EP2330898A2 - Produit de protection phytosanitaire et de protection de matériaux - Google Patents

Produit de protection phytosanitaire et de protection de matériaux

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Publication number
EP2330898A2
EP2330898A2 EP09777184A EP09777184A EP2330898A2 EP 2330898 A2 EP2330898 A2 EP 2330898A2 EP 09777184 A EP09777184 A EP 09777184A EP 09777184 A EP09777184 A EP 09777184A EP 2330898 A2 EP2330898 A2 EP 2330898A2
Authority
EP
European Patent Office
Prior art keywords
inhibitor
plants
infected
alkyl
plant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09777184A
Other languages
German (de)
English (en)
Inventor
Tedson Ngwenya
Gerhard Wolf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Georg August Universitaet Goettingen
Universitaetsmedizin Goettingen Georg August Universitaet
Original Assignee
Georg August Universitaet Goettingen
Universitaetsmedizin Goettingen Georg August Universitaet
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Filing date
Publication date
Application filed by Georg August Universitaet Goettingen, Universitaetsmedizin Goettingen Georg August Universitaet filed Critical Georg August Universitaet Goettingen
Priority to EP09777184A priority Critical patent/EP2330898A2/fr
Publication of EP2330898A2 publication Critical patent/EP2330898A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof

Definitions

  • the present invention relates to the use of inhibitors of enzymes, in particular hydrolases as agents for the control of particular harmful or phytopathogenic fungi and other microorganisms, especially in or on plants.
  • phytopathogenic fungi as the most important pathogens of plant diseases are used almost exclusively fungicides, i. Substances that usually kill the fungus via systemic spread in the plant by blocking essential intracellular metabolic pathways.
  • Typical for a stronger infestation of the crop is a relatively high proportion of small and shrunken grains, which, however, do not appear so strongly in the crop by sieving.
  • the cause of the formation of shrunken grains is the breakdown of the meal body, i. the strength of fungal amylases, with which the fungus opens up an important C source.
  • polysaccharide degrading enzymes such as e.g. Cellulases and amylases play an essential role.
  • extracellular polysaccharide-degrading enzymes can be considered as key enzymes of pathogenesis. This is also due to the close relationship between fungal biomass in the plant and key enzymes such as e.g. Cellulase, xylanase and protease expressed (AFSHARI, 1992).
  • amylase inhibitor acarbose is known as a pharmaceutical for the treatment of type 2 diabetes.
  • Acarbose reduces postprandial hyperglycemia by delaying the absorption of carbohydrates in the small intestine.
  • acarbose in combination with other anti-diabetes drugs leads to an improved glycemic control.
  • Recent studies have also shown that acarbose therapy can significantly reduce the risk of cardiovascular events in vulnerable individuals with glucose intolerance. (BREUER, 2003; WEHMEIER, 2004).
  • the amylase inhibitor miglitol is also able to reduce plasma glucose levels in fasting or postprandial type 2 diabetes patients.
  • Miglitol is particularly beneficial in the treatment of the elderly and those with hepatic or mild to moderate impairment of the kidney in which others antidiabetic agents are contraindicated or must be used with caution. (SCOTT & SPENCER, 2000)
  • Amylases can be divided into other subgroups. While beta-amylases and gamma-amylases are exo-cleaving enzymes (they cleave from the nonreducing end of a starch molecule), alpha-amylases are endo-cleaving enzymes, i. they can split anywhere within the starch molecule. The latter thus represent a key enzyme in starch degradation, since they are necessary for the first stage of degradation.
  • FIGUEIRA 2003, discloses in vitro enzyme inhibition assays of the proteinogenic alpha-amylase inhibitor from Zea mays with an alpha-amylase from Fusarium verticillioides. However, there is no evidence that this approach is apt to inhibit fungal growth, and b) to inhibit fungal growth in the plant. With regard to a), it should be noted that proof of inhibition of germination by no means provides evidence of inhibition of hyphae growth since both stages may in principle differ from one another (see also the examples of the present invention). NARAYANAN, 1967, describes the non-specific and strongly concentration-dependent inhibition of an amylase from Fusarium vasinfectum by Mn 2+ and Zn 2+ in vitro.
  • Palladium complexes e.g. Sodium hexachloro-palladate (IV) tetrahydrate has been shown to potentially inhibit cellobiohydrolase I (CBH I) and endoglucanase II (EG II), two cellulases produced by Trichoderma reesei. The inhibition of cellulase (avicelase) and beta-glucosidase activities is also described. (SHULTZ, 1995)
  • the present invention relates to the use of a compound of the formula A or the formula C or of agrochemical salts thereof as an agent for controlling fungi or other microorganisms.
  • the invention relates to the use of a compound of the formula B or agrochemical salts thereof as agents for controlling fungi or other microorganisms.
  • the present invention relates to compositions for controlling fungi or other microorganisms in or on plants, seeds and / or material, in particular wood, containing at least one of the compounds of formula A or C and agrochemical or conventional materials protection auxiliaries and / or additives. Furthermore, the invention relates to agents for controlling fungi or other microorganisms in or on plants and / or material, in particular wood, containing at least one of the compounds of the formula B and agrochemical or conventional in materials protection auxiliaries and / or additives.
  • the invention relates to seed treated with at least one compound of the formula A or C.
  • the invention relates to a method for screening for fungal or microorganism infestation inhibiting substances, comprising the following steps: a) providing a candidate substance capable of inhibiting an enzyme which is involved in the penetration or spreading of the fungus or the Microorganism is involved in the plant, and b) determining whether the substance is capable of inhibiting fungal or microorganism infestation of plants.
  • a first aspect of the present invention relates to the use of arcose or a compound of formula A or of palladate or a compound of formula C or of agrochemical salts thereof as an agent for controlling fungi or other microorganisms.
  • the compound of the formula A is one or more aminocyclic derivatives of the general formula A.
