Fungicidal compositions

Abstract

The present invention relates to a fungicidal composition comprising a component A comprising one or more streptimidazole or stereoisomers thereof represented by formula (I) as defined in claim 1 and a component B comprising a compound represented by formula (II) or a stereoisomer thereof as defined in claim 1. The present invention further relates to a method of controlling or preventing a phytopathogenic disease or a phytopathogenic fungus on a plant, the locus thereof or propagation material thereof, which comprises applying the composition to the plant, the locus thereof or the propagation material thereof; and a coated plant propagation material comprising the composition.

Description

[0001] The present invention relates to novel fungicidal compositions for controlling fungi. Also disclosed are methods for controlling or preventing phytopathogenic diseases or phytopathogenic fungi on plants or their propagation materials. Background Art

[0002] Streptothricin (also known as nourseothricin, racemomycin, geomycin, and yazumycin) is an antibiotic produced by various Streptomyces species and was initially isolated from Streptomyces lavendulae (Waksman S.A. and Woodruff H.B., 1942, doi: 10.3181 / 00379727-49-13515). Streptothricin contains variable β-lysine peptide chains for identifying various streptothricins (such as A, B, C, D, E, F, and X). Streptothricin exhibits antibacterial and antifungal activities and can be used to control bacterial and fungal diseases in the agricultural field. Streptothricin inhibits protein synthesis by inducing misencoding.

[0003] Venturicidin (also known as aabomycin) is a group of antibiotics produced by various Streptomyces species. The first member, venturicidin A, was first isolated from a Streptomyces species in 1961 (Rhodes A. et al., 1961, doi: 10.1038 / 192952a0). Venturicidin has been shown to control phytopathogenic fungi (Shaaban K.A. et al., 2014, doi: 10.1038 / ja.2013.113; Wang et al., 2022, doi:10.3390 / microorganisms [Microorganisms] 10081612). It has been reported that venturicidin A inhibits bacterial and mitochondrial ATP-synthase complexes.

[0004] However, streptothricin and venturicidin themselves are not necessarily effective enough and there is a risk of developing resistance. Therefore, there is still a need for improved antifungal compositions for controlling phytopathogenic fungi. Summary of the Invention

[0005] The present invention discloses an unexpected synergistic fungicidal effect of a composition comprising one or more streptothricins represented by formula (I) or their stereoisomers and a compound represented by formula (II) or its stereoisomers, particularly wherein the compound is venturicidin A.

[0006] According to another aspect of the invention, a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi, preferably plant pathogenic fungi, on plants, their sites, or their propagation material is provided, the method comprising applying a composition as defined according to the invention to the plant, its site, or its propagation material. Preferably, the method comprises applying the composition according to the invention to the plant or its site, more preferably to the plant. Preferably, the method comprises applying the composition according to the invention to the propagation material of the plant.

[0007] According to another aspect of the invention, a coated plant propagation material is provided, wherein the coating comprises a composition according to the invention.

[0008] According to another aspect of the invention, the use of a composition comprising components A and B as defined according to the invention as a fungicide is provided, wherein the use is not for treating a human or animal body by surgery or therapy.

[0009] It has been found that compositions comprising the following can unexpectedly and substantially enhance the effectiveness of the latter component against fungi, and vice versa: component A comprising streptotricin or a stereoisomer thereof represented by formula (I), preferably wherein n is an integer selected from 1 to 4; and component B comprising a compound or a stereoisomer thereof represented by formula (II), a compound or a stereoisomer thereof represented by formula (III), or a compound or a stereoisomer thereof represented by formula (IV), preferably wherein the compound is strychnine A. Furthermore, the compositions of the present invention can effectively combat a broader spectrum of such fungi than when the individual active ingredients are used alone.

[0010] The benefits provided by the specific fungicidal compositions according to the invention may also include, in particular, favorable levels of biological activity for protecting plants from fungal diseases or superior properties for use as agricultural chemical active ingredients (e.g., greater biological activity, favorable activity spectrum, increased safety, improved physicochemical properties, or increased biodegradability). Detailed Implementation

[0011] This invention relates to an antifungal composition comprising:

[0012] (i) Component A, wherein component A comprises one or more streptococcalins or stereoisomers thereof represented by formula (I):

[0013] (I),

[0014] Where n is an integer selected from 1 to 7; and

[0015] (ii) Component B, wherein component B comprises a compound or a stereoisomer thereof represented by formula (II):

[0016] (II),

[0017] Where R 1 Selected from CONH2 and H;

[0018] Where R 2 R 4 R 6 and R 7 Each is independently selected from CH3 and H;

[0019] Where R 3 Selected from OH and H; and

[0020] Where R 5 Selected from CH2CH3 and CH3.

[0021] Component A comprises one or more streptococcalins or their stereoisomers represented by formula (I):

[0022] (I),

[0023] Where n is an integer selected from 1 to 7.

[0024] As used in this paper, equation (I) can also be expressed by equation (Ia):

[0025] (Ia),

[0026] Where n is an integer selected from 1 to 7.

[0027] Preferably, component A comprises one or more streptococcalin or its stereoisomers represented by formula (I), wherein n is an integer selected from 1 to 4, more preferably wherein n is 3 or 4.

[0028] Preferably, component A comprises streptotricin or a stereoisomer thereof represented by formula (I), wherein n is 3 and 4; or wherein component A comprises streptotricin or a stereoisomer thereof represented by formula (I), wherein n is 1 and 3. Preferably, component A according to the invention comprises streptotricin or a stereoisomer thereof represented by formula (I), wherein n is 1, 2, 3 and 4. Suitably, component A according to the invention comprises streptotricin or a stereoisomer thereof represented by formula (I), wherein n is 1, 2, 3, 4, 5 and 6.

[0029] Preferably, component A comprises streptotrichum or its stereoisomer represented by formula (I) (where n is 3) and streptotrichum or its stereoisomer represented by formula (I) (where n is 4). Preferably, component A comprises streptotrichum or its stereoisomer represented by formula (I) (where n is 1) and streptotrichum or its stereoisomer represented by formula (I) (where n is 3). Preferably, component A comprises streptotrichum or its stereoisomer represented by formula (I) (where n is 1), streptotrichum or its stereoisomer represented by formula (I) (where n is 2), streptotrichum or its stereoisomer represented by formula (I) (where n is 3), and streptotrichum or its stereoisomer represented by formula (I) (where n is 4).

[0030] Typically, streptocytin A is represented herein by formula (I), where n is 6; streptocytin B is represented herein by formula (I), where n is 5; streptocytin C is represented herein by formula (I), where n is 4; streptocytin D is represented herein by formula (I), where n is 3; streptocytin E is represented herein by formula (I), where n is 2; streptocytin F is represented herein by formula (I), where n is 1; and streptocytin X is represented herein by formula (I), where n is 7. Preferably, component A according to the invention comprises one or more streptocytins selected from the group consisting of: streptocytin A, streptocytin B, streptocytin C, streptocytin D, streptocytin E, streptocytin F and streptocytin X, or stereoisomers thereof. Preferably, component A according to the present invention comprises streptococcin C, streptococcin D, streptococcin E and / or streptococcin F, or stereoisomers thereof, more preferably streptococcin C and / or streptococcin D, or stereoisomers thereof.

[0031] Suitablely, component A further comprises one or more streptococcins selected from the group consisting of: streptococcin A, streptococcin B, streptococcin C, streptococcin D, streptococcin E, streptococcin F and streptococcin X, or stereoisomers thereof.

[0032] Suitablely, component A comprises two, three, four or more streptococci having formula (I) as defined above, or their stereoisomers. Preferably, component A comprises streptococci C, D, E or F, and one or more other streptococci having formula (I) as defined above, or their stereoisomers.

[0033] Streptomycins (also known as norsticin, strychnine, dysmycin, and glutenin) are antibiotics produced by various species of the genus *Streptomyces*, but were initially isolated from *Streptomyces lilacinus*. Streptomycins contain variable β-lysine peptide chains that recognize various streptomycins (e.g., A, B, C, D, E, F, and X). Streptomycins exhibit antibacterial and antifungal activity and can be used in agriculture to control bacterial and fungal diseases. Streptomycins inhibit protein synthesis by inducing miscoding.

