CN119768055A - Fungicidal composition - Google Patents

Abstract

The present invention relates to a composition suitable for controlling diseases caused by plant pathogens, comprising pentocyclanil as component (A) and epoxiconazole as component (B), or agrochemically acceptable salts, stereoisomers, diastereomers, enantiomers and tautomers thereof.

Description

Fungicidal compositions

The present invention relates to novel fungicidal compositions, to their use in agriculture or horticulture for controlling diseases caused by plant pathogens, in particular phytopathogenic fungi, and to a method of controlling diseases on useful plants.

While many fungicidal compounds and compositions belonging to a variety of different chemical classes have been developed or are being developed for use as fungicides in crops of useful plants, crop tolerance and activity against specific phytopathogenic fungi in many respects does not always meet the needs of agricultural practices. Accordingly, there is a continuing need to find new compounds and compositions having excellent biological properties for controlling or preventing infestation of plants by phytopathogenic fungi. For example, compounds having greater biological activity, a favorable activity profile, increased safety, improved physicochemical properties, increased biodegradability. Or in addition, compositions having a broader spectrum of activity, improved crop tolerance, improved synergistic interaction or enhanced properties, or compositions that exhibit a faster onset or have longer lasting residual activity or are capable of reducing the number of and/or rate of application of compounds and compositions required for effective control of plant pathogens, thereby enabling beneficial tolerance management practices, reducing environmental impact and reducing operator exposure.

Some of these needs may be addressed using compositions comprising a mixture of different fungicidal compounds having different modes of action (e.g., by combining fungicides having different activity profiles).

Certain pyrazolyl-carboxamide derivatives are known from WO 2008/148570, WO 2010/063600, WO 2010/084078 and WO 2008/151828 to have biological activity against phytopathogenic fungi. On the other hand, the application of various fungicidal compounds of different chemical classes as plant fungicides in various cultivated plant crops is well known. However, crop tolerance and activity against phytopathogenic plant fungi do not always meet the needs of agricultural practices in many situations and aspects. To overcome this problem, some binary mixtures of pyrazolyl-carboxamides with certain fungicides are provided, for example in WO 2012/041874, WO 2015/049178 and WO 2017029177.

According to the present invention there is provided a composition suitable for controlling diseases caused by plant pathogens comprising as component (a) fluxapyroxad hydroxylamine or an agrochemically acceptable salt, stereoisomer, diastereomer, enantiomer and tautomer thereof, and as component (B) epoxiconazole or an agrochemically acceptable salt, stereoisomer, diastereomer, enantiomer and tautomer thereof.

Fluxapyroxad hydroxylamine, also known as 3- (difluoromethyl) -N-methoxy-1-methyl-N- [ 1-methyl-2- (2, 4, 6-trichlorophenyl) ethyl ] pyrazole-4-carboxamide, which can be known and prepared according to the description in, for example, WO 2010/067300.

Epoxiconazole is a triazole fungicide belonging to the class of demethylating inhibitors (FRAC classification G1), which can be known and prepared as described, for example, in EP 0196038. Compounds can be depicted by the following structural formula:

further according to the present invention there is provided a method of controlling diseases caused by plant pathogens on useful plants or on propagation material thereof, which method comprises applying to these useful plants, to the locus thereof or to propagation material thereof a composition as defined according to the present invention.

Further according to the present invention there is provided a composition suitable for controlling diseases caused by plant pathogens comprising as component (a) fluxapyroxad hydroxylamine and as component (B) epoxiconazole or an agrochemically acceptable salt, stereoisomer, diastereomer, enantiomer and tautomer thereof, further comprising an agronomically acceptable carrier and/or formulation aid and optionally a surfactant.

Further according to the present invention there is provided the use of a composition comprising component (a) and component (B) as fungicides. According to this particular aspect of the invention, the use may not include methods of treating the human or animal body by surgery or therapy.

Further according to the present invention there is provided a method of protecting a natural substance of plant and/or animal origin and/or processed forms thereof taken from the natural life cycle, which method comprises applying to said natural substance of plant and/or animal origin or processed forms thereof a combination of components (a) and (B) as defined according to the present invention.

It has been found that the use of epoxiconazole in combination with fluxapyroxad hydroxylamine surprisingly and substantially enhances the effectiveness of the latter against fungi and vice versa. Furthermore, the use of the compositions of the present invention is effective against a broader spectrum of such fungi than would be possible if the individual active ingredients were used alone.

The benefits provided by certain fungicidal mixture compositions according to the present invention may also include, inter alia, advantageous levels of biological activity for protecting plants against diseases caused by fungi or superior properties for use as agrochemical active ingredients (e.g. greater biological activity, advantageous activity profile, increased safety, improved physicochemical properties, or increased biodegradability).

In each case, the fluxapyroxad hydroxylamine and epoxiconazole are present in free form, in oxidized form, such as N-oxide, or in salt form (e.g., in agronomically useful salt form). The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing heteroaromatic compound. Albini and S.Pietra are described, for example, in the publication of Bokaraton (Boca Raton) CRC Press by A.Albini and S.Pietra under the name "Heterocholic N-oxides [ Heterocyclic N-oxides ]".

As used herein, the term "component (a)" is to be understood as fluxapyroxad hydroxylamine, or an agrochemically acceptable salt, N-oxide, diastereomer, enantiomer or tautomer thereof.

As used herein, the term "component (B)" is understood to mean epoxiconazole, or an agrochemically acceptable salt, N-oxide, diastereomer, enantiomer or tautomer thereof.

In general, the weight ratio of component (a) to component (B) is from 1000:1 to 1:1000, especially from 50:1 to 1:50, more especially at a ratio from 40:1 to 1:40, even more especially at a ratio from 20:1 to 1:20, even more especially still from 10:1 to 1:10, and very especially from 5:1 and 1:5. Ratios from 2:1 to 1:2 are given with particular preference, and ratios from 4:1 to 2:1 are particularly preferred. Preferred specific individual ratios include the following ratios ：1:1、5:1、5:2、5:3、5:4、4:1、4:2、4:3、3:1、3:2、2:1、1:5、2:5、3:5、4:5、1:4、2:4、3:4、1:3、2:3、1:2、1:600、1:300、1:150、1:100、1:50、1:40、1:35、1:20、2:35、4:35、1:10、1:75、2:75、4:75、1:6000、1:3000、1:1500、1:350、2:350、4:350、1:750、2:750 and 4:750.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is from 100:1 to 1:100.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is 50:1 to 1:50.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is from 25:1 to 1:25.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is from 10:1 to 1:10.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is from 9:1 to 1:9.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is from 5:1 to 1:5.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is 4:1 to 1:4.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is 3:1 to 1:3.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the present invention is 1.5:1.

In one embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is 1:1.

