EP1232149A2 - Derives de melitthiazol fongicides - Google Patents

Derives de melitthiazol fongicides

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Publication number
EP1232149A2
EP1232149A2 EP00988747A EP00988747A EP1232149A2 EP 1232149 A2 EP1232149 A2 EP 1232149A2 EP 00988747 A EP00988747 A EP 00988747A EP 00988747 A EP00988747 A EP 00988747A EP 1232149 A2 EP1232149 A2 EP 1232149A2
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EP
European Patent Office
Prior art keywords
group
formulae
alkyl group
compound
formula
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.)
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Application number
EP00988747A
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German (de)
English (en)
Inventor
Oliver Meyer
Werner Simon
Gerhard Hoefle
Udo Soeker
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.)
Helmholtz Zentrum fuer Infektionsforschung HZI GmbH
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Helmholtz Zentrum fuer Infektionsforschung HZI GmbH
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Publication of EP1232149A2 publication Critical patent/EP1232149A2/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Withdrawn legal-status Critical Current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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/24—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/28—Radicals substituted by nitrogen atoms

Definitions

  • This invention relates to melithiazole derivatives, a novel process for their preparation, compositions containing such compounds, a method for combating a fungus at a locus comprising treating the locus with such compounds, and their use as fungicides.
  • Fungicides are thus an important agricultural technology which can be used to protect crops and foods from fungus and fungal diseases.
  • the preparation of melithiazole C by reductive cleavage of myxothiazol A with subsequent transformation of the resulting melithiazole C amide into the corresponding methyl ester has been described by a poster of B. B ⁇ hlendorf et al. presented at the Dechema Naturstofftagung in Irsee, Germany in 1996. Melithiazole C disclosed on this poster shows weak in vitro activity against Bortrytis ci ⁇ erea.
  • the present invention provides a fungicidal compound which contains essentially equimolar amounts of the enantiomer pair of formulae lA and IB:
  • R 1 represents a hydrogen atom or an optionally substituted alkyl, alkenyl, or aryl group
  • R 2 , R 3 , R 4 and R 5 each independently represent an alkyl group
  • R 6 represents a group of formula -COOR 7 or -CONR 7 R 8 , in which R 7 and R 8 each independently represent a hydrogen atom or an alkyl group
  • L 1 represents a hydrogen or halogen atom or an optionally substituted alkyl group
  • the zigzag line indicates that the alkoximino group may have the
  • the new compounds are easily produced and combine excellent fungicidal activities against a broad range of phytopathogenic fungi in various crops with comparably high systemicities.
  • the present invention relates to a process for the preparation of the novel compound of formulae IA and IB, and to the novel intermediate compounds of formula II
  • R and L are as hereinbefore defined for formula I and L 2 represents a halogen atom
  • a fungicidal compound which contains essentially equimolar amounts of the enantiomer pair of formulae lA and IB: wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and L 1 are as hereinbefore defined possess excellent fungicidal activity against diseases caused by phytopathogenic fungi at low dose rates with high bioavailability due to their high systemicity.
  • the skilled worker would not expect that this racemic mixture would have the almost the same fungicidal activity as the optically pure enantiomers disclosed by WO 98/46583.
  • Optionally substituted moieties in the compounds of formula I may be unsubstituted or have from one up to the maximal possible number of substituents. Typically, 0 to 2 substituents are present.
  • Each optionally substituted group is independently substituted by one or more halogen atoms, or nitro, cyano, cycloalkyl, preferably C 3 _s cycloalkyl, cycloalkenyl, preferably C 3 .
  • cycloalkenyl haloalkyl, preferably C-
  • halogen atom denotes a bromine, iodine, chlorine or fluorine atom, and is preferably a bromine, chlorine or fluorine atom.
  • racemate IA/IB denotes equimolar amounts of the enantiomer pair of formulae IA and IB.
  • alkyl refers to a straight or branched chain radical or moiety.
  • such radicals have up to 10, in particular up to 6, carbon atoms.
  • an alkyl or alkoxy moiety has from 1 to 6 carbon atoms, and most preferably, from 1 to 5 carbon atoms.
  • a preferred alkyl moiety is the methyl, ethyl, n-propyl, isopropyl or n-butyl group.
  • An aryl group as substituent or part of other substituents is suitably an optionally substituted phenyl or naphthyl group.
