Stericidal composition

Abstract

A fungicidal composition containing a mixture of components (A) and (B) as defined in claim 1, and the use of the composition in agriculture or horticulture for controlling or preventing infection of plants by phytopathogenic microorganisms, preferably fungi.

Description

Technical Field

[0001] The present invention relates in particular to novel bactericidal compositions (or fungicidal compositions) for treating phytopathogenic diseases affecting useful plants caused by phytopathogenic fungi, and to methods for controlling such diseases and / or fungi affecting useful plants.

Background Art

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

[0003] However, there continues to be a need to find novel compositions having excellent biological properties for use in controlling or preventing ectoparasitism of plants by phytopathogenic fungi. For example, compositions having a broader activity spectrum, improved crop tolerance, synergistic interactions or enhanced properties, or compositions that exhibit a more rapid onset of action, or have a longer-lasting residual activity, or that enable a reduction in the number of applications and / or the application rate of the compounds and compositions required for effective control of plant pathogens, thereby enabling the implementation of beneficial resistance management, reduced environmental impact, and reduced exposure to workers.

[0004] The use of a composition containing a mixture of different bactericidal compounds having different mechanisms of action can meet some of these requirements (for example, by combining fungicides having different spectra of activity).

SUMMARY OF THE INVENTION

MEANS FOR SOLVING THE PROBLEM

[0005] According to the present invention, there is provided a bactericidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a cyclic depsipeptide of formula (I):

CHEMICAL

[0006] Generally, the weight ratio of component (A) to component (B) can be from 100:1 to 1:500, preferably from 100:1 to 1:200, more preferably from 10:1 to 1:80.

[0007] In some preferred embodiments of the present invention, the weight ratio of component (A) to component (B) can be 1:1, or 1:2, or 1:4, or 2:1, or 4:1, or 8:1, or 16:1, or 1:200, or 1:100, or 1:50, or 1:25, or 1:20, or 1:12.5, or 1:10, or 1:6.2, or 1:5, or 1:2.5.

[0008] According to a second aspect of the present invention, there is provided a method for controlling or preventing phytopathogenic diseases, particularly those caused by phytopathogenic fungi, in useful plants or their propagation materials, which method comprises applying to the useful plant, its habitat or its propagation materials a composition as defined in the present invention. A method comprising applying the composition according to the present invention to a useful plant or its habitat, more preferably to a useful plant, is preferred. Even more preferably, the method comprises applying the composition according to the present invention to the propagation material of the useful plant.

[0009] According to a third aspect of the present invention, there is provided the use of a composition comprising components (A) and (B) as defined in the present invention as a fungicide.

[0010] Surprisingly and substantially, it has been found that by using in combination the compound of formula (I), the compound of component (B), and optionally the compound of component (C), the effectiveness of the compound of formula (I) against fungi can be enhanced, and vice versa. Also, the use of the composition of the present invention can be effective against a broader range of such fungi than those that can be controlled by the individual active ingredients when used alone.

[0011] The benefits conferred by the specific fungicidal compositions according to the present invention can include, inter alia, an advantageous level of biological activity for protecting plants from diseases caused by fungi, or excellent properties for use as an agrochemical active ingredient (such as high biological activity, advantageous activity spectrum, increased safety profile, improved physicochemical properties, or increased biodegradability).

[0012] As used herein, the term "cyclic depsipeptide" refers to consecutive units derived from 2-hydroxy-3-methylalkanoic acid and α-amino acid A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8refers to a cyclic peptide consisting of units derived from, where the α - amino acid residue A 8 is bonded via an ester group to the -OCH(CH(CH3)R of 2 - hydroxy - 3 - methylalkanoic acid 1 ) moiety to form a -C(=O)OCH(CH(CH3)R 1 ) moiety, and, the α - amino acid residues A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 are bonded to each other via peptide bonds. 2 - Hydroxy - 3 - methylalkanoic acid can be 2(R) - hydroxy - 3(R) - methylpentanoic acid or 2(R) - hydroxy - 3 - methylbutanoic acid.

Mode for Carrying Out the Invention

[0013] In a first embodiment of the present invention, component (A) is one or more cyclic depsipeptides of formula (I - A):

Chemical formula

[0014] Preferably, the compound of formula (I) according to the present invention is selected from compounds 1.001 to 1.035 listed in Table A (below) or compounds 2.001 to 2.045 listed in Table B (below).

[0015] The following list provides definitions regarding the substituents R 1 , A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 relating to, including preferred definitions. For any one of these substituents, any of the definitions shown below may be combined with any of the definitions of any of the other substituents shown elsewhere herein or below.

[0016] Table A: This table discloses 35 compounds of formula (I), where R 1 , A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 are as described in Table A below.

[0017]

Table 1-1

Table 1-2

[0018] Table B: This table discloses 45 compounds of formula (I), where R 1 is ethyl, A 1 is L-MeVal, A 4 is L-Pro, A 6 is L-MeVal, and A 7is L-Leu, and A 2 A 3 A 5 and A 8 are as described in Table B below.

[0019]

Table 2-1

Table 2-2

[0020] In the first modification of this first embodiment of the present invention, component (A) is a cyclic depsipeptide of formula (I-A1), which is hereinafter referred to as aureobasidin A in this specification:

Chemical formula

[0021] As used herein, the term "aureobasidin A" refers to a cyclic depsipeptide of formula (I-A1) consisting of units derived from consecutive 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-phenylalanine (L-Phe), N-methyl-L-phenylalanine (L-MePhe), L-proline (L-Pro), L-alloisoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu) and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), or a stereoisomer thereof.

[0022] In the second modification of this first embodiment of the present invention, component (A) is a cyclic depsipeptide of formula (I-A2), which is hereinafter referred to as aureobasidin E in this specification:

Chemical formula

[0023] As used herein, the term "aureobasidin E" refers to a cyclic depsipeptide of formula (I-A2) consisting of units derived from consecutive 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), L-proline (L-Pro), L-alloisoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu), and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), or a stereoisomer thereof.

[0024] In a third variant of this first embodiment of the present invention, component (A) is a cyclic depsipeptide of formula (I-A3), hereinafter referred to as aureobasidin G in the present specification:

Chemical formula

[0025] As used herein, the term "aureobasidin G" refers to a cyclic depsipeptide of formula (I-A3) consisting of units derived from consecutive 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-phenylalanine (L-Phe), N-methyl-L-phenylalanine (L-MePhe), L-proline (L-Pro), L-alloisoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu), and N-methyl-L-valine (L-MeVal), or a stereoisomer thereof.

[0026] In one embodiment according to the present invention, component (A) comprises two or more cyclic depsipeptides of formula (I-A) as defined above or stereoisomers thereof.

[0027] In the first modification of the present embodiment of the present invention, component (A) includes aureobasidin A and one or more other cyclic depsipeptides of formula (I-A) as defined above or stereoisomers thereof.

[0028] In the second modification of the present embodiment of the present invention, component (A) includes aureobasidin E and one or more other cyclic depsipeptides of formula (I-A) as defined above or stereoisomers thereof.

[0029] In a preferred embodiment according to the present invention, component (A) includes aureobasidin A and one or more cyclic depsipeptides of formula (I) selected from the group consisting of Compounds 1.001 to 1.004 and 1.006 to 1.035 described in Table A or stereoisomers thereof. Preferably, component (A) includes aureobasidin A and at least one other cyclic depsipeptide of formula (I-A) selected from the group consisting of aureobasidin E and aureobasidin G or stereoisomers thereof.

[0030] In another preferred embodiment according to the present invention, component (A) includes aureobasidin A and one or more cyclic depsipeptides of formula (I) selected from the group consisting of Compounds 2.001 to 2.045 described in Table B or stereoisomers thereof.

[0031] In an embodiment where component (A) includes aureobasidin A and one or more other cyclic depsipeptides of formula (I-A) or stereoisomers thereof, the component (A) typically comprises: 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight of aureobasidin A, and 0.1% to 90% by weight, preferably 0.1% to 80% by weight, more preferably 0.1% to 60% by weight of one or more other cyclic depsipeptides of formula (I-A) or stereoisomers thereof and contains.

[0032] In an embodiment where component (A) comprises aureobasidin E and one or more other cyclic depsipeptides of formula (I-A) or stereoisomers thereof, said component (A) typically comprises: 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight of aureobasidin E, and 0.1% to 90% by weight, preferably 0.1% to 80% by weight, more preferably 0.1% to 60% by weight of one or more other cyclic depsipeptides of formula (I-A) or stereoisomers thereof and comprises.

[0033] In one embodiment according to the present invention, component (A) typically comprises: 60% to 99.5% by weight of aureobasidin A, 0.05% to 5% by weight of aureobasidin E, optionally 0.1% to 30% by weight of aureobasidin G, optionally 0.1% to 10% by weight of one or more other cyclic depsipeptides of formula (I-A) or stereoisomers thereof and comprises.

[0034] In a second embodiment of the present invention, component (A) is one or more cyclic depsipeptides of formula (I-B):

Chemical formula

[0035] As used herein, the term "persephanine residue" refers to the formula:

Chem.

[0036] In the first variant of this second embodiment of the present invention, component (A) is a cyclic depsipeptide of formula (I - B1), hereinafter referred to as Persephacin A in the present specification:

Chem.

[0037] As used herein, the term "Persephacin A" refers to a cyclic depsipeptide of formula (I-B1) consisting of units derived from consecutive 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-persephanine, sarcosine (Sar), L-proline (L-Pro), L-alloisoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu) and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), or a stereoisomer thereof.

[0038] In a second variant of this second embodiment of the present invention, component (A) is a cyclic depsipeptide of formula (I-B2), hereinafter referred to as Persephacin B in the present specification:

Chemical formula

[0039] As used herein, the term "Persephacin B" refers to a cyclic depsipeptide of formula (I-B2) consisting of units derived from consecutive 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-persephanine, sarcosine (Sar), L-proline (L-Pro), L-alloisoleucine (L-AIle), L-alloisoleucine (L-AIle), L-leucine (L-Leu) and β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), or a stereoisomer thereof.