In a preferred embodiment, the weight ratio of fluxapyroxad hydroxylamine to epoxiconazole in the composition according to the invention is the following weight ratios 9:1, 5:1, 3:1, 1.5:1, 1:1, 1:3, 1:5 and 9:1.

In particular, the composition of fluxapyroxad hydroxylamine and epoxiconazole according to the invention can be used for controlling diseases caused by fusarium species and more particularly fusarium graminearum (Fusarium graminearum) and fusarium asiaticum (Fusarium asiasticum).

Further in accordance with the present invention, there is provided a method of controlling fusarium species and more particularly fusarium graminearum and fusarium asiaticum on useful plants, comprising applying to the useful plants, the locus thereof or propagation material thereof an effective amount of a composition comprising fluxapyroxad hydroxylamine and epoxiconazole.

It has been found that, surprisingly, certain weight ratios of component (a) to component (B) result in synergistic activity. Thus, another aspect of the invention is a composition wherein component (a) and component (B) are present in the composition in amounts that produce a synergistic effect. In a preferred embodiment, a composition is provided wherein component (a) and component (B) are present in synergistically effective amounts.

This synergistic activity is evident from the fact that the fungicidal activity of the composition comprising component (A) and component (B) is greater than the sum of the fungicidal activities of component (A) and component (B). This synergistic activity expands the range of action of component (A) and component (B) in two ways. First, the application rate of component (a) and component (B) is reduced, however the effect remains equally good, which means that the active ingredient mixture achieves a high degree of plant pathogen control even if both individual components have become completely ineffective in such a low application rate range.

There is a synergistic effect as long as the effect of the combination of active ingredients is greater than the sum of the effects of the individual components. For a given combination of active ingredients, the expected E obeys the so-called Colbi (COLBY) formula and can be calculated as follows (COLBY, s.r. "Calculating SYNERGISTIC AND antagonistic responses of herbicide combination [ calculate synergistic and antagonistic responses of herbicide combinations ]".weeds [ Weeds ], volume 15, pages 20-22; 1967):

ppm = milligrams of active ingredient (=a.i.) per liter of spray mixture

X =% action on active ingredient (a) using p ppm of active ingredient

Y =% action on active ingredient (B) using q ppm of active ingredient.

The expected effect of (additive) active ingredients (A) + (B) is, according to the Columby, with p+q ppm of active ingredient

If the actual observed effect (O) is greater than the expected effect (E), then the combined effect is superadditive, i.e., there is a synergistic effect. Mathematically, the synergy corresponds to a positive value of the difference of (O-E). In the case of purely complementary added actives (expected activity), the difference (O-E) is zero. Negative values of the difference (O-E) indicate a loss of activity compared to the expected activity.

Another method of assessing synergistic effects can be assessed by co-toxicity coefficient (CTC) according to Sun-YP method (Yun-Pei,Sun."Toxicity Index-An Improved Method of Comparing the Relative Toxicity of Insecticides.[ toxicity index, a method of comparing improvements in relative toxicity of insecticides, "Journal of Economic Entomology J.Economy 1 (1950): 45-53. CTC values less than 80 indicate antagonistic effects, CTC values of 80-120 indicate additive effects, and CTC values greater than or equal to 120 indicate synergistic effects.

CTC=(ATI/TTI)*100

Component a represents the standard active ingredient (in this case component a is fluxapyroxad hydroxylamine) and component B represents the component to be mixed with the standard active ingredient (in this case component B is epoxiconazole).

ATI (measured toxicity index of mixture) = (EC ₅₀ of standard AI/EC ₅₀ of mixture) ×100

TTI (theoretical toxicity index of mixture) = (TI _A*P_A+TI_B*P_B) ×100

TI _A (toxicity index of component A) =EC ₅₀ of component A/EC of component A ₅₀

P _A percentage of component A in the mixture

TI _B (toxicity index of component B) =EC ₅₀ of component A/EC of component B ₅₀

P _B percentage of component B in the mixture

Another method of assessing the synergistic effect is by the Wadley method, which is based on EC50 values (the effective concentration required to obtain 50% effect), typically derived from linear or nonlinear regression of the dose-response experiment, thereby avoiding errors due to the nonlinear nature of the dose-response curve.

In the Wadley method, E (expected EC 50) can be expressed as:

where a and B are the weight ratios of compounds a and B in the mixture (EC 50 values), and EC50 (Ao) and EC50 (Bo) are experimentally observed (o) EC50 values obtained using the dose response curves of the individual compounds. The synergistic ratio (R) is calculated as the ratio between the expected and observed values, EC50 a+b (e)/EC 50 a+b (o).

If A+B (observed) > A+B (expected), a synergistic effect (R > 1) is exhibited. If r=1, the effect is additive, and if R <1, antagonism is exhibited.

However, the compositions according to the invention may have further unexpectedly advantageous properties in addition to the actual synergistic effect with respect to fungicidal activity. Examples of such advantageous properties that may be mentioned are more favourable degradability, improved toxicological and/or ecotoxicological behaviour, or improved characteristics of the useful plants, including emergence, crop yield, more developed root system, increased tillering, increased plant height, larger leaves, fewer basal leaves death, stronger tillers, greener leaves colour, less fertilizer needed, less seeds needed, more tillers, earlier flowering, earlier grain maturation, less lodging (lodging) of the plants, enhanced shoot growth, improved plant vigor and early germination.

Some compositions according to the invention have a systemic effect and can be used as fungicides for foliar, soil and seed treatments.

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

The composition according to the invention can be applied to phytopathogenic microorganisms, to useful plants threatened by microbial attack, to their locus, to their propagation material, to stored goods or technical materials.

The composition according to the invention can be applied before or after the useful plants, their propagation material, stored goods or technical material are infected with the microorganism.

Another aspect of the invention is a method of controlling diseases caused by plant pathogens on useful plants or on propagation material thereof, which method comprises applying to these useful plants, to the locus thereof or to propagation material thereof a composition according to the invention. Preferably a method comprising applying a composition according to the invention to a useful plant or locus thereof, more preferably to a useful plant. Further preferred is a method comprising applying the composition according to the invention to propagation material of useful plants.

Throughout this document, the expression "composition" means a different mixture or combination of components (a) and (B), for example in the form of a single "ready-to-use" admixture, in the form of a combined spray mixture (consisting of individual formulations of the single active ingredient components) (e.g. "tank mix"), and in the use of a combination of the single active ingredients (when applied in a sequential manner, i.e. one after a reasonably short period of time of the other, such as hours or days). The order in which components (a) and (B) are administered is not critical to the practice of the present invention.

These active ingredient combinations are effective against harmful microorganisms (e.g. microorganisms) causing phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria.

The compositions are effective in controlling a broad spectrum of plant diseases, such as foliar pathogens of ornamental plants, turf, vegetables, fields, cereals, and fruit crops.