[0034] Noursin (also known as clonNAT) is a composition containing streptin C, D, E, and F, produced by fermentation of *Streptomyces noursei*. Noursin is commercially available. Noursin sulfate is registered under CAS 96736-11-7 and is commercially available. Zhongshengmycin is a composition containing streptin A, B, C, D, E, F, and X, produced by fermentation of *Streptomyces lavendulae var. hainanensis*. Zhongshengmycin is registered under CAS 861228-39-9 and is commercially available. Streptomycin, particularly streptin F, can also be chemically synthesized using procedures known in the art.

[0035] As used herein, the term "fermentation broth" refers to a composition obtained from the fermentation process of a strain.

[0036] In another embodiment of the invention, component A is a fermentation broth comprising two or more streptococci having formula (I) as defined above, or their stereoisomers. In an embodiment of the invention, component A is a fermentation broth comprising streptococci C, D, E, or F, and one or more other streptococci having formula (I) as defined above, or their stereoisomers. In an embodiment of the invention, component A is a fermentation broth comprising streptococci C and D, or their stereoisomers, or streptococci D and F, or their stereoisomers. Preferably, component A is a fermentation broth comprising streptococci C, D, E, and F, or their stereoisomers.

[0037] The compounds and compositions of components A and B are referred to herein and above by the so-called "ISO common name" or another "common name" or trade name used in individual cases. The compounds and compositions of components A and B are known and commercially available and / or can be prepared using procedures known in the art and / or procedures reported in the literature.

[0038] The antifungal composition according to the invention comprises component B, wherein component B comprises a compound represented by formula (II) or a stereoisomer thereof:

[0039] (II),

[0040] Where R 1 Selected from CONH2 and H;

[0041] Where R 2 R 4 R 6 and R 7 Each is independently selected from CH3 and H;

[0042] Where R 3 Selected from OH and H; and

[0043] Where R 5 Selected from CH2CH3 and CH3.

[0044] Suitable alternatives to or in addition to the compound represented by formula (II) or its stereoisomers, component B may also include:

[0045] Compounds or their stereoisomers represented by formula (III):

[0046] (III),

[0047] Where R 1 Selected from CONH2 and H; or

[0048] Compounds or their stereoisomers represented by formula (IV):

[0049] (IV).

[0050] Preferably, component B comprises a compound represented by formula (II) or a stereoisomer thereof, wherein R 1 Selected from CONH2 and H;R 2 Selected from CH3 and H;R 3 It is H; R 4 It is CH3; R 5 Selected from CH2CH3 and CH3; R 6 It is H; and R 7 It is H. More preferably, R 1 Selected from CONH2 and H;R 2 It is CH3; R 3 It is H; R 4 It is CH3; R 5 It is CH3; R 6 It is H; and R 7 It's H.

[0051] Suitablely, component B comprises compounds selected from the group consisting of: cypermethrin A, cypermethrin B, cypermethrin C, cypermethrin D, cypermethrin E, cypermethrin F, cypermethrin G, cypermethrin H, cypermethrin I, cypermethrin J, X-14952B, 17-hydroxycypermethrin A (YP-02259L-C), irumamycin (AM 3603), and 3'-O-decarbamoylirumamycin (AM-3603A-3), or their stereoisomers. Suitably, component B comprises compounds selected from the group consisting of: meliocin A, meliocin B, meliocin C, meliocin D, meliocin F, meliocin G, meliocin H, meliocin I, meliocin J, X-14952B, and 17-hydroxymeliocin A (YP-02259L-C), or their stereoisomers. Suitably, component B comprises compounds selected from the group consisting of: meliocin A, meliocin D, and meliocin F, or their stereoisomers. Suitably, component B comprises compounds selected from the group consisting of: meliocin A, meliocin B, meliocin G, meliocin H, meliocin I, and meliocin J, or their stereoisomers. Preferably, component B comprises a compound selected from the group consisting of: meliocin A, meliocin B, meliocin C, and meliocin I. More preferably, component B comprises a compound selected from the group consisting of: meliocin A, meliocin B, and meliocin C. More preferably, component B comprises meliocin A and / or meliocin B. Even more preferably, component B according to the present invention comprises meliocin A.

[0052] Suitablely, compounds having formula (II) are selected from compounds 1.001 to 1.010 listed in Table A below. The following list provides the substituents R of compounds having formula (II) according to the present invention. 1 R 2 R 3 R 4 R 5 R 6 and R 7 The definitions, including preferred definitions, are provided below. Any definition given below for any of these substituents may be combined with any definition of any other substituent given below or elsewhere in this document.

[0053] Table A: This table discloses 10 compounds having formula (II), of which R 1 R 2 R 3 R 4 R5 R 6 and R 7 As shown in Table A below. The (general) name for the "ID" indicator structure is also as follows.

[0054] Table A

[0055]

[0056] Preferably, the compound having formula (II) is typically styraxin A or its stereoisomer represented by formula (IIa):

[0057] (IIa).

[0058] Suitablely, compounds having formula (II) are typically represented by formula (IIb) styraxin B or its stereoisomers:

[0059] (IIb).

[0060] Suitablely, compounds having formula (II) are typically represented by formula (IIc) as styraxin C or its stereoisomers:

[0061] (IIc).

[0062] Suitablely, compounds having formula (II) are typically represented by formula (IId) as styraxin I or its stereoisomers:

[0063] (IId).

[0064] Suitablely, compounds having formula (II) are typically represented by formula (IIe) as styraxin F or its stereoisomers:

[0065] (IIe).

[0066] Methionin F is a stereoisomer of methionin A.

[0067] Preferably, the compound having formula (III) is typically represented by cipromycin (AM3603) or its stereoisomer, as represented by formula (IIIa):

[0068] (IIIa).

[0069] Preferably, the compound having formula (III) is typically 3'-O-decarbamoyl viridiomycin (AM-3603A-3) or its stereoisomer, represented by formula (IIIb):

[0070] (IIIb).

[0071] Preferably, the compound having formula (IV) is strychnine E or its stereoisomer.

[0072] In this paper, styracin (also known as apomycin) and its stereoisomers, represented by compounds having formulas (II), (III), and (IV), constitute a group of antibiotics produced by various Streptomyces species. The first member, styracin A, was first isolated from a Streptomyces species in 1961. Styracin has been shown to control plant pathogenic fungi. Styracin A has been reported to inhibit bacterial and mitochondrial ATP-synthesizing enzyme complexes.

[0073] As reported in the literature, styracil can be produced through fermentation of various Streptomyces species. Styracil A is registered under CAS 33538-71-5 and is commercially available. Styracil B is registered under CAS 33538-72-6 and is commercially available.

[0074] In another embodiment of the invention, component B is a fermentation broth containing a compound having formula (II) as defined above, or a stereoisomer thereof, preferably wherein the compound is sclerotin A.

[0075] In another embodiment of the invention, component B is a fermentation broth comprising two or more compounds having formula (II) as defined above, or stereoisomers thereof. In an embodiment of the invention, component B is a fermentation broth comprising sclerotin A and one or more other compounds having formula (II) as defined above, or stereoisomers thereof, preferably wherein the one or more other compounds having formula (II) are sclerotin B.

[0076] Preferably, the composition according to the invention comprises 10% to 99.9% by weight, preferably 20% to 99.9% by weight, more preferably 40% to 99.9% by weight, of streptotricin C or its stereoisomer, and 0.1% to 90% by weight, or 0.1% to 80% by weight, or 0.1% to 60% by weight, of one or more other streptotricin or its stereoisomer represented by formula (I). Preferably, the composition according to the invention comprises at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% or 40% by weight, and even more preferably at least 50%, 60%, or 70% by weight, of streptotricin C or its stereoisomer, of component A.

[0077] Suitably, the composition according to the invention comprises 10% to 99.9% by weight, or 20% to 99.9% by weight, or 40% to 99.9% by weight, of streptotricin D or a stereoisomer thereof, and 0.1% to 90% by weight, or 0.1% to 80% by weight, or 0.1% to 60% by weight, of one or more other streptotricin D or a stereoisomer thereof represented by formula (I). Suitably, the composition according to the invention comprises at least 10% by weight, or at least 20%, 30%, 40%, 50%, 60%, or 70% by weight, of streptotricin D or a stereoisomer thereof, of component A.

