008] The benefits provided by the specific fungicidal compositions according to the invention may also include, in particular, favorable levels of biological activity for protecting plants from fungal diseases or superior properties for use as agricultural chemical active ingredients (e.g., greater biological activity, favorable activity spectrum, increased safety, improved physicochemical properties, or increased biodegradability).

[0009] As used herein, a chemical residue refers to a derivative of a portion present in a particular product. In order to form the product, at least one atom of the portion is replaced by a bond with a second portion, such that the product contains a derivative of the portion. For example, an amino acid residue in a product can refer to a cyclic peptide as described herein, having an amino acid incorporated therein by forming one or more peptide bonds, and such residues may be interchangeably referred to herein as amino acids or amino acid residues.

[0010] As used herein, the term "cyclic ester peptide" refers to a cyclic peptide composed of units derived from 2-hydroxy-3-methylalkanic acid or 2-hydroxy-3-hydroxymethylalkanic acid and units derived from the following α-amino acid residues in sequence: a first α-amino acid residue selected from N-methyl-L-valine (L-MeVal) and L-valine (L-Val); a second α-amino acid residue selected from L-phenylalanine (L-Phe), o-fluoro-N-methyl-L-phenylalanine (LoF-MePhe), m-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), 2-hydroxy-phenylalanine (L-2OH-Phe), 3-hydroxy-phenylalanine (L-3OH-Phe), and L-tyrosine (L-Tyr); and a third α-amino acid residue A. 3 The fourth α-amino acid residue is selected from L-proline (L-Pro), L-thioproline (L-SPro), and 4-hydroxy-L-proline (L-4Hyp); the fifth α-amino acid residue A 5 ; Sixth α-amino acid residue A 6 ; Seventh α-amino acid residue A 7 ; and the eighth α-amino acid residue A 8 In which the α-amino acid residue A 8 -OCH(CH(R) via ester group bonding to 2-hydroxy-3-methylalkanoic acid 2 )R 1 The part forms -C(=O)OCH(CH(R) 2 )R 1 (part or α-amino acid residue A) 8 -OCH(CH(OCH)R, which is bonded to 2-hydroxy-3-hydroxymethylalkanoic acid via ester group. 1 The part forms -C(=O)OCH(CH(OCH)R 1 The α-amino acid residues, namely the first, second, third, fourth, fifth, sixth, seventh, and eighth α-amino acid residues, are linked to each other by peptide bonds. The 2-hydroxy-3-methylalkanic acid can be 2(R)-hydroxy-3(R)-methylvaleric acid, 2(R)-hydroxy-3-methylbutyric acid, 2,5-dihydroxy-3-methylvaleric acid, 2,4-dihydroxy-3-methylvaleric acid, or D-2-hydroxyisovaleric acid, and preferably 2(R)-hydroxy-3(R)-methylvaleric acid or 2(R)-hydroxy-3-methylbutyric acid. The 2-hydroxy-3-hydroxymethylalkanic acid can be 2-hydroxy-3-hydroxymethylvaleric acid.

[0011] Preferably, component A according to the invention comprises an active ingredient, preferably wherein the active ingredient comprises a fungicide. Preferably, the active ingredient is a cyclic ester peptide according to the invention, and more preferably a fungicide.

[0012] Preferably, component A according to the invention comprises a cyclic ester peptide or a stereoisomer thereof represented by formula (I):

[0013] (I),

[0014] in:

[0015] R 1 It is methyl or ethyl;

[0016] R 2 It is methyl, hydroxymethyl, or hydroxyethyl;

[0017] R 3 It is hydrogen or methyl;

[0018] X 1 X 2 and X 3 Each is hydrogen, or X 1 X 2 and X 3 It is hydrogen, fluorine, or hydroxyl, provided that X 1 X 2 and X 3 Only one of them is fluorine or hydroxyl;

[0019] X 4 It is CH2, S, or hydroxymethylene;

[0020] A 3It is selected from the following α-amino acid residues: N-methyl-L-phenylalanine (L-MePhe), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), o-fluoro-N-methyl-L-phenylalanine (LoF-MePhe), m-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), p-bromo ... L-phenyl-N-methyl-L-phenylalanine (Lm-Br-MePhe), p-bromo-N-methyl-L-phenylalanine (Lp-Br-MePhe), m-iodo-N-methyl-L-phenylalanine (LmI-MePhe), p-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) 3-(4-pyridyl)-N-methyl-L-phenylalanine, 4-(4-pyridyl)-N-methyl-L-phenylalanine, 3-(1-pyridyl)-N-methyl-L-phenylalanine, 4-(1-pyridyl)-N-methyl-L-phenylalanine, 4-(2-chloro-4-pyridyl)-N-methyl-L-phenylalanine, 3-(2-chloro-5-pyridyl)-N-methyl-L-phenylalanine, 4-(2-chloro-5-pyridyl)-N -Methyl-L-phenylalanine, 3-[4-(piperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 4-[4-(piperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 4-[4-(4-methylpiperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, β-oxo-N-methyl-L-phenylalanine (L-β-oxo-MePhe), β-R 4 ON-methyl-L-phenylalanine (where R) 4 It is a lower acyl group with 1 to 4 carbon atoms (L-β-R) 4 OMePhe), N-methyl-L-tyrosine (L-MeTyr), O-methyl-N-methyl-L-tyrosine [L-MeTyr(Me)], N-methyl-L-alanine (L-MeAla), N-methyl-L-serine (L-MeSer), sarcosine (Sar), N-methyl-D-phenylalanine (D-MePhe), N-methyl-D-alanine (D-MeAla), N-methyl-D-valine (D-MeVal) and N-methyl-D-serine (D-MeSer) residues;

[0021] A 5It is selected from the following α-amino acid residues: L-alloleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle), L-valine (L-Nva), L-valine (L-Val) and L-methionine sulfoxide (L-Met(O));

[0022] A 6 It is selected from the following α-amino acid residues: N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), N-methyl-L-isoleucine (L-MeAIle) and L-valine (L-Val) residues;

[0023] A 7 It is selected from the following α-amino acid residues: L-alloleucine (L-AIle), L-leucine (L-Leu), and L-n-valine (L-Nva) residues; and

[0024] A 8 It is selected from the following α-amino acid residues: β-methyl-L-phenylalanine (L-β-Phe), 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 The residues include 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).

[0025] Preferably, β-R 4 ON-methyl-L-phenylalanine is β-acetoxy-N-methyl-L-phenylalanine (L-β-AcO-MePhe).

[0026] Preferably, component A according to the invention comprises a cyclic ester peptide or its stereoisomer represented by formula (Ia):

[0027] (Ia),

[0028] in:

[0029] R 1 It is methyl or ethyl;

[0030] X 1 X 2 and X 3 Each is hydrogen, or X 1 X 2 and X 3 It is hydrogen, fluorine, or hydroxyl, provided that X 1 X 2 and X 3 Only one of them is fluorine or hydroxyl;

[0031] X 4 It is CH2, S, or hydroxymethylene;

[0032] A 3 It is selected from the following α-amino acid residues: N-methyl-L-phenylalanine (L-MePhe), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), o-fluoro-N-methyl-L-phenylalanine (LoF-MePhe), m-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), p-bromo ... L-phenyl-N-methyl-L-phenylalanine (Lm-Br-MePhe), p-bromo-N-methyl-L-phenylalanine (Lp-Br-MePhe), m-iodo-N-methyl-L-phenylalanine (LmI-MePhe), p-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) 3-(4-pyridyl)-N-methyl-L-phenylalanine, 4-(4-pyridyl)-N-methyl-L-phenylalanine, 3-(1-pyridyl)-N-methyl-L-phenylalanine, 4-(1-pyridyl)-N-methyl-L-phenylalanine, 4-(2-chloro-4-pyridyl)-N-methyl-L-phenylalanine, 3-(2-chloro-5-pyridyl)-N-methyl-L-phenylalanine, 4-(2-chloro-5-pyridyl)-N -Methyl-L-phenylalanine, 3-[4-(piperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 4-[4-(piperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 4-[4-(4-methylpiperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, β-oxo-N-methyl-L-phenylalanine (L-β-oxo-MePhe), β-R 4 ON-methyl-L-phenylalanine (where R) 4It is a lower acyl group with 1 to 4 carbon atoms (L-β-R) 4 OMePhe), N-methyl-L-tyrosine (L-MeTyr), O-methyl-N-methyl-L-tyrosine [L-MeTyr(Me)], N-methyl-L-alanine (L-MeAla), N-methyl-L-serine (L-MeSer), sarcosine (Sar), N-methyl-D-phenylalanine (D-MePhe), N-methyl-D-alanine (D-MeAla), N-methyl-D-valine (D-MeVal) and N-methyl-D-serine (D-MeSer) residues;

[0033] A 5 It is selected from the following α-amino acid residues: L-alloleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle), L-valine (L-Nva), L-valine (L-Val) and L-methionine sulfoxide (L-Met(O));

[0034] A 6 It is selected from the following α-amino acid residues: N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), N-methyl-L-isoleucine (L-MeAIle) and L-valine (L-Val) residues;

[0035] A 7 It is selected from the following α-amino acid residues: L-alloleucine (L-AIle), L-leucine (L-Leu), and L-n-valine (L-Nva) residues; and

[0036] A 8 It is selected from the following α-amino acid residues: β-methyl-L-phenylalanine (L-β-Phe), 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 The residues include 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).

[0037] Preferably, β-R4 ON-methyl-L-phenylalanine is β-acetoxy-N-methyl-L-phenylalanine (L-β-AcO-MePhe).

[0038] Preferably, the compounds having formula (I) according to the invention are selected from compounds 1.001 to 1.044 listed in Table A (hereinafter) or compounds 2.001 to 2.035 listed in Table B (hereinafter). The following list provides the substituents R of the compounds having formula (I) according to the invention. 1 R 2 R 3 X 1 X 2 X 3 A 3 X 4 A 5 A 6 A 7 and A 8 The definitions, including preferred definitions, are provided below. Any definition given below for any of these substituents may be combined with any definition of any other substituent given below or elsewhere in this document.

[0039] Table A: This table discloses 44 compounds having formula (I), of which R 1 R 2 R 3 X 1 X 2 X 3 A 3 X 4 A 5 A 6 A 7 and A 8 As shown in Table A below. “ID” indicates that this structure is also known as the (abbreviated) gold-basidioidin variant.

[0040] Table A

[0041]

[0042] Table B: This table discloses 35 compounds having formula (I), of which R 1 It is ethyl, R 2 It is methyl, R 3 It is methyl, X 4 It's L-Pro, A 6 It is L-MeVal, and A 7 It is L-Leu, and X 1 X2 X 3 A 3 A 5 and A 8 As shown in Table B below.

[0043] Table B

[0044]

[0045] Preferably, component A according to the present invention comprises a cyclic ester peptide selected from the group consisting of: acubin A (AbA), acubin B (AbB), acubin C (AbC), acubin D (AbD), acubin E (AbE), acubin F (AbF), acubin G (AbG), acubin H (AbH), acubin I (AbI), acubin J (AbJ), acubin K (AbK), acubin L (AbL), acubin M (AbM), acubin N (AbN), and acubin O (AbA). (bO), acubin P (AbP), acubin Q (AbQ), acubin R (AbR), acubin S1 (AbS1), acubin S2a (AbS2a), acubin S2b (AbS2b), acubin S3 (AbS3), acubin S4 (AbS4), acubin T1 (AbT1), acubin T2 (AbT2), acubin T3 (AbT3), acubin T4 (AbT4), acubin U1 (AbU1), and acubin U2 (AbU2), or their stereoisomers. More preferably, the cyclic ester peptide is selected from the group consisting of: acubin A (AbA), acubin E (AbE), acubin G (AbG), acubin D (AbD), and acubin I (AbI). More preferably, the cyclic ester peptide is selected from the group consisting of: acupuncture point A (AbA), acupuncture point E (AbE), and acupuncture point G (AbG).

[0046] Preferably, component A according to the present invention comprises gold basidiomycin A (AbA).

[0047] Preferably, the compound of formula (I) according to the present invention is a gold basidiomycin A (AbA) or its stereoisomer, preferably represented by formula (Ib):

[0048] (Ib).

[0049] A gold basidiosin A represents a cyclic ester peptide of formula (Ib) or its stereoisomers, composed of units derived from 2(R)-hydroxy-3(R)-methylvaleric 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-alloseleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu), and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal) in sequence.