[0040] In a third variant of this second embodiment of the present invention, component (A) is a cyclic depsipeptide of formula (I-B3), hereinafter referred to as Persephacin C in the present specification:

Chemical formula

[0041] As used herein, the term "Persephacin C" refers to a cyclic depsipeptide of formula (I-B3) consisting of consecutive units derived from 2(R)-hydroxy-3(R)-methylpentanoic acid ((2R,3R)-Hmp), N-methyl-L-valine (L-MeVal), L-persephanine, sarcosine (Sar), L-proline (L-Pro), L-alloisoleucine (L-AIle), N-methyl-L-valine (L-MeVal), L-leucine (L-Leu) and N-methyl-L-valine (L-MeVal), or a stereoisomer thereof.

[0042] In one embodiment according to the present invention, component (A) comprises two or more cyclic depsipeptides of formula (I-B) as defined above or stereoisomers thereof.

[0043] In a modification of this embodiment of the present invention, component (A) comprises Persephacin A and one or more other cyclic depsipeptides of formula (I-B) as defined above or stereoisomers thereof.

[0044] In an embodiment where component (A) comprises Persephacin A and one or more other cyclic depsipeptides of formula (I-B) or stereoisomers thereof, said component (A) typically comprises: 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight of Persephacin A, and 0.1% to 90% by weight, preferably 0.1% to 80% by weight, more preferably 0.1% to 60% by weight of one or more other cyclic depsipeptides of formula (I-B) or stereoisomers thereof and comprises.

[0045] In another embodiment according to the present invention, component (A) includes one or more cyclic depsipeptides of formula (I-A) or stereoisomers thereof, and one or more cyclic depsipeptides of formula (I-B) or stereoisomers thereof as defined above.

[0046] In a modification of this embodiment of the present invention, component (A) includes aureobasidin A and one or more cyclic depsipeptides of formula (I-B) or stereoisomers thereof as defined above.

[0047] In another modification of this embodiment of the present invention, component (A) includes aureobasidin A, one or more other cyclic depsipeptides of formula (I-A) or stereoisomers thereof as defined above, and one or more cyclic depsipeptides of formula (I-B) or stereoisomers thereof as defined above.

[0048] In another modification of this embodiment of the present invention, component (A) includes aureobasidin A, at least one other cyclic depsipeptide of formula (I-A) or stereoisomers thereof selected from the group consisting of aureobasidin E and aureobasidin G, and one or more cyclic depsipeptides of formula (I-B) or stereoisomers thereof as defined above.

[0049] In another embodiment according to the present invention, component (A) is a strain of Aureobasidium pullulans, generally a strain of Aureobasidium pullulans R106.

[0050] Without limiting the scope of the present invention, it is understood that one or more cyclic depsipeptides of formula (I-A) or stereoisomers thereof as defined above are obtainable from the fermentation broth of a strain of Aureobasidium pullulans, generally a strain of Aureobasidium pullulans R106.

[0051] In another embodiment of the present invention, component (A) is a strain of Sphaceloma coryli or a genetically engineered strain.

[0052] Without limiting the scope of the present invention, it is understood that one or more of the cyclic depsipeptides of formula (I-B) or their stereoisomers as defined above are obtainable from the fermentation broth of a strain of Sphaceloma coryli or a genetically engineered strain.

[0053] As used herein, the term "fermentation broth" refers to a composition obtained from the fermentation process of a strain.

[0054] In another embodiment of the present invention, component (A) is a fermentation broth containing two or more of the cyclic depsipeptides of formula (I) or their stereoisomers as defined above.

[0055] In a first variant of this embodiment of the present invention, component (A) is a fermentation broth containing two or more of the cyclic depsipeptides of formula (I-A) or their stereoisomers as defined above.

[0056] In one embodiment of the present invention, component (A) is a fermentation broth containing aureobasidin A and one or more other cyclic depsipeptides of formula (I-A) or their stereoisomers as defined above.

[0057] In another embodiment of the present invention, component (A) is a fermentation broth containing aureobasidin E and one or more other cyclic depsipeptides of formula (I-A) or their stereoisomers as defined above.

[0058] In the second variant of the present embodiment of the present invention, component (A) is a fermentation broth containing two or more cyclic depsipeptides of formula (I-B) as defined above or stereoisomers thereof, and preferably, component (A) is a fermentation broth containing Persephacin A and one or more other cyclic depsipeptides of formula (I-B) as defined above or stereoisomers thereof.

[0059] The component (B) compound is referred to herein and above herein by the so-called "ISO common name" or other "common names" used in individual cases or trade names. The component (B) compound is known, commercially available, and / or can be prepared using methods known in the art and / or methods reported in the literature.

[0060] In a preferred embodiment according to the present invention, component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil.

[0061] In a preferred composition according to the present invention, component (A) contains one or more cyclic depsipeptides of formula (I-A) as defined above or stereoisomers thereof, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil, where the weight ratio of component (A) to component (B) is 100:1 to 1:500, preferably 100:1 to 1:200, more preferably 10:1 to 1:80.

[0062] In another preferred composition according to the present invention, component (A) is aureobasidin A, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil, where the weight ratio of component (A) to component (B) is 100:1 to 1:500.

[0063] In another preferred composition according to the present invention, component (A) is aureobasidin A, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil, wherein the weight ratio of component (A) to component (B) is from 100:1 to 1:200.

[0064] In another preferred composition according to the present invention, component (A) is aureobasidin A, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:80.

[0065] In another preferred composition according to the present invention, component (A) is aureobasidin E, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil, wherein the weight ratio of component (A) to component (B) is from 100:1 to 1:500.

[0066] In another preferred composition according to the present invention, component (A) is aureobasidin E, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil, wherein the weight ratio of component (A) to component (B) is from 100:1 to 1:200.

[0067] In another preferred composition according to the present invention, component (A) is aureobasidin E, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:80.

[0068] In another preferred composition according to the present invention, component (A) includes aureobasidin A and one or more cyclic depsipeptides of formula (I) or stereoisomers thereof selected from the group consisting of compounds 1.001 to 1.004 and 1.006 to 1.035 described in Table A. Preferably, component (A) includes aureobasidin A and at least one other cyclic depsipeptide of formula (I-A) or stereoisomers thereof selected from the group consisting of aureobasidin E and aureobasidin G. Also, component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil. Here, the weight ratio of component (A) to component (B) is 100:1 to 1:500.

[0069] In another preferred composition according to the present invention, component (A) includes aureobasidin A and one or more cyclic depsipeptides of formula (I) or stereoisomers thereof selected from the group consisting of compounds 1.001 to 1.004 and 1.006 to 1.035 described in Table A. Preferably, component (A) includes aureobasidin A and at least one other cyclic depsipeptide of formula (I-A) or stereoisomers thereof selected from the group consisting of aureobasidin E and aureobasidin G. Also, component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil. Here, the weight ratio of component (A) to component (B) is 100:1 to 1:200.

[0070] In another preferred composition according to the present invention, component (A) includes aureobasidin A and one or more cyclic depsipeptides of formula (I) or stereoisomers thereof selected from the group consisting of compounds 1.001 to 1.004 and 1.006 to 1.035 described in Table A. Preferably, component (A) includes aureobasidin A and at least one other cyclic depsipeptide of formula (I-A) or stereoisomers thereof selected from the group consisting of aureobasidin E and aureobasidin G. Also, component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil. Here, the weight ratio of component (A) to component (B) is 10:1 to 1:80.

[0071] In another preferred composition according to the present invention, component (A) is a strain of Aureobasidium pullulans, generally a strain of Aureobasidium pullulans R106, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim and pyrimethanil, wherein the weight ratio of component (A) to component (B) is 100:1 to 1:500, preferably 100:1 to 1:200, more preferably 10:1 to 1:80.

[0072] In another preferred composition according to the present invention, component (A) is a fermentation broth containing one or more cyclic depsipeptides of formula (I-A) as defined above or stereoisomers thereof, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim and pyrimethanil, wherein the weight ratio of component (A) to component (B) is 100:1 to 1:500, preferably 100:1 to 1:200, more preferably 10:1 to 1:80.

[0073] In another preferred composition according to the present invention, component (A) is a fermentation broth containing aureobasidin A and one or more other cyclic depsipeptides of formula (I-A) as defined above or stereoisomers thereof, and component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim and pyrimethanil, wherein the weight ratio of component (A) to component (B) is 100:1 to 1:500, preferably 100:1 to 1:200, more preferably 10:1 to 1:80.

[0074] The composition of the present invention may, in certain circumstances, contain a component (C) which is an additional active ingredient different from component (B), wherein component (C) is selected from the group consisting of inhibitors (B.1) and (B.2) of amino acid and protein synthesis as defined in the present invention.

[0075] In an embodiment of the present invention where the composition contains component (A), component (B), and component (C), the weight ratio of component (A) to the sum of component (B) and component (C) can be from 100:1 to 1:500, more preferably from 100:1 to 1:200, and even more preferably from 10:1 to 1:80.

[0076] In some preferred embodiments of the present invention, the weight ratio of component (A) to the sum of component (B) and component (C) can be 1:1, or 1:2, or 1:4, or 2:1, or 4:1, or 8:1, or 16:1, or 1:200, or 1:100, or 1:50, or 1:25, or 1:20, or 1:12.5, or 1:10, or 1:6.2, or 1:5, or 1:2.5.