[0078] Preferably, the composition according to the invention comprises 10% to 99.9% by weight, preferably 20% to 99% by weight, more preferably 60% to 95% by weight of streptococcalin C and D, and component A comprising 0.1% to 30% by weight, or 2% to 25% by weight, or 5% to 22% by weight of streptococcalin E and F.

[0079] Preferably, the composition according to the invention comprises 10% to 99.9% by weight, preferably 20% to 99% by weight, more preferably 30% to 95% by weight, of one or more streptococcalin C or D, and component A comprising 0.1% to 30% by weight, or 2% to 20% by weight, or 5% to 15% by weight of one or more streptococcalin E or F.

[0080] Suitably, the weight ratio of component A to component B in the composition according to the invention is 60000:1 to 1:1000, 30000:1 to 1:1000, 20000:1 to 1:1000, 10000:1 to 1:1000, 5000:1 to 1:1000, 1000:1 to 1:1000, 1000:1 to 1:400, 1000:1 to 1:200, 1000:1 to 1:100, 1000:1 to 1:80, 1000:1 to 1:40, 1000:1 to 1:40, 1000:1 to 1:20, 1000:1 to 1:10, 1000: 1 to 1 : 4, 400 : 1 to 1 : 1000, 400 : 1 to 1 : 400, 400 : 1 to 1 : 200, 400 : 1 to 1 : 100, 400 : 1 to 1 : 80, 400 : 1 to 1 : 40, 400 : 1 to 1 : 20, 400 : 1 to 1 : 10, 400 : 1 to 1 : 4, 200 : 1 to 1 : 1000, 200 : 1 to 1 : 400, 200 : 1 to 1 : 200, 200 : 1 to 1 : 100, 200 : 1 to 1 : 80, 200 : 1 to 1 : 40, 200 : 1 to 1 : 20, 200 : 1 to 1 : 10, 200 : 1 to 1 : 4, 100 : 1 to 1 : 1000, 100 : 1 to 1 : 400, 100 : 1 to 1 : 200, 100 : 1 to 1 : 100, 100 : 1 to 1 : 80, 100 : 1 to 1 : 40, 100 : 1 to 1 : 20, 100 : 1 to 1 : 10, 100 : 1 to 1 : 4, 80 : 1 to 1 : 1000, 80 : 1 to 1 : 400, 80 : 1 to 1 : 200, 80 : 1 to 1 : 100, 80 : 1 to 1 : 80, 80: 1 to 1 : 40, 80 : 1 to 1 : 20, 80 : 1 to 1 : 10, 80 : 1 to 1 : 4, 40 : 1 to 1 : 1000, 40 : 1 to 1 : 400, 40 : 1 to 1 : 200, 40 : 1 to 1 : 100, 40 : 1 to 1 : 80, 40 : 1 to 1 : 40, 40 : 1 to 1 : 20, 40 : 1 to 1 : 10, 40 : 1 to 1 : 4, 20 : 1 to 1 : 1000, 20 : 1 to 1 : 400, 20 : 1 to 1 : 200, 20 : 1 to 1 : 100, 20:1 to 1 : 80, 20 : 1 to 1 : 40, 20 : 1 to 1 : 20, 20 : 1 to 1 : 10, 20 : 1 to 1 : 4, 10 : 1 to 1 : 1000, 10 : 1 to 1 : 400, 10 : 1 to 1 : 200, 10 : 1 to 1 : 100, 10 : 1 to 1 : 80, 10 : 1 to 1 : 40, 10 : 1 to 1 : 20, 10 : 1 to 1 : 10, 10 : 1 to 1 : 4, 4 : 1 to 1 : 4.

[0081] Preferably, the weight ratio of component A to component B in the composition according to the invention is 60000:1 to 1:1000, wherein component A comprises streptomycin C and / or D and component B comprises styracil A. Suitably, the weight ratio is 10000:1 to 1:1000, 1000:1 to 1:1000, 200:1 to 1:200, or 50:1 to 1:50.

[0082] Preferably, the weight ratio of component A to component B in the composition according to the invention is 1000:1 to 1:1000, wherein component A comprises streptococcin C and / or D and one or more other streptococcins having formula (I) or their stereoisomers. Suitably, the weight ratio is 200:1 to 1:200 or 50:1 to 1:50.

[0083] Suitably, component A is a fermentation broth containing one or more streptococci represented by formula (I) as defined above. Suitably, component B is a fermentation broth containing a compound represented by formula (II) as defined above. Suitably, the composition according to the invention is a fermentation broth.

[0084] Suitably, component A is a fermentation broth containing one or more streptococins represented by formula (I) as defined above, or their stereoisomers, and component B contains styraxanthin A. Preferably, component A is a fermentation broth containing streptococins C and / or D, and component B contains styraxanthin A. Preferably, component A is a fermentation broth containing streptococins C, D, E, and F, and component B contains styraxanthin A. Suitably, component A is a fermentation broth containing streptococins C and D, and component B contains styraxanthin A, styraxanthin B, styraxanthin C, or styraxanthin I. Suitably, component A is a fermentation broth containing streptococins C, D, E, and F, and component B contains styraxanthin A, styraxanthin B, styraxanthin C, or styraxanthin I.

[0085] Suitablely, component A is a fermentation broth containing streptococcin C and / or D, and component B contains styraxone A, wherein the weight ratio of component A to component B is 60000:1 to 1:1000, 10000:1 to 1:1000, 1000:1 to 1:1000, 30000:1 to 1:100, 5000:1 to 1:100, 100:1 to 1:100, 40:1 to 1:40, or 4:1 to 1:4.

[0086] Suitablely, component A is a fermentation broth containing streptococcin C, D, E and F, and component B contains styraxone A, wherein the weight ratio of component A to component B is 60000:1 to 1:1000, 10000:1 to 1:1000, 1000:1 to 1:1000, 30000:1 to 1:100, 5000:1 to 1:100, 100:1 to 1:100, 40:1 to 1:40, or 4:1 to 1:4.

[0087] Compounds having formula (I) or their stereoisomers can be prepared by methods known to those skilled in the art. Compounds having formula (I) can be prepared commercially or by synthetic or semi-synthetic chemical or fermentation methods.

[0088] For example, compounds having formula (I), particularly those where n is 1, or their stereoisomers, can be prepared by methods known in Kusumoto et al., 1982, “Total synthesis of antibiotic streptothricin F”, Tetrahedron Letters, doi: 10.1016 / S0040-4039(00)87506-1 and Dowgiallo et al., 2022, “The convergent total synthesis and antibacterial profile of the natural product streptothricin F”, Chemical Science, doi: 10.1039 / D1SC06445B.

[0089] For example, fermentation broth or a composition containing one or more compounds of formula (I) or their stereoisomers can be obtained from the fermentation process of Streptomyces strains, typically Streptomyces northerly or Streptomyces lilacinus. The fermentation broth may not require purification. Alternatively, one or more compounds of formula (I) can be separated and purified from the fermentation broth, for example by chromatography using adsorbents (e.g., silica gel and reversed-phase silica gel, optically active adsorbents, resins) or one or more solvents (e.g., separation, countercurrent separation, mixtures of multiphase solvents) or other chemical means (e.g., crystallization, recrystallization, salt formation, and precipitation) to achieve the final purity.

[0090] Compounds having formulas (II), (III), and (IV), or their stereoisomers, particularly styraxone A, B, C, D, E, F, G, H, I, and J, can be prepared by methods known to those skilled in the art. Compounds having formulas (II), (III), and (IV), or their stereoisomers, particularly styraxone A, B, C, D, E, F, G, H, I, and J, can be purchased or prepared using fermentation methods.