[0050] The known stereoisomer of AbA is gold basidiomin T1 (AbT1), which is a cyclic ester peptide of formula (Ib) or its stereoisomers, composed of units derived from 2(R)-hydroxy-3(S)-methylvaleric acid ((2R,3S)-Hmp), N-methyl-L-valine (L-MeVal), L-phenylalanine (L-Phe), N-methyl-L-phenylalanine (L-MePhe), L-proline (L-Pro), L-alloseleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu), and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal) in sequence.

[0051] Preferably, the compound of formula (I) according to the present invention comprises gold basidiomycin E (AbE) or its stereoisomer, preferably represented by formula (Ic):

[0052] (Ic).

[0053] Golden basidiomycin E represents a cyclic ester peptide or its stereoisomers having the formula (Ic) composed of units derived from 2(R)-hydroxy-3(R)-methylvaleric 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-alloseleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu), and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal) in sequence.

[0054] Preferably, the compound of formula (I) according to the present invention comprises gold basidiomycin G (AbG) or its stereoisomer, preferably represented by formula (Id):

[0055] (Id).

[0056] Golden basidiosin G represents a cyclic ester peptide or its stereoisomers having the formula (Id) composed of units derived from 2(R)-hydroxy-3(R)-methylvaleric 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-alloseleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu), and N-methyl-L-valine (L-MeVal) in sequence.

[0057] Preferably, the compound of formula (I) according to the present invention comprises gold basidiomycin D (AbD) or its stereoisomer, preferably represented by formula (Ie):

[0058] (Ie).

[0059] Golden basidiosin D represents a cyclic ester peptide or its stereoisomers having the formula (Ie) composed of units derived from 2(R)-hydroxy-3(R)-methylvaleric 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-isoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu), and γ-hydroxy-N-methyl-L-valine (L-γ-OH-MeVal) in sequence.

[0060] Preferably, the compound of formula (I) according to the present invention comprises gold basidiomycin I (AbI) or its stereoisomer, preferably represented by formula (If):

[0061] (If).

[0062] Golden basidiosin I represents a cyclic ester peptide or its stereoisomers having the formula (If) composed of units derived from 2(R)-hydroxy-3(R)-methylvaleric 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-leucine (L-Leu), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu), and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal) in sequence.

[0063] Preferably, component A according to the invention further comprises one or more other cyclic ester peptides represented by formula (I) or their stereoisomers. Preferably, component A according to the invention further comprises one or more other cyclic ester peptides represented by formula (Ia) or their stereoisomers.

[0064] Preferably, component A according to the invention comprises two or more cyclic ester peptides having formula (I) as defined above, or their stereoisomers. Preferably, component A comprises gold basidioidin A and one or more other cyclic ester peptides having formula (I) as defined above, or their stereoisomers. Preferably, component A comprises gold basidioidin E and one or more other cyclic ester peptides having formula (I) as defined above, or their stereoisomers. Preferably, component A comprises gold basidioidin A and gold basidioidin E or gold basidioidin G. Preferably, component A comprises gold basidioidin A and gold basidioidin D or gold basidioidin I.

[0065] Preferably, component A according to the invention further comprises at least one other cyclic ester peptide having formula (I) or a stereoisomer thereof selected from the group consisting of: acubin E (AbE) and acubin G (AbG).

[0066] Preferably, component A according to the invention comprises two or more cyclic ester peptides having formula (Ia) as defined above, or stereoisomers thereof. Preferably, component A comprises gold basidioidin A and one or more other cyclic ester peptides having formula (Ia) as defined above, or stereoisomers thereof. Preferably, component A comprises gold basidioidin E and one or more other cyclic ester peptides having formula (Ia) as defined above, or stereoisomers thereof. Preferably, component A comprises: (i) gold basidioidin A; and (ii) gold basidioidin E or gold basidioidin G. Preferably, component A comprises: (i) gold basidioidin A; and (ii) gold basidioidin D or gold basidioidin I.

[0067] Preferably, component A comprises: (i) a metal basidioidin A or a stereoisomer thereof; and (ii) a metal basidioidin E or a stereoisomer thereof, or a metal basidioidin G or a stereoisomer thereof. Preferably, component A comprises: (i) a metal basidioidin A or a stereoisomer thereof; and (ii) a metal basidioidin D or a stereoisomer thereof, or a metal basidioidin I or a stereoisomer thereof.

[0068] Preferably, component A according to the invention further comprises at least one other cyclic ester peptide having formula (I) or stereoisomer thereof having formula (Ia) selected from the group consisting of: acubin E (AbE) and acubin G (AbG).

[0069] Preferably, component A according to the invention comprises a gold basidioidin A and one or more other cyclic ester peptides of formula (I) selected from the group consisting of compounds 1.001 to 1.005 and 1.007 to 1.044 as shown in Table A, or stereoisomers thereof. Preferably, component A comprises a gold basidioidin A and at least one other cyclic ester peptide of formula (Ia) selected from the group consisting of gold basidioidin E and gold basidioidin G, or stereoisomers thereof. Preferably, component A according to the invention comprises a gold basidioidin A and one or more cyclic ester peptides of formula (I) selected from the group consisting of compounds 2.001 to 2.035 as shown in Table B, or stereoisomers thereof.

[0070] In another embodiment of the invention, component A comprises a strain of *Brachymycosis buddingae*, typically strain *Brachymycosis buddingae* R106.

[0071] It should be understood that, without limiting the scope of the invention, one or more cyclic ester peptides having formula (I) as defined above, or stereoisomers thereof, can be obtained from the fermentation broth of a strain of *Brachystomata* (typically *Brachystomata* R106).

[0072] As used herein, the term "fermentation broth" refers to a composition obtained from the fermentation process of a strain.

[0073] In another embodiment of the invention, component A is a fermentation broth containing two or more cyclic ester peptides having formula (I) as defined above, or their stereoisomers.

[0074] In a variant of this embodiment of the invention, component A is a fermentation broth containing two or more cyclic ester peptides having formula (Ia) as defined above, or their stereoisomers.

[0075] In an embodiment of the invention, component A is a fermentation broth containing a gold basidiin A and one or more other cyclic ester peptides of formula (I) or stereoisomers thereof as defined above, or cyclic ester peptides of formula (Ia) or stereoisomers thereof.

[0076] In another embodiment of the invention, component A is a fermentation broth containing amberidin E and one or more other cyclic ester peptides having formula (I) or stereoisomers thereof as defined above, or cyclic ester peptides having formula (Ia) or stereoisomers thereof.

[0077] In an embodiment of the invention, component A is a fermentation broth containing aurabasitin A or its stereoisomer.

[0078] In another embodiment of the invention, component A comprises a fermentation broth containing a gold basidiin A or its stereoisomer.

[0079] In another embodiment of the invention, component A comprises a fermentation broth containing acrobaticin A or its stereoisomer and acrobaticin E or its stereoisomer.

[0080] In another embodiment of the invention, component A comprises a fermentation broth containing aurabasin A or its stereoisomer and aurabasin G or its stereoisomer.

[0081] In another embodiment of the invention, component A comprises a fermentation broth containing aurabasin A or its stereoisomer and aurabasin D or its stereoisomer.

[0082] In another embodiment of the invention, component A comprises a fermentation broth containing two or more cyclic ester peptides having formula (I) as defined above, or stereoisomers thereof.

[0083] In a variant of this embodiment of the invention, component A comprises a fermentation broth containing two or more cyclic ester peptides having formula (Ia) as defined above, or stereoisomers thereof.

[0084] In an embodiment of the invention, component A comprises a fermentation broth containing a gold basidiin A and one or more other cyclic ester peptides having formula (I) or stereoisomers thereof as defined above, or cyclic ester peptides having formula (Ia) or stereoisomers thereof.

[0085] In another embodiment of the invention, component A further comprises a fermentation broth containing aurabatin E and one or more other cyclic ester peptides having formula (I) or stereoisomers thereof as defined above, or cyclic ester peptides having formula (Ia) or stereoisomers thereof.

[0086] Component A of the composition according to the invention may further comprise a fermentation broth containing one or more other cyclic ester peptides having formula (I) as defined above, or stereoisomers thereof. Suitably, component A may further comprise a fermentation broth containing one or more other cyclic ester peptides having formula (Ia) as defined above, or stereoisomers thereof. Suitably, component A may further comprise a fermentation broth containing a gold basididin G or a stereoisomer thereof. Suitably, component A may further comprise a fermentation broth containing a gold basididin E or a stereoisomer thereof.

[0087] The antifungal composition according to the invention comprises component B, wherein component B comprises natamycin or kasugamycin.

[0088] Component B is referred to herein and above by its so-called "ISO common name" or another "common name" or trade name, as used in individual cases. Component B is known and commercially available and / or can be prepared using procedures known in the art and / or procedures reported in the literature.

[0089] Preferably, component B according to the invention comprises an active ingredient, preferably wherein the active ingredient comprises a fungicide. Preferably, according to the invention, natamycin or kasugamycin is the active ingredient, preferably a fungicide.

[0090] Preferably, component B according to the invention comprises natamycin. Natamycin, also known as pimaricin, is registered under CAS 7681-93-8. Preferably, natamycin is represented by formula (II):

[0091] (II).

[0092] Natamycin is a polyene antimicrobial agent, first isolated from cultures of *Streptomyces natalensis*. It is used in the medical industry to treat fungal infections and in the food industry to reduce fungal growth.

[0093] Natamycin can be produced by several species of the *Streptomyces* genus, such as *Streptomyces natalatum*, *Streptomyces lydicus*, *Streptomyces chattanoogensis*, and *Streptomyces gilvosporeus*. On an industrial scale, it is typically produced through fermentation of various *Streptomyces* strains. Natamycin is marketed under, for example, by trademarks such as CeraMax®, Natamycin L, and Zivion. TM M, BIOSPECTRA® 100SC, BIOSHIELD TM 100SC and Nature's Shield® 100SC are commercially available.

[0094] Preferably, component B according to the invention comprises kasugamycin. Kasugamycin is registered under CAS 6980-18-3. Preferably, kasugamycin is represented by formula (IIIa) or (IIIb):

[0095] (IIIa),

[0096] (IIIb).

[0097] Kasugamycin is an aminoglycoside antibiotic and fungicide, first isolated from *Streptomyces kasugaensis*. It is considered for use as an agricultural chemical.

[0098] Kasugamycin is typically produced through fermentation by various Streptomyces strains. Kasugamycin is commercially available, for example, under the brand names Kasumin® 2L, Biomycin, and GRALIZ®.

[0099] Preferably, the composition according to the invention comprises 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight, of a basidiosin A or its stereoisomer, 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 ester peptides or their stereoisomers represented by formula (I).

[0100] Preferably, the composition according to the invention comprises 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight, of a basidiosin A or its stereoisomer, 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 ester peptides or their stereoisomers represented by formula (Ia).

[0101] Preferably, the composition according to the invention comprises 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight, of a basidiosin E or its stereoisomer, 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 ester peptides or their stereoisomers represented by formula (I).

[0102] Preferably, the composition according to the invention comprises 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight, of a basidiosin E or its stereoisomer, 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 ester peptides or their stereoisomers represented by formula (Ia).

[0103] Preferably, the composition according to the invention comprises 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight, of a basidiosin G or its stereoisomer, 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 ester peptides or their stereoisomers represented by formula (I).

[0104] Preferably, the composition according to the invention comprises 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight, of a basidiosin G or its stereoisomer, 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 ester peptides or their stereoisomers represented by formula (Ia).

[0105] In embodiments of the invention, component (A) typically comprises:

[0106] The product comprises, by weight, 60% to 99.5% of acupuncture point A, 0.05% to 5% of acupuncture point E, optionally 0.1% to 30% of acupuncture point G, and optionally 0.1% to 10% of one or more other cyclic ester peptides of formula (Ia) or stereoisomers thereof.