  • a heteroaryl group as substituent or part of other substituents is preferably an optionally substituted 5- or 6-membered heterocyclic group containing one or more heteroatoms selected from nitrogen, oxygen and sulfur, with at least one oxygen, one sulfur atom or 1 to 3 nitrogen atoms being preferred. Examples of such groups are thienyl, furanyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidyl, py dazinyl, and triazinyl groups.
  • 5- or 6-membered heterocycles may be fused with a benzene ring.
  • Aryl preferably represents a phenyl group substituted by one or more of the same or different substituents selected from halogen atoms, alkyl groups, alkoxy groups, cyano groups, haloalkyl groups, haloalkoxy groups, alkylthio groups and haloalkylthio groups.
  • the invention particularly relates to compounds of racemate IA/IB in which any alkyl part of the groups R , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and 1_ , which may be straight chained or branched, contains 1 to 10 carbon atoms, preferably 1 to 9 carbon atoms, more preferably 1 to 6 carbon atoms, and, in which each optionally substituted group may be independently substituted by one or more halogen atoms or nitro, cyano, cycloalkyl, preferably C 3 . 6 cycloalkyl, cycloalkenyl, preferably C 3 .
  • cycloalkenyl haloalkyl, preferably C- ⁇ haloalkyl, halocycloalkyl, preferably C 3 _5 halocycloalkyl, alkoxy, preferably C ⁇ alkoxy, haloalkoxy, preferably C-
  • the invention especially relates to compounds of the general formula I in which R 1 represents a straight-chained or branched C ⁇ _ 0 alkyl, in particular, a straight-chained C 1 . 6 alkyl group, in which the alkyl moiety may be unsubstituted or substituted by 1 to 3 substituents selected from the group 10 consisting of halogen atoms, aryl, alkoxy, haloalkyl and haloalkoxy groups, most preferably being a methyl, ethyl, propyl or benzyl group.
  • racemates IA/IB in which R 2 represents a C ⁇ Q alkyl group, preferably a C- ⁇ alkyl, and most preferably a methyl group.
  • R 3 represents a C ⁇ _ 10 alkyl group, preferably a C ⁇ _4 alkyl, in particular, a methyl group.
  • racemates IA/IB wherein R 4 represents a hydrogen atom or a C 1 .
  • Q alkyl group preferably a C- ⁇ alkyl, in particular a methyl group.
  • Most preferred are those racemates IA/IB in which both 20 R 3 and R 4 represents a C- ⁇ alkyl, in particular, a methyl group.
  • racemates IA/IB are those in which R 5 represents a C-i-10 alkyl group, preferably a C-
  • R 7 represents a C-
  • racemates IA/IB are oils, gums, or crystalline solid materials and possess valuable fungicidal properties when used as a fungicide for control of diseases in agronomic crops, additionally, the compound may be used as a biocide for the control of insect pests and nematodes, as a biocide of human/animal diseases/pests, and as a protectant or preservative for wood, leather or tissue.
  • the compounds of the present invention can curatively and protectively be used against a broad spectrum of diseases in plant and fruit production such as grain producing crops (wheat, barley, rice, rye, triticale, oat, maize, sorghum and others), grape vine plants and fruits, solanaceous crops (potato, tomato, tobacco, pepper and others), top fruit, stone fruits, soft fruits and fruit crops (apples, pears, citrus, mango, bananas, coffee, cocoa and others), oil producing crops (soybeans, sunflowers, groundnuts, rape, olives, palms and others), vegetables (like beans, lettuce, cucumbers, pumpkins, brassicas and others), horticultural plants, hops, sugarbeets, ornamentals, flowers, forestry trees and crops and others.
  • grain producing crops wheat, barley, rice, rye, triticale, oat, maize, sorghum and others
  • grape vine plants and fruits solanaceous crops (potato, tomato, tobacco, pepper and
  • Examples (but not excluding others) of such diseases are powdery mildews, downy mildews and late blights, anthracnoses, septorioses, blasts and blights, scabs and spots, blotches, rots on fruits, stems, leaves and roots, rusts, alternarioses, cercosporoses, sclerotinioses, moulds, wilts, smuts and bunts and others.