These pathogens may include oomycetes, including phytophthora such as those caused by phytophthora capsici (Phytophthora capsici), phytophthora infestans (Phytophthora infestans), phytophthora sojae (Phytophthora sojae), phytophthora strawberry (Phytophthora fragariae), phytophthora nicotianae (Phytophthora nicotianae), phytophthora camphorata (Phytophthora cinnamomi), phytophthora citrus (Phytophthora citricola), phytophthora citrus (Phytophthora citrophthora) and pythium potato (Phytophthora erythroseptica), pythium diseases such as those caused by Pythium aphanidermatum (Pythium aphanidermatum), jiang Xiong (Pythium arrhenomanes), pythium gracile (Pythium graminicola), pythium irregulare (Pythium irregulare) and Pythium ultimum (Pythium ultimum), diseases caused by downy mildew (Peronosporale) such as downy mildew (Peronosporale) of the order Allium, downy mildew (Peronosporale), grape downy mildew (Peronosporale), sunflower downy mildew (Peronosporale), white rust (Peronosporale), rice downy mildew (Peronosporale) and lactucae (Bremia) and others such as those caused by Pythium graciliates (Peronosporale), phaffia, and Phaffia of the fungus (Peronosporale;

Ascomycetes, including spot, leaf spot, blast or epidemic disease and/or rot, such as those caused by Gramineae, e.g., alternaria alliacea (Stemphylium solani), narcissus tainanensis (Stagonospora tainanensis), cyclosporium oleae, alternaria corn (Setosphaeria turcica), equisqualis (Pyrenochaeta lycoperisici), alternaria alternata, phoma solid (Phoma destructiva), cytospora fuliginea, Wheat She An coccidioides (Phaeosphaeria herpotrichoides), gao Manni Cryptococcus palmatus (Phaeocryptocus gaeumannii), snake spore intracavity (Ophiosphaerella graminicola), wheat take-all (Ophiobolus graminis), cruciferae globus (Leptosphaeria maculans), soft rot (Hendersonia creberrima), needle-leaved blight (Helminthosporium triticirepentis), Corn maculosis (Setosphaeria turcica), soybean inner navel vermicularia (DRECHSLERA GLYCINES), gummy stem blight (DIDYMELLA BRYONIAE), olive peacock spot pathogen (Cycloconium oleagineum), corynespora polymorpha (Corynespora cassiicola), alternaria graminea, dragon fruit black spot pathogen (Bipolaris cactivora), apple scab, nux vomica, oat straw nuclear cavity bacteria (Pyrenophora tritici-repentis), Alternaria alternata, alternaria brassicae (ALTERNARIA BRASSICICOLA), alternaria solani and Alternaria tomato (ALTERNARIA TOMATOPHILA), and coal (Capnodiales) from the order of Celloides farinose, cephalosporium glumae, cephalosporium sojae (Septoria glycines), cercospora arachidae (Cercospora arachidicola), alternaria sojae, alternaria zeae, alternaria shepherdostana (Cercosporella capsellae) and Triticum She Baimei (Cercosporella herpotrichoides), Peach scab germ (Cladosporium carpophilum), cladosporium cucumerinum (Cladosporium effusum), brown spore mildew (Passalora fulva), aculeatum (Cladosporium oxysporum), bursaphelema pinnata (Dothistroma septosporum), brown spot germ (Isariopsis clavispora), black streak germ of banana, globus hystericus (Mycosphaerella graminicola), and black streak germ, The preparation method comprises the following steps of performing fermentation on Brevibacterium roseum (Mycovellosiella koepkeii), aureobasidium toruloides (Phaeoisariopsis bataticola), bremia viticola (Pseudocercospora vitis), leptosphaeria gracilis, leptosphaeria exigua (Ramularia collo-cygni); the order of Gekko Swinhonis, such as wheat take-all germ, rice blast germ (Magnaporthe grisea), pyricularia oryzae, and the order of Gekko Swinhonis, such as Hazelnut east fusarium wilt, A Pi Aonuo Morgania Erla Ban Da (Apiognomonia errabunda), aschersonia phoenix (Cytospora platani), north America phoma, curvularia catarrhalis (Discula destructiva), japanese strawberry (Gnomonia fructicola), ulmaria vinifera (Melanconium juglandinum), ulmaria Juglandis (Phomopsis viticola), ulmaria Juglandis (Sirococcus clavigignenti-juglandacearum), The fungus Cyathea fumartensii (Tubakia dryina), the species Eupatorium (DICARPELLA spp.), and the species Malus pumila rot (Valsa ceratosperma); and others, such as Alinocelim glabra Nisin (Actinothyrium graminis), alaska, aspergillus flavus, aspergillus fumigatus, aspergillus nidulans, phlebsiella papaya (Blumeriella jaapii), candida species, soot bacteria (Capnodium ramosum), The species of genus Sphaeroides Luo Suoka (Cephaloascus spp.), rhizoctonia cerealis (Cephalosporium gramineum), coracoid (Ceratocystis paradoxa), chaetomium species, pachyrhizus (Hymenoscyphus pseudoalbidus), coptosporum species, leptosphaeria prunifolia (Cylindrosporium padi), geotrichum (Diplocarpon malae), phanerochaete brassicae (Drepanopeziza campestris), chaetomium brassicae (Drepanopeziza campestris), The preparation method comprises the steps of elsino (Elsinoe ampelina), epicoccus nigrum, epidermophyton species, grape top blight, geotrichum candidum, gramineae housing Gibellina cerealis, botrytis cinerea (Gloeocercospora sorghi), botrytis cinerea (Gloeodes pomigena), alternaria dormitoides (Gloeosporium perennans), endophyte of Porphyra cinerea (Gloeotinia temulenta), pityrosporum catheter (Griphospaeria corticola), cytophyte of Porphyra, cytophyton graminium, cytophyton, and Cytophyton, Li Niqiu Aureobasidium (Kabatiella lini), myxospora microsporum (Leptographium microsporum), calnocystis crassifolium (Leptosphaerulinia crassiasca), disrupted speckle Shell (Lophodermium seditiosum), gu Pan Mortierella gracilis (Marssonina graminicola), rhizoctonia cerealis (Microdochium nivale), brown rot of America type Nuclear fruit (Monilinia fructicola), and, Rice cloud disease (Monographella albescens), melon black spot root rot fungus (Monosporascus cannonballus), rhizoctonia species (Naemacyclus spp.), new fusarium ulmarium (Ophiostoma novo-ulmi), paracoccidiosis brasiliensis (Paracoccidioides brasiliensis), penicillium expansum (Penicillium expansum), mucor rhodochrous (Pestalotia rhododendri), and, The species of the genus Eumycota (Petriellidium spp.), the species of the genus Pantoea (Pezicula spp.), the species brown rot of the soybean (Phialophora gregata), the species black nevus rensis (Phyllachora pomigena), the species Oenobasidium omum (Phymatotrichum omnivora), the species Leptosphaeria longifolia (Physalospora abdita), the species Aschersonia tabaci (Plectosporium tabacinum), the species Phytophthora potato (Polyscytalum pustulans), the species Phytophthora sojae (Amersham) and the species Phytophthora sojae, Pseudosclerotium alfalfa (Pseudopeziza medicaginis), sclerotinia brassicae (Pyrenopeziza brassicae), aschersonia sorghum (Ramulispora sorghi), douglaia tsugae (Rhabdocline pseudotsugae), pholiota nameko (Rhynchosporium secalis), cladosporium cucumerinum (Sacrocladium oryzae), podophyllum species (Scedosporium spp.), and the like, Sclerotinia sclerotiorum (Schizothyrium pomi), sclerotinia sclerotiorum (Sclerotinia sclerotiorum), sclerotinia sclerotiorum (Sclerotinia minor), sclerotinia species (Sclerotium spp.), ramaria cinerea (Typhula ishikariensis), myxoplasma maritima (Seimatosporium mariae), alternaria arborescens (Lepteutypa cupressi), alternaria purpurea (Septocyta ruborum), alternaria lunata (Septocyta ruborum), Avocado scab germ (Sphaceloma perseae), alfalfa branch and stem edge shell (Sporonema phacidioides), millennium jujube eye spot germ (Stigmina palmivora), tagetes lendi (Tapesia yallundae), pear outer cyst germ (Taphrina bullata), cotton black root rot germ (Thielviopsis basicola), tricks Li Yafu Lu Diji na (Trichoseptoria fructigena), The fly feces germ (Zygophiala jamaicensis), powdery mildew, such as from the order of Erysiphe (ERYSIPHALES) such as Erysiphe graminis (Blumeria graminis), erysiphe graminis (Erysiphe polygoni), leptospira viticola (Uncinula necator), erysiphe cucumeris (Sphaerotheca fuligena), leptospira graminis (Podosphaera leucotricha), erysiphe macerans (Podospaera macularis), Powdery mildew (Golovinomyces cichoracearum), leveillula taurica (Leveillula taurica), leveillula taurica (Microsphaera diffusa), alternaria gossypii (Oidiopsis gossypii), corylus filbertensis (PHYLLACTINIA GUTTATA) and Alternaria sanguinea (Oidium arachidis), mildew, such as those caused by Phellinus viticola (Botryosphaeriales) such as Alternaria parvula (Dothiorella aromatica), alternaria pinnatis (5334), Saccharopolyspora crassa (Diplodia seriata), bryonia bivaliae (Guignardia bidwellii), botrytis cinerea, succinum (Botryotinia allii), succinum falcatum (Botryotinia fabae), clostridium amygdalium (Fusicoccum amygdali), pyricularia longan (Lasiodiplodia theobromae), phoma tea (Macrophoma theicola), rhizopus oryzae (Macrophoma theicola), Anthracnose, such as those caused by Sphaeromyces phaseoli, cucurbitaceae, phyllotreta (Phyllosticta cucurbitacearum), anthrax, e.g., by small Cong Ke mesh (Glommerelales) such as colletotrichum gloeosporioides (Colletotrichum gloeosporioides), anthrax melo (Colletotrichum lagenarium), colletotrichum cotton (Colletotrichum gossypii), periclase (Glomerella cingulata), colletotrichum gloeosporioides, And anthrax graminearum (Colletotrichum graminicola), and fusarium or epidemic diseases, such as those caused by sarcoplasmales, such as Acremonium straight, purple ergobacterium, fusarium asiaticum, fusarium xanthophyllum, fusarium graminearum, fusarium soyabean sudden death syndrome (Fusarium virguliforme), fusarium oxysporum, fusarium mucilaginosum, fusarium gulum (Fusarium oxysporum f.sp.circumference), fusarium nivalem (GERLACHIA NIVALE), Gibberella, gibberella zeae, leptospora species, verrucaria verrucosa, lambda Lei Congchi shellac (Nectria ramulariae), trichoderma viride, trichothecene rubrum, and those caused by avocado root rot pathogen (Verticillium theobromae);