  • X is OH 5 OR 6 , SH, SR 7 , NH 2 or NHR 7 , preferably OR 6 ;
  • Y is alkyl, aryl, alkylaryl or arylalkyl substituents, which may optionally be substituted, CH 2 N 3 , CH 2 NH 2 , CH 2 NHAc, CH 2 OCH 3 or CO 2 CH 3; preferably C 1 -C 6 -alkyl, more preferably CH 3 ;
  • Z is H, OH, O-C 1 -C 6 -alkyl, preferably OCH 3 , OTs, OTr, OMs or OAc, preferably OH;
  • R 1 , R 2 , R 3 and R 4 are independently H, alkyl, aryl, alkylaryl or arylalkyl substituents, which may be optionally substituted; Ac, Ts or Ms; preferably independently of one another are H, C 1 -C 6 -alkyl, preferably CH 3 , Ac, Ts or Ms; preferably H;
  • R 5 is H, alkyl, aryl, alkylaryl or arylalkyl substituents which may optionally be substituted, Ac, Ts, Ms or
  • R 6 is H, alkyl, aryl, alkylaryl or arylalkyl substituents which may optionally be substituted, Ac, Ts, Ms or
  • R 7 are independently alkyl, aryl, alkylaryl or arylalkyl substituents, which may be optionally substituted; Ac, Ts or Ms; preferably independently of one another are C 1 -C 6 -alkyl, preferably CH 3 , Ac, Ts or Ms; preferably CH 3; R 8 , R 9 , R 10 , R ", R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19
  • H alkyl, aryl, alkylaryl or arylalkyl substituents, which may optionally be substituted, Ac, Ts or Ms; preferably independently of one another are H, C 1 -C 6 -alkyl, preferably CH 3 ; particularly preferably H; m is 0, 1, 2 or 3, preferably 0; n is 0, 1, 2 or 3, preferably 1;
  • the dashed bond means that there is a single bond or a double bond at this position, preferably a double bond is present.
  • Suitable substituents of the aforementioned alkyl, aryl, alkylaryl or arylalkyl substituents are e.g. Alcohol groups, ester groups, ether groups or halogen groups.
  • the alkyl, aryl, alkylaryl or arylalkyl substituents preferably have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms and especially 1 to 5 carbon atoms, e.g. B. 1 or 2 carbon atoms.
  • Particular preference is given to compounds of the formula A in which: X is OR 6 ; Y is CH 3 ; ZOH; R 1 , R 2 , R 3 and R 4 independently of one another are H or CH 3 , preferably H,
  • R 5 is H or CH 3 , preferably H
  • R 14 , R 15 , R 16 , R 17 , R 18 , R 1 independently of one another are H or CH 3 , preferably H; n 1; the dashed bond means that there is a single bond or a double bond at this position, preferably a double bond is present.
  • the compound of formula A is acarbose, i. the radicals and groups in formula A mean:
  • X is OR 6;
  • R 1 , R 2 R 3 and R 4 independently of one another H
  • the dashed bond means that there is a double bond at this position.
  • radicals OMs, OTs, OAc and OTf as well as Ms, Ts, Ac and Tf have the following meanings: OMs mesylate;
  • Tf trifluoromethanesulfonyl Tf trifluoromethanesulfonyl.
  • the aminocyclic derivatives of the formula A can be prepared according to or analogously to processes known to the person skilled in the art. Suitable methods are described, for example, in DE-A 2 347 782; DE-A 2 614 393; US 4,175,123; US 4,197,292; DE-A 2 855 409, DE-A 3 123 520 and Nat. Prod. Rep., 2003, 20, 137-166 and the literature cited therein. The more preferably used acarbose is further commercial.
  • Compound C is one or more metallic compounds of the general formula:
  • X alkali metal preferably selected from Na, Li and K, more preferably Na; or NH 4
  • M transition metal preferably selected from Pd, Pt, Ni, Os and Ir, more preferably Pd;
  • Hal is halogen, preferably selected from Cl, Br and I, more preferably Cl; x 0, 1, 2, 3, 4, 5 or 6, preferably 0, 4 or 6, preferably 4. beonders
  • Suitable metallic compounds of the formula (C) are, for example, Na 2 PdCl 6 * 4 H 2 O; Na 2 PtCl 6 "6 H 2 O; Na 2 OsCl 6 " x H 2 O or Na 2 IrCl 6 '6 H 2 O. Very particular preference is given to Na 2 PdCl 6 - 4 H 2 O (palladate).
  • the metallic compounds of the formula (C) are commercially available or can be prepared by processes known to those skilled in the art.
  • Another aspect of the present invention relates to the use of miglitol or a compound of formula B or of agrochemical salts thereof as agents for controlling fungi or other microorganisms.
  • the compound of the formula (B) is the substance having the general formula (B) and / or one or more derivatives thereof having the general formula (B)
  • R 21 , R 22 , R 23 , R 24 independently of one another are H, alkyl, aryl, alkylaryl or arylalkyl substituents, which may optionally be substituted; preferably independently of one another are H, C 1 -C 6 -alkyl or hydroxy-substituted C 1 -C 6 -alkyl; particularly preferably H;
  • R 20 is an alkyl, aryl, alkylaryl or arylalkyl substituent which is optionally substituted; preferably C 1 -C 6 -alkyl or hydroxy-substituted C 1 -C 6 -alkyl; particularly preferably 2-hydroxyethyl.
  • Derivatives of the substance are to be understood in particular as meaning its ethers, esters and also partial ethers and partial esters, such as palmitate, acetates and amides. Also included are salts and acid adducts of these compounds. Preferred derivatives are N-substituted derivatives.
  • Suitable substituents of the aforementioned alkyl, aryl, alkylaryl or arylalkyl substituents are e.g. Alcohol groups, ester groups, ether groups or halogen groups.
  • the alkyl, aryl, alkylaryl or arylalkyl substituents preferably have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms and especially 1 to 5 carbon atoms, e.g. B. 1 or 2 carbon atoms. Very particular preference is given to alcohols of substituted alkyl substituents, such as 2-hydroxyethyl.
  • the compound of formula B is miglitol, i. the radicals and groups in formula B mean:
  • R 20 is 2-hydroxyethyl.
  • the compounds of the formula B can be prepared according to or analogously to processes known to the person skilled in the art. Suitable processes are mentioned, for example, in DE-A 23 47 782. The particularly preferred Miglitol is further commercially available.