[0107] Preferably, the weight ratio of component A to component B in the composition according to the invention is 100:1 to 1:5000, more preferably 100:1 to 1:4000, 100:1 to 1:3000, 100:1 to 1:2000, 100:1 to 1:1000, 100:1 to 1:800, 100:1 to 1:500, 100:1 to 1:200, 100:1 to 1:100, 100:1 to 1:50, 100:1 to 1:20, 100:1 to 1:10, 50:1 to 1:5000, 50:1 to 1:4000, 50: 1 to 1 : 3000, 50 : 1 to 1 : 2000, 50 : 1 to 1 : 1000, 50 : 1 to 1 : 800, 50 : 1 to 1 : 500, 50 : 1 to 1 : 200, 50 : 1 to 1 : 100, 50 : 1 to 1 : 50, 50 : 1 to 1 : 20, 50 : 1 to 1 : 10, 20 : 1 to 1 : 5000, 20 : 1 to 1 : 4000, 20 : 1 to 1 : 3000, 20 : 1 to 1 : 2000, 20 : 1 to 1 : 1000, 20 : 1 to 1 : 800, 20 : 1 to 1 : 500, 20 : 1 to 1 : 200, 20 : 1 to 1 : 100, 20 : 1 to 1 : 50, 20 : 1 to 1 : 20, 20 : 1 to 1 : 10, 10 : 1 to 1 : 5000, 10 : 1 to 1 : 4000, 10 : 1 to 1 : 3000, 10 : 1 to 1 : 2000, 10 : 1 to 1 : 1000, 10 : 1 to 1 : 800, 10 : 1 to 1 : 500, 10 : 1 to 1 : 200, 10 : 1 to 1 : 100, 10 : 1 to 1 : 50, 10 : 1 to 1 : 20, 10:1 to 1:10, 1:1 to 1:5000, 1:1 to 1:4000, 1:1 to 1:3000, 1:1 to 1:2000, 1:1 to 1:1000, 1:1 to 1:800, 1:1 to 1:500, 1:1 to 1:200, 1:1 to 1:100, 1:1 to 1:50, 1:1 to 1:20, 1:1 to 1:10, 1:10 to 1:5000, 1:10 to 1:4000, 1:10 to 1:3000, 1:10 to 1: 2000, 1:10 to 1:1000, 1:10 to 1:800, 1:10 to 1:500, 1:10 to 1:200, 1:10 to 1:100, 1:10 to 1:50, 1:10 to 1:20, 1:20 to 1:5000, 1:20 to 1:4000, 1:20 to 1:3000, 1:20 to 1:2000, 1:20 to 1:1000, 1:20 to 1:800, 1:20 to 1:500, 1:20 to 1:200, 1:20 to 1:100, or 1: More preferably, the weight ratio of component A to component B in the composition according to the invention is 100:1 to 1:1000, 100:1 to 1:800, 100:1 to 1:500, 100:1 to 1:200, 50:1 to 1:800, 50:1 to 1:200, 50:1 to 1:100, 50:1 to 1:20, 20:1 to 1:600, 20:1 to 1:40, 20:1 to 1:20, or 10:1 to 1:80.

[0108] Preferably, the weight ratio of component A to component B in the composition according to the invention is 100:1 to 1:5000, more preferably 100:1 to 1:4000, 100:1 to 1:3000, 100:1 to 1:2000, 100:1 to 1:1000, 100:1 to 1:800, 100:1 to 1:500, 100:1 to 1:200, 100:1 to 1:100, 100:1 to 1:50, 100:1 to 1:20, 100:1 to 1:10, 50:1 to 1:5000, 50:1 to 1:4000, 50: 1 to 1 : 3000, 50 : 1 to 1 : 2000, 50 : 1 to 1 : 1000, 50 : 1 to 1 : 800, 50 : 1 to 1 : 500, 50 : 1 to 1 : 200, 50 : 1 to 1 : 100, 50 : 1 to 1 : 50, 50 : 1 to 1 : 20, 50 : 1 to 1 : 10, 20 : 1 to 1 : 5000, 20 : 1 to 1 : 4000, 20 : 1 to 1 : 3000, 20 : 1 to 1 : 2000, 20 : 1 to 1 : 1000, 20 : 1 to 1 : 800, 20 : 1 to 1 : 500, 20 : 1 to 1 : 200, 20 : 1 to 1 : 100, 20 : 1 to 1 : 50, 20 : 1 to 1 : 20, 20 : 1 to 1 : 10, 10 : 1 to 1 : 5000, 10 : 1 to 1 : 4000, 10 : 1 to 1 : 3000, 10 : 1 to 1 : 2000, 10 : 1 to 1 : 1000, 10 : 1 to 1 : 800, 10 : 1 to 1 : 500, 10 : 1 to 1 : 200, 10 : 1 to 1 : 100, 10 : 1 to 1 : 50, 10 : 1 to 1 : 20, 10:1 to 1:10, 1:1 to 1:5000, 1:1 to 1:4000, 1:1 to 1:3000, 1:1 to 1:2000, 1:1 to 1:1000, 1:1 to 1:800, 1:1 to 1:500, 1:1 to 1:200, 1:1 to 1:100, 1:1 to 1:50, 1:1 to 1:20, 1:1 to 1:10, 1:10 to 1:5000, 1:10 to 1:4000, 1:10 to 1:3000, 1:10 to 1: 2000, 1:10 to 1:1000, 1:10 to 1:800, 1:10 to 1:500, 1:10 to 1:200, 1:10 to 1:100, 1:10 to 1:50, 1:10 to 1:20, 1:20 to 1:5000, 1:20 to 1:4000, 1:20 to 1:3000, 1:20 to 1:2000, 1:20 to 1:1000, 1:20 to 1:800, 1:20 to 1:500, 1:20 to 1:200, 1:20 to 1:100, or 1: More preferably, the weight ratio of component A to component B in the composition according to the invention is 100:1 to 1:1000, 100:1 to 1:800, 100:1 to 1:500, 100:1 to 1:200, 50:1 to 1:800, 50:1 to 1:200, 50:1 to 1:100, 50:1 to 1:20, 20:1 to 1:600, 20:1 to 1:40, 20:1 to 1:20, or 10:1 to 1:80, wherein component A comprises gold basidiomycin A (AbA).

[0109] Preferably, the weight ratio of component A to component B in the composition according to the invention is 100:1 to 1:1000, more preferably 100:1 to 1:800, 100:1 to 1:500, 100:1 to 1:200, 100:1 to 1:100, 100:1 to 1:50, 100:1 to 1:20, 100:1 to 1:10, 50:1 to 1:1000, 50:1 to 1:800, 50:1 to 1:500, 50:1 to 1:200, 50:1 to 1:100, 50:1 to 1:50, 50:1 to 1: ... 20, 50: 1 to 1: 10, 20: 1 to 1: 1000, 20: 1 to 1: 800, 20: 1 to 1: 500, 20: 1 to 1: 200, 20: 1 to 1: 100, 20: 1 to 1: 50, 20: 1 to 1: 20, 20: 1 to 1: 10, 10: 1 to 1: 1000, 10: 1 to 1: 800, 10: 1 to 1: 500, 10: 1 to 1: 200, 10: 1 to 1: 100, 10: 1 to 1: 50, 10: 1 to 1: 20, 10: 1 to 1 : 10, 1:1 to 1: 1000, 1:1 to 1: 800, 1:1 to 1: 500, 1:1 to 1: 200, 1:1 to 1: 100, 1:1 to 1: 50, 1:1 to 1: 20, 1:1 to 1: 10, 1:10 to 1: 1000, 1:10 to 1: 800, 1:10 to 1: 500, 1:10 to 1: 200, 1:10 to 1: 100, 1:10 to 1: 50, 1:10 to 1: 20, 1:20 to 1: 1000, 1:20 to 1: 800, 1:20 to 1:500, 1:20 to 1:200, 1:20 to 1:100, or 1:20 to 1:50, wherein component B contains natamycin.

[0110] Preferably, the weight ratio of component A to component B in the composition according to the invention is 100:1 to 1:5000, more preferably 100:1 to 1:4000, 100:1 to 1:3000, 100:1 to 1:2000, 100:1 to 1:1000, 100:1 to 1:800, 100:1 to 1:500, 100:1 to 1:200, 100:1 to 1:100, 100:1 to 1:50, 50:1 to 1:5000, 50:1 to 1:4000, 50:1 to 1:3000, 50:1 to 1:2000, 50: 1 to 1 : 1000, 50 : 1 to 1 : 800, 50 : 1 to 1 : 500, 50 : 1 to 1 : 200, 50 : 1 to 1 : 100, 50 : 1 to 1 : 50, 20 : 1 to 1 : 5000, 20 : 1 to 1 : 4000, 20 : 1 to 1 : 3000, 20 : 1 to 1 : 2000, 20 : 1 to 1 : 1000, 20 : 1 to 1 : 800, 20 : 1 to 1 : 500, 20 : 1 to 1 : 200, 20 : 1 to 1 : 100, 20 : 1 to 1 : 50, 10 : 1 to 1 : 5000, 10 : 1 to 1 : 4000, 10 : 1 to 1 : 3000, 10 : 1 to 1 : 2000, 10 : 1 to 1 : 1000, 10 : 1 to 1 : 800, 10 : 1 to 1 : 500, 10 : 1 to 1 : 200, 10 : 1 to 1 : 100, 10 : 1 to 1 : 50, 1 : 1 to 1 : 5000, 1 : 1 to 1 : 4000, 1 : 1 to 1 : 3000, 1 : 1 to 1 : 2000, 1 : 1 to 1 : 1000, 1 : 1 to 1 : 800, 1 : 1 to 1 : 500, 1:1 to 1:200, 1:1 to 1:100, 1:1 to 1:50, 1:10 to 1:5000, 1:10 to 1:4000, 1:10 to 1:3000, 1:10 to 1:2000, 1:10 to 1:1000, 1:10 to 1:800, 1:10 to 1:500, 1:10 to 1:200, 1:10 to 1:100, 1:10 to 1:50, 1:20 to 1:5000, 1:20 to 1:4000, 1:20 to 1:3000, 1 20 to 1: 2000, 1: 20 to 1: 1000, 1: 20 to 1: 800, 1: 20 to 1: 500, 1: 20 to 1: 200, 1: 20 to 1: 100, 1: 20 to 1: 50, or 1: 20 to 1: 50, wherein component B contains kasugamycin.

[0111] Preferably, the weight ratio of component A to component B in the composition according to the invention is 100:1 to 1:1000, wherein component A contains AbA and component B contains natamycin. More preferably, the weight ratio is 100:1 to 1:200 or 20:1 to 1:100.

[0112] Preferably, the weight ratio of component A to component B in the composition according to the invention is 100:1 to 1:5000, wherein component A contains AbA and component B contains kasugamycin. More preferably, the weight ratio is 100:1 to 1:2000 or 20:1 to 1:500.

[0113] Preferably, the weight ratio of component A to component B in the composition according to the invention is from 100:1 to 1:5000, wherein component A comprises AbA and one or more other cyclic ester peptides of formula (I) or stereoisomers thereof selected from the group consisting of compounds 1.001 to 1.005 and 1.007 to 1.044 as shown in Table A, preferably wherein component A comprises AbA and at least one other cyclic ester peptide of formula (Ia) or stereoisomers thereof selected from the group consisting of AbE and AbG. More preferably, the weight ratio is from 100:1 to 1:2000.

[0114] Preferably, the weight ratio of component A to component B in the composition according to the invention is from 50:1 to 1:500, wherein component A comprises AbA and one or more other cyclic ester peptides of formula (I) or stereoisomers thereof selected from the group consisting of compounds 1.001 to 1.005 and 1.007 to 1.044 as shown in Table A, preferably wherein component A comprises AbA and at least one other cyclic ester peptide of formula (Ia) or stereoisomers thereof selected from the group consisting of AbE and AbG. More preferably, the weight ratio is from 20:1 to 1:200.

[0115] Preferably, component A of the composition according to the invention is a fermentation broth containing one or more cyclic ester peptides having formula (I) as defined above or their stereoisomers, and component B contains natamycin or kasugamycin, wherein the weight ratio of component A to component B is 100:1 to 1:5000, preferably 100:1 to 1:1000, more preferably 50:1 to 1:500, and even more preferably 20:1 to 1:200.

[0116] Preferably, component A of the composition according to the invention is a fermentation broth containing AbA and one or more other cyclic ester peptides having formula (I) as defined above or their stereoisomers, and component B contains natamycin or kasugamycin, wherein the weight ratio of component A to component B is 100:1 to 1:5000, preferably 100:1 to 1:1000, more preferably 50:1 to 1:500, and even more preferably 20:1 to 1:200.