Basidiomycetes, including smut, such as those caused by ustilaginoidea, e.g., ustilago oryzae (Ustilaginoidea virens), barley smut (Ustilago nuda), wheat smut (Ustilago tritici), corn smut (Ustilago zeae), rust, e.g., by rust, e.g., rust fig (Cerotelium fici), rust spruce (Chrysomyxa arctostaphyli), sweet potato sheath rust (Coleosporium ipomoeae), Alternaria caffei (Hemileia vastatrix), alternaria arachnoidis (Puccinia arachidis), alternaria southwest (Puccinia cacabata), alternaria graminea (Puccinia graminis), alternaria secoisolaris (Puccinia recondita), alternaria sorghum (Puccinia sorghi), alternaria barley (Puccinia hordei), alternaria bardansis (Puccinia striiformis f.sp.Hordei), Leptospira tritici (Puccinia striiformis f.sp.Secalis), leptospira filberti (Pucciniastrum coryli), or Leptospira farinacea (Cronartium ribicola), leptospira sabinensis (Gymnosporangium juniperi-viginianae), leptospira populi (Melampsora medusae), leptospira meyenii (Phakopsora pachyrhizi), leptospira meyenii (Pucciniastrum coryli), Those caused by rust (Phragmidium mucronatum), rust (Physopella ampelosidis), rust (Tranzschelia discolor), and rust (Uromyces viciae-fabae) of monospore horsebean; and other rot and disease, such as those caused by Cryptococcus species, alternaria species (Exobasidium vexans), inonodammar microcosmia (Marasmiellus inoderma), The species of the genus Pleurotus, the species of the genus head smut (Sphacelotheca reiliana), the species of the genus Rabdosia (Typhula ishikariensis), the species of the species Leuconostoc nikoense (Urocystis agropyri), the species of the species Pycnospora spinosa (Itersonilia perplexans), the species Neisseria suis Fu Gejun (Corticiuminvisum), the species Phanerochaete licheniformis (LAETISARIA FUCIFORMIS), the species Phanerochaete chrysosporium (WAITEA CIRCINATA), the species Phanerochaete chrysosporium, Those caused by rhizoctonia solani, leather melon (Thanetephorus cucurmeris), black powder dahlia (Entyloma dahliae), black powder microsporum (Entylomella microspora), black powder grass of marsh (Neovossia moliniae) and black powder wheat fishy smell (TILLETIA CARIES);

The class Rhizopus, such as Arthropoda zeae (Physoderma maydis);

Mucorales, such as cucurbitaceae (Choanephora cucurbitarum); rhizopus species (Mucor spp.);

along with diseases caused by other species and genera closely related to those listed above.