  • the compounds used according to the invention have a strong antifungal activity and can therefore be used for controlling fungi and / or other undesired microorganisms, such as bacteria, in crop protection and in the protection of materials. It has been found that with a high selectivity, fungal enzymes which are necessary for the penetration and spread of the pathogen or pest, and are mostly specific for microorganisms, in particular for fungi, are inhibited, while the corresponding Plant enzymes continue to show functional activity. Thus, the specific inhibitors of extracellular enzymes of fungi used in the present invention provide a completely novel concept for controlling such fungi (see Examples). Since other microbial microorganisms secrete enzymes with similar activity and structure, it can be assumed that the inhibitors used according to the invention are also active against other unwanted microorganisms, such as bacteria.
  • the compounds used according to the invention have antifungal properties and can be used in particular for controlling phytopathogenic fungi, such as, for example, Plasmodiophoromycetes, Oomycetes, Chytridio-mycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc.
  • microorganisms are understood to mean in particular fungi, bacteria and other microorganisms which are harmful to plants, in particular lead to plant diseases or which lead to an undesired infestation and / or undesired destruction of materials.
  • the compounds used according to the invention can be used in particular in crop protection, for example for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • brassicae Phytophthora species, such as Phytophthora infestans; Plasmopara species, such as Plasmopara viticola; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species such as Pythium ultimum; Leaf spot diseases and leaf wilt caused by eg Alternaria species such as Alternaria solani; Cercospora species, such as Cercospora beticola; Cladiosporum species, such as Cladiosporium cucumerinum; Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, Syn: Helminthosporium); Colletotrichum species, such as Colletotrichum lindemuthanium; Cycloconium species such as cycloconium oleaginum; Dia
  • Oryzae Pectobacterium spp. and species such as Clavibacter michiganensis ssp. Sepedonicus, Ralstonia solanacearum Pseudomonas syringae pv. Lachrymans or Erwnnia amylovora.
  • the use according to the invention according to the first aspect of the invention relates to a use of the compounds of the formula A or C for controlling fungi or other microorganisms in or on plants and / or seeds.
  • the use according to the invention according to the second aspect of the invention in a preferred embodiment relates to a use of the compounds of formula B for controlling fungi or other microorganisms in or on plants.
  • the term "plant” also includes plant parts, which is why in the context of the present invention it is possible in particular to treat above-ground plant parts as well as plant parts of the soil.
  • the compounds of the use according to the invention can therefore be used to protect plants within a certain period of time after the treatment against the infestation by said pathogens.
  • the period within which protection is provided generally extends from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active ingredients.
  • the compounds of the formula A and C can be used for the treatment of seeds and seeds.
  • the active compounds according to the invention are also suitable for increasing crop yield. They are also low toxicity and have good plant tolerance.
  • the active compounds according to the invention may optionally also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of other active ingredients.
  • all plants and parts of plants can be treated.
  • plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant breeders' rights.
  • Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds (the latter only in the case of the compounds of the formula A and C) as well as roots, tubers and rhizomes can be listed.
  • the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds (the latter only in the case of the compounds of formula A and C).
  • the treatment according to the invention of the plants and plant parts with the active ingredients is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, spreading, spreading and in propagation material, in particular in seeds, further by single or multi-layer wrapping.
  • the compounds of the formula A, B or C are used in the context of the protection of materials, in particular as wood preservatives.
  • the substances according to the invention can be used to protect industrial materials against infestation and destruction by undesired microorganisms.
  • Technical materials as used herein mean non-living materials that have been prepared for use in the art.
  • technical materials to be protected from microbial change or destruction by the active compounds of the invention may be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastics, coolants, and other materials that may be infested or degraded by microorganisms .
  • materials to be protected are also parts of production plants, such as cooling water circuits, called, which can be affected by the proliferation of microorganisms.
  • technical materials preferably adhesives, glues, papers and cardboard, leather, wood, paints, coolants and
  • Called heat transfer fluids particularly preferably wood.
  • the active compounds according to the invention preferably act against fungi, in particular wood-discoloring and wood-destroying mold fungi (Basidiomycetes).
  • fungi in particular wood-discoloring and wood-destroying mold fungi (Basidiomycetes).
  • Basidiomycetes wood-discoloring and wood-destroying mold fungi
  • Alternaria such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, like Chaetomium globosum; Coniophora, like Coniophora puetana; Lentinus, like Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma, like Trichoderma viride,
  • Mold in particular Trametes versicolor, Gloeophyllum trabeum and Poria placenta; wood decomposing fungi which cause high economic damage in lumber and other wood products and are important in material protection (e.g., wood fiber panels, medium density fiberboard (MDF), oriented beach board (OSB), chipboard);
  • MDF medium density fiberboard
  • OSB oriented beach board
  • Red rot such as Heterobasidion annosum
  • Blue fungi e.g. Mushrooms of the Ceratocystis family
  • Brown rot such as Coniophora arida, Coniophora mertdioides, Coniophora souna, Daedalea quercina, Fistuiina hepatica, Fomitopsis rosea, Gloeophyllum abietmum, Gloeophyllum sepia ⁇ um, Gloeophyllum striatum, Gloeophyllum subferrugilaeum, Gloeophyllum trabeum, Laetiporus sulphureus, Lentinus cyathiformis, Keminus lepideus, Paxillus panuoides, Phaeohis schweinitzii, Poria monticola , Poria xantha, Serpula cmffluens, Serpula himantioides, Serpula lacrymans, Tyromyces caesius;
  • Ascomycetes such as Fungi imperfecti, Aureobasidium pulullans, Botryosphaeria rhodina, Ceratocystis pilifera, Chaetomium globosum, Dothichiza populea; and white rot, such as Armillariella mellea, Bjerkandera adusta, Chondrostereum purpureum, Collybia butyracea, Collybia velutipes, Coriolus versicolor, Fomes fomentarius, Heterobasidion annosum, Hirschioporus abietinus, Hirschioporus fuscoviolacens, Innonotus obliqutls, Perenniporia subacida, Phellinus igniarius, Phellinus pini, Phlebia giganlea, Pleurotus ostreatus, Rigidoporus nigrescens, Schizophyllum commune.
  • the active compounds can be converted into the customary formulations depending on their respective physical and / or chemical properties in the context of the present invention, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in encapsulants for seeds, as well as ULV-KaIt and warm mist formulations.
  • formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, that is to say liquid solvents, liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-forming agents.
  • extenders that is to say liquid solvents, liquefied gases under pressure and / or solid carriers
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-forming agents.
