EP1114036A1 - Sulfonyl oxazolones and their use for combating undesirable microorganisms - Google Patents

Sulfonyl oxazolones and their use for combating undesirable microorganisms

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Publication number
EP1114036A1
EP1114036A1 EP99969088A EP99969088A EP1114036A1 EP 1114036 A1 EP1114036 A1 EP 1114036A1 EP 99969088 A EP99969088 A EP 99969088A EP 99969088 A EP99969088 A EP 99969088A EP 1114036 A1 EP1114036 A1 EP 1114036A1
Authority
EP
European Patent Office
Prior art keywords
formula
methyl
alkyl
oxazolones
sulfonyloxazolones
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Withdrawn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
EP99969088A
Other languages
German (de)
French (fr)
Inventor
Lutz Assmann
Manfred Jautelat
Ulrike Wachendorff-Neumann
Klaus Stenzel
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.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1114036A1 publication Critical patent/EP1114036A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/80—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 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/36—One oxygen atom
    • C07D263/38—One oxygen atom attached in position 2

Definitions

  • the present invention relates to new sulfonyloxazolones, a process for their preparation and their use for controlling unwanted microorganisms.
  • R 1 represents alkyl or optionally substituted heterocyclyl or a radical of the formula
  • R 3 represents halogen, alkyl or phenyl
  • R 4 represents hydrogen or alkyl
  • R 5 represents alkyl or optionally substituted phenyl
  • R 2 represents alkyl
  • R 2 has the meaning given above
  • R 1 has the meaning given above and Hal represents chlorine or bromine
  • the sulfonyloxazolones of the formula (I) have very good microbicidal properties and can be used to combat unwanted microorganisms in crop protection and in agriculture.
  • Formula (I) has a better activity against undesired microorganisms, in particular against fungi, than the structurally most similar, previously known substances with the same direction of action.
  • R 1 preferably represents alkyl having 1 to 4 carbon atoms or a heterocyclyl radical with 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, which radical can contain a keto or imino group and can be monosubstituted to trisubstituted, identical or different, by halogen, cyano, nitro, amino, hydroxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, Haloalkoxy with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms,
  • R 1 also preferably represents a radical of the formula
  • R 3 preferably represents fluorine, chlorine, bromine, alkyl having 1 to 6 carbon atoms or phenyl.
  • R 4 preferably represents hydrogen or alkyl having 1 to 6 carbon atoms.
  • R 5 preferably represents alkyl having 1 to 6 carbon atoms or phenyl which can be monosubstituted to trisubstituted, identical or different, by halogen, nitro, C r C 6 alkyl, C r C 6 alkoxy, C r C 6 - Alkylthio, C r C 6 - haloalkyl with 1 to 5 identical or different halogen atoms, C j - C 6 haloalkoxy with 1 to 5 identical or different halogen atoms,
  • Ci-Cg-haloalkylthio with 1 to 5 identical or different halogen atoms, cyano and / or cycloalkyl with 3 to 6 carbon atoms.
  • R 2 preferably represents alkyl having 1 to 6 carbon atoms.
  • R 1 particularly preferably represents methyl, ethyl, propyl, isopropyl or furyl, thienyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrirnidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl , 1,2,4-triazinyl, 1,3,5-triazinyl, pyrrolidinyl, piperidinyl or morpholinyl, it being possible for these radicals to be substituted once, twice or three times, in the same or different manner, by fluorine, chlorine, bromine, cyano, nitro, amino , Hydroxyl, carbamoyl, methyl, ethyl, n- or i-propyl, n-, i-
  • R 1 also particularly preferably represents a radical of the formula
  • R 3 particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or phenyl.
  • R 4 particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.
  • R 5 particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl, or phenyl which can be monosubstituted to trisubstituted in the same or different manner by Fluorine, chlorine, bromine, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,
  • R 2 particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.
  • R 1 very particularly preferably represents methyl, ethyl, isopropyl or furyl, thienyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, 1, 2,4-triazinyl, pyrroli- dinyl, piperidinyl or morpholinyl, where these radicals can be substituted once, twice or three times, in the same way or differently, by fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, carbamoyl, methyl, ethyl, n- or i-propyl, cyclopropyl , Methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, acetyl, methoxycarbonyl, eth
  • R ' also very particularly preferably represents a radical of the formula
  • R 3 very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or phenyl.
  • R 4 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl,
  • R 5 very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl, or phenyl, which can be monosubstituted to trisubstituted in the same or different manner by fluorine, chlorine, bromine, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy , Cyano, cyclopropyl, cyclopentyl and / or cyclohexyl.
  • R 2 also very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.
  • the substituent meanings given above can be combined with one another in any manner. In addition, individual definitions can also be omitted.
  • Formula (II) provides a general definition of the oxazolones required as starting materials when carrying out the process according to the invention.
  • R 2 preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention.
  • the oxazolones of the formula (II) are hitherto unknown. They can be produced by using hydroxyketones of the formula in a first step
  • R 2 has the meaning given above
  • Formula (IV) provides a general definition of the hydroxy ketones required as starting materials for carrying out this process.
  • R ⁇ preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention.
  • hydroxyketones of the formula (IV) are known or can be prepared by known methods.
  • reaction temperatures can be varied within a substantial range when carrying out the above process for the preparation of oxazolones of the formula (II).
  • the first step is carried out at temperatures between 10 ° C. and 160 ° C., preferably between 20 ° C. and 140 ° C.
  • the second step is generally carried out at temperatures between 10 ° C. and 100 ° C., preferably between 20 ° C. and 80 ° C.
  • both the first step and the second step are generally carried out under atmospheric pressure. But it is also possible to work under increased pressure.
  • the reaction mixture is concentrated, the remaining residue via an adsorbent Filtered material, the residue obtained after concentrating the eluate is stirred with water and the resulting precipitate is suction filtered and dried.
  • the intermediate is reacted with an excess of phosphorus oxychloride.
  • the processing takes place according to usual methods. In general, the procedure is such that the reaction mixture is suctioned off through an adsorbent material, the filtrate is added to water, the resulting mixture is extracted with a water-insoluble organic solvent and the combined organic phases are dried and concentrated under reduced pressure.