[0117] Compounds having formula (I) or stereoisomers thereof according to the present invention can be prepared by methods known to those skilled in the art. Compounds having formula (I) can be prepared by commercial or synthetic or semi-synthetic chemical- or fermentation methods. For example, compounds having formula (I) or stereoisomers thereof, or compounds having formula (Ia) or stereoisomers thereof, 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. Fermentation broth containing one or more compounds of formula (I) or stereoisomers thereof, or compounds of formula (Ia) or stereoisomers thereof, can be obtained from the fermentation process of a strain of *Brachystomata buddingae* (typically *Brachystomata buddingae* R106). The fermentation broth may not require purification. Alternatively, one or more compounds of formula (I) can be isolated and purified from the fermentation broth, for example by chromatography using an adsorbent (e.g., silica gel and reversed-phase silica gel, optically active adsorbents, resins) or one or more solvents (e.g., separation, countercurrent separation, mixtures of multiphase solvents) or other chemical means (e.g., crystallization, recrystallization, salt formation, and precipitation) to achieve the final purity. The purity of a compound having formula (I) or its stereoisomers may be, but is not limited to, a range of 10% to 20%, or 20% to 30%, or 30% to 40%, or 40% to 50%, or 50% to 60%, or 60% to 70%, or 70% to 80%, or 80% to 90%, or 90% to 100%. The purity of a compound having formula (I) or its stereoisomers may be measured by any technique known to those skilled in the art, including NMR, mass spectrometry, liquid chromatography-mass spectrometry (LCMS), high-performance liquid chromatography (HPLC), and other analytical methods.

[0118] As used herein, the term "fungicide" refers to a compound that controls, alters, or prevents the growth of fungi. The term "effective fungicide amount" refers to the amount of such a compound or combination of such compounds that can affect fungal growth. Controlling or altering effects include all deviations from natural development, such as killing, inhibiting, etc., and prevention includes the formation of barriers or other defenses within or on the plant to prevent fungal infection.

[0119] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits.

[0120] The term "plant propagation material" refers to all reproductive parts of a plant, such as seeds or vegetative parts like cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and other parts of the plant.

[0121] As used herein, the term "site" means the place in which or on which a plant grows, or the place where the seeds of a cultivated plant are sown, or the place where the seeds will be placed in the soil. It includes soil, seeds and seedlings, and established vegetation.

[0122] Throughout this document, the term "composition" refers to different mixtures or combinations of components A and B (including the examples defined above), for example, in a single "ready-to-use with water" form, in a combined spray mixture (which consists of individual formulations of single active ingredient components) (such as a "tank mix"), and when applied in a sequential manner (i.e., one after another for a reasonably short period of time, such as hours or days).

[0123] The compositions according to the invention are effective against harmful microorganisms (such as microorganisms) that cause plant pathogenic diseases, especially against plant pathogenic fungi.

[0124] The compositions of the present invention can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens belonging to the classes Basidiomycete, Ascomycete, Oomycete and / or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and / or Mucoromycete.

[0125] Oomycetes include 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*; and Pythium diseases, such as those caused by *Pythium aphanidermatum*, *Pythium arrhenomanes*, *Pythium graminicola*, *Pythium irregulare*, and *Pythium tertrum*. Diseases caused by *Peronosporales*, such as *Peronospora destructor*, *Peronospora parasitica*, *Peronospora manshurica*, *Peronospora abacina*, *Plasmopara viticola*, *Plasmopara halstedii*, *Pseudoperonospora cubensis*, *Albugo candida*, *Sclerophthora macrospora*, and *Bremia lactucae*; and others, such as *Aphanomyces cochlioides*, *Labyrinthula zosterae*, *Peronosclerospora sorghi*, and *Sclerospora graminicola*.

[0126] Ascomycetes, including diseases such as spot, blight, wilt, or downy mildew and / or rot, such as those caused by: *Stemphylium solani*, *Stagonosporatainanensis*, *Spilocaea oleaginea*, *Setosphaeri aturcica*, *Pyrenochaeta lycoperisici*, *Pleospora herbarum*, *Phoma destructiva*, *Phaeosphaeria herpotrichoides*, *Phaeocryptocus gaeumannii*, *Ophiosphaerella graminicola*, *Ophiobolus graminis*, *Leptosphaeria maculans*, and *Hendersonia*. *Creberrima*, *Helminthosporium triticirepentis*, *Drechslera glycines*, *Didymella bryoniae*, *Cycloconium oleagineum*, *Corynespora cassiicola*, *Cochliobolus sativus*, *Bipolaris cactivora*, *Venturia inaequalis*, *Pyrenophora teres*, *Pyrenophoratritici-repentis*, *Alternaria alternata*, *Alternaria brassicicola*, *Alternaria solanacea* *Septoria solani* and *Alternaria tomatophila*, belonging to the order Capnodiales, such as *Septoria tritici*, *Septoria nodorum*, *Septoria glycines*, *Cercospora arichidola*, and *Cercospora spp.*The fungi causing the following diseases are listed: *Cercospora beticola*, *Cercospora sojina*, *Cercospora zeae-maydis*, *Cercosporella capsellae*, *Cercosporella herpotrichoides*, *Cladosporium carpophilum*, *Cladosporium effusum*, *Passalora fulva*, *Cladosporium oxysporum*, *Dothistroma septosporum*, *Isariopsis clavispora*, *Mycosphaerella fijiensis*, *Mycosphaerella graminicola*, *Mycovellosiella koepkeii*, and *Phaeoisariopsis*. * *Pseudocercospora vitis*, *Pseudocercosporella herpotrichoides*, *Ramularia beticola*, *Ramularia collo-cygni*, *Magnaporthales*, such as *Gaeumannomyces graminis*, *Magnaporthe grisea*, *Magnaporthe oryzae*, *Diaporthales*, such as *Anisogrammaanomala*, *Apiognomonia errabunda*, *Cytospora platani*, *Diaporthe phaseolorum*, *Discula destructiva*, *Gnomonia fructicola*, *Greeneria*. * *Uvicola*, *Melanconium juglandinum*, *Phomopsis viticola*, *Sirococcus* (the causal agent of walnut canker)*Clavivigignenti-juglandacearum*, *Tubakia dryina*, species of *Dicarpella*, *Valsa ceratosperma* (the causal agent of apple tree rot), and others such as *Actinothyrium graminis*, *Ascochyta pisi*, *Aspergillus flavus*, *Aspergillus fumigatus*, *Aspergillus nidulans*, *Asperisporium caricae*, *Blumeriella jaapii* (the causal agent of cherry leaf spot), species of *Candida* spp., *Capnodium ramosum*, species of *Cephaloascus*, *Cephalosporium gramineum*, *Ceratocystis paradoxa*, and species of *Chaetomium*. *Hymenoscyphus pseudoalbidus*, *Coccidioides* spp., *Cylindrosporium padi*, *Diplocarponmalae*, *Drepanopeziza campestris*, *Elsinoe ampelina*, *Epicoccum nigrum*, *Epidermophyton* spp., *Eutypa lata*, *Geotrichum candidum*, *Gibellina cerealis*, *Gloeocercospora sorghi*, *Gloeodes pomigena*, *Gloeosporium perennans*; *Gloeotinia* endophytic fungi. temulenta), Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia*Crassula crassiasca*, *Lophodermium seditiosum*, *Marssonina graminicola*, *Microdochium nivale*, *Monilinia fructicola*, *Monilinia laxa*, *Monilinia fructigena*, *Monographella albescens*, *Monosporascus cannonballus*, *Naemacyclus* spp., *Ophiostoma novo-ulmi*, *Paracoccidioides brasiliensis*, *Penicillium expansum*, *Pestalotia rhododendri*, *Petriellidium* spp., *Pezicula* spp.), Phialophora gregata (soybean stem brown rot), Phialophora tetraspora, Phylllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum (tobacco cyst shell), Polyscytalum pustulans (potato skin spot), Pseudopeziza medicaginis (alfalfa pseudodisc), Pyrenopeziza brassicae (brassicae), Ramulispora sorghi (sorghum spores), Rhabdocline pseudotsugae (barley cloud spot), Rhynchosporium secalis (rice broom broom broom), Sacrocladium oryzae (rice broom broom), Species of Scedosporium spp. (foot actinomycetes), Schizothyrium (pome fruit cracking shield). pomi), Sclerotinia sclerotiorum, Sclerotinia minor, Sclerotium speciesspp.), Typhulaishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrinabullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; powdery mildew, for example, from Erysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinulanecator, Sphaerotheca acuminata. * *Podosphaeraleucotricha*, *Podospaera macularis*, *Podosphaerapannosa*, *Golovinomyces cichoracearum*, *Leveillulataurica*, *Microsphaera diffusa*, *Oidiopsis gossypii*, *Phyllactinia guttata*, and *Oidium arachidis*; molds, such as those caused by *Botryosphaeriales*, including *Dothiorella aromatica*, *Diplodia seriata*, *Guignardia bidwellii*, *Botrytis cinerea*, and *Botrytis tubularis*. *Botryotinia tracheiphila*, *Botryotinia allii*, *Botryotinia fabae*, *Fusicoccuma mygdali*, *Lasiodiplodia* (the fungus that causes scorching of longan)Those caused by *Theobromae*, *Macrophomatheicola*, *Macrophomina phaseolina*, and *Phyllostictacucurbitacearum*; anthracnose, such as those caused by *Colletotrichum gloeosporioides*, *Colletotrichum lagenarium*, *Colletotrichum gossypii*, *Glomerella cingulata*, and *Colletotrichum graminicola*; and wilt or blight, such as those caused by *Acremonium strictum*, *Claviceps purpurea*, *Fusarium culmorum*, and *Fusarium graminicola*. *Fusarium graminearum*, *Fusarium brasiliense*, *Fusarium tucumaniae*, *Fusarium cuneirostrum*, *Fusarium virguliforme*, *Fusarium oxysporum*, *Fusarium subglutinans*, *Fusarium oxysporum f.sp. cubense*, *Gerlachia nivale*, *Gibberella fujikuroi*, *Gibberella zeae*, *Gliocladiumspp.*, *Myrothecium verrucaria*, *Nectria ramulariae*, *Trichoderma viride*, *Trichothecium roseum*, and *Verticillium* (the pathogen causing avocado root rot). Those caused by theobromae;

[0127] Basidiomycetes, including smut, such as those caused by Ustilaginales (e.g., *Ustilaginoidea virens*, *Ustilago nuda*, *Ustilagotritici*, *Ustilago zeae*); and rust, such as those caused by Pucciniales (e.g., *Cerotelium fici*, *Chrysomyxa arctostaphyli*, *Coleosporium ipomoeae*, *Hemileiavastatrix*, *Puccinia arachidis*, *Puccinia cacabata*, *Puccinia graminis*, *Puccinia cryptica*). *Puccinia recondita*, *Puccinia sorghi*, *Puccinia hordei*, *Puccinia striiformis f.sp. hordei*, *Puccinia striiformis f.sp. secalis*, *Pucciniastrum coryli*, or rust fungi such as *Cronartium ribicola*, *Gymnosporangium juniperi-viginianae*, *Melampsora medusae*, *Phakopsora pachyrhizi*, *Phakopsora meibomiae*, *Phragmidium mucronatum*, *Physopella ampelosidis*, and *Tranzschelia*. (discolor) and broad bean rust fungus (Uromycesviciae-fabae); as well as other rots and diseases, such as those caused by species of Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, and Mycenaspp.The fungi causing corn smut include *Sphacelotheca reiliana*, *Typhulaishikariensis*, *Urocystis agropyri*, *Itersoniliahaperplexans*, *Corticium invisum*, *Laetisaria fuciformis*, *Waitea circinata*, *Rhizoctonia solani*, *Thanetephorus cucurmeris*, *Entyloma dahliae*, *Entylomella microspora*, *Neovossia moliniae*, and *Tilletia caries*.

[0128] Blastodactylus class, such as *Physoderma maydis*; and

[0129] Mucormycetes, such as *Choanephora cucurbitarum*; species of the genus *Mucor*; *Rhizopus arrhizus*, *Rhizopus oryzae*, *Rhizopus stolonifera*, *Rhizopus nigricans*, and diseases caused by other species and genera closely related to those listed above.

