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
  • A01N49/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
  • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
  • C12N1/14—Fungi; Culture media therefor
  • C12N1/145—Fungal isolates
• • 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
  • A01N63/00—Biocides, pest repellants or attractants, or plant growth regulators containing microorganisms, viruses, microbial fungi, animals or substances produced by, or obtained from, microorganisms, viruses, microbial fungi or animals, e.g. enzymes or fermentates
  • A01N63/30—Microbial fungi; Substances produced thereby or obtained therefrom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
  • C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P17/00—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
  • C12P17/16—Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms containing two or more hetero rings
  • C12P17/162—Heterorings having oxygen atoms as the only ring heteroatoms, e.g. Lasalocid
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
  • C12R2001/00—Microorganisms ; Processes using microorganisms
  • C12R2001/645—Fungi ; Processes using fungi

Definitions

• the present invention relates to fungicidally active compounds and derivatives thereof, and processes and microorganisms for producing such compounds. Furthermore the invention relates to fungicidal compositions comprising these compounds, either alone or in combination with other biocides or growth regulators, and to the use of the compounds or compositions of the invention for controlling fungi.
• Natural products can often provide an alternative to synthetic fungicides in that they may have another mode of action, may be more biodegradable and safer in the environment. It is consequently an object of the invention to identify novel fungicidally active compounds such as microbial secondary metabolites which originates from natural sources or are direct derivatives of such compounds.
• the invention concerns compounds closely related to the compound described in the above US Patent No. 5,008,187 and their use in agriculture for controlling fungi.
• R 1 1 is hydrogen, straight or branch ⁇ ed alkyl with 1 to 6 carbon atoms, such as methyl, straight or branched hydroxyalkyl with 1 to 6 carbon atoms, such as CH 2 OH, straight or branched alkylethers with 1 to 6 carbon atoms or optionally substituted aromatic ethers; each R 2 independently are hydrogen, straight or branched alkyl with 1 to 6 carbon atoms, such as methyl, straight or branched hydroxyalkyl with 1 to 6 carbon atoms, such as CH 2 OH, straight or branched alkylethers with 1 to 6 carbon atoms, or optionally substituted aromatic ethers; and each R3 independently are hydrogen, hydroxy, methoxy, acetoxy, straight or branched alkylethers with 1 to 6 carbon atoms, or optionally substituted aromatic ethers; and wherein the chiral centres a, b, c, d, e, f, and g each independently may have the R
• Said compounds exhibit antifungal activity and can be used as an agricultural, horticultural antifungal compound for protection of plants against fungi.
• the compounds of formulae la and lb are obtainable by cultivation of a microorganisms belonging to the genus Fusarium, specifically microorganisms belonging to the species Fusarium pallidoroseum, and more specifically the strain designated Fusarium pallidoroseum (IMI CC No. 351439) and subsequent recovery of the active compounds from the biomass. These isolated compounds can thereafter be treated chemically to produce the derivatives indicated above.
• Another method for producing the compounds of the invention is by traditional chemical synthesis from appropriate starting materials.
• compositions comprising the novel compounds of the invention in combination with suitable excipients, such as diluents, car ⁇ riers, etc.
• the invention also relates to the use of microorganisms producing the compounds of the invention as fungicidal compositions.
• microorganisms producing the compounds of the invention as fungicidal compositions.
• it is also contemplated to combine the novel compounds of the invention with known biocides or plant growth regulators for making up novel combination compositions.
• the invention in a fourth aspect relates to methods of controlling plant diseases by application of compositions comprising the novel compounds of the invention to infested areas.
• the invention relates to the use of the novel compounds or compositions of the invention for combating or controlling plant diseases, especially fungal attack.
• the invention relates to an isolated pure culture of the microorganism Fusarium pallidorseum (IMI CC No. 351439).
• IMI CC Fusarium pallidoroseum
• IMI CC International Mycological Institute Culture Collection
• Ferry Lane Kew, Surrey TW9 3AF, England
• IMI CC being an interna ⁇ tional depository under the Budapest Treaty affords permanence of the deposit in ac ⁇ cordance with rule 9 of said treaty.