[0091] For example, compositions or fermentation broths comprising one or more compounds having formula (II) or (IV) or their stereoisomers, preferably styracil A, can be obtained from the fermentation process of *Streptomyces* strains, such as *Streptomyces* species SN5452, MST-117594, NRRL S-4, MA1078, *Streptomyces aureofaciens* (DUGGAR), *Streptomyces* strain US80, *Streptomyces* species 135, or *Streptomyces* species TS-2-2. Compositions or fermentation broths comprising one or more compounds having formula (III) or their stereoisomers can be obtained from the fermentation process of *Streptomyces subflavus* subsp. *irumaensis* AM-3603 or *Streptomyces* strain US80. The fermentation broth may not require purification. Alternatively, one or more compounds having formulas (II), (III), (IV) or their stereoisomers, preferably formula (II), more preferably styraxone A and / or B, can be separated and purified from the fermentation broth, for example by chromatography using an adsorbent (e.g., silica gel and reversed-phase silica gel, optically active adsorbent, resin) or one or more solvents (e.g., separation, countercurrent separation, mixture of multiphase solvents) or other chemical means (e.g., crystallization, recrystallization, salt formation and precipitation) to achieve the final purity.

[0092] As used herein, the term "fungicide" means a compound that controls, alters, or prevents the growth of fungi. The term "effective fungicide amount" means the amount of such a compound or combination of such compounds that can affect fungal growth. Controlling or altering effects include all deviations from natural development, such as killing, inhibiting, etc., and prevention includes the formation of barriers or other defenses within or on the plant to prevent fungal infection.

[0093] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, culms, leaves, and fruits.

[0094] The term "plant propagation material" refers to all reproductive parts of a plant, such as seeds or vegetative parts like cuttings and tubers. It includes seeds in the strict sense, as well as roots, fruits, tubers, bulbs, rhizomes, and other plant parts. Preferably, "plant propagation material" should be understood to mean seeds. In another aspect, the invention also relates to plant propagation material coated with a composition according to the invention.

[0095] As used herein, the term "site" means the place in which or on which a plant grows, or the place where the seeds of a cultivated plant are sown, or the place where the seeds will be placed in the soil. It includes soil, seeds and seedlings, and established vegetation.

[0096] Throughout this document, the term "composition" refers to different mixtures or combinations of components A and B (including the examples defined above), for example, in a single "ready-to-use with water" form, in a combined spray mixture (which consists of individual formulations of single active ingredient components) (such as a "tank mix"), and when applied in a sequential manner (i.e., one after another for a reasonably short period of time, such as hours or days).

[0097] The compositions according to the invention are effective against harmful microorganisms (such as microorganisms) that cause plant pathogenic diseases, especially against plant pathogenic fungi.

[0098] The compositions of the present invention can be used to control plant diseases caused by a broad spectrum of fungal plant pathogens belonging to the classes Basidiomycete, Ascomycete, Oomycete, Deuteromycete, Blastodactycete, Chrytidiomycete, Glomeromycete, and / or Mucoromycete. Therefore, the methods for controlling or preventing plant pathogenic diseases or plant pathogenic fungi according to the present invention are particularly effective against plant pathogenic fungi selected from the classes Basidiomycete, Ascomycete, Oomycete, Deuteromycete, Blastodactycete, Chrytidiomycete, Glomeromycete, and / or Mucoromycete.

[0099] The compositions and methods according to the invention are particularly effective against plant pathogenic fungi belonging to the following classes: Ascomycetes; Basidiomycetes; Fungi imperfecti (also known as Deuteromycetes); Oomycetes, such as *Phytophthora*, *Peronospora*, *Pseudoperonospora*, *Albugo*, *Bremia*, *Pythium*, *Pseudosclerospora*, and *Plasmopara*, preferably Ascomycetes; Basidiomycetes; and Fungi imperfecti.

[0100] Preferably, the compositions and methods according to the invention are effective against plant pathogenic fungi selected from the group consisting of: *Alternaria*, *Ascochyta*, *Botrytis*, *Cercospora*, *Cochliobolus sativus*, *Colletotrichum*, *Colletotrichum lagenarium*, *Corynespora*, *Erysiphe*, *Erysiphe cichoracearum*, *Sphaerothecafuliginea*, *Fusarium*, *Fusarium oxysporum*, *Gäumannomyces graminis*, *Guignardia*, *Helminthosporium*, and *Hemileia*. Vastatrix, Magnaporthe, Magnaporthe oryzae, Monilinia, Mycosphaerella, Mycosphaerella aracchidis, Phakpsora, Phona, Phopsis, Puccinia, Pseudocercosporella, Pseudopezicula, Phragmidium mucronatum, Podosphaera, Pyrenophora, Pyrenophora teres, Pyricularia, Pyricularia oryzae, Ramularia, Ramularia leaf spot fungus * *Collo-cygni*, *Rhizoctonia*, *Rhizoctonia solani*, *Rhynchosporium secalis*, *Sclerotinia*, *Septoria*, *Septoria tritici*, *Sphacelotheca*The genera include *Reilliana*, *Tilletia*, *Urocystis occulta*, *Uncinula*, *Ustilago*, *Venturia*, *Monilia*, and *Penicillium*.

[0101] The compositions and methods of the present invention are particularly effective against plant pathogenic fungi selected from the group consisting of: *Alternaria*, *Botrytis*, *Cercospora*, *Anthracis*, *Corynebacterium*, *Fusarium*, *Glomerella*, *Glomerella*, *Glomerella*, *Glomerella*, *Glomerella*, *Glomerella*, *Glomerella*, *Glomerella*, *Glomerella*, *Penicillium*, *Laminaria*, *Pseudomonas*, *Glomerella*, *Glomerella*, *Glomerella*, *Glomerella*, *Glomerella*, *Glomerella*, and *Zymoseptoria*, more preferably selected from the group consisting of: *Alternaria*, *Botrytis*, *Fusarium*, *Glomerella*, *Glomerella*, and *Zymoseptoria*.

[0102] The compositions and methods of the present invention are particularly effective against plant pathogenic fungi selected from the group consisting of: *Alternaria solani*, *Alternaria alternata*, *Alternaria porri*, *Botrytis cinerea*, *Botrytis allii*, *Botrytis squamosa*, *Cercospora capsici*, *Anthracnose fungi*, *Corynespora cassiicola*, *Fusarium culmorum*, *Fusarium oxysporum*, *Glomerella lagenarium*, *Guignardia bidwellii*, *Rice frost*, *Monilinia fructicola*, *Monilinia fructigena*, *Monilinia laxa*, and *Penicillium*. *Penicillium digitatum*, *Penicillium italicum*, *Penicillium expansum*, *Phomopsis viticola*, *Podosphaera leucotricha*, *Podosphaera xanthii*, *Pseudopezicula tracheiphila*, *Rhizoctonia solani*, *Uncinula necator*, *Venturia inaequalis*, and *Zymoseptoria*. (tritici), more preferably selected from the group consisting of: Alternaria solanacea, Alternaria alternifolia, Alternaria allium, Botrytis cinerea, Botrytis cinerea, Botrytis cinerea, Cercospora capsici, Anthracnose of cucurbits, Corynebacterium multiflorum, Fusarium oxysporum, Fusarium oxysporum, Microcystis cucurbita, Botrytis cinerea, Prunus persica brown rot, Prunus persica brown rot, Sclerotium sclerotiorum, Sclerotium sclerotiorum, Peanut coccidioides, Penicillium fingertips, Penicillium italicum, Penicillium expansum, Prunus persica stem spot, Monocystis leucocephala, Monocystis powdery mildew, Prunus persica angular leaf scorch, Sinapis trifoliata, Sinapis trifoliata, Acer macrantha, and Sinapis trifoliata, even more preferably selected from the group consisting of: Alternaria solanacea, Botrytis cinerea, Fusarium oxysporum, Microcystis cucurbita, Peanut coccidioides, and Sinapis trifoliata, and ... Sinapis trifoliata, and Sinapis trifoliata, and S

[0103] According to the present invention, "useful plants" typically include the following perennial or annual plants: cereals; fruits and tree nuts; vegetables; field crops; oil crops; forage crops; fiber crops; forest plants; horticultural crops; floricultural, greenhouse and nursery plants; propagation materials; edible herbs and spices; and medicinal herbs. Preferably, useful plants are selected from the group consisting of: fruits and tree nuts, vegetables, horticultural crops and floricultural plants.