[0130] The compositions according to the invention are particularly effective against plant pathogenic fungi belonging to the following classes: Ascomycota (e.g., *Venturia*, *Alternaria*, *Podosphaera*, *Erysiphe*, *Magnaporthe*, *Monilinia*, *Mycosphaerella*, *Uncinula*); Basidiomycota (e.g., *Hemileia*, *Rhizoctonia*, *Phakopsora*, *Puccinia*, *Ustilago*, *Tilletia*); Fungi (e.g., *Fungi*). (also known as Deuteromycetes; for example, *Botrytis*, *Colletotrichum*, *Helminthosporium*, *Rhynchosporium*, *Fusarium*, *Septoria*, *Cercospora*, *Alternaria*, *Penicillium*, *Pyricularia*, and *Pseudocercosporella*)); Oomycetes (for example, *Phytophthora*, *Peronospora*, *Pseudoperonospora*, *Albugo*, *Bremia*, *Pythium*, *Pseudosclerospora*, and *Plasmopara*)).

[0131] Preferably, the composition according to the invention is effective against plant pathogenic fungi selected from the group consisting of: *Alternaria*, *Ascochyta*, *Botrytis*, *Cercospora*, *Cyclocarya*, *Anthracnose*, *Anthracnose of Cucurbita*, *Corynespora*, *Erysiphe cichoracearum*, *Sphaerotheca fuliginea*, *Fusarium*, *Fusarium oxysporum*, *Gäumannomyces graminis*, *Guignardia*, *Helicobacter*, *Camponotus cacaoense*, *Mycosphaerella*, *Rhizoctonia solani*, *Mycosphaerella oryzae*, *Mycosphaerella spp.* The genera *Arachidis* include: *Phoma*, *Phomopsis*, *Pseudopezicula*, *Pseudopezicula*, *Pseudomonas*, *Pyrenophora*, *Pyrenophora*, *Pyricularia*, *Pyricularia*, *Ramularia*, *Ramularia*, *Rhizoctonia*, *Rhizoctonia*, *Sclerotinia*, *Sphacelotheca reilliana*, *Urocystis occulta*, *Ustilago*, *Ustilago*, *Monilia*, and *Penicillium*.

[0132] The compositions of the present invention are particularly effective against plant pathogenic fungi selected from the group consisting of: *Alternaria*, *Botrytis*, *Cercospora*, *Anthracis*, *Corynebacterium*, *Fusarium*, *Globosa*, *Globosa*, *Globosa*, *Globosa*, *Globosa*, *Sclerotium*, *Penicillium*, *Laminaria*, *Pseudomonas*, *Cercospora*, *Cercospora*, *Sclerotium*, *Uncaria*, and *Asterix*. More preferably, they are selected from the group consisting of: *Alternaria*, *Botrytis*, *Cercospora*, *Anthracis*, *Corynebacterium*, *Globosa*, *Globosa*, *Globosa*, *Sclerotium*, *Penicillium*, *Laminaria*, *Pseudomonas*, *Cercospora*, *Anthracis*, *Corynebacterium*, *Globosa*, *Globosa*, *Sclerotium*, *Penicillium*, *Laminaria*, *Pseudomonas*, *Cercospora*, *Sclerotium*, *Uncaria*, and *Asterix*. Preferably, they are selected from the group consisting of: *Alternaria* and *Botrytis*.

[0133] The compositions of the present invention are particularly effective against plant pathogenic fungi selected from the group consisting of: *Alternaria porri*, *Alternaria alternifolia*, *Alternaria porri*, *Botrytis allii*, *Botrytis squamosa*, *Cercospora capsici*, *Anthracnose fungi*, *Cyclophorus multifiliis*, *Fusarium oxysporum*, *Botrytis cinerea*, *Rhizoctonia solani*, *Prunus oryzae*, *Prunus oryzae*, *Penicillium digitatum*, *Penicillium italicum*, *Penicillium expansum*, *Pseudomonas stolonifera*, *Podosphaera xanthii*, and *Pseudopezicula*. The fungi selected from the following groups are preferred: *Alternaria tracheiphila*, *Rhizoctonia solani*, *Syneocarpus zeyrinus*, *Uncaria rhynchophylla*, and *Aureobasidium foetida*, more preferably from the group consisting of: *Alternaria solanacea*, *Alternaria alternifolia*, *Alternaria onionii*, *Botrytis cinerea*, *Botrytis cinerea*, *Cercospora capsici*, *Anthracnose fungi*, *Cyclospora multiflora*, *Botrytis cinerea*, *Prunus sylvestris*, *Sclerotium sclerotiorum*, *Penicillium fingertips*, *Penicillium italicum*, *Penicillium expansum*, *Pseudomonas sclerotiorum*, *Monophyllum leucosus*, *Monophyllum sclerotiorum*, *Aureobasidium foetida*, *Aureobasidium foetida*, *Aureobasidium foetida*, *Aureobasidium foetida*, and *Aureobasidium foetida*, preferably from the group consisting of: *Alternaria solanacea* and *Botrytis cinerea*.

[0134] According to the present invention, "useful plants" typically include the following perennial or annual plants:

[0135] Cereals, such as barley, corn, millet, oats, rice, rye, sorghum, tritordeum, and wheat, amaranth, buckwheat, chia, quinoa, and canihua;

[0136] Fruits and tree nuts, such as grapevines (table grapes and wine grapes), almonds, apples, apricots, avocados, bananas, blackberries, blueberries, breadfruit, cocoa, cashews, custard apples, cherries, chestnuts (for nuts), rowan, citrus fruits (including grapefruit, lime, lemon, orange, mandarin lemon), coconuts, coffee beans, cranberries, currants, dates, feijoa fruit, figs, hazelnuts, currants, guavas, kiwifruit, lychees, macadamia nuts, mangoes, nectarines, olives, papayas, passion fruit, peaches, pears, pecans, persimmons, pineapples, pistachios, plums (including prunes), pomegranates, quince, raspberries, strawberries, Suriname cherries, and walnuts;

[0137] Vegetables such as artichokes, asparagus, beans (peas, tender peas, dried peas, edible beans), beets (edible beets), broccoli raab, Brussels sprouts, cabbage (including Chinese cabbage), carrots, cauliflower, root celery, celery, chickpeas, chives, collard (including headless kale), cucumbers, edamame, eggplant, endive, peas (green peas, dried peas, edible peas), garlic, horseradish, kohlrabi, leeks, lentils, lettuce, melons, mushrooms (cultivated varieties), mustard greens and other leafy greens, okra, onions, parsley, parsley, peppers, potatoes, cactus fruit, squash, radishes, rhubarb, turnips, ginseng, spinach, squash (zucchini and winter squash), sweet corn, sweet potatoes, leaf beets, taro, tomatoes / green tomatoes, turnips, and watermelons;

[0138] Field crops, such as sugar beets, sugarcane, tobacco, peanuts, and soybeans;

[0139] Oilseed crops, such as rapeseed (canola), mustard greens, shepherd's purse, sea cabbage, sunflower, poppy, sesame, and safflower;

[0140] Forage crops, such as alfalfa, clover, cowpea, vetch, red bean grass, lupin, beetroot, ryegrass, Kentucky bluegrass, bulrush, and orchard grass; fiber crops, such as cotton, flax, hemp, jute, and sisal;

[0141] Forest plants include coniferous species (such as larch, fir, or pine), temperate and tropical hardwoods (such as oak, birch, beech, teak, or mahogany), and species in arid zones (such as eucalyptus).

[0142] Horticultural crops, such as hops, maple (maple syrup), tea, natural rubber plants, and turfgrasses (e.g., creeping bentgrass, Kentucky bluegrass, ryegrass, dandelion, bermudagrass, centipede grass, crested hairgrass, kerrygrass, st. Augustinegrass, zoysia grass, dichondra, cat's tail grass, tufted hairgrass);

[0143] Floriculture, greenhouse, and nursery plants, including flowering plants, broadleaf trees, or evergreens such as begonias, dahlias, geraniums, impatiens, petunias, variegated clover, marigolds, pansies, snapdragons, African violets, azaleas, florist chrysanthemums, bulbous flowers, hydrangeas, lilies, orchids, poinsettias, roses, astilbe, coreopsis, delphiniums, dianthus, heuchera, hostas, basilica, goldenrod, and sage. Grasses, periwinkles, columbine, daylilies, garden chrysanthemums, ivy, ornamental grasses, peonies, delphiniums, gladioli, irises, snapdragons, tulips, eucalyptus, pittosporum, ferns, anthuriums, dieffenbachia, dracaena, banyan trees, philodendrons, peace lilies, pineapples, cacti, palms, balsam fir, blue spruce, Douglas fir, Fraser fir, red fir, Scots pine, white pine, magnolia, ash, elm, cherry blossoms, elm-leaf plum, hawthorn, redbud, and tamarisk;

[0144] Propagation materials, such as bare-root division, cuttings, liner, plug seedlings, seeds, tissue culture seedlings and pre-made plants;

[0145] Cooked herbs and spices, such as allspice, Angelica spp., star anise, annatto, arugula, asafoetida, basil (all types), bay (culinary), seaweed, Bolivian coriander, borage, calendula (herbal use), nutmeg, capers, coriander, cardamom, cinnamon, cassia bark, basil, cloves, catnip, chamomile, radish, chicory, myrrh, coriander leaves, comfrey, watercress, cumin, curry, dill, fennel, fenugreek, filé (culinary), fingerroot, galangal. Ginger, hops, bitter pepper, hyssop, lavender, lemon balm, lemon thyme, ravioli, nutmeg, mahala, malabathrum, marjoram, mint (all types), artemisia, nutmeg, oregano, orris root, paprika, parsley, pepper, rosemary, rue, saffron, sage (all types), peppermint (all types), rhubarb, tarragon, thyme, turmeric, vanilla, wasabi, and watercress; and

[0146] Herbs, such as taro plants, Artemisia species, Astragalus, Bordeaux leaves, Comfrey, Chrysanthemum morifolium, Fenugreek, Wild Chamomile, Foxglove, Ginkgo, Ginseng, Goat's bean, Ranunculus, European wild wormwood, Mint, Horsetail, Lavender, Licorice, Althaea sylvestris, Mullein, Nettle, Passionflower, Patchouli, Peppermint, American pokeweed, Twinkle, Rhubarb, St. John's wort, Senna, Sow thistle, Stevia, Tansy, Witch hazel, Stachys, Artemisia, Yarrow, California mint (Yerba buena), and Ylang-ylang.

[0147] This list does not represent any limitation; however, preferably, useful plants can be selected from the group consisting of: wheat, barley, rice, soybeans, apples, almonds, cherries, raspberries, grapes, cucumbers, peanuts, tomatoes, strawberries, citrus fruits, and bananas. Preferably, useful plants can be selected from the group consisting of: apples, apricots, cherries, raspberries, grapes, cucumbers, peanuts, tomatoes, strawberries, citrus fruits, and bananas. Preferably, useful plants can be selected from: fruits and tree nuts, vegetables, horticultural crops, and floriculture.

[0148] The term "useful plants" should be understood to also include useful plants that have been conditioned to herbicides such as bromobenzonitrile or herbicides (e.g., HPPD inhibitors, ALS inhibitors such as flusulfuron, flusulfuron, and triflusulfuron, EPSPS (5-enol-pyruvyl-shikimate-3-phosphate synthase) inhibitors, and GS (glutamine synthase) inhibitors) through conventional breeding or genetic engineering methods. An example of a crop conditioned to imidazolinones (e.g., methoxyfenozide) through conventional breeding methods (mutation) is Clearfield® Summer Canola (Canola). Examples of crops conditioned to herbicides or herbicides through genetic engineering include glyphosate- and glufosinate-resistant corn varieties, commercially available under the brand names RoundupReady®, Herculex I®, and LibertyLink®.

[0149] The term "useful plant" should be understood to also include useful plants that have been transformed using recombinant DNA technology to enable them to synthesize one or more selectively acting toxins, such as those known to originate from toxin-producing bacteria. Examples of toxins that can be expressed include delta-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins from nematode-parasitic bacteria, and toxins produced by scorpions, arachnids, wasps, and fungi.

[0150] The compositions according to the invention are particularly effective in controlling or preventing plant pathogenic diseases (especially powdery mildew, rust, leaf spot, early blight, or mildew) caused by certain plant pathogenic fungi on cereals, fruits and tree nuts, vegetables, field crops, oil crops, forage crops, forest plants, horticultural crops, floriculture, greenhouse and nursery plants, propagation materials, edible herbs and spices, and medicinal herbs, such as:

[0151] Alternaria solanacearum, preferably Alternaria solanacearum found on tomatoes.

[0152] Alternaria alternifolia, preferably Alternaria alternifolia from eggplant.

[0153] Alternaria alli, preferably Alternaria alli found on onions.