  • racemates IA IB possess a high degree of fungicidal activity over a wide concentration range. Moreover, the compounds according to the invention show enhanced curative and residual control of fungi and fungal diseases such as cereal, grape, apple and solanaceous crops diseases, and improved foliar systemicity compared with conventional fungicides.
  • R 1 represents a C- ⁇ alkyl group
  • L 1 represents a hydrogen atom or a C-i_4 alkyl group
  • R 2 represents a C -6 alkyl or benzyl group, the phenyl moiety of which may be unsubstituted or substituted by one or two substituents selected from the group consisiting of halogen atoms, C- ⁇ alkyl, C-
  • R 3 , R 4 and R 5 each represent a methyl group.
  • the compounds of the present invention are prepared via a process which comprises the steps of
  • R and L 1 are as hereinbefore defined and L 2 represents a suitable leaving group
  • R 3 , R 4 , R 5 and R 6 are as hereinbefore
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group, or R 9 and R 10 taken together represent an alkylenediyl, preferably an ethylene-1 ,2- diyl, a propylene-1 ,3-diyl or a 1 ,1 ,2,2-tetramethylethylene-1 ,2-diyl group, in the presence of a transition metal or a transition metal complex and optionally a base, and
  • the intermediates may themselves be prepared according to established methods or routine adaptations thereof. Substituents which are not compatible with the selected reaction conditions may be introduced afterwards. They may be generated by known methods such as subsequent derivatization or substitution of a suitable group or by cleaving off a suitable protecting group.
  • the compounds of formula II, wherein L 2 represents halogen atom can be prepared by metal halogen exchange of known 2,4-dihalothiazoles (e.g., Reynaud er a/., Bull. Soc. Chim. France, 1962, 1735) with alkyllithium or lithium naphthale ⁇ ide to generate 4-halothiazol-2-yl-lithium, which is subsequently reacted with an alkyl alkanoate.
  • 2,4-dihalothiazoles e.g., Reynaud er a/., Bull. Soc. Chim. France, 1962, 1735
  • any inert organic solvent is suitable, preferably aliphatic, cycloaliphatic or aromatic hydrocarbons, which may be halogenated such as hexane, ligroine, petrol ethers, cyclohexane, benzene, toluene, xylene, di-, tri- or tetrachloromethane, ethylenechloride, t chloroethylene and chlorobenzene; ethers such as diethylether, methylethylether, methyl-tert- butylether, diisopropylether, dibutylether, tetrahydrofuran and dioxane; ketones such as acetone and butan-2-one; nithles, such as acetonithle and propionitrile, carboxylic esters, such as ethyl acetate and amyl acetate; carboxylic esters, such as ethyl acetate and amyl acetate;
  • Suitable bases for use in the process of the present invention are inorganic and organic bases such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium ethylate, sodium methylate, potassium tert-butylate, triethylamine, dimethylaminopy dine, pyhdine, sodium hydride, sodium amide, butyllithium and lithium diisopropylamide.
  • Suitable transition metals for the use in the process of the present invention are palladium and nickel, in particular palladium which is complexed by phosphine ligands such as triphenylphosphine, tricyclohexylphosphine or t -isopropylphosphine, most preferred is tetrakis-(triphenylphosphine)-palladium or a mixture of palladium acetate and triphenylphosphine.
  • the prepared racemates IA IB may be isolated and purified using conventional methods and techniques.
  • the starting compounds for the preparation of compounds of this invention are either known or can be prepared according to known methods.
  • the molar ratio between the compounds of formula II and formulae IIIA/IIIB in step (a) is as a rule in the range of 0.3 to 1.9, preferably 0.8 to 1.2, and in particular, 0.9 to 1.1. Most preferably, the compounds of formulae II and IIIA/IIIB are used in about equimolar ratios.
  • the reaction is preferably carried out at a temperature from 0 to 150 °C, and preferably from 25 to 120 °C.
  • IVA/IVB in step (b) is as a rule in the range of 0.8 to 2.5, preferably 1 to 2.0, and, in particular, 1.1 to 1.8.
  • the reaction is preferably carried out at a temperature from 0 to 150 °C, and, preferably, at ambient temperature. Due to their biological activity, the racemates IA IB may be used in cultivation of all plants where infection by phytopathogenic fungi is not desired, e.g. cereals, solanaceous crops, vegetables, legumes, apples, and vines.