[0104] However, this list does not represent any limitation. Preferably, useful plants can be selected from the group consisting of: apples, apricots, cherries, raspberries, grapes, cucumbers, peanuts, tomatoes, strawberries, citrus fruits, and bananas. Suitably, useful plants can be selected from the group consisting of: grapevines, strawberries, apples, cherries, peaches, nectarines, blueberries, caneberries, tomatoes, potatoes, gourds, cucumbers, eggplants, lettuce, legumes, brassicas, peas, rapeseed, soybeans, sugar beets, sunflowers, rice, peanuts, coffee, ornamental plants, and turfgrass.

[0105] Preferred is a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi, preferably plant pathogenic fungi, according to the present invention, the method comprising applying the composition according to the present invention to a useful plant.

[0106] The term "useful plants" should be understood to also include useful plants that have developed tolerance to herbicides such as bromobenzonitrile or herbicides (e.g., HPPD inhibitors, ALS inhibitors such as flusulfuron, flusulfuron, and triflusulfuron, EPSPS (5-enol-pyruvyl-shikimate-3-phosphate synthase) inhibitors, and GS (glutamine synthase) inhibitors) through conventional breeding or genetic engineering. An example of a crop that has developed tolerance to imidazolinones (e.g., methoxyfenozide) through conventional breeding methods (mutation) is Clearfield® summer canola. Examples of crops that have developed tolerance to herbicides or herbicides through genetic engineering include glyphosate- and glufosinate-resistant corn varieties, commercially available under the brand names RoundupReady®, Herculex I®, and LibertyLink®.

[0107] The term "useful plant" should be understood to also include useful plants that have been transformed using recombinant DNA technology to enable them to synthesize one or more selectively acting toxins, such as those known to originate from toxin-producing bacteria. Examples of toxins that can be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins from bacterial colonizing nematodes, and toxins produced by scorpions, arachnids, wasps, and fungi.

[0108] Some compositions according to the present invention have systemic action and can be used as fungicides for leaf, soil and seed treatment.

[0109] Using the composition according to the invention, plant pathogenic microorganisms present on various useful plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) can be inhibited or destroyed, while also protecting later-growing plant parts from attack by plant pathogenic microorganisms. Preferably, the microorganisms are fungi.

[0110] The compositions according to the invention can be applied to plant pathogenic microorganisms, useful plants threatened by microbial attack, their sites, their propagation materials, stored goods, or technical materials. Preferably, the microorganisms are fungi.

[0111] The compositions according to the invention can be applied before or after useful plants, their propagation materials, stored goods, or technical materials are infected by microorganisms. Preferably, the microorganisms are fungi.

[0112] The amount of the composition according to the invention to be applied will depend on various factors, such as the compound used; the object to be treated, such as plants, soil or seeds; the type of treatment, such as spraying, dusting or seed dressing; the purpose of the treatment, such as prevention or treatment; the type of fungus to be controlled or the time of application.

[0113] Compositions containing a combination of component A and component B can be applied, for example, as a single “ready-to-use” form, as a combined spray mixture (consisting of separate formulations of a single active ingredient component) (such as a “tank mix”), and when applied in a sequential manner (i.e., one after another for a reasonably short period of time, such as hours or days).

[0114] The compositions according to the invention are active ingredients with preventive and / or therapeutic value in the field of pest control, even at low application rates.

[0115] Suitablely, according to the method of the invention, component A is applied in combination with component B at a ratio of 0.5 g ai / ha to 2000 g ai / ha at a ratio of 10 g ai / ha to 3000 g ai / ha.Combined location, group A to 10 g ai / ha to 3000g ai / ha ratio 0.5 g ai / ha to 2000 g ai / ha, 0.5 g ai / ha to 1500 g ai / ha, 0.5 g ai / ha to 1000 g ai / ha, 0.5 g ai / ha to 500 g ai / ha, 0.5 g ai / ha to 250 g ai / ha, 0.5 g ai / ha to 100 g ai / ha, 0.5 g ai / ha to 50 g ai / ha, 5 g ai / ha to 2000 g ai / ha, 5 g ai / ha to 1500 g ai / ha, 5 g ai / ha to 1000 g ai / ha, 5 g ai / ha to 500 g ai / ha, 5 g ai / ha to 250 g ai / ha, 5 g ai / ha up to 100g ai / ha, 5g ai / ha up to 50g ai / ha, 10g ai / ha up to 2000g ai / ha, 10g ai / ha up to 1500g ai / ha, 10g ai / ha up to 1000g ai / ha, 10g ai / ha up to 500g ai / ha, 10g ai / ha up to 250g ai / ha, 10g ai / ha up to 100g ai / ha, 10g ai / ha up to 50g ai / ha, 20g ai / ha up to 2000g ai / ha, 20g ai / ha up to 1500g ai / ha, 20g ai / ha up to 1000g ai / ha, 20g ai / ha up to 500g ai / ha, 20g ai / ha up to 250g ai / ha, 20g ai / ha to 100 g ai / ha, 20 g ai / ha to 50 g ai / ha, 50 g ai / ha to 2000 g ai / ha, 50 g ai / ha to 1500 g ai / ha, 50 g ai / ha to 1000 g ai / ha, 50 g ai / ha to 500 g ai / ha, 50 g ai / ha to 250 g Combined application of ai / ha or 50 g ai / ha to 100 g ai / ha.

[0116] Suitablely, according to the method of the invention, component A is applied in combination with component B at a ratio of 25 g ai / ha to 3000 g ai / ha to 0.5 g ai / ha to 2000 g ai / ha.Combined location, group A to 25 g ai / ha to 2000g ai / ha ratio given 0.5 g ai / ha to 2000 g ai / ha, 0.5 g ai / ha to 1500 g ai / ha, 0.5 g ai / ha to 1000 g ai / ha, 0.5 g ai / ha to 500 g ai / ha, 0.5 g ai / ha to 250 g ai / ha, 0.5 g ai / ha to 100 g ai / ha, 0.5 g ai / ha to 50 g ai / ha, 5 g ai / ha to 2000 g ai / ha, 5 g ai / ha to 1500 g ai / ha, 5 g ai / ha to 1000 g ai / ha, 5 g ai / ha to 500 g ai / ha, 5 g ai / ha to 250 g ai / ha, 5 g ai / ha up to 100g ai / ha, 5g ai / ha up to 50g ai / ha, 10g ai / ha up to 2000g ai / ha, 10g ai / ha up to 1500g ai / ha, 10g ai / ha up to 1000g ai / ha, 10g ai / ha up to 500g ai / ha, 10g ai / ha up to 250g ai / ha, 10g ai / ha up to 100g ai / ha, 10g ai / ha up to 50g ai / ha, 20g ai / ha up to 2000g ai / ha, 20g ai / ha up to 1500g ai / ha, 20g ai / ha up to 1000g ai / ha, 20g ai / ha up to 500g ai / ha, 20g ai / ha up to 250g ai / ha, 20g ai / ha to 100 g ai / ha, 20 g ai / ha to 50 g ai / ha, 50 g ai / ha to 2000 g ai / ha, 50 g ai / ha to 1500 g ai / ha, 50 g ai / ha to 1000 g ai / ha, 50 g ai / ha to 500 g ai / ha, 50 g ai / ha to 250 g Combined application of ai / ha or 50 g ai / ha to 100 g ai / ha.

[0117] In a preferred embodiment of the invention, a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi, preferably on useful plants or their propagation material, comprises applying a composition as defined according to the invention to the plant, its site, or its propagation material, wherein component A is applied in combination with component B at a ratio of 10 g ai / ha to 3000 g ai / ha to 0.5 g ai / ha to 2000 g ai / ha or 10 g ai / ha to 1500 g ai / ha.

[0118] In a preferred embodiment of the invention, a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi, preferably on useful plants or their propagation material, comprises applying a composition as defined according to the invention to the plant, its site, or its propagation material, wherein component A is applied in combination with component B at a ratio of 25 g ai / ha to 3000 g ai / ha to 0.5 g ai / ha to 2000 g ai / ha or 10 g ai / ha to 1500 g ai / ha.