In addition to their fungicidal activity, these compositions may also have activity against bacteria such as erwinia amylovora, erwinia soft rot (Erwinia caratovora), xanthomonas campestris, pseudomonas syringae, potato scab (Strptomyces scabies) and other related species, along with certain protozoa.

The composition according to the invention is particularly effective against phytopathogenic fungi belonging to the class of the sub-classes Phycomycetes (for example, cercospora, leptosphaera); basidiomycetes (e.g., camelina (hermineia), rhizoctonia, phaeomyces, puccinia, tibetan), halibut (also known as halibut, e.g., botrytis, vermicularia, corallospora, fusarium, septoria, cercospora, alternaria, pyriform and cercospora), oomycetes (e.g., phytophthora, downy mildew, pseudoperonospora, white rust, aureobasidium, pythium, pseudodactylum, monoaxial mold).

Useful plant crops in which the compositions according to the invention can be used include perennial and annual crops, such as berry plants, for example blackberry, blueberry, cranberry, raspberry and strawberry; grains such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, such as cotton, flax, hemp, jute, and sisal; field crops, such as sugar beet and fodder beet, coffee beans, hops, mustard, rape (canola), poppy, sugarcane, sunflower, tea and tobacco, fruit trees, such as apples, apricots, avocados, bananas, cherries, oranges, nectarines, peaches, pears and plums, grasses, such as bermuda grass, blueberries, bunte grass, centipeda grass, cow-hair grass, ryegrass, holy-grass and zoysia, herbs, such as basil, borage, chives, coriander, lavender, pubescent angelica, peppermint, oregano, parsley, rosemary, sage and thyme, beans, such as beans, lentils, peas and soybeans, nuts, such as almonds, cashew nuts, groundnuts, nuts, such as almonds, pistachios, such as flowers, shrubs and trees, other trees, such as cocoa, coco, olive trees, and rubber trees, such as vegetables, such as potatoes, lettuce, potatoes, lettuce, herbs, cucurbits, cucumbers, cucurbits, melons, cucumbers, tence and thymes.

Crops are understood to be those which occur naturally, are obtained by conventional breeding methods or are obtained by genetic engineering. They include crops with so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

Crops are understood to also include those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides like ALS-, EPSPS-, GS-, HPPD-and PPO-inhibitors. Examples of crops which have been rendered tolerant to imidazolinones (e.g. imazethapyr) by conventional breeding methods areCanola in summer. Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include, for example, glyphosate and glufosinate resistant maize varieties that are under the trade nameAndAre commercially available.

Crops are also understood as being those crops which are naturally or have been rendered resistant to harmful insects. This includes plants transformed by using recombinant DNA techniques, for example, to synthesize one or more selectively acting toxins, as are known from, for example, toxin-producing bacteria. Examples of toxins that may be expressed include d-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of nematode parasitic bacteria, and toxins produced by scorpions, arachnids, wasps, and fungi.

Examples of crops that have been modified to express Bacillus thuringiensis toxins are Bt mail(First just seed company (SYNGENTA SEEDS)). Examples of crops comprising more than one gene encoding insecticidal resistance and thereby expressing more than one toxin are(Seed of first-come). The crop or seed material thereof may also be resistant to multiple types of pests (so-called superposition transgenic events when produced by genetic modification). For example, plants may have the ability to express insecticidal proteins while being tolerant to herbicides, e.g(Tao Shiyi agricultural Co (Dow AgroSciences), pioneer stock International Inc. (Pioneer Hi-Bred International)).

According to the invention, "useful plants" typically include plant species such as grape vine, cereal such as wheat, barley, rye or oat, sugar beet such as sugar beet or fodder beet, fruit such as pear, stone fruit or soft fruit, for example apple, pear, plum, peach, almond, cherry, strawberry, raspberry or blackberry, legumes such as beans, lentils, peas or soybeans, oil crops such as rape, mustard, poppy, olive, sunflower, coconut, castor oil plants, cocoa beans or groundnut, cucumber plants such as pumpkin, cucumber or melon, fiber plants such as cotton, flax, hemp or jute, citrus fruits such as orange, lemon, grapefruit or citrus, vegetables such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, melons or capsicum, such as avocado, cinnamon or camphor, maize, tobacco, nuts, sugar cane, tea, this plant, banana, vine, durian, turf, natural plants such as pine, or natural flowers such as pine, or pine. This list is not meant to be limiting in any way.

The term "useful plants" is to be understood as also including useful plants which have been rendered tolerant to herbicides like bromoxynil or herbicides like e.g. HPPD inhibitors, ALS inhibitors (e.g. primisulfuron, prosulfuron and trifloxysulfuron), EPSPS (5-enol-pyruvyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors due to conventional breeding or genetic engineering methods. Examples of crops which have been rendered imidazolinone (e.g. imazethapyr) tolerant by conventional breeding methods (mutagenesis) areSummer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties, which are under the trade nameAndAre commercially available.

The term "useful plant" is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA technology that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as those from Bacillus cereus (Bacillus cereus) or Bacillus thuringiensis (Bacillus popliae); or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, e.g., cryIA (b), cryIA (c), cryIF (a 2), cryIIA (b), cryIIIA, cryIIIB (b 1), or Cry9c, or Vegetative Insecticidal Proteins (VIP), e.g., VIP1, VIP2, VIP3, or VIP3A; or nematicidal proteins of nematophytic bacteria, for example, the Photorhabdus species (Photorhabdus spp.) or the Xenorhabdus species (Xenorhabdus spp.), such as, for example, the light-emitting bacteria (Photorhabdus luminescens), the pathogenic bacteria nematophila (Xenorhabdus nematophilus), toxins produced by animals, such as, for example, scorpions, spider toxins, bee toxins and other insect-specific neurotoxins, toxins produced by fungi, such as, for example, streptomycins, plant lectins (lecins), such as, for example, pea lectins, barley lectins or snowflake lectins, lectins (agglutinin), protease inhibitors, such as, for example, trypsin inhibitors, serine protease inhibitors, potato glycoproteins, cystatin, papain inhibitors, ribosome-inactivating proteins (RIP), such as, for example, ricin, maize-RIP, abrin, luffa seed proteins, saporin or heterologous mycoproteins, steroid metabolizing enzymes, such as, for example, 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl transferase, cholesterol oxidase, ecdysone, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

Within the context of the present invention, delta-endotoxins (e.g. CryIA (b), cryIA (c), cryIF (a 2), cryIIA (b), cryIIIA, cryIIIB (b 1) or Cry9 c) or Vegetative Insecticidal Proteins (VIP) (e.g. VIP1, VIP2, VIP3 or VIP 3A) are understood to obviously also include mixed toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by a new combination of different domains of those proteins (see, e.g., WO 02/15701). An example of a truncated toxin is truncated CryIA (b), which is expressed in Bt11 maize from seed of first-reach (SYNGENTA SEED SAS) as described below. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, protease recognition sequences that are not naturally occurring are preferably inserted into the toxin, such as, for example, in the case of CryIIIA055, cathepsin-D-recognition sequences are inserted into the CryIIIA toxin (see WO 03/018810).