[0077] The compound of formula (I) according to the present invention or its stereoisomers can be prepared by methods known to those skilled in the art. The compound of formula (I) is available for purchase or can be prepared using synthetic or semi-synthetic chemistry or fermentation processes. For example, the compound of formula (I-A) or its stereoisomers can be prepared by the 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 broths containing one or more compounds of formula (I-A) or their stereoisomers are available from the fermentation process of strains of Aureobasidium pullulans, generally strains of Aureobasidium pullulans R106. Fermentation broths containing one or more compounds of formula (I-B) or their stereoisomers are available from the fermentation process of strains of Sphaceloma coryli. Fermentation broths may not require purification. Alternatively, one or more compounds of formula (I) can be isolated and purified from the fermentation broth by chromatography using adsorbents (e.g., silica and reverse-phase silica gel, optically active adsorbents, resins) or one or more solvents (e.g., partitioning, countercurrent separation, mixtures of multiphase solvents) or other chemical means (e.g., crystallization, recrystallization, salt formation, and precipitation) to achieve the final purity. The purity of the compound of formula (I) or its stereoisomers is not particularly limited, but can include ranges 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 the compound of formula (I) or its stereoisomers can 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 means.

[0078] As used herein, the term "fungicide" means a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidally effective amount" means an amount of such a compound or combination of such compounds that is capable of effecting the growth of fungi. The control or modifying effect includes all deviations from natural development such as death, retardation, etc., and prevention includes barriers or other defenses formed in plants to prevent infection by fungi.

[0079] As used herein, the term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, petioles, foliage, and fruits.

[0080] As used herein, the term "plant propagation material" means all reproductive parts of a plant, such as growing parts of a plant like seeds or cuttings or tubers. This includes not only seeds in the strict sense, but also roots, fruits, tubers, bulbs, rhizomes, and parts of plants.

[0081] As used herein, the term "habitat" means a field in which a plant is growing, or a field in which seeds of a cultivated plant are to be sown, or a field in which seeds are to be sown into the soil. This includes the soil, seeds and seedlings, as well as established vegetation.

[0082] Throughout this specification, the expression "composition" means various mixtures or combinations of components (A) and (B) (including the embodiments defined above), for example, a single "formulated" form, a complex spray mixture such as a "tank mixture" composed of individual formulations of a single active ingredient element, and, when applied sequentially (i.e., one after another within a moderately short time such as several hours or days), a combination of single active ingredients. The order of application of components (A) and (B) is not important for the action of the present invention.

[0083] The compositions of the present invention are effective against harmful microorganisms such as microorganisms that cause phytopathogenic diseases, particularly phytopathogenic fungi and bacteria.

[0084] The composition of the present invention can be used to control plant diseases caused by a wide range of fungal plant pathogens in the classifications of basidiomycetes, ascomycetes, oomycetes and / or imperfect fungi, Blasocladiomycete, Chrytidiomycete, Glomeromycete and / or Mucoromycete: Oomycetes, including those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, Phytophthora erythroseptica and other Phytophthora diseases; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Peronospora manshurica, Peronospora tabacina, 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; Ascomycetes, such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Drechslera glycines, Didymella bryoniae, Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solaniPleosporales such as *Solanum* spp. and *Alternaria tomatophila*; Capnodiales such as *Septoria tritici*, *Septoria nodorum*, *Septoria glycines*, *Cercospora arachidicola*, *Cercospora beticola*, *Cercospora sojina*, *Cercospora zeae-maydis*, *Cercosporella capsellae*, and *Cercosporella herpotrichoides*; *Cladosporium carpophilum*, *Cladosporium effusum*, *Passalora fulva*, *Cladosporium oxysporum*, *Dothistroma septosporum*, *Isariopsis clavispora*, *Mycosphaerella fijiensis*, *Mycosphaerella graminicola*, *Mycovellosiella koepkeii*, *Phaeoisariopsis bataticola*, *Pseudocercospora vitis*, *Pseudocercosporella herpotrichoides*, *Ramularia beticola*, *Ramularia collo-cygni*, *Gaeumannomyces graminis*Magnaporthe grisea, Magnaporthe oryzae, and other Magnaporthales such as Magnaporthe graminis; Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsa ceratosperma, and other Diaporthales; and Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, ChaetomiumThose caused by other things such as spp.), Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans, etc., such as blotch diseases, leaf spot diseases, blast diseases or trunk rot diseases and / or rot diseases; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale, Monilinia fructicola, Monilinia laxa, Monilinia fructigena, Monographella albescens, Monosporascuscannonballus), species of the genus Naemacyclus, Ophiostomanovo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, species of the genus Petriellidium, species of the genus Pezicula, Phialophora gregata, Phialophora tetraspora, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor, Sclerotium spp, Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis;Powdery mildew diseases caused by Erysiphales such as, for example, Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis, Podospaera pannosa, Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis; molds caused by Botryosphaeriales such as, for example, Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botrytis tracheiphila, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta cucurbitacearum, etc.Anthracnose caused by Glommerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola; and wilt or stem blight caused by Hypocreales such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium brasiliense, Fusarium tucumaniae, Fusarium cuneirostrum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp.cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae; Basidiomycetes including smut fungi such as those caused by the Ustilaginales, such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, etc., for example, Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp.Those caused by rust fungi such as Pucciniastrum secalis, Pucciniastrum coryli, etc. of the order Pucciniales, or rust fungi such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phakopsora meibomiae, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor, and Uromyces viciae-fabae of the order Uredinales; and species of the genus Cryptococcus, Exobasidium vexans, Marasmiellus inoderma, and species of the genus Mycena) other rot diseases and diseases caused by, for example, Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia haperplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae, and Tilletia caries;. Blastocladiomycetes such as Physoderma maydis; and diseases caused by Choanephora cucurbitarum; species of the genus Mucor; Mucoromycetes such as Rhizopus arrhizus, Rhizopus oryzae, Rhizopus stolonifera, and Rhizopus nigricans, and other species and genera related to those listed above.

[0085] In addition to its bactericidal activity, the composition may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Streptomyces scabies and other related species, as well as certain protozoa.

[0086] The composition according to the present invention is particularly effective against phytopathogenic fungi belonging to the classification of Ascomycetes (e.g., Venturia, Alternaria, Podosphaera, Erysiphe, Magnaporthe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g., Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (also known as Deuteromycetes; e.g., Botrytis, Colletotrichum, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Penicillium, Pyricularia, and Pseudocercosporella); Oomycetes (e.g., Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora, Plasmopara).

[0087] Preferably, the composition according to the present invention is Alternaria, Ascochyta, Botrytis, Cercospora, Cochliobolus sativus, Colletotrichum, Colletotrichum lagenarium, Corynespora, Erysiphe, Erysiphe cichoracearum, Sphaerotheca fuliginea, Fusarium, Fusarium oxysporum, Gaeumannomyces graminis, Guignardia, Helminthosporium, Hemileia vastatrix, Magnaporthe, Magnaporthe oryzae, Monilinia, Mycosphaerella, Mycosphaerella arachidis, Phakopsora, Phoma, Phomopsis, Puccinia, Pseudocercosporella, Pseudopezicula, Phragmidium mucronatum, Podosphaera, Pyrenophora, Pyrenophora teres, Pyricularia, Pyricularia oryzae, Ramularia, Ramularia collo-cygni, Rhizoctonia, RhizoctoniaIt may be effective against phytopathogenic fungi selected from the group consisting of Alternaria solani, Rhynchosporium secalis, Sclerotinia, Septoria, Septoria tritici, Sphacelotheca reilliana, Tilletia, Urocystis occulta, Uncinula, Ustilago, Venturia, Monilia, and Penicillium.

[0088] The composition of the present invention may be particularly effective against phytopathogenic fungi selected from the group consisting of Alternaria, Botrytis, Cercospora, Colletotrichum, Corynespora, Guignardia, Mycosphaerella, Monilinia, Penicillium, Phakopsora, Phomopsis, Podosphaera, Pseudopezicula, Septoria, Uncinula, and Venturia.

[0089] The composition of the present invention can be particularly effective against phytopathogenic fungi selected from the group consisting of Alternaria solani, Alternaria alternata, Alternaria porri, Botrytis cinerea, Botrytis allii, Botrytis squamosa, Cercospora capsici, Colletotrichum lagenarium, Corynespora cassiicola, Guignardia bidwellii, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Penicillium digitatum, Penicillium italicum, Penicillium expansum, Phomopsis viticola, Podosphaera leucotricha, Podosphaera xanthii, Pseudopezicula tracheiphila, Septoria tritici, Uncinula necator, and Venturia inaequalis.