[0154] Botrytis cinerea, preferably found on tomatoes, peppers, onions, pears, stone fruits, kiwifruit, blueberries, sugar beets, or grapes.

[0155] Botrytis cinerea, preferably Botrytis cinerea from onions.

[0156] Botrytis cinerea, preferably Botrytis cinerea from onions.

[0157] Capsicum, preferably Capsicum from pepper.

[0158] *Cyclocarya polyspora*, preferably found on tomatoes.

[0159] Staphylococcus aureus, preferably Staphylococcus aureus from grapes.

[0160] The preferred pathogen for peach brown rot is the fungus found on cherries, peaches, plums, prunes, nectarines, or almonds.

[0161] Fruit-growing *Streptococcus sclerotiorum* is preferred, especially *Streptococcus sclerotiorum* found on cherries, peaches, plums, prunes, nectarines, or almonds.

[0162] Sclerotium sclerotiorum, preferably found on cherries, peaches, plums, prunes, nectarines, or almonds.

[0163] Grape-grown pseudostem mold, preferably grape-grown pseudostem mold.

[0164] White forked single-shell, preferably from apples.

[0165] The preferred fungus for powdery mildew is the one found on cucurbit vegetables.

[0166] Grape angular leaf scorch fungus, preferably the grape angular leaf scorch fungus found on grapes.

[0167] Grape scabs, preferably grape scabs from grapes.

[0168] Apple black spot fungus, preferably found on apples.

[0169] Furthermore, the compositions according to the invention are particularly effective against seed-borne and soil-borne diseases, such as species of *Alternaria*, *Alternaria*, *Botrytis*, *Cercospora*, *Ergali*, *Cyclophorus*, *Hylocereus*, *Anthracis*, *Pseudomonas*, *Fusarium*, *Fusarium moniliforme*, *Fusarium oxysporum*, *Fusarium proliferatum*, *Fusarium solani*, *Fusarium glomeratum*, *Gäumannomyces graminis*, *Helicobacter*, *Pyrenophora graminea*, *Pyrenophora oryzae*, *Rhizoctonia solani*, *Rhizoctonia graminis*, and *Rhizoctonia graminis*. cerealis), species of the genus *Sclerotium*, species of the genus *Syngonium*, species of *Ustilago maydis*, species of the genus *Ustilago maydis*, *Typhula incarnata*, *Ustilago maydis*, species of the genus *Ustilago maydis*, or species of the genus *Verticillium*; particularly resistant to pathogens of cereals such as wheat, barley, rye, or oats; corn; rice; cotton; soybeans; turf; sugar beets; rapeseed; potatoes; legumes such as peas, lentils, or chickpeas; and sunflowers.

[0170] Furthermore, the compositions according to the invention are particularly effective against post-harvest diseases such as Botrytis cinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotrichum candida, Prunus sylvestris, Sclerotinia sclerotiorum, Sclerotinia sclerotiorum, Mucor piriformis, Penicillium italicum, Penicillium solitum, Penicillium digitatum, or Penicillium expansum; especially against pathogens of fruits such as pomegranates (e.g., apples and pears), stone fruits (e.g., peaches and plums), citrus fruits, melons, papayas, kiwifruit, mangoes, berries (e.g., strawberries), avocados, pomegranates, and bananas, as well as nuts.

[0171] The present invention further provides the use of compositions comprising components A and B as defined according to the invention as fungicides. Suitably, this use is non-therapeutic.

[0172] Some compositions according to the present invention have systemic action and can be used as fungicides for leaf, soil and seed treatment.

[0173] When using the composition according to the invention, plant pathogenic microorganisms present in various useful plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) can be inhibited or destroyed, while also protecting later-growing plant parts from attack by plant pathogenic microorganisms.

[0174] The compositions according to the invention can be applied to plant pathogenic microorganisms, useful plants threatened by microbial attack, their sites, their propagation materials, stored goods or technical materials.

[0175] The composition according to the invention can be applied before or after useful plants, their propagation materials, stored goods or technical materials are infected by microorganisms.

[0176] The amount of the combination of the present invention to be applied will depend on various factors, such as the compounds used; the object to be treated, such as plants, soil or seeds; the type of treatment, such as spraying, dusting or seed dressing; the purpose of the treatment, such as prevention or treatment; the type of fungus to be controlled; or the timing of application.

[0177] Compositions containing a combination of component A and component B can be applied, for example, as a single “ready-to-use” form, as a combined spray mixture (consisting of separate formulations of a single active ingredient component) (such as a “tank mix”), and when applied in a sequential manner (i.e., one after another for a reasonably short period of time, such as hours or days).

[0178] The compositions according to the invention are active ingredients with preventive and / or therapeutic value in the field of pest control, even at low application rates.

[0179] Preferably, according to the method of the invention, component A is applied in combination with component B at a ratio of 10 g ai / ha to 500 g ai / ha to 5 g ai / ha to 2000 g ai / ha.Preferredly, group A is divided into the following ratios: 10 g ai / ha to 500 g ai / ha, 5 g ai / ha to 1500 g ai / ha, 5 g ai / ha to 1000 g ai / ha, 5 g ai / ha to 500 g ai / ha, 5 g ai / ha to 250 g ai / ha, 5 g ai / ha to 100 g ai / ha, 5 g ai / ha to 50 g ai / ha, 10 g ai / ha to 2000 g ai / ha, 10 g ai / ha to 1500 g ai / ha, 10 g ai / ha to 1000 g ai / ha, 10 g ai / ha to 500 g ai / ha, 10 g ai / ha to 250 g ai / ha, 10 g ai / ha to 100 g ai / ha, and 10 g ai / ha to 100 g ai / ha. ai / ha up to 50 g ai / ha, 20 g ai / ha up to 2000 g ai / ha, 20 g ai / ha up to 1500 g ai / ha, 20 g ai / ha up to 1000 g ai / ha, 20 g ai / ha up to 500 g ai / ha, 20 g ai / ha up to 250 g ai / ha, 20 g ai / ha up to 100 g ai / ha, 20 g ai / ha up to 50 g ai / ha, 25 g ai / ha up to 2000 g ai / ha, 25 g ai / ha up to 1500 g ai / ha, 25 g ai / ha up to 1000 g ai / ha, 25 g ai / ha up to 500 g ai / ha, 25 g ai / ha up to 250 g ai / ha, 25 g ai / ha up to 100 g ai / ha, 25 g ai / ha to 50 g ai / ha, 50 g ai / ha to 2000 g ai / ha, 50 g ai / ha to 1500 g ai / ha, 50 g ai / ha to 1000 g ai / ha, 50 g ai / ha to 500 g ai / ha, 50 g ai / ha to 250 g ai / ha or 50 g ai / ha to 100 g ai / ha group B combined application. Best choice, Part B includes Kasuga Kasumi. Best choice, Part B includes other materials.

[0180] Preferably, according to the method of the invention, component A is applied in combination with component B at a ratio of 25 g ai / ha to 500 g ai / ha to 5 g ai / ha to 2000 g ai / ha.Preferredly, group A is divided into the following ratios: 25 g ai / ha to 500 g ai / ha, 5 g ai / ha to 1500 g ai / ha, 5 g ai / ha to 1000 g ai / ha, 5 g ai / ha to 500 g ai / ha, 5 g ai / ha to 250 g ai / ha, 5 g ai / ha to 100 g ai / ha, 5 g ai / ha to 50 g ai / ha, 10 g ai / ha to 2000 g ai / ha, 10 g ai / ha to 1500 g ai / ha, 10 g ai / ha to 1000 g ai / ha, 10 g ai / ha to 500 g ai / ha, 10 g ai / ha to 250 g ai / ha, 10 g ai / ha to 100 g ai / ha, and 10 g ai / ha to 100 g ai / ha. ai / ha up to 50 g ai / ha, 20 g ai / ha up to 2000 g ai / ha, 20 g ai / ha up to 1500 g ai / ha, 20 g ai / ha up to 1000 g ai / ha, 20 g ai / ha up to 500 g ai / ha, 20 g ai / ha up to 250 g ai / ha, 20 g ai / ha up to 100 g ai / ha, 20 g ai / ha up to 50 g ai / ha, 25 g ai / ha up to 2000 g ai / ha, 25 g ai / ha up to 1500 g ai / ha, 25 g ai / ha up to 1000 g ai / ha, 25 g ai / ha up to 500 g ai / ha, 25 g ai / ha up to 250 g ai / ha, 25 g ai / ha up to 100 g ai / ha, 25 g ai / ha to 50 g ai / ha, 50 g ai / ha to 2000 g ai / ha, 50 g ai / ha to 1500 g ai / ha, 50 g ai / ha to 1000 g ai / ha, 50 g ai / ha to 500 g ai / ha, 50 g ai / ha to 250 g ai / ha or 50 g ai / ha to 100 g ai / ha group B combined application. Best choice, Part B includes Kasuga Kasumi. Best choice, Part B includes other materials.

[0181] Preferably, according to the method of the invention, component A is applied in combination with component B at a ratio of 10 g ai / ha to 500 g ai / ha to 5 g ai / ha, wherein component A comprises AbA.Preferred, group A is divided into the following ratios: 10 g ai / ha to 500 g ai / ha, 5 g ai / ha to 1500 g ai / ha, 5 g ai / ha to 1000 g ai / ha, 5 g ai / ha to 500 g ai / ha, 5 g ai / ha to 250 g ai / ha, 5 g ai / ha to 100 g ai / ha, 5 g ai / ha to 50 g ai / ha, 10 g ai / ha to 2000 g ai / ha, 10 g ai / ha to 1500 g ai / ha, 10 g ai / ha to 1000 g ai / ha, 10 g ai / ha to 500 g ai / ha, 10 g ai / ha to 250 g ai / ha, 10 g ai / ha to 100 g ai / ha, and 10 g ai / ha to 50 g ai / ha, 20 g ai / ha to 2000 g ai / ha, 20 g ai / ha to 1500 g ai / ha, 20 g ai / ha to 1000 g ai / ha, 20 g ai / ha to 500 g ai / ha, 20 g ai / ha to 250 g ai / ha, 20 g ai / ha to 100 g ai / ha, 20 g ai / ha to 50 g ai / ha, 25 g ai / ha to 2000 g ai / ha, 25 g ai / ha to 1500 g ai / ha, 25 g ai / ha to 1000 g ai / ha, 25 g ai / ha to 500 g ai / ha, 25 g ai / ha to 250 g ai / ha, 25 g ai / ha to 100 g ai / ha, 25 g ai / ha to 50 g ai / ha, 50 g ai / ha to 2000 g ai / ha, 50 g ai / ha to 1500 g ai / ha, 50 g ai / ha to 1000 g ai / ha, 50 g ai / ha to 500 g ai / ha, 50 g ai / ha to 250 g ai / ha or 50 g ai / ha to 100 g ai / ha group B combined application, which includes group A AbA.

[0182] Preferably, according to the method of the invention, component A is administered in combination with component B at a ratio of 25 g ai / ha to 500 g ai / ha, wherein component B contains kasugamycin.

[0183] Preferably, according to the method of the invention, component A is administered in combination with component B at a ratio of 25 g ai / ha to 500 g ai / ha to 10 g ai / ha to 2000 g ai / ha, wherein component B contains natamycin.

[0184] Preferably, when applied to plants according to the invention, preferably useful plants, component A is applied in combination with component B at a ratio of 10 g ai / ha to 500 g ai / ha to 10 g ai / ha to 2000 g ai / ha or 20 g ai / ha to 500 g ai / ha. Preferably, when applied to plants, preferably useful plants, component A is applied in combination with component B at a ratio of 25 g ai / ha to 500 g ai / ha to 10 g ai / ha to 2000 g ai / ha or 20 g ai / ha to 500 g ai / ha.

[0185] In a preferred embodiment of the invention, a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi on plants, preferably useful plants or their propagation material, the method comprising applying a composition as defined according to the invention to the plant, its site or its propagation material, wherein component A is applied in combination with component B at a ratio of 10 g ai / ha to 500 g ai / ha to 10 g ai / ha to 2000 g ai / ha or 20 g ai / ha to 500 g ai / ha.

[0186] In a preferred embodiment of the invention, a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi on plants, preferably useful plants or their propagation material, the method comprising applying a composition as defined according to the invention to the plant, its site or its propagation material, wherein component A is applied in combination with component B at a ratio of 25 g ai / ha to 500 g ai / ha to 10 g ai / ha to 2000 g ai / ha or 20 g ai / ha to 500 g ai / ha.