  • the invention further provides a fungicidal composition which. comprises an active ingredient, which is at least one racemate IA/IB as defined above, and one or more carriers.
  • a method of making such a composition is also provided which comprises bringing a compound of formula I as defined above into association with the carrier(s).
  • Such a composition may contain a single active ingredient or a mixture of several active ingredients of the present invention. It is also envisaged that different isomers or mixtures of isomers may have different levels or spectra of activity and thus compositions may comprise individual isomers or mixtures of isomers.
  • a composition according to the invention preferably contains from 0.5% to 95% by weight (w/w) of active ingredient with a suitable carrier.
  • a carrier in a composition according to the present invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may be, for example, a plant, seed, soil, or water in which a plant grows, or to facilitate storage, transport or handling.
  • a carrier may be a solid or a liquid, including material which is normally a gas but which has been compressed to form a liquid.
  • compositions of the present invention may be manufactured into suitable agricultural formulations, e.g., emulsion concentrates, solutions, oil in water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, micro-capsules, gels, tablets and other formulation types by well-established procedures. These procedures include intensive mixing and/or milling of the active ingredients with other substances, such as fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally solid and/or liquid auxiliaries and/or adjuvants.
  • the form of application such as spraying, atomizing, dispersing or pouring may be chosen, like the compositions, according to the desired objectives and the given circumstances.
  • Typical solvents are those such as aromatic hydrocarbons, e.g., Solvesso ® 200, substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, e.g., cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, e.g., ethanol, ethyleneglycol mono- and dimethyl ether, keto ⁇ es such as cyclohexa ⁇ one, strongly polar solvents such as N-methyl-2-pyrrolidone, or ⁇ -butyrolactone, higher alkyl pyrrolidones, e.g., n-octylpyrrolidone or cyclohexylpyrrolidone, epoxidized plant oil esters, e.g., methylated coconut or soybean oil ester and water. Mixtures of different liquids are often suitable.
  • Solid carriers which may be used for dusts, wettable powders, water dispersible granules, or granules, may be mineral fillers, such as calcite, talc, kaolin, montmorillonite or attapulgite. The physical properties may be improved by addition, of highly dispersed silica gel or polymers. Carriers for granules may be porous material, e.g., pumice, kaolin, sepiolite, be ⁇ tonite; non-sorptive carriers may be calcite or sand. Additionally, a multitude of pre- granulated inorganic or organic materials may be used, such as dolomite or crushed plant residues.
  • Pesticidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application.
  • a carrier which is a surfactant facilitates this process of dilution.
  • at least one carrier in a composition according to the invention is a surfactant.
  • the composition may contain at two or more carriers, at least one of which is a surfactant.
  • Surfactants may be nonionic, anionic, cationic or zwitterionic substances with good dispersing, emulsifying and wetting properties depending on the nature of racemates IA/IB to be formulated. Surfactants may also mean mixtures of individual surfactants.
  • compositions of the invention may, for example, be formulated in a variety of forms such as wettable powders, water dispersible granules, dusts, granules, tablets, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.
  • Wettable powders usually contain 5 to 90% w/w of active ingredient and usually contain in addition to solid inert carrier, 3 to10% w/w of dispersing and wetting agents and, where necessary, 0 to 10% w/w of stabilizer(s) and/or other additives such as penetrants or stickers.
  • Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and may be diluted in the field with further solid carrier to give a composition usually containing 0.5 to 10% w/w of active ingredient.
  • Water dispersible granules and granules are usually prepared to have a size between 0.15 mm and 2.0 mm and may be manufactured by a variety of techniques. Generally, these types of granules will contain 0.5 to 90% w/w active ingredient and 0 to 20% w w of additives such as stabilizer, surfactants, slow release modifiers and binding agents.
  • the so-called "dry flowables" consist of relatively small granules having a relatively high concentration of active ingredient.
  • Emulsifiable concentrates usually contain, in addition to a solvent or a mixture of solvents, 1 to 80% w/v active ingredient, 2 to 20% w/v emulsifiers and 0 to 20% w/v of other additives such as stabilizers, penetrants and corrosion inhibitors.
  • Suspension concentrates are usually milled so as to obtain a stable, non-sedimenting flowable product and usually contain 5 to 75% w/v active ingredient, 0.5 to 15% w/v of dispersing agents, 0.1 to 10% w/v of suspending agents such as protective colloids and thixotropic agents, 0 to 10% w/v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation and crystalization or as antifreeze agents for water.