  • organic solvents can be used as auxiliary solvents.
  • Suitable solid carriers are: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates.
  • ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth
  • ground synthetic minerals such as finely divided silica, alumina and silicates.
  • Suitable solid carriers for granules are: e.g. Cracked and fractionated natural rocks such as calcite, pumice, marble, sepiolite, dolomite and synthetic
  • Granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stems.
  • Suitable emulsifiers and / or foam-forming agents are: e.g. nonionic and anionic
  • Emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
  • Alkylaryl polyglycol ethers alkyl sulfonates, alkyl sulfates, arylsulfonates and
  • Protein hydrolysates are: e.g. Lignin-sulphite liquors and methylcellulose.
  • Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-form polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids may be used in the formulations.
  • Other additives may be mineral and vegetable oils.
  • Dyes such as inorganic pigments such as iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used
  • the formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%, preferably between 0.7 and 85%, more preferably between 1 and 80%, even more preferably between 1, 5 and 75%.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules.
  • the application is done in the usual way, e.g. by pouring, splashing, spraying, scattering,
  • Dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
  • the seeds of the plants may also be treated.
  • the application rates can be varied within a relatively wide range, depending on the mode of administration.
  • the application rates of active ingredient are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha.
  • the application rates of active ingredient are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed.
  • the application rates of active ingredient are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
  • plants and their parts can be treated.
  • wild species or plant species obtained by conventional biological breeding methods such as crossing or protoplast fusion
  • plant varieties and their parts are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the term “parts” or “parts of plants” or “plant parts” has been explained above.
  • Plant varieties are understood to be plants having new traits which have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques, which may be varieties, breeds, biotypes and genotypes.
  • the plants may be non-transgenic as well as transgenic plants.
  • Preferred non-transgenic plants are cereals (wheat, rice), corn, soy, potato, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and grapes), more preferably cereals, most preferably wheat.
  • the transgenic (genetically engineered) plants or plant varieties to be treated according to the invention also include all plants which have obtained genetic material by the genetic engineering modification which gives these plants particularly advantageous valuable properties ("traits".) Examples of such properties are better plant growth.
  • transgenic plants include the important crops such as cereals (wheat, rice), corn, soybean, potato, cotton, tobacco, oilseed rape and fruit plants (with the fruits apple, pear, citrus and grape), with cereals, corn, soy , Potato, cotton, tobacco and oilseed rape especially and especially wheat are highlighted.
  • Traits that are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins produced in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CryLA (a ), CrylA (b), CrylA (c), CryllA, CrylTIA, CryITJB2, Cry9c Cry2Ab, Cry3Bb and CrylF, and combinations thereof) are produced in the plants (hereinafter "Bt plants”) as properties (“traits”)
  • Bt plants systemic acquired resistance
  • SAR systemin
  • phytoalexins phytoalexins
  • elicitors elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (eg "PAT” gene) .
  • the genes conferring the desired properties (“traits") may also occur in combinations with each other in the transgenic plants.
  • Examples of “Bt plants” are maize varieties, cotton varieties, soybean varieties and potato varieties which are sold under the trade names YIELD GARD® (eg corn, cotton, soya), KnockOut® (eg maize), StarLink® (eg maize), Bollgard® ( Cotton), Nucoton® (cotton) and NewLeaf® (potato).
  • herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soya), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), EVfl® (Tolerance to imidazolinone) and STS® (tolerance to sulfonylureas eg corn).
  • Herbicide-resistant (conventionally grown on herbicide tolerance) plants are also the varieties marketed under the name Clearfield® (eg corn) mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.
  • the fungi or microorganisms are phytopathogenic, i. they are a pathogen for the particular plant.
  • the compound of the use according to the invention or the agrochemical salt thereof is used in combination with another active ingredient selected from the group consisting of insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, Fertilizers or Semiochemicals used.
  • the active compounds according to the invention can also be used in admixture with known fungicides, bactericides, acaricides, nematicides or insecticides, so as to obtain e.g. to broaden the spectrum of action or to prevent development of resistance. In many cases synergistic effects, i. E. the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • Fungicides are suitable as mixed partners: Fungicides:
  • Azoxystrobin Cyazofamide, Dimoxystrobin, Enestrobin, Famoxadone, Fenamidone, Fluoxastrobin, Kresoximethyl, Metominostrobin, Orysastrobin, Pyraclostrobin, Picoxystrobin 3.4 Decoupler
  • Chlozolinate iprodione, procymidone, vinclozoline, pyrazophos, edifenphos, iprophf (IBP), isoprothiolane, tolclofos-methyl, biphenyl iodocarb, propamocarb, propamocarb hydrochloride
  • carbamates e.g., alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, azamethiphos, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxime,
  • organophosphates eg acephates, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion, chloroethoxyfos, chlorfenvin-phos, chloroforms, chlorpyrifos (-methyl / -ethyl), Coumaphos, Cyanofenphos, Cyanophos, Chlorofenvinphos, Demeton-S-methyl, Demeton-S-methylsulphone, Dialifos, Diazinon, Dichlofenthione, Dichlorvos / DDVP, Dicrotophos, Dimethoates, Dimethylvinphos, Dioxabenzofos, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitrothion, F
  • Sodium Channel Modulators / Voltage-Dependent Sodium Channel Blockers 2.1 Pyrethroids (eg acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlo-vaporthrin, cis-cypermethrin, cis -Resmethrin, cis-permethrin, clocthrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, DDT, deltamethrin, empenthrin (IR isomer), es
  • Oxadiazines e.g., Indoxacarb
  • chloronicotinyls / neonicotinoids e.g., acetamiprid, clothianidin, dinotefuran, imidacloprid, ni-tenpyram, nithiazines, thiacloprid, thiamethoxam
  • Fiproles e.g., acetoprole, ethiprole, fipronil, vaniliprole
  • Mectins e.g., abamectin, avermectin, emamectin, emamectin benzoate, ivermectin, milbemectin, milbemycin
  • diacylhydrazines e.g., chromafenozides, halofenozides, methoxyfenozides, tebufenozides
  • Inhibitors of chitin biosynthesis 9.1 Benzoylureas (eg bistrifluron, chlorofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, trifluoron)
  • Benzoylureas eg bistrifluron, chlorofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, trifluoron
  • Organotin e.g., azocyclotin, cyhexatin, fenbutatin oxides
  • METrs e.g., Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, 15 Tolfenpyrad
  • 16.2 tetramic acids e.g. 3- (2,5-Dimethylphenyl) -8-methoxy-2-oxo-1-azaspiro [4.5] dec-3-en-4-yl ethyl carbonate (also known as: Carbonic acid, 3- (2,5-dimemylphenyl) -8-methoxy-2-oxo-1-azaspiro [4.5] dec-3-en-4-yl ethyl ester, CAS Reg.