[0119] The present invention also relates to a coated plant propagation material, wherein the coating of the plant propagation material comprises applying a composition according to the invention. The present invention further relates to a coated plant propagation material, wherein the coating comprises a composition according to the invention. Preferably, when the composition according to the invention is used to treat seeds, a ratio of 0.001 to 50 g of component A compound / kg seed, preferably 0.01 to 10 g / kg seed, and 0.001 to 50 g of component B compound / kg seed, preferably 0.01 to 10 g / kg seed, is generally sufficient.

[0120] Suitably, according to the method of the invention, component A is applied in combination with component B at a ratio of at least 0.001 ppm.

[0121] Suitably, according to the method of the invention, component A is administered in combination with component B at a ratio of at least 0.005 ppm and at least 0.005 ppm or 0.01 ppm. Suitably, according to the method of the invention, component A is administered in combination with component B at a ratio of at least 0.01 ppm and at least 0.005 ppm or 0.01 ppm. Suitably, according to the method of the invention, component A is administered in combination with component B at a ratio of at least 0.1 ppm and at least 0.01 ppm or 0.1 ppm.

[0122] The preferred composition according to the invention comprises component A containing norsuldin (a composition containing streptococcin C, D, E and F) and component B containing sclerotin A. Preferably, the weight ratio of norsuldin to sclerotin A is 1:4 to 4:1.

[0123] A preferred method according to the invention comprises a method for controlling or preventing plant pathogenic diseases or plant pathogenic fungi on plants, their sites, or their propagation material, the method comprising applying a composition according to the invention to the plant, its site, or its propagation material, wherein component A comprises nouricin and component B comprises styraxanthin A. Preferably, nouricin is applied in combination with styraxanthin A at a ratio of 0.0078 ppm to 0.5 ppm. Preferably, the plant pathogenic fungi are selected from the group consisting of: *Alternaria solanacea*, *Botrytis cinerea*, *Fusarium oxysporum*, *Microcystis suis*, *Gnaphalium arachidii*, and *Syngonium ferrugineum*. Preferably, nouricin is applied in combination with styraxanthin A at a ratio of 0.0156 ppm to 0.0625 ppm, wherein the plant pathogenic fungus is *Alternaria solanacea*. Preferably, norsinolide is applied in combination with 0.0078 ppm to 0.0625 ppm of sulfadiazine A at a ratio of 0.0156 ppm to 0.125 ppm, wherein the plant pathogenic fungus is *Botrytis cinerea*. Preferably, norsinolide is applied in combination with about 0.0625 ppm of sulfadiazine A at a ratio of 0.0156 ppm to 0.125 ppm, wherein the plant pathogenic fungus is *Botrytis cinerea*. Preferably, norsinolide is applied in combination with 0.5 ppm to 1 ppm of sulfadiazine A at a ratio of 0.0625 ppm to 0.25 ppm, wherein the plant pathogenic fungus is *Fusarium oxysporum*. Preferably, norsinolide is applied in combination with 0.5 ppm to 1 ppm of sulfadiazine A at a ratio of about 0.25 ppm, wherein the plant pathogenic fungus is *Fusarium oxysporum*. Preferably, norsinolate is applied in combination with 0.03 ppm to 0.5 ppm of cypermethrin A at a ratio of 0.03 ppm to 0.125 ppm, wherein the plant pathogenic fungus is *Trichophyton cucumeris*. Preferably, norsinolate is applied in combination with about 0.125 ppm of cypermethrin A at a ratio of 0.03 ppm to 0.5 ppm, wherein the plant pathogenic fungus is *Trichophyton cucumeris*. Preferably, norsinolate is applied in combination with 0.0078 ppm to 0.0156 ppm of cypermethrin A at a ratio of 0.0039 ppm to 0.0313 ppm, wherein the plant pathogenic fungus is *Gnaphalium arachidii*. Preferably, norsinolide is applied in combination with 0.0078 ppm to 0.0313 ppm of cypermethrin A at a ratio of 0.01 ppm to 0.13 ppm, wherein the plant pathogenic fungus is *Syngonium fermentum*. Preferably, norsinolide is applied in combination with about 0.0313 ppm of cypermethrin A at a ratio of 0.01 ppm to 0.13 ppm, wherein the plant pathogenic fungus is *Syngonium fermentum*.

[0124] Preferably, the compositions according to the invention comprise an agriculturally acceptable carrier and / or formulation adjuvant and optionally a surfactant. The invention also provides fungicidal compositions comprising synergistically effective amounts of the combination of components A and B as mentioned above, along with an agriculturally acceptable carrier and optionally a surfactant. In said compositions, as described above, the weight ratio of component A to component B is preferably 1000:1 to 1:1000, more preferably 100:1 to 1:100, even more preferably 40:1 to 1:40, and still more preferably about 4:1 to about 1:4.

[0125] The compositions of the present invention can be used in any conventional form, such as in the form of double-packaged powders for dry seed treatment (DS), emulsions for seed treatment (ES), flowable concentrates for seed treatment (FS), solutions for seed treatment (LS), water-dispersible powders for seed treatment (WS), capsule suspensions for seed treatment (CF), gels for seed treatment (GF), emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), dispersible oil suspensions (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical grade (TK), dispersible concentrates (DC), wettable powders (WP), or any technically feasible formulations in combination with agriculturally acceptable adjuvants.

[0126] Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with a suitable formulation inert agent (diluent, solvent, filler, and optionally other formulation ingredients). Conventional sustained-release formulations designed for long-term sustained efficacy can also be used. In particular, formulations to be applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules, may contain compounds that provide adjuvant action. In some embodiments, the compositions of the present invention can be produced by mixing a fermentation broth containing one or more streptococcalins or stereoisomers of formula (I) with a compound of component B.

[0127] Using the composition and diluent according to the invention, the seed dressing formulation is applied to seeds in a manner known to them, in a suitable seed dressing formulation form, such as an aqueous suspension or a dry powder form having good adhesion to seeds. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example, as a sustained-release capsule or microcapsule.

[0128] Typically, formulations contain 0.01% to 90% by weight of an active agent, 0% to 20% by weight of an agriculturally acceptable surfactant, and 10% to 99.99% by weight of a solid or liquid formulation inert agent and one or more adjuvants. The active agent consists at least of a compound having formula (I) together with compounds having formulas (II), (III), or (IV) and other active agents (particularly microbicides or preservatives). Concentrated forms of the composition typically contain between about 2% and 80% by weight, preferably between about 5% and 70% by weight of the active agent. Application forms of the formulation may, for example, contain 0.01% to 20% by weight, preferably 0.01% to 5% by weight of the active agent. However, commercial products are preferably formulated as concentrates, and end users will typically use diluted formulations.

[0129] It has been unexpectedly discovered that components A and B in specific weight ratios can produce synergistic activity. Therefore, another aspect of the invention is a composition in which components A and B are present in an amount that produces a synergistic effect. This synergistic activity is evident from the fact that the fungicidal activity of a composition containing components A and B is greater than the sum of the fungicidal activities of components A and B. This synergistic activity expands the scope of action of components A and B in two ways. First, by reducing the application ratio of components A and B while maintaining the same level of effectiveness, this means that even if the two individual components become completely ineffective at such low application ratios, the mixture of active ingredients still achieves a high degree of plant pathogen control. Second, the spectrum of controllable plant pathogens is significantly broadened.

[0130] Synergistic effects exist when the combined effect of active ingredients is greater than the sum of the effects of the individual components. For a given combination of active ingredients, the expected effect E follows the so-called Colby formula and can be calculated as follows (COLBY, SR, "Calculating synergistic and antagonistic responses of herbicide combination," Weeds, Vol. 15, pp. 20-22; 1967):

[0131] ppm = the number of milligrams of active ingredient (= ai) per liter of spray mixture.

[0132] X = % effect of active ingredient (A) using p ppm.

[0133] Y = % effect of active ingredient (B) using q ppm of active ingredient.