  • the biological activity of the active ingredient can also be increased by including an adjuvant in the spray dilution.
  • An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active.
  • the adjuvant can either be included in the formulation as a coformulant or carrier, or can be added to the spray tank together with the formulation containing the active ingredient.
  • the compositions may preferably be in a concentrated form whereas the end user generally employs diluted compositions.
  • compositions may be diluted to a concentration down to 0.001% of active ingredient to provide doses usually in the range of from 0.01 to 10 kg a.i./ha.
  • Compositions obtained by diluting the formulated product according to the invention with water, such as aqueous dispersions and emulsions also lie within the scope of the invention.
  • formulations according to the invention are: Emulsion Concentrate (EC) Active Ingredient Racemate IA1/IB1 30 % (w/v)
  • Solvent Shellsol ® A (mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics / mixture containing calcium alkyl aryl sulfonate, fatty alcohol ethoxylates and light aromatics)
  • Solvent Shellsol ® A 2 to 1000 ml
  • Carrier / Filler Kaolin 35 % (w/w)
  • Binding agent mixture of sodium salts of condensed naphthalene sulfo ⁇ ic acid and alkyl sulfonates
  • compositions of this invention can also comprise other compounds having biological activity, e.g., compounds having similar or complementary pesticidal activity or compounds having plant growth regulating, fungicidal or insecticidal activity.
  • These mixtures of pesticides can have a broader spectrum of activity than the compound of general formula I alone.
  • the other pesticides can have a synergistic effect on the pesticidal activity of the racemate IA IB.
  • the other fungicidal compounds can be, for example, one which is also capable of combating diseases of cereals (e.g., wheat) such as those caused by Erysiphe, Puccinia, Septo ⁇ a, Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on vines, early and late blight on solanaceous crops, and powdery mildew and scab on apples etc.
  • cereals e.g., wheat
  • wheat e.g., wheat
  • AC 382042 alanycarb, aldimorph, ampropyifos, andoprim, anilazine, azaconazole, azafenidin, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacril, bialaphos, biloxazol, binapacryl, biphenyl, bitertanol, blasticidin S, Bordeaux mixture, bromuconazole, bupirimate, butenachlor, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, carvone, chinomethionate, chlorbenzthiazon, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, copper-containing compounds such as copper oxychloride, and copper sulfate, cufraneb, cycloheximide, cymox
  • compositions according to the invention may contain at least one compound of formula I and any of the following classes of biological control agents such as viruses, bacteria, nematodes, fungi, and other microorganisms which are effective in the control of insects, weeds or plant diseases, or to induce host resistance in the plants.
  • biological control agents such as viruses, bacteria, nematodes, fungi, and other microorganisms which are effective in the control of insects, weeds or plant diseases, or to induce host resistance in the plants.
  • biological control agents are: Bacillus thu ⁇ ngiensis, Verticillium lecanii, Autographica califomica NPV, Beauva ⁇ a bassiana, Ampelomyces quisqualis, Bacilis subtilis, Pseudomonas cholororaphis, Pseudomonas fluorescens, Steptomyces g ⁇ seovi ⁇ dis and Trichoderma harzianum.
  • the co-formulations according to the invention may contain at least one racemate IA/IB and a chemical agent that induces the systemic acquired resistance in plants such as, for example, isonicotinic acid or derivatives thereof, 2,2-dichloro-3,3-dimethylcyclopropylcarboxylic acid or BION.
  • a chemical agent that induces the systemic acquired resistance in plants such as, for example, isonicotinic acid or derivatives thereof, 2,2-dichloro-3,3-dimethylcyclopropylcarboxylic acid or BION.
  • the racemate IA/IB can be mixed with soil, peat or other rooting media for the protection of the plants against seed-borne, soil-borne or foliar fungal diseases.
  • the invention still further provides the use as a fungicide of a racemate IA/IB as defined above or a composition as defined above, and a method for combating fungus at a locus, which comprises treating the locus, which may be, for example, plants subject to or subjected to fungal attack, seeds of such plants or the medium in which such plants are growing or are to be grown, with such a compound or composition.
  • the present invention is of wide applicability in the protection of crop and ornamental plants against fungal attack.