  • Carboxamides eg flonicamide
  • Octopaminergic agonists e.g., Amitraz
  • fumigants e.g., aluminum phosphides, methyl bromides, sulfuryl fluorides
  • mite growth inhibitors e.g., clofentezine, etoxazole, hexythiazox
  • a further aspect of the invention relates to a composition for controlling fungi or other microorganisms in or on plants, seeds and / or material, in particular wood, containing at least one of the compounds of the formula A or C and agrochemical or protective materials and / or usual in the protection of materials additives.
  • Another further aspect of the invention relates to a composition for controlling fungi or other microorganisms in or on plants and / or wood, containing at least one of the compounds of the formula B and agrochemical or conventional in materials protection auxiliaries and / or additives.
  • compositions according to the invention for the compositions according to the invention, the preferred embodiments and examples given above within the context of the use according to the invention are correspondingly applicable. This applies in particular to the auxiliaries and additives.
  • the agent according to the invention also contains at least one further active ingredient selected from the group consisting of insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.
  • at least one further active ingredient selected from the group consisting of insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.
  • the fungi are selected from the group consisting of Blumeria graminis, Phakopsora pachyrhizi, Phytophthora infestans, Pythium ultimum, Magnaporthe grisea, Venturia inaequalis, Fusarium oxysporum, Rhizoctonia solani, Gibberella zeae, Sclerotinia sclerotiorum , Botrytis one ea, Alternaria solani, Puccinia graminis, Colletotrichum graminicola and Mycosphaerella graminicola.
  • the invention relates to a seed treated with at least one compound according to the use of the first aspect.
  • the seed has additionally been treated with another active ingredient selected from the group consisting of insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals. Also for this embodiment, the above examples apply.
  • the invention relates to a method for screening for fungal or microorganism infestation inhibiting substances, comprising the following steps: a) providing a candidate substance capable of inhibiting an enzyme involved in the penetration or spreading of the fungus or microorganism into the plant, and b) determining whether the substance is capable of fungal or To inhibit microorganism infestation of plants.
  • Candidate substances can be substances from a substance library.
  • substance libraries may include small chemical compounds, i. be organic or inorganic compounds, or be peptides or polypeptides.
  • the candidate substance may be known as an inhibitor of the enzyme or known as an inhibitor of an enzyme having the same enzymatic activity. However, the candidate substance may also be unknown in the context of inhibitor function.
  • the candidate substance may also be described in another context as an inhibitor, i. in another context, except as inhibitors which inhibit the penetration and spread of a fungus or a microorganism, e.g. be described in a medical application.
  • Enzymes involved in the penetration of the fungus or microorganism into the plant may be, for example, extracellular hydrolases, proteases, or polysaccharide degrading enzymes, e.g. Amylases, cutinases, pectinases, cellulases, ⁇ -glucanases, ⁇ -glucanases or xylanases.
  • Amylases cutinases, pectinases, cellulases, ⁇ -glucanases, ⁇ -glucanases or xylanases.
  • Such enzymes may be due to the penetration of the fungus into the plant tissue, the term “intrusion” being understood here in its broadest form, The term “intrusion” is hereby intended to include any form of penetration of the plant or seed, such as eg hydrolysis of the cell wall or other tissues and / or polypeptides of plant origin.
  • the term “spreading” in the context of this invention is understood to mean, among other things, the extraction of nutrients of plant origin by the fungus or microorganism with the aid of extracellular enzymes.
  • the development of nutrients includes, for example, the development of nitrogen and carbon sources, preferably carbon sources.
  • Non-limiting examples of enzymes involved in the propagation of a fungus or microorganism include, for example, amylases which enable the fungus or microorganism to convert the starch of a grain into sugars metabolizable to the fungus or microorganism
  • Nitrogen sources can be carried out, for example, by proteases, but spreading can also be understood as meaning the migration of the fungus or microorganism in the plant.
  • a difference measurement of the fresh weight of a fungal or microorganism infested young plant may be made in the presence or absence of the candidate substance.
  • a lower weight gain of the fresh weight indicates a stronger infestation by the fungus or microorganism.
  • the degree of infestation of the young plant can also be quantified by an ELISA.
  • a direct ELISA double sandwich ELISA according to CLARK and ADAMS (1977) can be used to detect F. graminearum.
  • step a) comprises the additional step of determining whether the candidate substance is capable of inhibiting an enzyme involved in the penetration or spreading of the fungus or microorganism in the plant involved is involved.
  • inhibitor in the context of this invention is to be equated with the term “inhibited” or “inhibition”.
  • the term “inhibit” or “inhibition” is to be understood here as complete or partial inhibition.
  • a substance inhibits the penetration and spread of the fungus or microorganism if the activity of the enzyme in the presence of the substance is at least 20%, at least 30%, at least 40%, at least 50%, compared to the activity of the enzyme in the absence of the substance. at least 60%, at least 70%, at least 80%, at least 90% or 100% is reduced.
  • an enzyme is initially provided together with its substrate, preferably a polymer of a polysaccharide.
  • the polymer used is cleaved by the enzyme into shorter fragments.
  • the addition of acid after a reaction time, in addition to stopping the enzyme reaction leads to precipitation of the unaffected, large molecules. These can be pelleted by centrifugation while the smaller cleavage products remain in the supernatant. These cause a coloration of the supernatant, the absorbance of which can be used as a measure of the enzyme activity.
  • the following polysaccharide or protein-dye conjugates were used: CMCelluloseRBB (1,4-glucan)
  • the methods according to the invention for screening for fungal or microorganism infestation-inhibiting substances can also be used in a high-throughput method. In doing so, many candidate substances can be simultaneously tested by mechanized procedures, allowing screening of a large number of candidate substances. More specific methods for determining the activity of an enzyme in a high throughput screening or whether the substance is capable of inhibiting fungal or microorganism infestation of plants are well known to those skilled in the art.