[0090] According to the present invention, "useful plants" typically include the following perennial or annual plants: Cereals such as barley, maize (corn), millet, rye, rice, wheat, sorghum, triticale, and durum wheat; grains such as amaranth, buckwheat, chia, quinoa, and canahua; Fruits such as grapes (table and wine grapes), almonds, apples, apricots, avocados, bananas, strawberries, blueberries, cloudberries, cocoa, cashews, cherimoyas, plums, chestnuts, dogwoods, citrus fruits (including grapefruit, limes, lemons, oranges, calamansi), coconuts, coffee, cranberries, elderberries, dates, figs, hazelnuts, gooseberries, guavas, kiwis, lychees, macadamias, mangoes, nectarines, olives, papayas, passion fruits, peaches, pears, pecans, persimmons, pineapples, pistachios, plums (including prunes), pomegranates, quinces, raspberries, strawberries, Surinam cherries, and walnuts; and tree nuts; Vegetables such as artichokes, asparagus, beans (snap beans, green beans, dry beans, edible beans), beets (tops), broccoli / Italian kale, Brussels sprouts, cabbages (including Chinese cabbage), carrots, cauliflower, celeriac, celery, chickpeas, chives, collard greens (including kale), cucumbers, edamame, eggplants, endives, field peas (garden pea, dry field pea, edible field pea), garlic, horseradish, kohlrabi, leeks, lentils, lettuce, melons, mushrooms (cultivated), mustard and other leafy greens, okra, onions, parsley, parsnips, peppers, potatoes, prickly pear fruits, pumpkins, daikon radishes, burdocks, rutabagas, salsify, spinach, squashes (summer squash and winter squash), sweet corn, sweet potatoes, turnips, taro, tomatoes / tomatillos, kohlrabi, and watermelons; Agricultural crops such as sugar beets, sugar cane, tobacco, peanuts, and soybeans; Oilseed crops such as rape (canola), mustard, camelina, false flax, sunflower, safflower, sesame, and safflower; For example, forage crops such as alfalfa, clover, soybean, chickpea, mung bean, lupinus, fodder beet, triticale, Kentucky bluegrass, cowpea, orchardgrass; Fiber crops such as cotton, flax, hemp, jute, and sisal; Coniferous tree species such as larch, spruce, or pine, temperate and tropical hardwoods (e.g., oak, maple, beech, teak, or mahogany), and forest plants including tree species in arid zones such as eucalyptus; Hops, maple (maple syrup), tea, natural rubber plants, and turfgrass (e.g., bentgrass, Kentucky bluegrass, triticale, cowpea, zoysiagrass, centipedegrass, crested hairgrass, miscanthus, Saint Augustine grass, fescue, blue moss, giant reed, Japanese silver grass, etc.) horticultural crops; Examples include begonia, dahlia, geranium, petunia, petunia, coleus, marigold, pansy, carnation, saintpaulia, azalea, chrysanthemum, flower bulbs, hydrangea, lily, orchid, poinsettia, rose, astilbe, goldenrod, gypsophila, heuchera, cineraria, rudbeckia, salvia, vinca, camellia, magnolia, garden chrysanthemum, ivy, decorative turf, peony, delphinium, gladiolus, iris, carnation, tulip, eucalyptus, dieffenbachia, dracaena, ficus, philodendron, spathiphyllum, pineapple, cactus, palm, balsam fir, bunge nettle tree, Japanese red pine, Fraser fir, noble fir, European larch, white pine, Japanese hemlock, torreya, alder, ornamental cherry, ornamental European plum, Japanese quince, American mountain ash, and fruits of nandina, including flowers, broad-leaved trees or evergreen trees, flower gardening, greenhouse, and nursery plants; Propagation materials such as bare seedlings, cuttings, liners, cell-formed seedlings, seeds, tissue-cultured small plants, and prefinished plants; For example, culinary herbs and spices such as allspice, Angelica spp., anise, Japanese angelica tree, white mustard, agi, basil (all species), ginkgo (cultivars), bladderwrack (seaweed), Bolivian coriander, purple gromwell, calendula (used as a herb), candlenut, caper, caraway, cardamom, cassia spice, cinnamon, clary sage, clove, Japanese mint, chamomile, chervil, chicory, celery, cilantro, comfrey, coriander, mustard, cumin, curry, dill, shepherd's purse, perilla, phyllanthus (cultivars), fingerroot, galangal, ginger, hop, Japanese savory, hyssop, lavender, lemon essential oil, lemon thyme, lovage, mace, mahaleb, Malabar tamarind, marjoram, mint (all species), mugwort, Japanese butterbur, oregano, orris root, paprika, parsley, pepper, rosemary, rue, saffron, sage (all species), celery (all species), purslane, tarragon, thyme, turmeric, vanilla, wasabi, and Japanese horseradish; and For example, medicinal herbs such as alder, Artemisia spp., astragalus, Bordeaux mixture, comfrey, coneflower, perilla, white chrysanthemum, Japanese butterbur, ginkgo, ginseng, gotu kola, hydrastis, gypsywort, Japanese savory, houttuynia, lavender, licorice, white peony, Japanese arrowroot, nettles, sedum, purslane, English plantain, Japanese mugwort, mugwort, Japanese knotweed, Japanese mint, yerba buena, and Indian sassafras.

[0091] This list is not meant to represent any limitation, however, preferably, useful plants can be selected from the group consisting of wheat, barley, rice, soybean, apple, almond, cherry, raspberry, grape, cucumber, peanut, tomato, strawberry, citrus and banana.

[0092] The term "useful plant" should be understood to also include useful plants that have been rendered resistant to herbicides such as bromoxynil, or certain classes of herbicides (e.g., HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyruvyl-shikimate-3-phosphate synthase) inhibitors, GS (glutamine synthetase) inhibitors, etc.) by conventional breeding or genetic engineering methods. An example of a crop that has been rendered resistant to imidazolinones such as imazamox by conventional breeding methods (mutation induction) is Clearfield® summer canola. Examples of crops that have been rendered resistant to herbicides or certain classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant corn varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

[0093] The term "useful plant" should be understood to also include useful plants transformed using recombinant DNA technology such that they are capable of synthesizing one or more selectively acting toxins, such as those known from toxin-producing bacteria. Examples of toxins that may be expressed include δ-endotoxin, vegetative insecticidal protein (Vip), insecticidal proteins from nematode symbiotic bacteria, and toxins produced by scorpions, arachnids, large wasps and fungi.

[0094] An example of a crop modified to express Bacillus thuringiensis toxin is Bt corn KnockOut® (Syngenta Seeds). An example of a crop containing two or more genes encoding insecticidal resistance and thus expressing two or more toxins is VipCot® (Syngenta Seeds). The crop or its seed material can also be resistant to multiple pests (so-called stacked transgenic events when formed by genetic modification). For example, a plant can be herbicide resistant, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International), and at the same time have the ability to express an insecticidal protein.

[0095] Examples of toxins that can be expressed by such genetically modified plants include insecticidal proteins such as insecticidal proteins derived from Bacillus cereus or Bacillus popliae; or insecticidal proteins derived from Bacillus thuringiensis such as δ-endotoxins such as CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidal proteins (VIP) such as VIP1, VIP2, VIP3 or VIP3A; or insecticidal proteins of nematode symbiotic bacteria such as Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens or Xenorhabdus nematophilus; toxins produced by animals such as scorpion toxin, spider toxin, large wasp toxin and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycete toxin, plant lectins such as pea lectin, barley lectin or pine mushroom lectin; agglutinin; protease inhibitors such as trypsin inhibitor, serine protease inhibitor, patatin, cystatin, papain inhibitor; ribosome-inactivating proteins (RIP) such as ricin, corn-RIP, abrin, luffin, saporin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor, HMG-COA-reductase, ion channel blockers such as sodium or calcium blockers, larval hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0096] In connection with the present invention, it should be understood that δ-endotoxins such as, for example, CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidal proteins (VIPs) such as, for example, VIP1, VIP2, VIP3 or VIP3A, are in particular also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by new combinations of different domains of these proteins (see, for example, WO 02 / 15701). An example of a truncated toxin is the truncated CryIA(b) expressed in Bt11 maize produced by Syngenta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the native toxin are replaced. In such amino acid substitutions, preferably a protease recognition sequence that does not occur naturally is inserted into the toxin, for example, in the case of CryIIIA055, a cathepsin D-recognition sequence is inserted into the CryIIIA toxin (see WO 03 / 018810).

[0097] Examples of such toxins, or of genetically modified plants capable of synthesizing such toxins, are disclosed, for example, in EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0098] The process for preparing such genetically modified plants is generally known to those skilled in the art and is described, for example, in the above-mentioned publications. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90 / 13651.

[0099] The toxins contained in genetically modified plants confer resistance to harmful insects on the plants. Such insects can be any of the insect taxa, but are particularly commonly found among beetles (Coleoptera), dipterous insects (Diptera) and butterflies (Lepidoptera).

[0100] Genetically modified plants containing one or more genes encoding insecticidal resistance and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants are as follows: YieldGard® (maize variety expressing the CryIA(b) toxin); YieldGard Rootworm® (maize variety expressing the CryIIIB(b1) toxin); YieldGard Plus® (maize variety expressing the CryIA(b) and CryIIIB(b1) toxins); Starlink® (maize variety expressing the Cry9(c) toxin); Herculex I® (maize variety expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing the CryIA(c) toxin); Bollgard I® (cotton variety expressing the CryIA(c) toxin); Bollgard II® (cotton variety expressing the CryIA(c) and CryIIA(b) toxins); VIPCOT® (cotton variety expressing the VIP toxin); NewLeaf® (potato variety expressing the CryIIIA toxin); NatureGard® and Protecta®.

[0101] Further examples of such genetically modified crops are as follows. 1. Bt11 maize produced by Syngenta Seed SAS, Chemin de l’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically engineered maize (Zea mays) with transgenic expression of a truncated CryIA(b) toxin, which confers resistance to European corn borer (Ostrinia nubilalis) and Mediterranean corn borer (Sesamia nonagrioides). Bt11 maize also achieves resistance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.

[0102] 2. Bt176 maize produced by Syngenta Seed SAS, Chemin de l’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically engineered maize (Zea mays) with transgenic expression of CryIA(b) toxin, which confers resistance to European corn borer (Ostrinia nubilalis) and Mediterranean corn borer (Sesamia nonagrioides). Bt176 maize also achieves resistance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.

[0103] 3. MIR604 maize produced by Syngenta Seed SAS, Chemin de l’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize with insect resistance conferred by transgenic expression of a modified CryIIIA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such genetically modified maize plants is described in International Publication No. 03 / 018810.

[0104] 4. MON863 maize produced by Monsanto Europe S.A., 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON863 expresses CryIIIB(b1) toxin and has resistance to certain coleopteran insects.

[0105] 5. IPC531 cotton produced by Monsanto Europe S.A., 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0106] 6. 1507 maize produced by Pioneer Overseas Corporation, Avenue Tedesco, 7 B - 1160 Brussels, Belgium, registration number C / NL / 00 / 10. Maize genetically engineered for the expression of the protein Cry1F to achieve resistance to certain lepidopteran insects and the expression of the PAT protein to achieve resistance to the herbicide glufosinate ammonium.

[0107] 7. NK603×MON810 maize produced by Monsanto Europe S.A., 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Consists of a conventional hybrid maize variety by crossing the genetically engineered varieties NK603 and MON810. NK603×MON810 maize transgenically expresses the protein CP4 EPSPS obtained from a strain CP4 of a species of the genus Agrobacterium sp., thereby conferring resistance to the herbicide Roundup® (containing glyphosate), and also transgenically expresses the CryIA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki, thereby resulting in resistance to certain lepidopterans including the Asian corn borer.