[0134] According to Colby, using p + q ppm of active ingredients, the expected (additive) effect of active ingredient (A) + (B) is

[0135] If the observed effect (O) is greater than the expected effect (E), then the combined effect is superadditive, i.e., a synergistic effect exists. Mathematically, a synergistic effect corresponds to a positive value of the difference (OE). In the case of perfectly complementary superposition of activities (expected activity), the difference (OE) is zero. A negative value of the difference (OE) indicates a loss of activity compared to the expected activity.

[0136] However, in addition to the actual synergistic effect relative to the fungicidal activity, the compositions according to the invention may also have other unexpectedly advantageous properties. Examples of such advantageous properties that may be mentioned are: more favorable degradability; improved toxicological and / or ecotoxicological behavior; or improved characteristics of useful plants, including: emergence, crop yield, more developed root system, increased tillering, increased plant height, larger leaves, less basal leaf mortality, stronger tillering, greener leaf color, less fertilizer required, less seed required, more tillering, earlier flowering, earlier grain maturity, less lodging, enhanced bud growth, improved plant vigor, and earlier germination.

[0137] The composition according to the invention is preferably in a synergistically effective amount. Preferably, component A and component B of the composition according to the invention are each in an amount that produces a synergistic effect, preferably a synergistic fungicidal effect. Preferably, the composition according to the invention has a weight ratio of component A to component B in a synergistically effective amount.

[0138] It has been found that when combined with one or more streptococci as defined above by formula (I), particularly where the streptococci include streptococci C, D, E, and F, nigrostriacin A advantageously provides more than additive fungicidal activity. Refer to the following examples, which disclose the synergistic antifungal activity of norostatin and nigrostriacin A.

[0139] The following examples are provided to illustrate the invention and are not intended to limit the invention in any way.

[0140] Biological examples

[0141] The biological (fungal) activity of the compositions according to the invention was tested using one or more methods as described in Examples 1 to 6.

[0142] Nourthrin is a composition comprising streptorin C, D, E, and F. Nourthrin sulfate is used in the examples. As previously indicated, nourthrin and nourthrin sulfate are known and commercially available. As previously indicated, strychnine A is known and commercially available.

[0143] The test methods and results for the bio (fungicide) activity of the compositions according to the invention are shown in Tables 1 to 6 below. These data indicate that the combination of norsinopicrin and nigrostrin A exhibits synergistic fungicidal activity against *Botrytis cinerea*, *Alternaria alternata*, *Microcystis cucurbita*, *Syngonium fermentum*, *Fusarium oxysporum*, and *Cyclocarya paliurus* at specific weight ratios. According to Colby, mathematically, the synergistic factor SF corresponds to O / E. In agricultural practice, an SF ≥ 1.1 indicates a significant improvement in activity relative to pure complementarity (expected activity), while an SF ≤ 0.9 in practical application conventions signifies a loss of activity compared to the expected activity.

[0144] Example 1

[0145] Botrytis cinerea (gray mold):

[0146] Frozen fungal conidia were directly mixed into nutrient liquid medium (Vogel's liquid medium). After placing a solution of the test compound (DMSO or DMSO / Tween 20) in a microtiter plate (96-well size), nutrient liquid medium containing fungal conidia was added. The test plate was incubated at 24°C for 72 hours, and growth inhibition was determined by photometry and visual inspection.

[0147] Table 1: The antifungal activity of the combination of norsinolate and nigrostriacin A as described above against Botrytis cinerea.

[0148]

[0149] Example 2

[0150] Alternaria alternata (early wilt disease):

[0151] Frozen fungal conidia were directly mixed into nutrient liquid medium (PDB: Potato Dextrose Liquid Medium). After placing a solution of the test compound (DMSO or DMSO / Tween 20) in a microtiter plate (96-well size), nutrient liquid medium containing fungal conidia was added. The test plate was incubated at 24°C for 48 hours, and growth inhibition was determined by photometry and visual inspection.

[0152] Table 2: The antifungal activity of the combination of norsinolate and nigericin A as described above against Alternaria solanacearum.

[0153]

[0154] Example 3

[0155] Anthracnose of cucurbits (also known as cucurbit anthracnose fungus) (cucurbit anthracnose):

[0156] Fungal conidia prepared from freshly cultured petri dishes were directly mixed into nutrient liquid medium (PDB potato dextrose broth). After placing a solution of the test compound (DMSO or DMSO / Tween 20) in a microtiter plate (96-well size), nutrient liquid medium containing fungal spores was added. The test plate was incubated at 24°C for 72 hours, and growth inhibition was determined by photometry and visual inspection.

[0157] Table 3: The antifungal activity of the combination of norsinolate and styraxin A as described above against Trichoderma cucumeroides.

[0158]

[0159] Example 4

[0160] Wheat fermentation spores (leaf blisters):

[0161] Frozen fungal conidia were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a solution of the test compound (DMSO or DMSO / Tween 20) in a microtiter plate (96-well size), nutrient liquid medium containing fungal spores was added. The test plate was incubated at 24°C for 72 hours, and growth inhibition was determined by photometry and visual inspection.

[0162] Table 4: The antifungal activity of the combination of norsinolate and nigericin A as described above against wheat fermentation spores.

[0163]

[0164] Example 5

[0165] Fusarium graminearum (Fusarium head blight):

[0166] Frozen fungal conidia were directly mixed into nutrient liquid medium (PDB potato dextrose broth). After placing a solution of the test compound (DMSO or DMSO / Tween 20) in a microtiter plate (96-well size), nutrient liquid medium containing fungal conidia was added. The test plate was incubated at 24°C, and growth inhibition was determined by photometry and visual inspection after 3 days.

[0167] Table 5: The antifungal activity of the combination of norsinolate and nigericin A as described above against Fusarium oxysporum.

[0168]

[0169] Example 6

[0170] Mycosphaerella arachidicola (also known as peanut coccidioidomyces) (early leaf spot disease of peanut):

[0171] Frozen-stored fungal conidia were directly mixed into nutrient liquid medium (PDB potato dextrose broth). After placing a solution of the test compound (DMSO or DMSO / Tween 20) in a microtiter plate (96-well size), nutrient liquid medium containing fungal conidia was added. The test plate was incubated at 24°C, and growth inhibition was determined by photometry and visual inspection after 4 days.

[0172] Table 6: The antifungal activity of the combination of norsinolate and nigericin A as described above against Arachis coccidioidomyces.

[0173] Example

[0174] Example 1. An antifungal composition comprising:

[0175] (i) Component A, wherein component A comprises one or more streptococcalins or stereoisomers thereof represented by formula (I):

[0176] (I),

[0177] Where n is an integer selected from 1 to 7; and

[0178] (ii) Component B, wherein component B comprises a compound or a stereoisomer thereof represented by formula (II):

[0179] (II),

[0180] Where R 1 Selected from CONH2 and H;

[0181] Where R 2 R 4 R 6 and R 7 Each is independently selected from CH3 and H;

[0182] Where R 3 Selected from OH and H; and

[0183] Where R 5 Selected from CH2CH3 and CH3.

[0184] Example 2. The composition as described in Example 1, wherein component A comprises one or more streptococcalins or stereoisomers thereof represented by formula (I), wherein n is an integer selected from 1 to 4, preferably wherein n is 3 or 4.

[0185] Example 3. A composition as described in Example 1 or 2, wherein component A comprises these streptococcins or their stereoisomers represented by formula (I), wherein n is 1, 2, 3 and 4.

[0186] Example 4. A composition as described in any one of Examples 1 to 3, wherein component B comprises the compound or its stereoisomer represented by formula (II), wherein R 1 Selected from CONH2 and H;R 2 Selected from CH3 and H;R 3 It is H; R 4 It is CH3; R 5 Selected from CH2CH3 and CH3; R 6 It is H; and R 7 It is H; preferably, R is... 1 Selected from CONH2 and H;R 2 It is CH3; R 3 It is H; R 4 It is CH3; R 5 It is CH3; R 6 It is H; and R 7 It's H.

[0187] Example 5. A composition as described in any one of Examples 1 to 4, wherein component B comprises styracil A or its stereoisomer, wherein styracil A is represented by formula (IIa):

[0188] (IIa).