• UVU CC designation IMI CC No. 351439
• IMI CC No. 351439 belongs to the class Deuteromycetes, and the order Moniliales. The fungus was isolated from plant material collected in the tropical area. DETAILED DESCRIPTION OF THE INVENTION
• R 1 1 is hydrogen, straight or branch ro ed alkyl with 1 to 6 carbon atoms, such as methyl, straight or branched hydroxyalkyl with 1 to 6 carbon atoms, such as CH 2 OH, straight or branched alkylethers with 1 to 6 carbon atoms or optionally substituted aromatic ethers
• each R 2 independently are hydrogen, straight or branched alkyl with 1 to 6 carbon atoms, such as methyl, straight or branched hydroxyalkyl with 1 to 6 carbon atoms, such as CH 2 OH, straight or branched alkylethers with 1 to 6 carbon atoms, or optionally substituted aromatic ethers
• each R- > independently are hydrogen, hydroxy, methoxy, acetoxy, straight or branched alkylethers with 1 to 6 carbon atoms, or optionally substituted aromatic ethers
• the chiral centres a, b, c, d, e, f, and g each independen
• the compounds of formula I may be prepared by aerobic cultivation on suitable nutrient media under conditions hereinafter described with a strain of a fungus belonging to the genus Fusarium especially the fungus Fusarium pallidoroseum (UvU CC No. 351439) and subsequent recovery of the active components from the biomass and/or fermentation medium.
• the natural metabolite may subsequently be modified chemically or by biotransformation in order to obtain various derivatives thereof.
• the derivatives may be produced in order to improve certain properties of the metabolite such as its solubility in aqueous media, its hydrophobicity, hydrophilicity, stability, specificity, etc.
• compounds according to the invention may be produced by well known chemical synthetic processes using available starting materials.
• the compounds of the invention have been found to exhibit antifungal activity, and they are consequently useful as active ingredients in fungicidal compositions.
• the present invention therefore also embraces fungicidal compositions containing the compounds of formula I as active components.
• the invention contemplates the use of any of the compounds of the invention used alone or in combination with any other of the compounds of the invention or any other biocidally active agent or plant growth regulator as active components in any fungicidal composition.
• a fungicidal composition according to the invention having a fungicidally active compound of the invention as its active ingredient may for agronomical and/or horticultural applica ⁇ tions be formulated by mixing the active principle with suitable inert and compatible carriers or diluents to obtain a composition of the type generally used in agricultural compositions such as a wettable powder, an emulsifiable concentrate, a concentrated emulsion, a granular formulation, a water soluble powder, an alginate, a xanthan gum and/or an aerosol.
• suitable inert and compatible carriers or diluents such as a wettable powder, an emulsifiable concentrate, a concentrated emulsion, a granular formulation, a water soluble powder, an alginate, a xanthan gum and/or an aerosol.
• solid carriers bentonite diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vermiculite, ground shells, and clay may be mentioned.
• a surface active agent may also be added with the purpose of producing a homogeneous and stable formulation.
• the diluent or carrier in the composition of the invention can as indicated be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent.
• Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulphates such as sodium dodecyl sulphate, sodium octadecyl sulphate or sodium cetyl sulphate; ethoxylated fatty alcohol sulphates; ethoxylated alkylphenol sulphates; lignin sulphonates; petroleum sulphonates; alkyl aryl sulphonates such as alkyl-benzene sulphonates or lower alky
• butyl-naphthalene sulphonate salts of sulphonated naphthalene-formaldehyde condensates; salts of sulphonated phenol-formaldehyde condensates; or more complex sulphonates such as the amide sulphonates, e.g. the sulphonated condensation product of oleic acid and N- methyl taurine or the dialkyl sulphosuccinates, e.g. the sodium sulphonate of dioctyl succinate.
• amide sulphonates e.g. the sulphonated condensation product of oleic acid and N- methyl taurine or the dialkyl sulphosuccinates, e.g. the sodium sulphonate of dioctyl succinate.
• Non-ionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- of alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetraethyl-5-decyn-4,7-diol, or ethoxylated acetylenic glycols.
• a cationic surface-active agent examples include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di- or polyamine; or a quaternary ammonium salt.
• compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous emulsion, a dusting powder, a seed dressing, a dispersible powder, an emulsifiable concentrate or granules. Moreover, it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.
• An emulsifiable concentrate comprises the active ingredient dissolved in a water-immiscible solvent which is formed into an emulsion with water in the presence of an emulsifying agent.
• a dusting powder comprises the active ingredient intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.
• a granular solid comprises the active ingredient associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or adsorbed on a pre- granular diluent for example, Fuller's earth, attapulgite or limestone grit.
• Wettable powders, granules or grains usually comprise the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay.
• Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the active ingredient with water or other liquid, a wetting agent and suspending agent.
• composition of the invention in addition to said fungicidally active compounds of the invention may also contain other active ingredients such as other biocides, such as fungicides, pesticides, herbicides, insecticides, nematocides, acaricides or plant nutrients or fertilizers.
• EBIs ergosterol biosynthesis inhibitors
• EBIs ergosterol biosynthesis inhibitors
• These are generally imidazole or triazole derivatives and examples include those known by the common names prochloraz, triadimefon, propiconazole, diclobutrazol, triadiminol, flusilazole, flutriafol, myclobutanil, penconazole, quinconazole, imazalil and diniconazole.
• non azole EBis include nuarimol, fenarimol, fenpropimorph, tridemorph and fenpropidine.
• anilides e.g. carboxin, matalaxyl, furalaxyl, ofurace, benalaxyl, mepronil, flutolanil, pencycuron and oxadixyl
• benzimidazoles e.g. benomyland carbendazim
• miscellaneous compounds including dithiocarbamates, bisdithiocarbamates, imidazoles, triazoles, phathalonitriles, polyhalogenalkylthio compounds, iminoctadine, guazatine, dicloran, chlorothalonil, pyrifexox, ethirimol, cymoxanil and anilazine.
• the invention in its fourth aspect relates to methods of combating fungi ON plants, wherein an effective amount of a fungicidally active compound of the invention is applied to a region to be treated.
• compositions of the invention may for agronomical or horticultural uses be applied to a region to be treated either directly to the soil as a pre- emergence treatment or to the foliage or fruits of the plants as a pre- and/or post- emergence treatment. Depending on the crop and circumstances the treatment may be postponed until seeds or fruits appear on the plants, wherein fungi are to be controlled.
• the active preparation or the compositions of the invention can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure. In both such cases the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged.
• the spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary.
• concentration of the active compounds of the invention described herein in the compositions of the invention may vary within a wide range depending on the type of formulation and the field of application.
• concentration of the fungicidally active compounds of the invention in the compositions of the present invention when used alone or in combination with a conventional fungicide, as applied to plants is preferably within the range from about 0.001 to about 30 per cent by weight, especially 0.01 to 3.0 per cent by weight.
• the amount of active compound can also vary widely and can be, for example, in the range from about 5 to about 95 per cent by weight of the composition.
• the concentration of the other fungicidally active ingredient in the mixed composition of the present invention, as applied to plants is preferably within the range of 0.001 to 50 per cent by weight, especially 0.01 to 10 per cent by weight.
• the amount of other active ingredient can vary widely and can be, for example, from 5 to 80 per cent by weight of the composition.
• a suitable rate of application is from 0.001 to 50 kg per hectare, preferably from 0.05 to 5 kg per hectare.
• the active preparation of the invention alone or in combination with a conventional biocide can also be applied to seeds or other habitats.
• the preparation can be applied directly to the soil before, at or after drilling so that the presence of active ingredient in the soil can control the growth of fungi which may attack seeds.
• compositions may be applied in amounts corresponding to from about 1 g to about 50 kg fungicidally active compound per hectare.
• the active preparation alone or in a mixture with the conventional biocide can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds.
• a suitable application rate is within the range of from 0.01 to 50 kg per hectare, more preferably from 0.05 to 5 kg per hectare.
• the fungicidally active compounds of the invention may be used for combating or controlling fungi in mammals, including humans; and for the preservation of wood by adding said compounds to wood preservation and/or impreg ⁇ nation compositions.
• the active compounds of the invention may be useful as a fungi ⁇ cide and preservant in paints - both to prevent growth in the paint during storage, and growth on the painted object such as the plastered surface of a house.
• Taxonomy and morphology of the organism are identical to each other.
• the fungus is identified as Fusarium pallidoroseum (Cooke) Sacc. (syn. F. semitectum Berk. & Rav) using: Burgess, W. & Liddell CM. (1983), Laboratory manual for Fusarium research: Incorporation a key and descriptions of common species found in Australia, The University of Sydney, Sydney, (ISBN 0-909798-39-7), Booth, C. (1971). The genus Fusarium. Commonwealth Mycological Institute, Kew Surrey, England, and Booth, C & B.C. Sutton, 1984. Fusarium pallidoroseum, the correct name for F. semitectum Auct. Trans. Br. Mycol. Soc. 83 (4): 702-704.
• the fungus belongs to the class Deuteromycetes, order Moniliales.