[0187] Preferably, according to the method of the invention, component A is administered in combination with component B at a ratio of at least 0.0001 ppm and at least 0.001 ppm. Preferably, according to the method of the invention, component A is administered in combination with component B at a ratio of at least 0.0001 ppm and at least 0.01 ppm, preferably wherein component B comprises kasugamycin. Preferably, according to the method of the invention, component A is administered in combination with component B at a ratio of at least 0.001 ppm and at least 0.001 ppm, preferably wherein component B comprises natamycin. Preferably, according to the method of the invention, component A is administered in combination with component B at a ratio of at least 0.0001 ppm and at least 0.0391 ppm or 0.0781 ppm, preferably wherein component B comprises kasugamycin. Preferably, according to the method of the invention, component A is administered in combination with component B at a ratio of at least 0.001 ppm and at least 0.0078 ppm, preferably wherein component B comprises natamycin. Preferably, according to the method of the invention, component A is applied in combination with component B at a ratio of 0.0001 ppm to 1 ppm. Preferably, according to the method of the invention, component A is applied in combination with component B at a ratio of 0.0001 ppm to 1 ppm.

[0188] The method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi according to the present invention is particularly effective against plant pathogenic fungi selected from the group consisting of: *Alternaria*, *Botrytis*, *Cercospora*, *Anthracis*, *Corynebacterium*, *Fusarium*, *Globosa*, *Globosa*, *Globosa*, *Globosa*, *Globosa*, *Penicillium*, *Laminaria*, *Pseudomonas*, *Cercospora*, *Pseudomonas*. Rhizoctonia, Synechia, Uncaria, and Stellarium, more preferably from the group consisting of: Alternaria, Botrytis, Cercospora, Anthrax, Corynebacterium, Globosa, Coccidioides, Alternaria, Penicillium, Laminaria, Pseudomonas, Pseudomonas, Synechia, Uncaria, and Stellarium, even more preferably from the group consisting of: Alternaria and Botrytis.

[0189] The method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi according to the present invention is particularly effective against plant pathogenic fungi selected from the group consisting of: *Alternaria solanacea*, *Alternaria alternifolia*, *Alternaria allium*, *Botrytis cinerea*, *Botrytis scabra*, *Botrytis cinerea*, *Cercospora capsici*, *Anthracnose fungi*, *Cyclocarya paliurus*, *Fusarium oxysporum*, *Botrytis cinerea*, *Phyllostachys oryzae*, *Phyllostachys oryzae*, *Phyllostachys oryzae*, *Penicillium fingernail*, *Penicillium italicum*, *Penicillium expansum*, *Phyllostachys pubescens*, *Monophyllum leucosus*, *Monophyllum leucosus*, *Gnaphalium angularis*, *Rhizoctonia solani*, *Syndrome aurea*, *Uncaria rhynchophylla*, and *Aureobasidium foetida*, more preferably selected from the group consisting of: The group consisting of: *Alternaria solanata*, *Alternaria alternifolia*, *Alternaria allium*, *Botrytis cinerea*, *Botrytis cinerea*, *Botrytis cinerea*, *Cercospora capsici*, *Anthracnose fungi*, *Cyclospora multiflora*, *Botrytis cinerea*, *Prunus sylvestris*, *Sclerotium truncatum*, *Sclerotium sclerotium*, *Penicillium fingertips*, *Penicillium italicum*, *Penicillium expansum*, *Pseudomonas stolonifera*, *Monophyllum leucosus*, *Monophyllum leucosus*, *Gnaphalium angularis*, *Syndrome aureum*, *Syndrome aureum*, and *Aureobasidium argentea*, or even more preferably, the group consisting of: *Alternaria solanata*, *Alternaria alternifolia*, *Alternaria allium*, *Botrytis cinerea*, *Botrytis cinerea*, and *Botrytis cinerea*, or even more preferably, the group consisting of: *Alternaria solanata* and *Botrytis cinerea*.

[0190] Preferred is a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi, preferably plant pathogenic fungi, according to the present invention, comprising applying the composition according to the present invention to useful plants selected from the group consisting of: cereals, fruits and tree nuts, vegetables, field crops, oil crops, forage crops, forest plants, horticultural crops, floriculture, greenhouse and nursery plants, propagation materials, edible herbs and spices, and medicinal herbs.

[0191] More preferably, according to the invention, is a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi, preferably plant pathogenic fungi, comprising applying the composition according to the invention to useful plants selected from the group consisting of: wheat, barley, rice, soybean, apple, almond, cherry, raspberry, grape, cucumber, peanut, tomato, strawberry, citrus, and banana. Even more preferably, according to the invention, is a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi, preferably plant pathogenic fungi, comprising applying the composition according to the invention to useful plants selected from the group consisting of: apple, apricot, cherry, raspberry, grape, cucumber, peanut, tomato, strawberry, citrus, and banana.

[0192] The preferred composition according to the invention comprises component A, which comprises amberidin A; and component B, which comprises kasugamycin. Preferably, the weight ratio of amberidin A to kasugamycin is 1:125 to 1:250. Preferably, the weight ratio of amberidin A to kasugamycin is 1:125 to 1:2000.

[0193] A preferred method according to the invention comprises a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi on plants or their propagation material, the method comprising applying a composition according to the invention to the plant, its location, or its propagation material, wherein component A comprises abamin A and component B comprises kasugamycin. Preferably, abamin A is applied in combination with kasugamycin at a ratio of 0.0003 ppm to 0.0012 ppm, preferably wherein the plant pathogenic fungus is *Botrytis cinerea*. Preferably, abamin A is applied in combination with kasugamycin at a ratio of 0.0006 ppm to 0.005 ppm, preferably wherein the plant pathogenic fungus is *Alternaria solanacea*. Preferably, the plant pathogenic fungus is selected from the group consisting of *Alternaria solanacea* and *Botrytis cinerea*.

[0194] The preferred composition according to the invention comprises component A, which comprises amberidin A; and component B, which comprises natamycin. Preferably, the weight ratio of amberidin A to natamycin is from 1:1.2 to 1:19.9. More preferably, the weight ratio of amberidin A to natamycin is from 1:1.2 to 1:9.9.

[0195] A preferred method according to the invention comprises a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi on plants or their propagation material, the method comprising applying a composition according to the invention to the plant, its location, or its propagation material, wherein component A comprises abamin A and component B comprises natamycin. Preferably, abamin A is applied in combination with natamycin at a ratio of 0.0063 ppm to 0.0125 ppm, preferably wherein the plant pathogenic fungus is *Botrytis cinerea*. Preferably, abamin A is applied in combination with natamycin at a ratio of 0.0063 ppm to 0.025 ppm, preferably wherein the plant pathogenic fungus is *Alternaria solanacea*. Preferably, the plant pathogenic fungus is selected from the group consisting of *Alternaria solanacea* and *Botrytis cinerea*.

[0196] Preferably, the compositions according to the invention comprise an agriculturally acceptable carrier and / or formulation adjuvant and optionally a surfactant. The invention also provides fungicidal compositions comprising synergistically effective amounts of the combination of components A and B as mentioned above, along with an agriculturally acceptable carrier and optionally a surfactant. In said compositions, as described above, the weight ratio of component A to component B is preferably 100:1 to 1:5000, more preferably 100:1 to 1:1000, even more preferably 50:1 to 1:500, and still more preferably 20:1 to 1:200.

[0197] It has been unexpectedly discovered that components A and B in specific weight ratios can produce synergistic activity. Therefore, another aspect of the invention is a composition in which components A and B are present in an amount that produces a synergistic effect. This synergistic activity is evident from the fact that the fungicidal activity of a composition containing components A and B is greater than the sum of the fungicidal activities of components A and B. This synergistic activity expands the scope of action of components A and B in two ways. First, by reducing the application ratio of components A and B while maintaining the same level of effectiveness, this means that even if the two individual components become completely ineffective at such low application ratios, the mixture of active ingredients still achieves a high degree of plant pathogen control. Second, the spectrum of controllable plant pathogens is significantly broadened.

[0198] Synergistic effects exist when the combined effect of active ingredients is greater than the sum of the effects of the individual components. For a given combination of active ingredients, the expected effect E follows the so-called Colby formula and can be calculated as follows (COLBY, SR, “Calculating synergistic and antagonistic responses of herbicide combination”, Weeds, Vol. 15, pp. 20-22; 1967):

[0199] ppm = the number of milligrams of active ingredient (= ai) per liter of spray mixture.

[0200] X = % effect of active ingredient (A) using p ppm.

[0201] Y = % effect of active ingredient (B) using q ppm of active ingredient.

[0202] According to Colby, using p + q ppm of active ingredients, the expected (additive) effect of active ingredient (A) + (B) is

[0203] If the observed effect (O) is greater than the expected effect (E), then the combined effect is superadditive, i.e., synergistic. Mathematically, synergism corresponds to a positive value of the difference (OE). In the case of purely complementary additive activity (expected activity), the difference (OE) is zero. A negative value of the difference (OE) signifies a loss of activity compared to the expected activity.

[0204] However, in addition to the actual synergistic effect relative to the fungicidal activity, the compositions according to the invention may also have other unexpectedly advantageous properties. Examples of such advantageous properties that may be mentioned are: more favorable biodegradability; improved toxicological and / or ecotoxicological behavior; or improved characteristics of useful plants, including: emergence, crop yield, more developed root system, increased tillering, increased plant height, larger leaves, less basal leaf mortality, stronger tillering, greener leaf color, less fertilizer required, less seed required, more tillering, earlier flowering, earlier grain maturity, less lodging, enhanced bud growth, improved plant vigor, and earlier germination.

[0205] The composition according to the invention is preferably in a synergistically effective amount. Preferably, component A and component B of the composition according to the invention are each in an amount that produces a synergistic effect, preferably a synergistic fungicidal effect. Preferably, the composition according to the invention has a weight ratio of component A to component B in a synergistically effective amount.

[0206] It has been found that kasugamycin or natamycin, when combined with cyclic ester peptides represented by formula (I), particularly AbA, advantageously provide more than additive antifungal activity. See the following examples, which disclose the synergistic antifungal activity of AbA and kasugamycin or natamycin.

[0207] The following examples are provided to illustrate the invention and are not intended to limit the invention in any way.

[0208] Biological examples

[0209] The biological (fungal) activity of the compositions according to the invention in the form of dimethyl sulfoxide (DMSO) solutions was tested using one or more of the following methods (Examples 1-1 and 1-2).

[0210] Amoxicillin A and its synthesis are known from Takesako et al., The Journal of Antibiotics, 1991, 44, 919-924. Amoxicillin A was separated 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 purified by silica gel column chromatography (silica gel, eluted with hexane:ethyl acetate) followed by reversed-phase column chromatography (RP18, eluted with acetonitrile:H2O). As already noted, amoxicillin and natamycin are known and commercially available and / or can be prepared using procedures known in the art and / or procedures reported in the literature.

[0211] Example 1-1: Botryotinia fuckeliana (gray mold);

[0212] Frozen fungal conidia were directly mixed into nutrient liquid medium (Vogel's liquid medium). Nutrient liquid medium containing fungal conidia was added after placing a (DMSO) solution or (aqueous) suspension of the test compound into a microtiter plate (96-well size). The test plate was incubated at 24°C, and inhibition of growth was determined by photometry and visual inspection after 72 hours.

[0213] Example 1-2: Alternaria alternata (early blight of tomato / potato)

[0214] Frozen fungal conidia were directly mixed into nutrient liquid medium (PDB: Potato Dextrose Liquid Medium). After placing a (DMSO) solution or (aqueous) suspension of the test compound into a microtiter plate (96-well size), nutrient liquid medium containing fungal conidia was added. The test plate was incubated at 24°C, and inhibition of growth was determined by photometry and visual inspection after 48 hours.

[0215] result

[0216] The results of the tests summarized above are shown in Tables 1 through 4 below. These data show that synergistic fungicidal activity against *Botrytis cinerea* and *Alternaria solanacearum* was observed for specific weight ratios of abamectin A combined with either kasugamycin or natamycin. According to Colby, mathematically, the synergistic factor SF corresponds to O / E. In agricultural practice, an SF ≥ 1.1 indicates a significant improvement in activity relative to a purely complementary additive effect (the expected activity), while in practical application practices, an SF ≤ 0.9 signifies a loss of activity compared to the expected activity.