  • Fig. 1 Influence of amylase inhibitor AI-I on the enzyme activity of amylases of different origin.
  • Fig. 2 Influence of the amylase inhibitor AI-2 on the enzyme activity of amylases of different origin.
  • FIG. 3 Influence of amylase inhibitors (AI-1 and AI-2) on the activity of cellulase (T.reesei 6 U / mg Fa. Sigma).
  • FIG. 4 Influence of the inhibitors (AI-I and AI-2) on the enzyme activity of amylases from the culture filtrate (straw extract) of in vitro grown F. graminearum.
  • FIG. 5 Influence of amylase inhibitors (AI-1 and AI-2) on the enzyme activity of amylases from winter wheat plants infected with F. graminearum in the greenhouse.
  • FIG. 6 Influence of the cellulase inhibitor CI) on the enzyme activity of amylases of different origin.
  • FIG. 7 Influence of cellulase inhibitor (CI) on the enzyme activity of amylases from the culture filtrate and from winter wheat plants infected with F. graminearum in the greenhouse.
  • Fig. 8 Influence of different concentrations of cellulase inhibitor CI on the growth of F. graminearum in Czapek-Dox medium (with sucrose as C-source).
  • FIG. 9 Influence of different concentrations of cellulase inhibitor CI on the growth of F. graminearum in czapek-Dox-CM-cellulose medium.
  • Fig. 10 Influence of different concentrations of the cellulase inhibitor CI on the growth of Fusarium in CD-starch substrate 14 days after inoculation with
  • Fig. 11 Influence of different concentrations of amylase inhibitor AI-1 on the growth of Fusarium in Czapek-Dox medium (sucrose) within 14 days after inoculation with F. graminearum.
  • Fig. 12 Influence of different concentrations of the amylase inhibitor AI-I on the growth of F. graminearum in CD-starch medium during the 14-day growth phase.
  • Fig. 13 Influence of different concentrations of the amylase inhibitor AI-2 on the growth of Fusarium in Czapek-Dox (sucrose) 8 days after inoculation with F. Gram inearum.
  • Fig. 14 Influence of different concentrations of the amylase inhibitor AI-2 on the growth of Fusarium in CD-starch substrate 14 days after inoculation with F graminearum.
  • Fig. 15 Correlation between cellulase activity and ELISA of wheat-grain extracts of different wheatgrass extracts heavily infested with Fgraminearum.
  • Fig. 16 Influence of the amymlase inhibitor AI-I and the cellulase inhibitor CI on the
  • Fig. 17 Influence of the amymlase inhibitor AI-I and the cellulase inhibitor CI on the
  • Fig. 18 Influence of the amymlase inhibitor AI-I and the cellulase inhibitor CI on the
  • K not infected
  • Fg infected with Fusarium graminearum
  • K + AI-I not infected + inhibitor AI-I
  • AI-I + Fg infected + AI-I treated
  • K + CI not infected + inhibitor CI
  • CI + Fg infected + cellulase inhibitor CI.
  • Fig. 19 Quantitative detection of Fusa ⁇ um graminearum in infected and uninfected wheat seedlings on folding filters with and without inhibitor treatment 2 weeks after inoculation.
  • K not infected
  • Rg. Infected with Fusarium graminearum
  • K + AI-I not infected + inhibitor AI-I
  • AI-I + Eg. infected + AI-I treated
  • K + CI not infected + inhibitor CI
  • CI + Rg. infected + cellulase inhibitor CI.
  • Fig. 20 Quantitative detection of Fusarium graminearum in the roots of infected and uninfected wheat plants on folding filters with and without
  • AI-I not infected + inhibitor AI-I
  • AI-I + Rg. Infected + AI-I treated
  • K + CI not infected + inhibitor CI
  • CI + Rg. Infected + cellulase inhibitor CI.
  • Fig. 21 Influence of the amymlase inhibitor AI-I and the cellulase inhibitor CI on the fresh leaf weight with F. graminearum infected and uninfected wheat young plants in soil substrate in the greenhouse after four weeks (experiment 1).
  • K not infected
  • Rg. Infected with Fusarium graminearum
  • K + AI-I not infected + inhibitor AI-I
  • AI-I + Rg. Infected + AI-I treated
  • K + CI not infected + inhibitor CI
  • CI + Rg. Infected + cellulase-inhibitor CI.
  • Fig. 22 Influence of the amymlase inhibitor AI-I and the cellulase inhibitor CI on the fresh leaf weight with F. graminearum infected and uninfected wheat young plants in soil substrate in the greenhouse after four weeks
  • Fig.24 Quantitative detection of Fusarium graminearum in infected and uninfected wheat seedlings in soil in the greenhouse with and without inhibitor treatment 4 weeks after inoculation (experiment 2).
  • K not infected
  • Fg infected with Fusarium graminearum
  • K + AI-I not infected + inhibitor AI-I
  • AI-I + Rg. Infected + AI- I treated
  • K + CI not infected + inhibitor CI
  • CI + Eg. infected + cellulase inhibitor CI.
  • Fig. 25 Influence of the amylase inhibitor AI-I (1 mg / ml) on the infestation of Blumeria graminis f. sp. tritici 1 dpi.
  • Fig. 26 Influence of the amylase inhibitor AI-2 (1 mg / ml) on the infestation of Blumeria graminis f. sp. tritici 7 dpi.
  • Fig. 27 Influence of the cellulase inhibitor CI (100 ⁇ g / ml) on the infestation of Blumeria graminis f. sp. tritici 7 dpi.