Examples of such toxins or transgenic 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.

Methods for preparing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. 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.

Toxins included in transgenic plants render the plants tolerant to harmful insects. Such insects may be present in any insect taxa, but are particularly common in beetles (coleoptera), diptera insects (diptera), and moths (lepidoptera).

Transgenic plants comprising 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: (maize variety, cryIA (b) toxin expression); YIELDGARD (Maize variety, cryIIIB (b 1) toxin expressed); YIELDGARD(Maize variety, expressing CryIA (b) and CryIIIB (b 1) toxins); (maize variety, expressing Cry9 (c) toxin); (maize variety, enzyme phosphinothricin N-acetyltransferase (PAT) expressing CryIF (a 2) toxin and obtaining tolerance to the herbicide phosphinothricin ammonium salt)); (NuCOTN) (Cotton variety, cryIA (c) toxin expressed); bollgard(Cotton variety, expressing CryIA (c) toxins); (cotton varieties expressing CryIA (c) and CryIIA (b) toxins); (cotton variety, expressing VIP toxin); (potato variety, expressing CryIIIA toxin); And

Further examples of such transgenic crops are:

Bt11 maize from the seed company, santa Classification, huo Bite (CHEMIN DE L' Hobit) 27, F-31 790 st Su Weier (St. Sauveur), france accession number C/FR/96/05/10. Genetically modified maize (Zea mays), has rendered resistant to attack by european corn borers (Ostrinia nubilalis) and cnaphalocrocis medinalis (Sesamia nonagrioides)) by transgenic expression of truncated CryIA (b) toxins. Bt11 maize also transgenically expresses PAT enzymes to obtain tolerance to the herbicide glufosinate ammonium.

Bt176 maize from seed of first come, huo Bite, line 27, F-31 790, san Su Weier, france accession number C/FR/96/05/10. Genetically modified maize has been rendered resistant to attack by european corn borers (corn borers and cnaphalocrocis medinalis) by transgenic expression of the CryIA (b) toxin. Bt176 maize also transgenically expresses PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.

MIR604 corn from seed of Fangda, huo Bite, line 27, F-31 790 san Su Weier, france accession number C/FR/96/05/10. The modified CryIIIA toxins have been rendered insect resistant by transgenic expression. The toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

MON 863 maize from Monsanto Europe S.A.), 270-272 Teflon (Avenue DE Tervuren), B-1150 Brussels, belgium, accession number C/DE/02/9.MON 863 expresses a CryIIIB (b 1) toxin and is resistant to certain coleopteran insects.

IPC 531 cotton from Mengshan European company, 270-272 Teflon, B-1150 Brussels, belgium, accession number C/ES/96/02.

6.1507 Maize from pioneer overseas company (Pioneer Overseas Corporation), the university of Tedesco, avenue Tedessco, 7B-1160 Brussell, belgium, accession number C/NL/00/10. Genetically modified maize, expressing the protein Cry1F to obtain resistance to certain lepidopteran insects, and PAT protein to obtain tolerance to the herbicide glufosinate ammonium.

NK603×MON 810 maize from Mengshan Du European company 270-272 Teflon, B-1150 Brussels, belgium under accession number C/GB/02/M3/03. By crossing the genetically modified varieties NK603 and MON 810, it is made up of a conventionally bred hybrid maize variety. NK 603X MON 810 maize transgenes express protein CP4 EPSPS obtained from Agrobacterium species (Agrobacterium sp.) strain CP4 conferring herbicide toleranceTolerance to glyphosate and also CryIA (b) toxins obtained from Bacillus thuringiensis subspecies kurst (Bacillus thuringiensis subsp. Kurstaki) to make them resistant to certain lepidopterans, including European corn borers.

Transgenic crops of insect-resistant plants are also described in BATS (biosafety and sustainable development center (Zentrum f u r Biosicherheit und Nachhaltigkeit), BATS center (Zentrum BATS), class Cui She (CLARASTRASSE) 13,4058 Basel (Basel), switzerland) report 2003 (http:// BATS. Ch).

The term "useful plant" is understood to also include useful plants which have been transformed in such a way by using recombinant DNA techniques that they are capable of synthesizing selectively acting antipathogenic substances, such as, for example, the so-called "disease-associated proteins" (PRP, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. Methods of producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

The anti-pathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium channels and calcium channels, for example viral KP1, KP4 or KP6 toxins, stilbene synthase, bibenzyl synthase, chitinase, glucanase, so-called "disease-associated proteins" (PRP; see, for example, EP-A-0 392 225), anti-pathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see, for example, WO 95/33818) or protein or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO 03/000906).

Useful plants of high interest in the present invention are cereals, soybeans, rice, canola, pome, stone fruits, peanuts, coffee, tea, strawberries, turf, vines and vegetables such as tomatoes, potatoes, melons and lettuce.

The term "locus" of a useful plant as used herein is intended to include the place where the useful plant grows, where the plant propagation material of the useful plant is sown or where the plant propagation material of the useful plant is to be placed in the soil. An example of such a locus is a field on which crop plants are grown.

The term "plant propagation material" is understood to mean the reproductive parts of the plant, such as seeds, which parts can be used for propagation of the plant, as well as the vegetative materials, such as cuttings or tubers (e.g. potatoes). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants to be transplanted after germination from the soil or after emergence of seedlings can also be mentioned. These young plants may be protected prior to transplanting by treatment, either entirely or partially, via dipping. Preferably, "plant propagation material" is understood to mean seeds.

A further aspect of the invention is a method of protecting a plant-and/or animal-derived natural substance and/or processed form thereof, taken from a natural life cycle, from fungal attack, the method comprising applying to said plant-and/or animal-derived natural substance or processed form thereof a combination of components (a) and (B).

According to the present invention, the term "plant-derived natural substance taken from the natural life cycle" refers to a plant or part thereof harvested from the natural life cycle and in the form of fresh harvest. Examples of natural substances of such plant origin are stems, leaves, tubers, seeds, fruits or grains. According to the invention, the term "processed form of a natural substance of plant origin" is understood to mean a form of a natural substance of plant origin which improves the result of the processing. Such improved processing may be used to convert natural substances of plant origin into a more storable form of such substances (store goods). Examples of such improved processes are pre-drying, wetting, crushing, comminuting, grinding, compressing or calcining. Also falling under the definition of the processed form of natural substances of vegetable origin are wood, whether in the form of logs, such as building timber, transmission towers and fences, or in the form of manufactured products, such as furniture or objects made from wood.