[0217] Table 1: Antifungal activity of the combination of basidiosin A and kasugamycin against Botrytis cinerea as described in Example 1-1 above.

[0218]

[0219] Table 2: Antifungal activity of the combination of basidiosin A and natamycin against Botrytis cinerea as described in Example 1-1 above.

[0220]

[0221] Table 3: Antifungal activity of the combination of basidiosin A and kasugamycin against Alternaria solanacearum as described in Examples 1-2 above.

[0222]

[0223] Table 4: Antifungal activity of the combination of basidiosin A and natamycin against Alternaria solanacearum as described in Examples 1-2 above.

[0224] Example

[0225] Example 1. A fungicidal composition comprising:

[0226] (i) Component A, wherein component A comprises a cyclic ester peptide, wherein the cyclic ester peptide is a gold basidiomycin A (AbA) or its stereoisomer, preferably wherein AbA is represented by formula (Ib):

[0227] (Ib); and

[0228] (ii) Component B, wherein component B contains kasugamycin or natamycin.

[0229] Example 2. The composition as described in Example 1, wherein component A further comprises one or more other cyclic ester peptides or stereoisomers thereof represented by formula (I):

[0230] (I),

[0231] in:

[0232] R 1 It is methyl or ethyl;

[0233] R 2 It is methyl, hydroxymethyl, or hydroxyethyl;

[0234] R 3 It is hydrogen or methyl;

[0235] X 1 X 2 and X 3 Each is hydrogen, or X 1 X 2 and X 3 It is hydrogen, fluorine, or hydroxyl, provided that X 1 X 2 and X 3 Only one of them is fluorine or hydroxyl;

[0236] X 4 It is CH2, S, or hydroxymethylene;

[0237] A 3It is selected from the following α-amino acid residues: N-methyl-L-phenylalanine (L-MePhe), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), o-fluoro-N-methyl-L-phenylalanine (LoF-MePhe), m-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), p-bromo ... L-phenyl-N-methyl-L-phenylalanine (Lm-Br-MePhe), p-bromo-N-methyl-L-phenylalanine (Lp-Br-MePhe), m-iodo-N-methyl-L-phenylalanine (LmI-MePhe), p-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) 3-(4-pyridyl)-N-methyl-L-phenylalanine, 4-(4-pyridyl)-N-methyl-L-phenylalanine, 3-(1-pyridyl)-N-methyl-L-phenylalanine, 4-(1-pyridyl)-N-methyl-L-phenylalanine, 4-(2-chloro-4-pyridyl)-N-methyl-L-phenylalanine, 3-(2-chloro-5-pyridyl)-N-methyl-L-phenylalanine, 4-(2-chloro-5-pyridyl)-N -Methyl-L-phenylalanine, 3-[4-(piperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 4-[4-(piperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 4-[4-(4-methylpiperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, β-oxo-N-methyl-L-phenylalanine (L-β-oxo-MePhe), β-R 4 ON-methyl-L-phenylalanine (where R) 4 It is a lower acyl group with 1 to 4 carbon atoms (L-β-R) 3 OMePhe), N-methyl-L-tyrosine (L-MeTyr), O-methyl-N-methyl-L-tyrosine [L-MeTyr(Me)], N-methyl-L-alanine (L-MeAla), N-methyl-L-serine (L-MeSer), sarcosine (Sar), N-methyl-D-phenylalanine (D-MePhe), N-methyl-D-alanine (D-MeAla), N-methyl-D-valine (D-MeVal) and N-methyl-D-serine (D-MeSer) residues;

[0238] A 5It is selected from the following α-amino acid residues: L-alloleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle), L-valine (L-Nva), L-valine (L-Val) and L-methionine sulfoxide (L-Met(O));

[0239] A 6 It is selected from the following α-amino acid residues: N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), N-methyl-L-isoleucine (L-MeAIle) and L-valine (L-Val) residues;

[0240] A 7 It is selected from the following α-amino acid residues: L-alloleucine (L-AIle), L-leucine (L-Leu), and L-n-valine (L-Nva) residues; and

[0241] A 8 It is selected from the following α-amino acid residues: β-methyl-L-phenylalanine (L-β-Phe), 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 The residues include 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).

[0242] Example 3. A composition as described in Example 1 or 2, wherein component A further comprises at least one other cyclic ester peptide having formula (I) or a stereoisomer thereof selected from the group consisting of: acrobaticin E (AbE) and acrobaticin G (AbG), preferably wherein AbE is represented by formula (Ic):

[0243] (Ic); and

[0244] Preferably, AbG is represented by formula (Id):

[0245] (Id).

[0246] Example 4. The composition as described in Example 2 or 3, wherein component A comprises 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight, of basidiosin A or its stereoisomer, and 0.1% to 90% by weight, preferably 0.1% to 80% by weight, more preferably 0.1% to 60% by weight, of the one or more other cyclic ester peptides represented by formula (I) or their stereoisomers.

[0247] Example 5. The composition as described in any one of Examples 1 to 4, wherein the weight ratio of component A to component B is 100:1 to 1:5000.

[0248] Example 6. The composition of any one of Examples 1 to 5, further comprising an agriculturally acceptable carrier and / or formulation adjuvant and optionally a surfactant.

[0249] Example 7. A method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi on plants or their propagation material, the method comprising applying a composition as described in any one of Examples 1 to 6 to the plant, its location, or its propagation material.

[0250] Example 8. The method as described in Example 7, wherein component A is applied in combination with component B at a ratio of 10 g ai / ha to 500 g ai / ha to 10 g ai / ha to 2000 g ai / ha.

[0251] Example 9. The method as described in Example 7 or 8, wherein the plant pathogenic fungus is selected from the group consisting of: *Alternaria*, *Botrytis*, *Cercospora*, *Anthracis*, *Corynebacterium*, *Fusarium*, *Globosa*, *Globosa*, *Globosa*, *Globosa*, *Pseudomonas*, *Laminaria*, *Pseudomonas ... and *Pseudomonas*, preferably selected from the group consisting of: *Alternaria* and *Botrytis*.

[0252] Example 10. The method of any one of Examples 7 to 9, wherein the plant is selected from useful plants including: cereals, fruits and tree nuts, vegetables, field crops, oil crops, forage crops, forest plants, horticultural crops, floriculture, greenhouse and nursery plants, propagation materials, edible herbs and spices and herbs, preferably wherein the useful plant is selected from: fruits and tree nuts, vegetables, horticultural crops and floriculture.

[0253] Example 11. The method as described in any one of Examples 7 to 10, wherein the plant is a useful plant selected from the group consisting of: apple, apricot, cherry, raspberry, grape, cucumber, peanut, tomato, strawberry, citrus and banana.

[0254] Example 12. Use of the composition comprising components A and B as described in any one of Examples 1 to 6 as a fungicide.

Claims

1. A fungicidal composition comprising: (i) Component A, wherein component A comprises a cyclic ester peptide, wherein the cyclic ester peptide is acrobaticin A (AbA) or a stereoisomer thereof; and (ii) Component B, wherein component B comprises kasugamycin or natamycin.

2. The composition according to claim 1, wherein, Component A further comprises one or more other cyclic ester peptides or stereoisomers thereof represented by formula (I): (I)， in: R 1 It is methyl or ethyl; R 2 It is methyl, hydroxymethyl, or hydroxyethyl; R 3 It is hydrogen or methyl; X 1 X 2 and X 3 Each is hydrogen, or X 1 X 2 and X 3 It is hydrogen, fluorine, or hydroxyl, provided that X 1 X 2 and X 3 Only one of them is fluorine or hydroxyl; X 4 It is CH2, S, or hydroxymethylene; A 3 It is selected from the following α-amino acid residues: N-methyl-L-phenylalanine (L-MePhe), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), o-fluoro-N-methyl-L-phenylalanine (LoF-MePhe), m-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LpF-MePhe), m-bromo-N-methyl-L-phenylalanine (LmF-MePhe), p-fluoro-N-methyl-L-phenylalanine (LmF-MePhe), p-bromo ... L-phenyl-N-methyl-L-phenylalanine (Lm-Br-MePhe), p-bromo-N-methyl-L-phenylalanine (Lp-Br-MePhe), m-iodo-N-methyl-L-phenylalanine (LmI-MePhe), p-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) 3-(4-pyridyl)-N-methyl-L-phenylalanine, 4-(4-pyridyl)-N-methyl-L-phenylalanine, 3-(1-pyridyl)-N-methyl-L-phenylalanine, 4-(1-pyridyl)-N-methyl-L-phenylalanine, 4-(2-chloro-4-pyridyl)-N-methyl-L-phenylalanine, 3-(2-chloro-5-pyridyl)-N-methyl-L-phenylalanine, 4-(2-chloro-5-pyridyl)-N -Methyl-L-phenylalanine, 3-[4-(piperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 4-[4-(piperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, 4-[4-(4-methylpiperazin-1-yl)phenyl]-N-methyl-L-phenylalanine, β-oxo-N-methyl-L-phenylalanine (L-β-oxo-MePhe), β-R 4 ON-methyl-L-phenylalanine (where R) 4 It is a lower acyl group with 1 to 4 carbon atoms (L-β-R) 3 OMePhe), N-methyl-L-tyrosine (L-MeTyr), O-methyl-N-methyl-L-tyrosine [L-MeTyr(Me)], N-methyl-L-alanine (L-MeAla), N-methyl-L-serine (L-MeSer), sarcosine (Sar), N-methyl-D-phenylalanine (D-MePhe), N-methyl-D-alanine (D-MeAla), N-methyl-D-valine (D-MeVal) and N-methyl-D-serine (D-MeSer) residues; A 5 It is selected from the following α-amino acid residues: L-alloleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle), L-valine (L-Nva), L-valine (L-Val) and L-methionine sulfoxide (L-Met(O)); A 6 It is selected from the following α-amino acid residues: N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), N-methyl-L-isoleucine (L-MeAIle) and L-valine (L-Val) residues; A 7 It is selected from the following α-amino acid residues: L-alloleucine (L-AIle), L-leucine (L-Leu), and L-n-valine (L-Nva) residues; and A 8 It is selected from the following α-amino acid residues: β-methyl-L-phenylalanine (L-β-Phe), 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 The residues include 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).

3. The composition according to claim 1 or 2, wherein, Component A further comprises at least one other cyclic ester peptide or its stereoisomer of formula (I) selected from the group consisting of: amoeboid E (AbE) and amoeboid G (AbG), preferably wherein AbE is represented by formula (Ic): (Ic); and Preferably, AbG is represented by formula (Id): (Id)。 4. The composition according to claim 2 or 3, wherein, Component A comprises 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight, of abaminin A or its stereoisomer, 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 ester peptides represented by formula (I) or their stereoisomers.

5. The composition according to any one of claims 1 to 4, wherein, The weight ratio of component A to component B is from 100:1 to 1:5000.

6. The composition according to any one of claims 1 to 5, wherein the composition further comprises an agriculturally acceptable carrier and / or formulation adjuvant and optionally a surfactant.

7. A method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi on plants or their propagation material, the method comprising applying a composition according to any one of claims 1 to 6 to said plant, its location or its propagation material.

8. The method according to claim 7, wherein, Component A is applied in combination with component B at a ratio of 10 g ai / ha to 500 g ai / ha to 10 g ai / ha to 2000 g ai / ha.

9. The method according to claim 7 or 8, wherein, The plant pathogenic fungi are selected from the group consisting of: *Alternaria*, *Botrytis*, *Cercospora*, *Anthracis*, *Corynebacterium*, *Fusarium*, *Globosa*, *Globosa*, *Globosa*, *Globosa*, *Pseudomonas*, *Laminaria*, *Pseudomonas ... and *Pseudomonas*, preferably from the group consisting of: *Alternaria* and *Botrytis*.

10. The method according to any one of claims 7 to 9, wherein, The plants are selected from the following useful plants: cereals, fruits and tree nuts, vegetables, field crops, oil crops, forage crops, forest plants, horticultural crops, floriculture, greenhouse and nursery plants, propagation materials, edible herbs and spices and medicinal herbs, preferably wherein the useful plants are selected from: fruits and tree nuts, vegetables, horticultural crops and floriculture.

11. The method according to any one of claims 7 to 10, wherein, The plants mentioned are useful plants selected from the group consisting of: apple, apricot, cherry, raspberry, grape, cucumber, peanut, tomato, strawberry, citrus and banana.

12. Use of the composition comprising components A and B according to any one of claims 1 to 6 as a fungicide.

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