• the aerial mycelium on Potato Sucrose Agar is floccose white gradually changing through peach, avellaneous to buff brown.
• Conidia of two types primary and secondary.
• the primary conidia are somewhat shorter than the secondary. They have a wedge-shaped foot cell, are hyaline, 0-5 septate and measure 7.5-35 x 2.5-4 ⁇ m. These primary conidia are formed as holoblastic conidia from polyblastic sympodially proliferating cells with up to six separate spores formed from each cell.
• the secondary conidia are formed from simple phialides. These conidia have a typical heeled foot cell (for further details see Booth and Sutton, 1984).
• a culture of the strain can be grown on potato dextrose agar (Difco) slants (12 ml/slant), autoclaved at 121 °C for 40 minutes and will hereafter be referred to as PD agar. After inoculation it can be incubated at 20 - 25° C for 2 days or longer.
• Difco potato dextrose agar
• the fungicide can also be produced in surface cultures in accordance with well known procedures.
• the fermentation can also be carried out in media containing other sources of carbon and nitrogen assimilable by the microorganism and generally low levels of inorganic salts.
• the media may be supplemented with trace metals, although if complex sources of carbon and nitrogen are employed, they are usually present in the complex sources.
• the compounds of the invention can also be extracted from the biomass and/or growth medium by any other conventional extraction method known in the art, such as with a lower chain alcohol, acetone, DMSO, ethylacetate etc.
• the concentrated extract can be purified by adsorption to a hydrophobic resin.
• the resin used are non-ionic, especially cross-linked styrene(divinyl-benzene-copolymers and halogenated styrene/divinyl-benzene- copolymers.
• a generally used adsorption resin is XAD-8 (Rohm and Haas Co.).
• a mixture of the two compounds can be obtained more than 90% pure by elution of this resin with increasing concentrations of a lower alcohol/acetone in water, preferably methanol or ethanol.
• a crude mixture of the two compounds can be obtained by combination and concentration of these fractions. If required the compounds can be further purified by known reversed phase chromatography using an acidic mobile phase, yielding two pure compounds.
• a slant culture of the strain grown on PD agar was inoculated into yeast extract-sucrose medium, fermented, and extracted as disclosed above.
• 1115 ml supernatant was concentrated under reduced pressure to 250 ml.
• the concentrated extract was applied to a 200 ml column of Amberlite XAD-8 (Rohm and Haas) which was eluted with a step gradient (0%, 30%, 50%, 70% and 100% each 200 ml) of aqueous ethanol.
• the activity of all fractions were monitored by a disk diffusion assay with Botrytis cinerea. The biological activity was found in the pale yellow fractions eluting with 30 to 50 % ethanol, which upon evaporation of the solvent yielded 780 mg of a yellow oil.
• the novel compound BK 219 assigned formula la is a colourless solid characterized by the following physico-chemical properties.
• the active compound assigned formula lb is a colourless solid characterized by the following physico-chemical properties.
• ⁇ -NMR data are given in table 1 and "C-NMR data are given in table 2.
• the compound is soluble in a variety of organic solvents such as methanol, ethanol, dimethylformamide, dimethyl sulphoxide, ethylacetate and the like.
• the compound is soluble in various organic solvents such as methanol, ethanol, dimethylformamide, dimethyl sulphoxide, ethylacetate and the like.
• Compound lb is identical to the compound described in US Patent No. 5,008,187.
• the compounds la and lb have been found to be active against a broad spectrum of fungi, rendering them adaptable for agricultural/horticultural applications. Activity against a bacteria and a yeast was also showed.
• Tomato plants (5 weeks old) were sprayed to run off with a liquid suspension using a handhold sprayer (Bink Bullows 900).
• the suspension contained different concentrations of either compound la and lb in combination or only compound la.
• the plants were kept 24 hours in a glasshouse to dry before they were inoculated with a spore suspension containing lxlO 5 spores per ml and 25 % grape juice.
• the inoculation was carried out with a handhold atomizer (Wagner, Pico Bel). The plants were then incubated (16 hours light (1000 lux) and 8 hours dark) at 15-20°C in clear polythene bags to raise the relative humidity to 95-100%
• Compound Ic has been found to have an in vitro inhibition on the growth of fungi belong to Ascomycetes and Deuteromycetes. It was found particular potent towards:
• the compound also showed in vitro inhibition effect on the growth of a bacteria belonging to the order Eubacteriales.

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