[0108] The term "useful plant" should be understood to include, for example, useful plants that have been genetically modified using recombinant DNA technology such that they are capable of synthesizing anti-pathogenic substances having a selective action, such as so-called "pathogenesis-related proteins" (PRPs, see for example European Patent Application Publication No. A-0 392 225). Examples of such anti-pathogenic substances and genetically modified plants capable of synthesizing such anti-pathogenic substances are known, for example, from European Patent Application Publication No. A-0 392 225, International Publication No. 95 / 33818 and European Patent Application Publication No. A-0 353 191. Methods for producing such genetically modified plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications.

[0109] Examples of anti-pathogenic substances that can be expressed by such genetically modified plants include, for example, ion channel blockers such as sodium and calcium channel blockers such as viral KP1, KP4 or KP6 toxins; stilbene synthase; bibenzyl synthase; chitinase; glucanase; so-called "pathogenesis-related proteins" (PRPs; see for example European Patent Application Publication No. A-0 392 225); for example peptide antibiotics or heterocyclic antibiotics (see for example International Publication No. 95 / 33818), or anti-pathogenic substances produced by microorganisms such as proteins or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes" described in International Publication No. 03 / 000906).

[0110] The composition according to the invention is particularly effective in controlling or preventing plant pathogenic diseases caused by certain plant pathogenic fungi, in particular powdery mildew, rust, leaf spot, late blight or mold, in cereals, fruits and nuts, vegetables, agricultural crops, oilseed crops, fodder crops, forest plants, horticultural crops, flower gardening, greenhouse and nursery plants, propagation materials, culinary herbs and spices, and herbs, as follows. Preferably Alternaria solani in tomatoes.

[0111] Preferably Alternaria alternata in eggplants.

[0112] Preferably Alternaria porri in onions.

[0113] Preferably Botrytis cinerea in tomatoes, peppers, onions, pomaceous fruits, stone fruits, kiwis, blueberries, sugar beets or grapes.

[0114] Preferably Botrytis allii in onions.

[0115] Preferably Botrytis squamosa in onions.

[0116] Preferably Cercospora capsici in peppers.

[0117] Preferably Corynespora cassiicola in tomatoes.

[0118] Preferably Guignardia bidwellii in grapes.

[0119] Preferably Monilinia fructicola in cherries, peaches, apricots, plums, nectarines or almonds.

[0120] Preferably Monilinia fructigena in cherries, peaches, apricots, plums, nectarines or almonds.

[0121] Preferably Monilinia laxa in cherry, peach, European peach, plum, nectarine or almond.

[0122] Preferably Phomopsis viticola in grape.

[0123] Preferably Podosphaera leucotricha in apple.

[0124] Preferably Podosphaera xanthii in cucurbitaceae plants.

[0125] Preferably Pseudopezicula tracheiphila in grape.

[0126] Preferably Uncinula necator in grape.

[0127] Preferably Venturia inaequalis in apple.

[0128] Furthermore, the composition according to the present invention is for Alternaria spp., Ascochyta spp., Botrytis cinerea, Cercospora spp., Claviceps purpurea, rice blast fungus, Colletotrichum spp., Epicoccum spp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium solani, Fusarium subglutinans, Gaeumannomyces graminis, Helminthosporium spp., Microdochium nivale, Phoma spp., Pyrenophora graminea, Pyricularia oryzae, Rhizoctonia solani, Rhizoctonia cerealis, Sclerotinia spp., Septoria spp., Sphacelotheca reilliana, Tilletia spp., Typhula incarnata, Urocystis occulta, Ustilago spp. or Verticillium spp.Against seed-borne and soil-borne diseases such as; in particular, pathogens of cereals such as wheat, barley, rye or triticale; maize; rice; cotton; soybean; turf; sugar beet; oilseed rape; potato; leguminous crops such as pea, lentil or chickpea; and is particularly effective against sunflower.

[0129] Furthermore, the composition according to the present invention is particularly effective against post-harvest diseases caused by pathogens of fruits such as Botrytis cinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum, Geotrichum candidum, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Mucor piriformis, Penicilium italicum, Penicilium solitum, Penicillium digitatum or Penicillium expansum, for example, pomaceous fruits such as apple and pear, stone fruits such as peach and apricot, citrus fruits, melon, papaya, kiwi, mango, berry fruits such as strawberry, avocado, pomegranate and banana, and nuts.

[0130] The composition of the present invention can also be used in the enhancement of crops. In the present invention, "enhancement of crops" means improvement of plant vigor, improvement of plant quality, improved tolerance to stress factors, and / or improved input use efficiency.

[0131] In the present invention, "improvement of plant vigor" means that a particular trait is improved qualitatively or quantitatively when compared to the same trait in a control plant grown under the same conditions in the absence of the method of the present invention. Such traits include, but are not limited to, early and / or improved germination, improved germination, the ability to use fewer seeds, increased root growth, a more developed root system, increased root nodulation, increased shoot growth, increased tillering, stronger tillering, more productive tillering, increased or improved plant stand, fewer plant lodgings, an increase and / or improvement in plant height, an increase in plant weight (fresh or dry), larger leaf blades, a greener leaf color, increased pigment content, increased photosynthetic activity, earlier flowering, longer spikes, early grains, increased seeds, fruits, or sheath size, increased number of sheaths or spikes, increased number of seeds per sheath or spike, increased seed mass, enhanced seed ripening, fewer basal leaves, delayed senescence, improvement of plant vigor, an increase in the amino acid level in storage tissues, and / or fewer required inputs (e.g., less required fertilizer, water, and / or labor). A plant with improved vigor may have any of the aforementioned traits, or any combination or increase of two or more of the aforementioned traits.

[0132] In the present invention, "improvement of plant quality" means that a particular trait is qualitatively or quantitatively improved when compared to the same trait in a control plant grown under the same conditions in the absence of the method of the present invention. Such traits include, but are not limited to, the appearance of the improved plant, reduced ethylene (reduced production and / or suppression of sensitivity), for example, improvement in the quality of harvested products such as seeds, fruits, leaves, vegetables, etc. (such improvement in quality may be manifested as an improvement in the visual appearance of the harvested product), improved carbohydrate content (e.g., increased amount of sugar and / or starch, improved sugar-acid ratio, reduced reducing sugars, increased sugar production rate), improved protein content, improved oil content and composition, improved nutritional value, reduction of anti-nutritional compounds, improved functional properties (e.g., improved taste), and / or may be manifested as improved consumer health benefits (e.g., increased levels of vitamins and antioxidants), improved post-harvest characteristics (e.g., enhanced shelf life and / or storage stability, easier processability, easier compound extraction), more uniform crop development (e.g., synchronized germination, flowering, and / or fruiting of plants), and / or improved seed quality (e.g., for use in the next cultivation period). A plant with improved quality may have any of the aforementioned traits, or any combination or increase of two or more of the aforementioned traits.

[0133] In the present invention, "improved tolerance to stress factors" means that a particular trait is qualitatively or quantitatively improved when compared to the same trait in a control plant grown under the same conditions in the absence of the method of the present invention. Such traits include, but are not limited to, increased tolerance and / or resistance to abiotic stress factors that cause suboptimal growth conditions such as drought (e.g., any stress that results in a lack of water in the plant, insufficient water uptake capacity, or a decrease in the supply of water to the plant), cold exposure, heat exposure, osmotic stress, UV stress, flooding, increased salinity (e.g., in the soil), exposure to increased minerals, ozone exposure, high light exposure, and / or limited availability of nutrients (e.g., nitrogen and / or phosphorus nutrients). A plant having improved tolerance to stress factors may have any of the aforementioned traits, or any combination or increase of two or more of the aforementioned traits. In the case of drought and nutrient stress, such improved tolerance may be due to, for example, more efficient uptake, use, or retention of water and nutrients.

[0134] In the present invention, "improved input use efficiency" means that a plant can grow more efficiently using a given input level as compared to the growth of a control plant grown under the same conditions in the absence of the method of the present invention. Specifically, inputs include, but are not limited to, fertilizers (nitrogen, phosphorus, potassium, micronutrients, etc.), light, and water. A plant having improved input use efficiency may have improved use of any of the aforementioned inputs, or any combination of two or more of the aforementioned inputs.

[0135] Other enhancements of the crops of the present invention include a reduction in plant height, or a reduction in tillering, which are beneficial features in crops or conditions where it is desirable to have less biomass and fewer tillers.

[0136] Any or all of the above crop enhancements can lead to an improvement in yield, for example, by improving the physiological functions of plants, plant growth and development, and / or plant structure. In the context of the present invention, "yield" includes, but is not limited to, (i) an increase in biomass production, grain yield, starch content, oil content, and / or protein content that can be attributed to (a) an increase in the amount produced by the plant itself, or (b) an improved ability to harvest the plant body; (ii) an improvement in the composition of the harvested product (e.g., an improved sugar-acid ratio, an improved oil composition, an increased nutritional value, a reduction in anti-nutritional compounds, an increased health benefit for consumers); and / or (iii) an increased / facilitated ability to harvest the crop, improved processability of the crop, and / or better storage stability / shelf life. An increased yield of agricultural plants means that, when quantitative measurements can be made, the yield of the product of each plant increases by a measurable amount compared to the yield of the same product of plants produced under the same conditions but without applying the present invention. According to the present invention, it is preferred that the yield increases by at least 0.5%, more preferably at least 1%, still more preferably at least 2%, and even more preferably at least 4%, preferably 5% or more.

[0137] Any or all of the above crop enhancements may also result in improved land use. That is, land that has not been available for cultivation or has not been optimally utilized may become available. For example, plants that exhibit an increased ability to survive in arid conditions may be cultivable in areas with suboptimal rainfall, such as perhaps around deserts or even in deserts themselves.

[0138] In certain embodiments of the present invention, crop enhancement is carried out in the substantial absence of pressure from pests and / or diseases and / or abiotic stress. According to a further aspect of the present invention, the improvement of plant vigor, stress tolerance, quality and / or yield is carried out in the substantial absence of pressure from pests and / or diseases. For example, pests and / or diseases can be controlled by an insecticidal treatment applied before or simultaneously with the method of the present invention. In yet another aspect of the present invention, the improvement of plant vigor, stress tolerance, quality and / or yield is carried out in the absence of pressure from pests and / or diseases. In further embodiments, the improvement of plant vigor, quality and / or yield is carried out in the absence or substantial absence of abiotic stress.