  • Typical crops which may be protected include vines, grain crops such as wheat and barley, rice, sugar beet, top fruit, peanuts, potatoes, vegetables and tomatoes.
  • the duration of the protection is normally dependent on the individual compound selected, and also a variety of external factors, such as climate, whose impact is normally mitigated by the use of a suitable formulation.
  • the compounds according to the invention have curative, protective and residual activity and are systemic in plants.
  • the compounds control diseases after foliar, soil, into water or seed application. They can be applied in different formulations.
  • the compounds have better curative and systemic properties than the presently commercialised strobilurine derivatives.
  • Test Plants Test plants were grown up in the greenhouse. Either seed, pregerminated seed or rooted vegetative plant material was planted in pots containing a fertilized soil/peat mixture. Test plants were used for treating them with the various fungicides when they were in the primary leaf stage (cereals) or in the 3-4 leaf stage (tomatoes). The number of leaves of vegetatively propagated plant material was cut back to 3-4 leaves per plant.
  • the test compounds were applied to the test plants using a had held airbrush at a pressure of 0.5 bar. 2-4 plants were used per treatment.
  • Inoculations and culture conditions For the protective tests, treated plants were kept 1 day in the greenhouse and then inoculated with a pathogen. For inoculation an aqueous spore suspension was sprayed or spores were dusted onto the plants. Then the plants were kept in specific chambers for incubation if required, and then were moved to a greenhouse for disease development. For curative tests, plants were inoculated and, if required, incubated 2 day before the application of the compound, and then moved to a greenhouse after application of the compounds. The temperature in the greenhouse was between 18 and 25 degree C. The relative humidity was about 50-80% in the greenhouses and up to 100% in the incubation chambers. The plants were watered as required for good plant growth. In the greenhouse additional light was supplied to maintain a 14 hours day and 10 hours night cycle.
  • % activity 100 x 100 % infection in untreated leaves
  • the diseases, dose rate and % activity is given in Tables I to III, in which the following abbreviations have been used:

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des composés contenant principalement des quantités équimolaires de la paire énantiomère des formules (IA et IB), où R1 représente un atome d'hydrogène ou un alkyle, alcényle ou groupe aryle éventuellement substitué; R?2, R3, R4 et R5¿ représentent indépendamment un groupe alkyle; et R6 représente un groupe de la formule -COOR7 ou -CONR?7R8, où R7 et R8¿ représentent indépendamment un atome d'hydrogène ou un groupe alkyle; L1 représente un atome d'hydrogène ou d'halogène ou un groupe alkyle éventuellement substitué; et la ligne en zigzag indique que le groupe alcoximino peut avoir la configuration (E)- ou (Z)-. Ces composés ont une excellente activité fongicide et une excellente systémicité.
EP00988747A 1999-11-24 2000-11-23 Derives de melitthiazol fongicides Withdrawn EP1232149A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US449143 1990-03-26
US44914399A 1999-11-24 1999-11-24
PCT/EP2000/011643 WO2001038317A2 (fr) 1999-11-24 2000-11-23 Derives de melitthiazol fongicides

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US5360811A (en) * 1990-03-13 1994-11-01 Hoechst-Roussel Pharmaceuticals Incorporated 1-alkyl-, 1-alkenyl-, and 1-alkynylaryl-2-amino-1,3-propanediols and related compounds as anti-inflammatory agents
DE4410449C2 (de) * 1994-03-25 2003-02-20 Biotechnolog Forschung Gmbh Melithiazole A und B, Herstellungsverfahren, Mittel mit einem Gehalt an Melithiazol A und/oder B und Melittangium lichenicola DSM 9004 mit der Fähigkeit, Melithiazole A und B zu bilden
US6380394B1 (en) * 1996-12-13 2002-04-30 The Scripps Research Institute Epothilone analogs
US6441186B1 (en) * 1996-12-13 2002-08-27 The Scripps Research Institute Epothilone analogs
WO1998046583A1 (fr) * 1997-04-11 1998-10-22 Gesellschaft Für Biotechnologische Forschung, Mbh Derives de melithiazole fongicides
WO1999003848A1 (fr) * 1997-07-16 1999-01-28 Schering Aktiengesellschaft Derives de thiazole, leur procede de production et leur utilisation

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AU2508201A (en) 2001-06-04
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