According to the present invention, the term "natural substances of animal origin and/or processed forms thereof taken from the natural life cycle" is understood to mean materials of animal origin, such as skins, hides, leather, furs, hair and the like, and not materials present on the body surface of living animals. Thus, the present invention does not extend to a method of treating a living animal.

The combination according to the invention may prevent adverse effects such as spoilage, discoloration or mildew.

A preferred embodiment is a method of protecting natural substances from fungal attack, taken from natural life cycle plant sources and/or processed forms thereof, which method comprises applying to said plant and/or animal source natural substances or processed forms thereof a synergistically effective amount of a combination of components (a) and (B).

Another preferred embodiment is a method of protecting fruits (preferably pomes, stone fruits, berries and citrus fruits) and/or processed forms thereof taken from the natural life cycle, which method comprises applying to said fruits and/or processed forms thereof a synergistically effective amount of a combination of components (a) and (B).

The combinations of the invention can also be used in the field of protecting industrial materials from fungal attack. According to the present invention, the term "industrial material" means a non-living material prepared for industrial use. For example, industrial materials intended to protect them from fungal attack may be gums, slurries (sizes), papers, boards, textiles, carpets, leather, wood, construction, paint, plastic items, cooling lubricants, aqueous hydraulic fluids, and other materials that can be infested or decomposed by microorganisms. Cooling and heating systems, ventilation and air conditioning systems, and parts of the production plant (e.g. cooling water lines) which can be damaged by the proliferation of microorganisms can also be mentioned among the materials to be protected. The combination according to the invention may prevent adverse effects such as spoilage, discoloration or mildew.

The combinations of the invention can also be used in the field of protection of technical materials against fungal attack. According to the present invention, the term "technical material" includes paper, carpets, buildings, cooling and heating systems, ventilation and air conditioning systems, etc. The combination according to the invention may prevent adverse effects such as spoilage, discoloration or mildew.

The combination according to the invention is particularly effective against powdery mildew, rust, leaf spot species, early blight and moulds, especially against septoria, puccinia, powdery mildew, sclerotium and tagatose (Tapesia) in cereals, layer rust in soybeans, camelina in coffee, polycytidea in roses, alternaria in potatoes, tomatoes and melons, sclerotinia in turf, vegetables, sunflower and rape, black rot, red flame, powdery mildew, gray mold and gummy rot in vine plants, gray botrytis in fruits, streptococci (monilia spp.) in fruits and penicillium in fruits.

Furthermore, the combination according to the invention is particularly effective against seed-borne (seedborne) and soil-borne diseases, such as Alternaria species, aschersonia species, botrytis cinerea, cercospora species, erysiphe, alternaria species, anthrax species, fusarium species (Epicoccum spp.), fusarium graminearum, fusarium moniliforme (Fusarium moniliforme), fusarium oxysporum, fusarium layering (Fusarium proliferatum), fusarium solani (Fusarium solani), fusarium mucilaginosa, fusarium graminearum,Graminis, helminthiosporium spp, trichoderma, phomopsis, sclerotium species, wheat-like sclerotium (Pyrenophora graminea), pyriform, rhizoctonia cerealis (Rhizoctonia cerealis), sclerotium species, septoria species, silk-shaft black powder, stinking-fish black powder species (Tilletia spp), sarcosporium (Typhula incarnata), cryptosporidium, melanomyces species (Ustilago spp) or Verticillium spp), in particular against pathogens of cereals, such as wheat, barley, rye or oats, maize, rice, cotton, soybeans, turf, sugar beet, oilseed rape, potatoes, legume crops (pulse crop) such as peas, lentils or chickpea, and sunflower.

Furthermore, the combination according to the invention is particularly effective against post-harvest diseases such as Botrytis cinerea, banana anthracis (Colletotrichum musae), curvularia lunata, fusarium seminulum (Fusarium semitecum), geotrichum candidum, mucor miehei, rhizoctonia solani, mucor amylovora (Mucor piriformis), penicillium italicum (Penicilium italicum), penicillium exsiccatum (Penicilium solitum), penicillium digitalis or Penicillium expansum, in particular against pathogens of fruits such as pome (e.g. apples and pears), stone fruits (e.g. peaches and plums), citrus, melon, papaya, kiwi, mango, berries (e.g. strawberries), avocados, pomegranates and bananas.

The amount of the combination of the invention to be applied will depend on various factors such as the compound used, the object of treatment such as, for example, plants, soil or seeds, the type of treatment such as, for example, spraying, dusting or dressing, the purpose of the treatment such as, for example, prophylaxis or therapy, the type of fungus to be controlled or the time of application.

The mixture comprising component (a) and component (B) may be applied, for example, in a single "ready-to-use" form, in a combined spray mixture (consisting of separate formulations of the single active ingredient components), such as a "tank mix", and when applied in a sequential manner (i.e., one after a reasonably short period of time, such as hours or days, of the other) in combination with the single active ingredient. The order in which components (a) and (B) are administered is not critical to the practice of the present invention.

Some of the combinations according to the invention have a systemic effect and can be used as fungicides for foliar, soil and seed treatments.

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

The combinations of the invention are particularly interesting for controlling fungi in different useful plants or their seeds, especially in field crops, such as potatoes, tobacco and sugar beets as well as wheat, rye, barley, oats, rice, maize, lawn, cotton, soybean, oilseed rape, bean crops, sunflower, coffee, sugarcane, fruits in horticultural and grape plants and ornamental plants, fungi in vegetables (e.g. cucumbers, beans and melons).

The combination according to the invention is applied by treating the fungus, the useful plant threatened by fungal attack, its locus, its propagation material, natural substances of plant and/or animal origin taken from the natural life cycle and/or processed forms thereof, or industrial materials, preferably in synergistically effective amounts of the combination of components (a) and (B).

The combination according to the invention may be applied before or after the useful plants, propagation material thereof, plant-derived and/or animal-derived natural substances taken from the natural life cycle and/or processed forms thereof, or industrial materials have been infected with fungi.

When applied to useful plants in combination with 1 to 5000g a.i./ha, in particular 2 to 2000g a.i./ha, e.g. 25, 50, 75, 100, 250, 500, 800, 1000, 1500g a.i./ha of component (B), component (a) is applied in a ratio of 5 to 2000g a.i./ha, in particular 10 to 1000g a.i./ha, e.g. 25, 50, 75, 100 or 200g a.i./ha.

In agricultural practice, the application rate of the combination according to the invention depends on the type of action desired and is typically in the range from 20 to 4000g of total combination per hectare.

When the combination of the invention is used for treating seeds, a ratio of from 0.001 to 50g of component (A)/kg of seed, preferably from 0.01 to 10g/kg of seed, and from 0.001 to 50g of component (B)/kg of seed, preferably from 0.01 to 10g/kg of seed, is generally sufficient.