[0139] The compositions of the present invention may be used in the field of protecting stored products from fungal attack. In the present invention, the term "stored product" is understood to mean natural substances of plant and / or animal origin and their processed forms for which long-term protection from their natural life cycle is desired. Stored products of plant origin, such as plants or parts thereof (e.g., stems, leaves, tubers, seeds, fruits, or grains), can be protected in their freshly harvested state or in a processed form such as pre-dried, humidified, ground, milled, pressed, or roasted. The definition of stored products also includes wood in the form of unprocessed wood (such as construction wood, power transmission towers, and fences) and wood in the form of finished products (such as furniture or wooden articles). Stored products of animal origin are leather, leather products, furs, and hairs. The compositions of the present invention can prevent adverse effects such as spoilage, discoloration, or mold growth. Preferably, "stored product" is understood to mean natural substances of plant origin and / or their processed forms, more preferably fruits and their processed forms (such as pomaceous fruits, stone fruits, berries, and citrus fruits, and their processed forms). In another preferred embodiment of the present invention, "stored product" is understood to mean wood.

[0140] Accordingly, a further aspect of the present invention is a method for protecting stored products, which comprises applying the compositions of the present invention to the stored products.

[0141] The composition of the present invention can also be used in the field of protecting industrial substrates from fungal attack. In the present invention, the term "industrial substrate" includes paper; carpets; buildings; cooling and heating systems; wall panels; ventilation and air conditioning systems, etc.; preferably, the "industrial substrate" is understood to mean wall panels. The composition of the present invention can prevent adverse effects such as decay, discoloration, or mold growth.

[0142] Some compositions according to the present invention have a penetration and translocation effect and can be used as foliar, soil, and seed treatment fungicides.

[0143] In the composition according to the present invention, it is possible to inhibit or control phytopathogenic microorganisms occurring in plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) in different useful plants, and moreover, at the same time, the parts of the plants that grow subsequently are also protected from attack by phytopathogenic microorganisms.

[0144] The composition according to the present invention is applicable to phytopathogenic microorganisms, useful plants threatened by microbial attack, their habitats, their propagation materials, storage supplies, or technical materials.

[0145] The composition according to the present invention can be applied before or after the infection of useful plants, their propagation materials, storage supplies, or technical materials by microorganisms.

[0146] The composition according to the invention can also be used in the field of protecting industrial materials from fungal attack. According to the invention, the term "industrial material" refers to inanimate materials prepared for use in industry. For example, industrial materials intended to be protected from fungal attack can be adhesives, glues, paper, cardboard, fabrics, carpets, leather, wood, structures, paints, plastic articles, cooling lubricants, aqueous working fluids and other materials that may be subject to ectoparasitism or degradation by microorganisms. Cooling and heating systems, ventilation and air conditioning systems and components of production plants, for example cooling water circuits that can be impaired by the growth of microorganisms, can also be described as one of the materials to be protected. The composition according to the invention can prevent adverse effects such as corrosion, discoloration or mold.

[0147] The amount of the combination according to the invention to be applied will depend on various factors such as the compound employed; the object to be treated, such as plants, soil or seeds; the type of treatment, such as spraying, dusting or seed coating; the purpose of the treatment, such as preventive or therapeutic; the type of fungus to be controlled; or the application time.

[0148] Compositions comprising component (A) in combination with component (B) can be applied, for example, in a single "ready-mixed" form, in a complex spray mixture such as a "tank mixture" composed of individual formulations of a single active ingredient, and, sequentially, i.e., in combination with a single active ingredient when applied successively, i.e., one after another within a moderately short period of time such as several hours or days. The order of application of the compound of component (A) and the active ingredient of component (B) is not important for the action of the invention.

[0149] The composition according to the invention is an active ingredient that is useful prophylactically and / or therapeutically in the field of pest control, even at low application rates.

[0150] When applied to useful plants, component (A) is applied in an amount of 25 g a.i. / ha to 500 g a.i. / ha, accompanied by 50 g a.i. / ha to 2000 g a.i. / ha of component (B).

[0151] In a preferred embodiment of the present invention, a method for controlling or preventing phytopathogenic diseases, especially those caused by phytopathogenic fungi, in useful plants or their propagation materials comprises applying to the useful plant, its habitat or its propagation materials a composition as defined in the present invention, where component (A) is applied in an amount of 25 g a.i. / ha to 500 g a.i. / ha, accompanied by 50 g a.i. / ha to 2000 g a.i. / ha of component (B).

[0152] The method for controlling or preventing phytopathogenic diseases according to the present invention may be particularly effective against phytopathogenic fungi selected from the group consisting of Alternaria, Botrytis, Cercospora, Colletotrichum, Corynespora, Guignardia, Mycosphaerella, Monilinia, Penicillium, Phakopsora, Phomopsis, Podosphaera, Pseudopezicula, Septoria, Uncinula and Venturia.

[0153] The method for controlling or preventing phytopathogenic diseases according to the present invention may be particularly effective against phytopathogenic fungi selected from the group consisting of Alternaria solani, Alternaria alternata, Alternaria porri, Botrytis cinerea, Botrytis allii, Botrytis squamosa, Cercospora capsici, Colletotrichum lagenarium, Corynespora cassiicola, Guignardia bidwellii, Monilinia fructicola, Monilinia fructigena, Monilinia laxa, Penicillium digitatum, Penicillium italicum, Penicillium expansum, Phomopsis viticola, Podosphaera leucotricha, Podosphaera xanthii, Pseudopezicula tracheiphila, Septoria tritici, Uncinula necator, and Venturia inaequalis.

[0154] A method is preferred which comprises applying the composition according to the invention to useful plants selected from the group consisting of cereals, fruits and tree nuts, vegetables, field crops, oilseed crops, forage crops, forest plants, horticultural crops, flower gardening, greenhouse and nursery plants, propagation material, culinary herbs and spices, and medicinal herbs, in particular for controlling or preventing phytopathogenic diseases caused by phytopathogenic fungi.

[0155] A more preferred method comprises 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 fruits and banana, in particular for controlling or preventing phytopathogenic diseases caused by phytopathogenic fungi.

[0156] The present invention also provides a fungicidal composition comprising, together with an agriculturally acceptable carrier and optionally a surfactant, a synergistically effective amount of the combination of components (A) and (B) as described above. In said composition, the weight ratio of (A) to (B) is preferably 100:1 to 1:500, more preferably 100:1 to 1:200, even more preferably 10:1 to 1:80, as already described herein.

[0157] The composition of the present invention can be employed in any conventional form, for example, two-component system, powder for dry seed treatment (DS), emulsion for seed treatment (ES), flowable concentrate for seed treatment (FS), solution for seed treatment (LS), water dispersible powder for seed treatment (WS), capsule suspension for seed treatment (CF), gel for seed treatment (GF), emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water dispersible granule (WG), emulsifiable granule (EG), emulsion, oil-in-water type (EO), emulsion, water-in-oil type (EW), microemulsion (ME), oil dispersion (OD), oil miscible flowable (OF), oil miscible liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), industrial concentrate (TK), dispersible concentrate (DC), wettable powder (WP), or any technically preferred formulation in combination with an agriculturally acceptable adjuvant.

[0158] Such compositions can be produced in a conventional manner, for example, by mixing the active ingredient with a suitable inert formulation (diluent, solvent, filler and optionally other formulation components). Also, conventional sustained-release formulations can be employed when long-lasting efficacy over time is intended. In particular, formulations applied in spray forms such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules can contain compounds that provide an adjuvant effect. In some embodiments, the compositions of the present invention can be produced by mixing a fermentation broth containing aureobasidin A and one or more other cyclic depsipeptides of formula (I-A) or stereoisomers thereof with component (B). In some other embodiments, the compositions of the present invention can be produced by mixing a fermentation broth containing Persephacin A and one or more other cyclic depsipeptides of formula (I-B) or stereoisomers thereof with component (B).

[0159] The seed coating formulations are applied to seeds in a manner known per se, in which the combinations and diluents of the present invention are utilized in a suitable seed coating formulation form, such as, for example, an aqueous suspension or a dry powder form having good adhesion to the seeds. Such seed coating formulations are known in the art. The seed coating formulations may contain a single active ingredient or, for example, a combination of active ingredients in encapsulated form, such as in sustained-release capsules or microcapsules.

[0160] Generally, the complex contains 0.01-90% by weight of the active agent, 0-20% of the agriculturally acceptable surfactant, and 10-99.99% of the solid or liquid inert complex and formulation aids. The active agent is composed of at least the compound of formula (I), component (B), and optionally component (C), and other active agents, especially fungicides or preservatives, etc. together. The concentrated form of the composition generally contains about 2-80%, preferably about 5-70% by weight of the active agent. The applied form of the formulation may contain, for example, 0.01-20% by weight, preferably 0.01-5% by weight of the active agent. Commercially available products are preferably formulated as concentrates, but end-users will usually utilize the diluted formulation.

[0161] Surprisingly, it has been found that a certain weight ratio of component (A) to component (B) can result in synergistic activity. Accordingly, a further aspect of the present invention is a composition in which component (A) and component (B) are present in the composition in amounts that result in a synergistic effect. This synergistic activity is evident from the fact that the bactericidal activity of the composition containing component (A) and component (B) is greater than the sum of the bactericidal activities of component (A) and component (B). This synergistic activity extends the scope of action of component (A) and component (B) in two ways. First, the application rates of component (A) and component (B) are reduced while the action remains equally good, which means that even in the low application rate range where the two individual components become completely ineffective, the active ingredient mixture can still achieve a high level of control of plant pathogens. Second, the range of plant pathogens that can be controlled is substantially expanded.