  • AI-I Acarbose (Amylase Inhibitor 1)
  • AI-2 Miglitol (Amylase Inhibitor 2)
  • CM-cellulose Carboxymethylcellulose (CM-cellulose) (Wolff Walsrode AG, Walsrode) CM-cellulose RBB, 1,4- ⁇ -glucan (Loewe, Otterfing) CM-Curdlan RBB, 1,3- ⁇ -glucan (Loewe, Otterfing) CM Gelatin RBB, water soluble protein (Loewe, Otterfing) Curdlan, ⁇ -1, 3 glucan (Wako Pure Chemical Industries Ltd.,
  • Glucose sucrose 15 g / 1 CM-cellulose, CM-curdlan, gelatin or soluble starch 5 g / l
  • Potato Dextrose Agar Potato Dextrose Agar (Potato Dextrose Agar, PDA)
  • Pea extract glucose medium Pea extract glucose medium, PEM
  • Carrot Juice Medium Carrot Juice Medium, CJM
  • Oat Starch Medium OSM
  • OSM Oat-Starch Medium
  • the mushrooms below were stored in polystyrene petri dishes (0 90 mm) on the lean straw extract agar at 6 ° C in the refrigerator and inoculated every 6 months.
  • CM-Cellulose RBB (1, 4 ⁇ -glucan)
  • CM-Curdlan-RBB (1,3- ⁇ -glucan)
  • CM-Cellulose RBB (4 mg / ml Fa. LOEWE) 100 ⁇ l of sample in 0.1 M sodium acetate buffer were incubated in a water bath Ih at 40 ° C, the blank batch was incubated without a sample. After the incubation, 100 ⁇ l of sample were pipetted into the blanks, then immediately stopped with 100 ⁇ l of IN HCl and placed on ice for 10 min. In the tests, 3 tests and 3 blanks were carried out per sample. After centrifuging the microtiter plates for 10 min at 2500 rpm, 100 ⁇ l of supernatant was transferred into microtiter plates with a well of 185 ⁇ l per well. The absorbance was measured in a microtiter plate photometer at a wavelength of 592 nm. The calculation of units was based on the reducing groups:
  • the Petri dishes filled with straw extract were each inoculated with a Fusarium-covered agar piece (0 4 mm). Two days after incubation in the dark at 20 ° C, the plates were incubated for 7 days at 20 ° C under 24 hours UV light. Spore production in the liquid straw extract medium proceeded as mentioned under example 3.
  • the sporulating fungal colonies were flooded under sterile conditions with 5-10 ml H 2 Ob, and carefully scraped off the agar with the aid of a flamed slide.
  • the suspension was filtered with the aid of a plastic gauze with 100 or 200 ⁇ m mesh size (depending on conidia size) and the conidial density was determined with the aid of a Fuchs-Rosenthal chamber.
  • Straw extract solution the straw was removed by gauze filtration.
  • the spore density was adjusted to 1.6 ⁇ 10 5 conidia / ml.
  • a direct ELISA double sandwich ELISA
  • CLARK and ADAMS (1977) was used for the detection of F. graminearum.
  • the sample extraction was carried out with the difference that in this case the PPK buffer (pH 7.4) was used instead of the sodium acetate-acetic acid buffer.
  • microtiter plates (Immulon F type, Dynatech) were used. The incubation of the plates was carried out at 37 ° C in a water bath. Optimal antibody / antibody conjugate / StrAP and sample concentrations were determined as described by CASPER and MEYER (1981).
  • the water-straw-meal suspension was filtered through a filter paper (round filter, 90 mm, Schleicher & Schuell, Dassei) under sterile conditions.
  • the filtrate was then diluted 1: 1 (or 2: 1 at low activity) with 0.1 M sodium acetate-acetic acid buffer (pH 5).
  • the enzyme was determined with the appropriate substrate as previously described.
  • Example 1 Influence of the amylase inhibitors All and AI2 and the cellulase inhibitor CI on the enzyme activity of various amylases and cellulases
  • Aspergillus oryzae amylase 35 U / mg, Fluka
  • Aspergillus oryzae amylase 200 U / mg, Sigma
  • Bacillus sp. (1500 - 3000 U / mg, Sigma) about 3000 U / mg amylase from human amylase (500 U / mg, Sigma)
  • T. reesei cellulase (6 U / mg) (Sigma).
  • T.reesei cellulase (10.4 U / mg (Sigma)
  • the amylase inhibitor Al-I completely inhibits the human salivary amylase against which the inhibitor was developed at a concentration of 250 ⁇ g / ml, while the Bacillus amylase is also inhibited by 0.5 mg / ml inhibited, but not totally turned off by this concentration. It is striking that the two Aspergillus amylases are not or only very slightly influenced.
  • amylase inhibitor AI-2 inhibits neither the human amylase nor the commercially available bacterial or fungal amylases, as can be seen from FIG. It is important to emphasize at this point that especially in the amylase Inhibitors a higher degree of specificity was observed (ZECHARIA M. 1989, MADARIAGA H. et al., 1988).
  • the amylases of plants infected with F. sraminearum are inhibited by the inhibitor Al-I at a concentration of 0.5 mg / ml up to 69.2%, but not completely eliminated (see Figure 5). Also in this case, the inhibitor AI-2 is ineffective.
  • FIG. 7 shows that the cellulase inhibitor CI does not or only insubstantially inhibits the amylases from the culture filtrate and those from wheat plants infected with Fusarium graminearum. Result
  • amylase inhibitor AI-I shows a classical inhibition curve for Fusarium graminearum, as has also been shown in the literature for human amylases (ARNUBIO et al., 2008). This justifies the assumption that in this way also the growth of the fungus can be inhibited.
  • the amylase inhibitor AI-2 which also inhibits the amylases of Bacillus sp., was unable to inhibit the two Aspergillus species and human amylase.
  • AI-2 had, as expected, no effect on the amylases of the plant extracts.
  • the synthetic Czapek-Dox medium with starch or cellulose were used as sole C source.
  • the inhibitory effect of the inhibitors was determined in comparison with the normal Czapek-Dox medium with sucrose as the C source. After preliminary tests, the following media proved to be optimal: Czapek-Dox medium
  • Agua bidest 1000 ml pH 6.5 optional C sources: sucrose 15 g
  • microtiter plates from SARSTEDT, Nümbrecht, were used. The plates were filled with 100 ⁇ l of the respective nutrient medium (see above) with different inhibitor concentrations as given below. Spore density was 1.6 x 10 5 conidia / ml in all cases. Each experiment was repeated three times. Check 3 wells / dilution with 100 ⁇ l spore suspension in double-distilled water.
  • the fungus was also inhibited by the cellulase inhibitor CI, but only from 75 ug / ml partially and totally only from 100 ug / ml. Lower concentrations of 6.5-12.5 ⁇ g / ml even resulted in verifiable growth promotion.