The present invention also provides fungicidal compositions comprising a synergistically effective amount of a combination of components (a) and (B) as mentioned above together with an agriculturally acceptable carrier and optionally a surfactant. In the composition, the weight ratio of (a) to (B) is preferably between 1000:1 and 1:1000, more preferably as described above.

The compositions OF the invention can be used in any conventional form, for example, in the form OF a double-pack, dry seed-treating powder (DS), seed-treating Emulsion (ES), seed-treating flowable concentrate (FS), seed-treating solution (LS), seed-treating water-dispersible powder (WS), seed-treating capsule suspension (CF), seed-treating Gel (GF), emulsion Concentrate (EC), suspension Concentrate (SC), suspension Emulsion (SE), capsule Suspension (CS), water-dispersible particles (WG), emulsifiable particles (EG), water-in-oil Emulsion (EO), oil-in-water Emulsion (EW), microemulsion (ME), oil Dispersion (OD), oil suspension (OF), oil-soluble concentrate (OL), soluble concentrate (SL), ultra-low volume Suspension (SU), ultra-low volume liquid (UL), master drug (TK), dispersible Concentrate (DC), wettable Powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with suitable formulation inert agents (diluents, solvents, fillers and optionally other formulation ingredients, such as surfactants, biocides, antifreeze agents, adhesion agents, thickeners and compounds which provide auxiliary effects). Conventional slow release formulations intended for long lasting efficacy may 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 surfactants such as wetting and dispersing agents and other compounds which provide auxiliary effects, for example condensation products of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates and ethoxylated alkylphenols and ethoxylated fatty alcohols.

The seed dressing formulations are applied to the seeds in a manner known per se in the form of suitable seed dressing formulations, for example in the form of aqueous suspensions or dry powders which have good adhesion to the seeds, using the combinations and diluents of the invention. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the individual active ingredients or combinations of active ingredients in encapsulated form, for example as slow release capsules or microcapsules.

Typically, the formulation comprises from 0.01% to 90% by weight of active ingredient, from 0 to 20% of agriculturally acceptable surfactant and from 10% to 99.99% of solid or liquid formulation inert agents and adjuvants, component (a) together with components (B) and (C) and optionally other active agents (in particular microbiocides or preservatives, etc.). The concentrated form of the composition typically contains between about 2% and 80%, preferably between about 5% and 70% by weight of active agent. The formulation may for example contain 0.01 to 20% by weight, preferably 0.01 to 5% by weight, of active agent in the form of administration. However, commercial products will preferably be formulated as concentrates and the end user will typically use dilute formulations.

Biological example

The combinations of the present invention were tested using one or more of the following protocols.

Fusarium species

The test was performed according to Pesticides guidelines for laboratory bioactivity tests,Part 2:Petri plate test for determining fungicides inhibition of mycelial growth[ pesticide laboratory biological activity test guidelines part 2, petri dish test to determine that fungicides inhibit hyphal growth (NY/T1156.2-2006). In particular, according to the result of the preliminary experiment, the optimal concentration ranges for determining the sensitivity of the pathogen to fluxapyroxad hydroxylamine, epoxiconazole and mixtures thereof were respectively determined, and 5-7 concentration gradients were set so that the inhibition ratio of the lowest concentration was close to 10% and the inhibition ratio of the highest concentration was close to 90%. The same volume of solutions of fluxapyroxad hydroxylamine, epoxiconazole, and mixtures thereof in DMSO were added to the thawed PDA medium, respectively, to prepare test plates, and PDA plates with the same volume of DMSO were used as controls.

A mycelium plug was prepared at the edge of the colony with a punch having a diameter of 5 mm. With mycelium upward, the mycelium plugs were transferred to the center of PDA culture substrates and control plates containing fluxapyroxad hydroxylamine, epoxiconazole, and mixtures thereof. After three days of incubation in the dark in a 25 ℃ incubator, the diameter of each hyphal colony on the PDA plate was measured vertically twice and then averaged. Inhibition (%) = (average diameter of hyphal colonies on control plate-average diameter of hyphal colonies on test plate)/(average diameter of hyphal colonies on control plate) ×100%.

EC ₅₀ values for each reagent tested and each mixture were calculated by linear regression analysis between the probability values of inhibition and the log values of a series of concentrations. Co-toxicity coefficients (CTCs) of the mixtures were calculated and evaluated according to Sun-YP method. The results are shown in tables 1 and 2 below.

TABLE 1 fungicidal Activity of fluxapyroxad hydroxylamine and epoxiconazole against Fusarium graminearum calculated using the CTC method

TABLE 2 fungicidal Activity of fluxapyroxad hydroxylamine and epoxiconazole against Fusarium Asini calculated using the CTC method

EC ₅₀ values were also calculated for each reagent tested and for each mixture using the Wadley method. The results are shown in tables 3 and 4 below.

TABLE 3 fungicidal Activity of Fusarium on Fusarium graminearum calculated using the Wadley method

TABLE 4 fungicidal Activity of Fusarium on Fusarium Asian by Fusarium and Fusarium calculated using the Wadley method

Claims (13)

1. A composition suitable for controlling diseases caused by plant pathogens comprising fluxapyroxad hydroxylamine as component (a) and epoxiconazole as component (B), or an agrochemically acceptable salt, stereoisomer, diastereomer, enantiomer and tautomer thereof.

2. The composition of claim 1 wherein components (a) and (B) are present in synergistically effective amounts.

3. The composition of claim 1 or claim 2, wherein the weight ratio of (a) to (B) is from 100:1 to 1:100.

4. A composition according to any one of claims 1 to 3, wherein the weight ratio of (a) to (B) is from 9:1 to 1:9.

5. The composition of any one of claims 1 to 4, wherein the weight ratio of (a) to (B) is 5:1 to 1:5.

6. The composition of any one of claims 1 to 5, wherein the weight ratio of (a) to (B) is 1.5:1.

7. The composition of any one of claims 1 to 5, wherein the weight ratio of (a) to (B) is 1:1.

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

9. A method of controlling diseases caused by plant pathogens on useful plants or on propagation material thereof, the method comprising applying to the useful plants, locus thereof or propagation material thereof a composition according to any one of claims 1 to 8.

10. A method for controlling fusarium species on a useful plant, the method comprising applying to the useful plant, locus thereof, or propagation material thereof an effective amount of the composition of any one of claims 1 to 8.

11. The method of claim 10, wherein the pathogen is fusarium graminearum or fusarium asiaticum.

12. Use of a composition according to any one of claims 1 to 8 as a fungicide.

13. A method of protecting a natural substance of plant and/or animal origin and/or processed forms thereof taken from the natural life cycle, which method comprises applying to said natural substance of plant and/or animal origin or processed forms thereof a combination of components (a) and (B) as defined in any one of claims 1 to 8.