[0162] The synergistic effect always exists when the action of the combination of active ingredients is greater than the sum of the actions of the individual components. The expected activity E for a given combination of active ingredients can be calculated according to the so-called COLBY's formula as follows (COLBY, S.R. “Calculating synergistic and antagonistic responses of herbicide combination”. Weeds, Vol. 15, pages 20-22; 1967): ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture X = percentage of action by active ingredient (A) using p ppm of active ingredient Y = percentage of action by active ingredient (B) using q ppm of active ingredient

[0163] According to COLBY, the expected (active) action of active ingredient (A) + (B) using p + q ppm of active ingredient is:

Equation

[0164] When the actually observed action (O) is greater than the expected action (E), the action of the combination is superadditive, i.e., there is a synergistic effect. In mathematical terms, the synergistic action corresponds to the positive value of the difference (O - E). In the case of pure complementary addition of activity (expected activity), the difference (O - E) is zero. A negative value of the difference (O - E) indicates that activity is lost compared to the expected activity.

[0165] However, apart from the actual synergistic action regarding bactericidal activity, the compositions of the present invention may further have even more surprising advantageous properties. Examples of such advantageous properties that can be mentioned are: more advantageous degradability; improved toxicological and / or biotoxicological behavior; or improved properties of useful plants (germination, crop yield, more developed root systems, increased tillering, increased plant height, larger leaf blades, fewer basal leaves, stronger tillering, greener leaf color, less fertilizer required, fewer seeds required, more productive tillering, earlier flowering, earlier grains, less plant lodging, increased shoot growth, improved plant vigor, and earlier germination, etc.).

[0166] The following examples are for illustrative purposes of the present invention and are not meant to limit the present invention in any way. Another aspect of the present invention may be as follows. 〔1〕A bactericidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a cyclic depsipeptide of formula (I-A1): [Chemical formula 1] JPEG0007696929000016.jpg78125 or a stereoisomer thereof; and Component (B) is an inhibitor of amino acid and protein synthesis: (B.1) A methionine synthesis inhibitor selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil; and (B.2) A protein synthesis inhibitor selected from the group consisting of blasticidin-S, kasugamycin, kasugamycin hydrochloride hydrate, milbemycin, streptomycin, and oxytetracycline A bactericidal composition selected from the group consisting of. 〔2〕The composition according to 〔1〕 above, wherein the weight ratio of (A) to (B) is 100:1 to 1:500, preferably 100:1 to 1:200, more preferably 10:1 to 1:80. 〔3〕Component (A) is one or more other cyclic depsipeptides of formula (I-A): [Chemical formula 2] JPEG0007696929000017.jpg85128 (wherein, R 1 is methyl or ethyl; X 1 、X 2 and each of X 3 is hydrogen, or X 1 、X 2 and X 3 are hydrogen, fluorine or hydroxyl, provided that only one of X 1 、X 2 and X 3 is fluorine or hydroxyl; X 4 is CH, S or hydroxymethylene; A 3 are N-methyl-L-phenylalanine (L-MePhe), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), ortho-fluoro-N-methyl-L-phenylalanine (L-o-F-MePhe), meta-fluoro-N-methyl-L-phenylalanine (L-m-F-MePhe), para-fluoro-N-methyl-L-phenylalanine (L-p-F-MePhe), meta-bromo-N-methyl-L-phenylalanine (L-m-Br-MePhe), para-bromo-N-methyl-L-phenylalanine (L-p-Br-MePhe), meta-iodo-N-methyl-L-phenylalanine (L-m-I-MePhe), para-iodo-N-methyl-L-phenylalanine (L-p-I-MePhe), 3-phenyl-N-methyl-L-phenylalanine, 4-phenyl-N-methyl-L-phenylalanine, 3-(4-fluorophenyl)-N-methyl-L-phenylalanine, 4-(4-fluorophenyl)-N-methyl-L-phenylalanine, 3-(4-pyridinyl)-N-methyl-L-phenylalanine, 4-(4-pyridinyl)-N-methyl-L-phenylalanine, 3-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-4-pyridinyl)-N-methyl-L-phenylalanine, 3-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 3-[4-(piperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4-(piperazin-1-yl)phen-1-yl]phenyl-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4-(4-methylpiperazin-1-yl)phen-1-yl]phenyl-N-methyl-L-phenylalanine, β-oxo-N-methyl-L-phenylalanine (L-β-oxo-MePhe), β-acetoxy-N-methyl-L-phenylalanine (L-β-AcO-MePhe), N-methyl-L-tyrosine (L-MeTyr),an α - amino acid residue selected from the group consisting of O - methyl - N - methyl - L - tyrosine [L - MeTyr(Me)], N - methyl - L - alanine (L - MeAla), N - methyl - L - serine (L - MeSer), N - methyl - D - phenylalanine (D - MePhe), N - methyl - D - alanine (D - MeAla), N - methyl - D - valine (D - MeVal), N - methyl - D - serine (D - MeSer) and N - methyl - L - serine (L - MeSer) residues; A 5 is an α-amino acid residue selected from the group consisting of L-allo-isoleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle), L-norvaline (L-Nva) and L-valine (L-Val) residues; A 6 is an α-amino acid residue selected from the group consisting of N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), N-methyl-L-allo-isoleucine (L-MeAIle) and L-valine (L-Val) residues; A 7 is an α-amino acid residue selected from the group consisting of L-leucine (L-Leu), L-allo-isoleucine (L-AIle) and L-norvaline (L-Nva) residues; and A 8 is 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 (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 an α-amino acid residue selected from the group consisting of N,β-dimethyl-L-aspartic acid (L-N,β-MeAsp) residues) The composition according to [1] or [2] above, further comprising the stereoisomer thereof. [4] Component (A) further comprises at least one other cyclic depsipeptide of formula (I-A) selected from the group consisting of aureobasidin E and aureobasidin G or a stereoisomer thereof, and the composition according to any one of [1] to [3] above. [5] Component (A) is 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight of the cyclic depsipeptide of formula (I-A1) or a stereoisomer thereof, and 0.1% to 90% by weight, preferably 0.1% to 80% by weight, more preferably 0.1% to 60% by weight of one or more other cyclic depsipeptides of formula (I-A) or a stereoisomer thereof The composition according to any one of [1] to [4] above. [6] Component (A) is one or more cyclic depsipeptides of formula (I-B): [Chemical formula 3] JPEG0007696929000018.jpg99130 (In the formula,[[]] R 1 is methyl or ethyl; X 4 is CH, S or hydroxymethylene; A 5 is an α-amino acid residue selected from the group consisting of L-allo-isoleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle) and L-valine (L-Val) residues; A 6 is an α-amino acid residue selected from the group consisting of N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), L-allo-isoleucine (L-AIle) and N-methyl-L-allo-isoleucine (L-MeAIle) residues; A 7 is an α-amino acid residue selected from the group consisting of L-leucine (L-Leu), L-allo-isoleucine (L-AIle) and L-norvaline (L-Nva) residues; and A 8 is β-hydroxy-N-methyl-L-valine (L-β-OH-MeVal), γ-hydroxy-N-methyl-L-valine (L-γ-OH-MeVal), N-methyl-L-valine (L-MeVal), N-methyl-2,3-didehydro-L-valine (L-MeDH 2,3 Val), N-methyl-3,4-didehydro-L-valine (L-MeDH 3,4 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 (L-N,β-MeAsp) residues, and is an α-amino acid residue selected from the group consisting of or a stereoisomer thereof, and the composition according to any one of [1] to [5] above. [7] The composition according to any one of [1] to [6] above, wherein component (B) is a compound selected from the group consisting of cyprodinil, mepanipyrim, and pyrimethanil. [8] The composition according to any one of [1] to [7] above, further comprising an agriculturally acceptable carrier and / or formulation adjuvant, and optionally a surfactant. [9] A method for controlling or preventing phytopathogenic diseases, particularly those caused by phytopathogenic fungi, in useful plants or their propagation materials, the method comprising applying the composition according to any one of [1] to [8] above to the useful plant, its habitat, or its propagation material.

[10] The method according to [9] above, wherein component (A) is applied in an amount of 25 g a.i. / ha to 500 g a.i. / ha, accompanied by 50 g a.i. / ha to 2000 g a.i. / ha of component (B).

[11] The method according to [9] or

[10] above, wherein the phytopathogenic fungus is selected from the group consisting of Alternaria, Botrytis, Cercospora, Colletotrichum, Corynespora, Guignardia, Mycosphaerella, Monilinia, Penicillium, Phakopsora, Phomopsis, Podosphaera, Pseudopezicula, Septoria, Uncinula, and Venturia. 〔12〕The useful plant is selected from cereals, fruits and tree nuts, vegetables, agricultural crops, oilseed crops, forage crops, forest plants, horticultural crops, flower gardening, greenhouse and nursery plants, propagation materials, culinary herbs and spices, and medicinal herbs, and is the method according to any one of the above items 〔9〕 to 〔11〕. 〔13〕The useful plant is selected from the group consisting of wheat, barley, rice, soybeans, apples, almonds, cherries, raspberries, grapes, cucumbers, peanuts, tomatoes, strawberries, citrus fruits and bananas, and is the method according to any one of the above items 〔9〕 to 〔12〕. 〔14〕Use of the composition comprising component (A) and component (B) according to any one of the above items 〔1〕 to 〔8〕 as a bactericide.

Example

[0167] Biological Example The composition according to the present invention is tested for its biological (fungicidal) activity using an application rate in which component (A) is applied in an amount of 25 g a.i. / ha to 500 g a.i. / ha, accompanied by component (B) of 50 g a.i. / ha to 2000 g a.i. / ha.

[0168] The composition according to the present invention is tested for its biological (fungicidal) activity as a dimethyl sulfoxide (DMSO) solution using one or more of the following protocols (Examples 1-1 and 1-2). A standard description of the liquid culture test is given in Example 1.

[0169] Aureobasidin A and its synthesis are known from Takesako et al., The Journal of Antibiotics, 1991, 44, 919-924. Aureobasidin A is 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 purification by silica gel column chromatography (silica gel, elution with hexane:ethyl acetate), followed by reverse phase column chromatography (RP18, elution with acetonitrile:H2O). As described above, component (B) of the composition is known and can be prepared using methods that are commercially available and / or reported in the literature and / or known in the art.