[0189] Example 6. A composition as described in any one of Examples 1 to 5, wherein component A comprises 10% to 99.9% by weight, preferably 20% to 99% by weight, of one or more streptococcalins represented by formula (I) or their stereoisomers, wherein n is 3 and / or 4, and 0.1% to 30% by weight, preferably 2% to 25% by weight, of one or more streptococcalins represented by formula (I) or their stereoisomers, wherein n is 1 and / or 2.

[0190] Example 7. The composition as described in any one of Examples 1 to 6, wherein the weight ratio of component A to component B is 60000:1 to 1:1000, preferably 1000:1 to 1:1000, more preferably 100:1 to 1:100, even more preferably 40:1 to 1:40, and even more preferably about 4:1 to about 1:4.

[0191] Example 8. The composition of any one of Examples 1 to 7 further comprises an agriculturally acceptable carrier and / or formulation adjuvant and optionally a surfactant.

[0192] Example 9. A method for controlling or preventing plant pathogenic fungi on, in or on a plant or its propagation material, the method comprising applying a composition according to any one of Examples 1 to 8 to the plant, in or on its propagation material.

[0193] Example 10. The method as described in Example 9, wherein component A is applied in combination with component B at a ratio of 10 g ai / ha to 3000 g ai / ha to 0.5 g ai / ha to 2000 g ai / ha.

[0194] Example 11. The method as described in Example 9 or 10, wherein the plant pathogenic fungi are selected from the group consisting of: *Alternaria*, *Botrytis*, *Cercospora*, *Anthracis*, *Corynebacterium*, *Powdery mildew*, *Fusarium*, *Microcystis*, *Globosa*, *Hemileia*, *Hypericum*, *Cytozoa*, *Penicillium*, *Laminaria*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pyrrosia*, *Rhynchosporium*, *Syndrome*, *Ustilago*, *Ustilago*, *Ustilago*, and *Syndrome*, preferably wherein the plant pathogenic fungi are selected from the group consisting of: *Alternaria*, *Botrytis*, *Fusarium*, *Microcystis*, *Globosa*, and *Syndrome*.

[0195] Example 12. The method of any one of Examples 9 to 11, wherein the plant is selected from useful plants including: cereals, fruits and tree nuts, vegetables, field crops, oil crops, forage crops, forest plants, horticultural crops, floriculture, greenhouse and nursery plants, propagation materials, edible herbs and spices and herbs, preferably wherein the useful plant is selected from: fruits and tree nuts, vegetables, horticultural crops and floriculture.

[0196] Example 13. The method of any one of Examples 9 to 12, wherein the plant is a useful plant selected from the group consisting of: grapevines, strawberries, apples, cherries, peaches, nectarines, blueberries, climbing berries, tomatoes, potatoes, gourds, cucumbers, eggplants, lettuce, legumes, brassicas, peas, rapeseed, soybeans, sugar beets, sunflowers, rice, peanuts, coffee, ornamental plants and turfgrasses, or wherein the plant is a useful plant selected from the group consisting of: apples, apricots, cherries, raspberries, grapes, cucumbers, peanuts, tomatoes, strawberries, citrus and bananas.

[0197] Example 14. A coated plant propagation material, wherein the coating comprises a composition as described in any one of Examples 1 to 8.

[0198] Example 15. Use of the composition as a fungicide as described in any one of Examples 1 to 8, wherein the use is not for the treatment of a human or animal body by surgery or therapy.

Claims

1. A fungicidal composition comprising: (i) Component A, wherein component A comprises one or more streptococcalins or stereoisomers thereof represented by formula (I): (I)， Where n is an integer selected from 1 to 7; and (ii) Component B, wherein component B comprises a compound represented by formula (II) or a stereoisomer thereof: (II), Where R 1 Selected from CONH2 and H; Where R 2 R 4 R 6 and R 7 Each is independently selected from CH3 and H; Where R 3 Selected from OH and H; and Where R 5 Selected from CH2CH3 and CH3.

2. The composition according to claim 1, wherein, The component A comprises one or more streptococcalins or their stereoisomers represented by formula (I), wherein n is an integer selected from 1 to 4, preferably wherein n is 3 or 4.

3. The composition according to any one of claims 1 or 2, wherein, Component A comprises streptococcin or its stereoisomer represented by formula (I), wherein n is 1, 2, 3 and 4.

4. The composition according to any one of claims 1 to 3, wherein, Component B comprises the compound represented by formula (II) or its stereoisomer, wherein R 1 Selected from CONH2 and H;R 2 Selected from CH3 and H;R 3 It is H; R 4 It is CH3; R 5 Selected from CH2CH3 and CH3; R 6 It is H; and R 7 It is H; preferably, R is... 1 Selected from CONH2 and H;R 2 It is CH3; R 3 It is H; R 4 It is CH3; R 5 It is CH3; R 6 It is H; and R 7 It's H.

5. The composition according to any one of claims 1 to 4, wherein, Component B comprises methamidophos A or its stereoisomer, wherein methamidophos A is represented by formula (IIa): (IIa)。 6. The composition according to any one of claims 1 to 5, wherein, Component A comprises 10% to 99.9% by weight, preferably 20% to 99% by weight, of one or more streptococcalins represented by formula (I) or their stereoisomers, wherein n is 3 and / or 4; and 0.1% to 30% by weight, preferably 2% to 25% by weight, of one or more streptococcalins represented by formula (I) or their stereoisomers, wherein n is 1 and / or 2.

7. The composition according to any one of claims 1 to 6, wherein, The weight ratio of component A to component B is 60000:1 to 1:1000, preferably 1000:1 to 1:1000, more preferably 100:1 to 1:100, even more preferably 40:1 to 1:40, and even more preferably 4:1 to 1:

4.

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

9. A method for controlling or preventing plant pathogenic fungi on, in, or on the propagation material of a plant, the method comprising applying a composition according to any one of claims 1 to 8 to said plant, in, or on the propagation material of said plant.

10. The method according to claim 9, wherein, Component A is applied in combination with component B at a ratio of 10 g ai / ha to 3000 g ai / ha to 0.5 g ai / ha to 2000 g ai / ha.

11. The method according to claim 9 or 10, wherein, The plant pathogenic fungi are selected from the group consisting of: *Alternaria*, *Botrytis*, *Cercospora*, *Anthracis*, *Corynebacterium*, *Powdery mildew*, *Fusarium*, *Microcystis*, *Globosa*, *Helicobacter*, *Campozoa*, *Malus*, *Malus*, *Malus*, *Penicillium*, *Laminaria*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pseudomonas*, *Pyrrosia*, *Rhizoctonia*, *Rhizoctonia*, *Syndrome*, *Syndrome*, *Syndrome*, *Syndrome*, and *Syndrome*. Preferably, the plant pathogenic fungi are selected from the group consisting of: *Alternaria*, *Botrytis*, *Fusarium*, *Microcystis*, *Globosa*, and *Syndrome*.

12. The method according to any one of claims 9 to 11, wherein, The plants are selected from the following useful plants: cereals, fruits and tree nuts, vegetables, field crops, oil crops, forage crops, forest plants, horticultural crops, floriculture, greenhouse and nursery plants, edible herbs and spices and medicinal herbs, preferably wherein the useful plants are selected from: fruits and tree nuts, vegetables, horticultural crops and floriculture.

13. The method according to any one of claims 9 to 12, wherein, The plants mentioned are useful plants selected from the group consisting of: grapevines, strawberries, apples, cherries, peaches, nectarines, blueberries, climbing berries, tomatoes, potatoes, gourds, cucumbers, eggplants, lettuce, legumes, brassica, peas, rapeseed, soybeans, sugar beets, sunflowers, rice, peanuts, coffee, ornamental plants and turfgrasses, or wherein said plants are useful plants selected from the group consisting of: apples, apricots, cherries, raspberries, grapes, cucumbers, peanuts, tomatoes, strawberries, citrus fruits and bananas.

14. A coated plant propagation material, wherein the coating comprises the composition according to any one of claims 1 to 8.

15. Use of the composition according to any one of claims 1 to 8 as a fungicide, wherein, The intended use is not for the treatment of human or animal bodies through surgery or therapy.

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