  • amylase inhibitor AI-I has no negative effect on fungal growth in czapek-Dox medium with sucrose as sole C source. Verified by repeated repetition, it can be stated that the growth was even promoted by the inhibitor (see Figure 11).
  • the fungus When the fungus grows in a medium with starch as the sole C source, it is already inhibited to about 50% even at a relatively low concentration of the amylase inhibitor AI-I of 15 ⁇ g / ml (see FIG. The inhibition is totally more effective at a concentration of 30 ⁇ g / ml and thus by a factor of 3 than the cellulase inhibitor over starch as a substrate.
  • AI-I amylase inhibitor
  • amylase Inhibitor (AI2) Influence of the Amylase Inhibitor (AI2) on the Growth of Fusarium sraminearum
  • the amylase inhibitor AI-2 has no effect on fungal growth, neither in the Czapek-Dox medium with sucrose as C source still in the medium with starch as sole C source (see Fig. 13 and 14).
  • amylase inhibitor Al-2 could inhibit neither the commercially available amylases or cellulases of the various microorganisms nor the amylases produced by Fusarium graminearum in vitro or in the plant. Therefore, it was logical that AI-2 had no inhibitory effect on the growth of the fungus in vitro.
  • Example 3 Influence of amylase and cellulase inhibitors on the infection of wheat plants with Fusarium graminearum under greenhouse conditions
  • Rg. Infected + AI-I treated
  • K + CI not infected + inhibitor CI
  • CI + Rg. Infected + cellulase inhibitor CI.
  • the water-straw suspension was filtered through a coarse-pored filter paper (round filter 90 mm, Schleicher & Schuell, Dassei). The straw was caught and then mixed with the soil.
  • Soil preparation 10 kg of soil (1: 2 sand / field soil) were thoroughly mixed with 72 g of infected straw prepared as described above.
  • An additional 10 kg of soil (1: 2 sand / field soil) was mixed well with 72 g of uninfected but autoclaved straw. Both floor treatments were each distributed in 30 pots (9x9 cm).
  • the wheat plants were harvested after one month and the effect of the respective inhibitor was examined by ELISA test. As expected, weight reduction in Fusarium-inoculated wheat plants compared to non-affected controls can also be observed in soil substrate under greenhouse conditions (see Figures 21 and 23).
  • the amylase inhibitor AI-I abolishes this fresh-weight depression, suggesting that the fungus is inhibited by the inhibitor. A negative influence of the inhibitor on plant growth in general can not be determined (see Figures 21, 22).
  • the cellulase inhibitor CI did not inhibit fungal growth under these conditions as compared to the plants grown on folding filters. Quantitative detection of F. sraminearum in infected wheat plants in soil using the ELISA
  • Cellulase inhibitor CI detect. A clear interpretation for this can not be found. It would be conceivable that, with a comparatively longer germination, the inhibitor CI partially diffuses out of the grain and bound to soil particles or through
  • amylase inhibitor AI-I works similarly well as in the
  • the cellulase inhibitor also amylases and beyond not only the growth of Fusarium graminearum on cellulose but also on starch was able to inhibit (see Fig. 10, 11, 14). Thus, this inhibitor must be considered partially unspecific.
  • Table 3 Evaluation of powdery mildew (Blumeria graminis sp tritici) according to MOLL et al. (1996) 7 dpi.
  • AI-2 greatly reduced the powdery mildew infestation with an infestation reduction from 60% control to 1%.
  • the two other amylase inhibitors also reduced the infection to 7% in the case of AI-I and 10% in the case of CI.
  • an explanation of the inhibitory effect of all inhibitors in the case of the mildew fungus could be explained in the case of the cellulase inhibitor with the inhibition of the required for the penetration of this biotrophic extracellular cellulase, but is certainly not in question for the inhibition of a fungal amylase, as extracellular amylases have not been described for this biotrophic fungus.
  • the amylase inhibitor AI-2 after inhibition in a solution of 1 mg / ml completely inhibits the germination of wheat plants and peas, but has no influence on the mature leaf, as trials with the wheat powdery mildew Blumeria graminis f. sp. From the germination inhibition of plants can be concluded that this inhibitor inhibits the plant's own amylase.
  • AI-2 inhibits not only the amylases but also other glucosidases, ie, apparently intervenes in other essential metabolic reactions, which could also explain the germination inhibition of plants (ROSEMARIE et al., 1990, MARCHYLO et al., 1976, WESELAKE et al , 1985; MYUKI et al., 2002.

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Abstract

L'invention concerne l'utilisation de composés de la formule A, B, ou C comme produits de lutte contre les champignons ou autres micro-organismes, notamment dans le cadre de la protection phytosanitaire et de la protection de matériaux.
EP09777184A 2008-07-15 2009-07-14 Produit de protection phytosanitaire et de protection de matériaux Withdrawn EP2330898A2 (fr)

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EP09777184A EP2330898A2 (fr) 2008-07-15 2009-07-14 Produit de protection phytosanitaire et de protection de matériaux

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EP08160456A EP2145538A1 (fr) 2008-07-15 2008-07-15 Produit de protection des plantes et des matériaux
EP09777184A EP2330898A2 (fr) 2008-07-15 2009-07-14 Produit de protection phytosanitaire et de protection de matériaux
PCT/EP2009/005115 WO2010006766A2 (fr) 2008-07-15 2009-07-14 Produit de protection phytosanitaire et de protection de matériaux

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CN105246478A (zh) * 2013-03-15 2016-01-13 优尼特尔病毒学公司 抗菌化合物

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DE2614393C3 (de) 1976-04-02 1980-04-03 Bayer Ag, 5090 Leverkusen Aminozucker-Derivate und diese Verbindungen enthaltende Arzneimittel
US4175123A (en) 1976-12-23 1979-11-20 Bayer Aktiengesellschaft Amino-sugar derivatives, process for their preparation and pharmaceutical composition thereof
JPS5953920B2 (ja) 1977-12-28 1984-12-27 東洋醸造株式会社 新規なアミノ糖化合物およびその製法
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WO2010006766A2 (fr) 2010-01-21
WO2010006766A3 (fr) 2011-04-28

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