[0170] Example 1: Liquid medium test in a well plate Freshly prepared from a fungal liquid medium or a fraction of mycelia or conidia suspension of a fungus stored at low temperature is directly mixed with a nutrient liquid medium. A DMSO solution of the test compound (up to 10 mg / mL) is diluted 50-fold with 0.025% Tween 20, and 10 μl of this solution is pipetted into a microtiter plate (96-well type). Then, a nutrient liquid medium containing the fungal spore / mycelia fraction is added to obtain the final concentration of the compound to be tested. The test plate is incubated in the dark at 24 °C and 96% relative humidity (rh). The inhibition of fungal growth is measured photometrically and visually 3 to 7 days later according to the pathogen response system, and the antifungal activity ratio against the untreated test subject is calculated.

[0171] Example 1-1: Botrytis cinerea (gray mold disease) Conidia of the fungus stored at low temperature were directly mixed with a nutrient liquid medium (PDB potato dextrose liquid medium). After putting the DMSO solution of the test composition into a microtiter plate (96-well type), a nutrient liquid medium containing the conidia of the fungus was added. The test plate was incubated at 24 °C, and the inhibition of growth was determined photometrically after 72 hours.

[0172] Example 1-2: Alternaria solani (tomato / potato early blight) Conidia of the fungus stored at low temperature were directly mixed with a nutrient liquid medium (PDB potato dextrose liquid medium). After putting the DMSO solution of the test composition into a microtiter plate (96-well type), a nutrient liquid medium containing the conidia of the fungus was added. The test plate was incubated at 24 °C, and the inhibition of growth was determined photometrically after 48 hours.

[0173] Results The results of the above tests are shown in Tables 1 and 2. These data indicate that a synergistic bactericidal activity is observed at a certain weight ratio for the combination of Aureobasidin A and other active ingredients of component (B) against Botrytis cinerea and Alternaria solani. According to COLBY, mathematically, the synergistic action factor SF corresponds to O / E. In actual agriculture, an SF of 1.1 or more indicates a significant improvement exceeding the purely complementary addition (expected activity), while an SF of 0.9 or less in actual application routines indicates a loss of activity compared to the expected activity.

[0174] [Table 3]

[0175] [Table 4]

Claims

1. A bactericidal composition comprising a mixture of components (A) and (B) as active ingredients, wherein component (A) is a cyclic depsipeptide of formula (I-A1): 【Chemical 1】 or a stereoisomer thereof; and Component (B) is cyprodinil, a bactericidal composition.

2. The composition according to claim 1, wherein the weight ratio of (A) to (B) is 100:1 to 1:500, preferably 100:1 to 1:200, more preferably 10:1 to 1:

80.

3. Component (A) is one or more other cyclic depsipeptides of formula (I-A): 【Chemical 2】 (wherein, R 1 is methyl or ethyl; X 1 、X 2 and X 3 each is hydrogen, or X 1 、X 2 and X 3 are hydrogen, fluorine or hydroxyl, provided that only one of X 1 、X 2 and X 3 is fluorine or hydroxyl; X 4 is CH2, S or hydroxymethylene; A 3are N-methyl-L-phenylalanine (L-MePhe), L-phenylalanine (L-Phe), β-hydroxy-N-methyl-L-phenylalanine (L-β-OH-MePhe), ortho-fluoro-N-methyl-L-phenylalanine (L-o-F-MePhe), meta-fluoro-N-methyl-L-phenylalanine (L-m-F-MePhe), para-fluoro-N-methyl-L-phenylalanine (L-p-F-MePhe), meta-bromo-N-methyl-L-phenylalanine (L-m-Br-MePhe), para-bromo-N-methyl-L-phenylalanine (L-p-Br-MePhe), meta-iodo-N-methyl-L-phenylalanine (L-m-I-MePhe), para-iodo-N-methyl-L-phenylalanine (L-p-I-MePhe), 3-phenyl-N-methyl-L-phenylalanine, 4-phenyl-N-methyl-L-phenylalanine, 3-(4-fluorophenyl)-N-methyl-L-phenylalanine, 4-(4-fluorophenyl)-N-methyl-L-phenylalanine, 3-(4-pyridinyl)-N-methyl-L-phenylalanine, 4-(4-pyridinyl)-N-methyl-L-phenylalanine, 3-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(1-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-4-pyridinyl)-N-methyl-L-phenylalanine, 3-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 4-(2-chloro-5-pyridinyl)-N-methyl-L-phenylalanine, 3-[4-(piperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4-(piperazin-1-yl)phen-1-yl]phenyl-N-methyl-L-phenylalanine, 3-[4-(4-methylpiperazin-1-yl)phenyl]phenyl-N-methyl-L-phenylalanine, 4-[4-(4-methylpiperazin-1-yl)phen-1-yl]phenyl-N-methyl-L-phenylalanine, β-oxo-N-methyl-L-phenylalanine (L-β-oxo-MePhe), β-acetoxy-N-methyl-L-phenylalanine (L-β-AcO-MePhe), N-methyl-L-tyrosine (L-MeTyr),An α - amino acid residue selected from the group consisting of O - methyl - N - methyl - L - tyrosine [L - MeTyr(Me)], N - methyl - L - alanine (L - MeAla), N - methyl - L - serine (L - MeSer), N - methyl - D - phenylalanine (D - MePhe), N - methyl - D - alanine (D - MeAla), N - methyl - D - valine (D - MeVal), N - methyl - D - serine (D - MeSer) and N - methyl - L - serine (L - MeSer) residues; A 5 is an α - amino acid residue selected from the group consisting of L - allo - isoleucine (L - AIIle), L - leucine (L - Leu), L - norleucine (L - Nle), L - norvaline (L - Nva) and L - valine (L - Val) residues; A 6 is an α - amino acid residue selected from the group consisting of N - methyl - L - valine (L - MeVal), N - methyl - L - leucine (L - MeLeu), N - methyl - L - allo - isoleucine (L - MeAIIle) and L - valine (L - Val) residues; A 7 is an α - amino acid residue selected from the group consisting of L - leucine (L - Leu), L - allo - isoleucine (L - AIIle) and L - norvaline (L - Nva) residues; and A 8 is an α - amino acid residue selected from the group consisting of 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 - MeD 2,3 Val), N - methyl - 3,4 - didehydro - L - valine (L - MeD 3,4 Val), N - methyl - L - phenylalanine (L - MePhe), β - hydroxy - N - methyl - L - phenylalanine (L - β - OH - MePhe), N - methyl - L - threonine (L - MeThr), sarcosine (Sar) and N,β - dimethyl - L - aspartic acid (L - N,β - MeAsp) residues. The composition according to claim 1 or claim 2, further comprising an enantiomer thereof.

4. The composition according to any one of claims 1 to 3, wherein component (A) further comprises at least one other cyclic depsipeptide of formula (I-A) selected from the group consisting of aureobasidin E and aureobasidin G, or an enantiomer thereof.

5. Component (A) is 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight of a cyclic depsipeptide of formula (I-A1) or an enantiomer thereof, and 0.1% to 90% by weight, preferably 0.1% to 80% by weight, more preferably 0.1% to 60% by weight of one or more other cyclic depsipeptides of formula (I-A) or an enantiomer thereof The composition according to any one of claims 1 to 4, comprising

6. Component (A) is one or more cyclic depsipeptides of formula (I-B): 【Chemical Formula 3】 (In the formula, R 1 is methyl or ethyl; X 4 is CH2, S or hydroxymethylene; A 5 is an α-amino acid residue selected from the group consisting of L-allo-isoleucine (L-AIle), L-leucine (L-Leu), L-norleucine (L-Nle) and L-valine (L-Val) residues; A 6 is an α-amino acid residue selected from the group consisting of N-methyl-L-valine (L-MeVal), N-methyl-L-leucine (L-MeLeu), L-allo-isoleucine (L-AIle) and N-methyl-L-allo-isoleucine (L-MeAIle) residues; A 7is an α - amino acid residue selected from the group consisting of L - leucine (L - Leu), L - allo - isoleucine (L - All), and L - norvaline (L - Nva) residues; and A 8 is an α - amino acid residue selected from the group consisting of β - hydroxy - N - methyl - L - valine (L - β - OH - MeVal), γ - hydroxy - N - methyl - L - valine (L - γ - OH - MeVal), N - methyl - L - valine (L - MeVal), N - methyl - 2,3 - didehydro - L - valine (L - MeDH 2,3 Val), N - methyl - 3,4 - didehydro - L - valine (L - MeDH 3,4 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 (L - N,β - MeAsp) residues) The composition according to any one of claims 1 to 5, further comprising or a stereoisomer thereof.

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

8. A method for controlling or preventing a phytopathogenic disease in a useful plant or its propagation material, comprising applying the composition according to any one of claims 1 to 7 to the useful plant, its habitat, or its propagation material.

9. The method according to claim 8, wherein the phytopathogenic disease is a phytopathogenic disease caused by a phytopathogenic fungus.

10. The component (A) is applied in an amount of 25 g a.i. / ha to 500 g a.i. / ha, and the component (B) is applied in an amount of 50 g a.i. / ha to 2000 g a.i. / ha, the method according to claim 8 or 9.

11. The plant pathogenic fungi are selected from the group consisting of Alternaria, Botrytis, Cercospora, Colletotrichum, Corynespora, Guignardia, Mycosphaerella, Monilinia, Penicillium, Phakopsora, Phomopsis, Podosphaera, Pseudopezicula, Septoria, Uncinula and Venturia, according to the method of claim 9.

12. The useful plants are selected from the group consisting of cereals, fruits and nuts, vegetables, field crops, oilseed crops, forage crops, forest plants, horticultural crops, flower gardening, greenhouse and nursery plants, propagation materials, culinary herbs and spices, and medicinal herbs, according to the method of any one of claims 8 to 11.

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

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

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