  • Formula (III) provides a general definition of the sulfonic acid halides required as reaction components for carrying out the process according to the invention.
  • R 1 preferably has the meaning which has already been stated as preferred for R 1 in connection with the description of the compounds of the formula (I) according to the invention.
  • X preferably represents chlorine.
  • the sulfonic acid halides of the formula (III) are known or can be prepared by known processes (cf. J. Heterocyclic Chem. 1981, 997-1006 and EP-A 0 238 824).
  • Suitable diluents for carrying out the process according to the invention are all inert organic solvents.
  • Aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobuty
  • Suitable acid binders for carrying out the process according to the invention are all customary inorganic or organic bases.
  • Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, are preferably usable.
  • Sodium hydroxide, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide are preferably usable.
  • DABCO diazabicyclooctane
  • DBN diazabicyclonones
  • DBU diazabicycloundecene
  • reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C.
  • the process according to the invention is generally carried out under atmospheric pressure. It is also possible, however, under increased or reduced pressure
  • the processing takes place according to usual methods.
  • the procedure is such that the reaction mixture is poured into water, the resulting mixture is extracted several times with an organic solvent which is sparingly soluble in water, and the combined organic phases are dried and concentrated under reduced pressure.
  • the Any remaining residue can, if necessary, be freed of any impurities that may still be present using customary cleaning methods.
  • the substances according to the invention have a strong microbicidal action and can be used to protect against undesired microorganisms, such as fungi and bacteria, in crop protection and in the material.
  • Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • Xanthomonas species such as, for example, Xanthomonas campestris pv. Oryzae;
  • Pseudomonas species such as, for example, Pseudomonas syringae pv. Lachrymans;
  • Erwinia species such as, for example, Erwinia amylovora;
  • Pythium species such as, for example, Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or
  • Plasmopara species such as, for example, Plasmopara viticola
  • Bremia species such as, for example, Bremia lactucae
  • Peronospora species such as, for example, Peronospora pisi or P. brassicae
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca fuliginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or P. graminea
  • Cochliobolus species such as, for example, Cochliobolus sativus
  • Drechslera (Conidial form: Drechslera, Syn: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Sclerotinia species such as, for example, Sclerotinia sclerotiorum
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae;
  • Pellicularia species such as, for example, Pellicularia sasakii;
  • Pyricularia species such as, for example, Pyricularia oryzae
  • Fusarium species such as, for example, Fusarium culmorum
  • Botrytis species such as, for example, Botrytis cinerea
  • Septoria species such as, for example, Septoria nodorum
  • Leptosphaeria species such as, for example, Leptosphaeria nodorum;
  • Cercospora species such as, for example, Cercospora canescens
  • Alternaria species such as, for example, Alternaria brassicae
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpotrichoides.
  • the active compounds according to the invention can be used with particularly good success to combat diseases in wine, fruit and vegetable cultivation, such as, for example, against Phytophthora species.
  • the active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.
  • the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
  • technical materials are to be understood as non-living materials that have been prepared for use in technology.
  • technical materials which are to be protected from microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which attack or decompose from microorganisms can be.
  • adhesives glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which attack or decompose from microorganisms can be.
  • Materials are also parts of production systems, such as cooling water circuits, that can be affected by the proliferation of microorganisms.
  • technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.
  • Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials.
  • the ones according to the invention preferably act
  • microorganisms of the following genera may be mentioned: Alternaria, such as Alternaria tenuis,
  • Aspergillus such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor,
  • Aureobasidium such as Aureobasidium pullulans
  • Sclerophoma such as Sclerophoma pityophila
  • Trichoderma such as Trichoderma viride
  • Escherichia such as Escherichia coli
  • Pseudomonas such as Pseudomonas aeruginosa
  • Staphylococcus such as Staphylococcus aureus.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes,
  • formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • water e.g. organic solvents can also be used as auxiliary solvents.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions
  • alcohols such as butanol or glycol
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
  • Solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • Liquefied gaseous extenders or carriers are those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.
  • aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide.
  • solid carriers for example, natural rock powders such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates.
  • Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.
  • Possible emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates.
  • Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. 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 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In many cases synergistic effects are obtained, ie the effectiveness of the mixture is greater than that
  • Debacarb dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dorphianon, dithianon, dithianon,
  • Fenpiclonil fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Flurprimidol, Flusilazol, Flusulfamid, Flutolanil, Flutriafol, Folpet, Fosetyl-Alminium, Fosetyl-Sodium, Fthalid, Fuberidazol, Furalaxyl, Furametpyr, Furcarboniloxol, Furcarbonil, Furcarbonil, Furcarbonil, Furcarbonil, Furcarbonil, Furcarbonil, Furcarbonil, Furcarbonil, Furcarbonil
  • Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
  • Oxadixyl Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
  • Paclobutrazole pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin
  • Tebuconazole Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazole, Thiabendazole, Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutichlamidid, Triazoxid, Triazoxid
  • Tricyclazole tridemorph, triflumizole, triforin, triticonazole,
  • Methane tetrathiol sodium salt Methyl 1 - (2,3-dihydro-2,2-dimethyl-1 H-inden-1-y 1) - 1 H-imidazole-5-carboxy lat,
  • N-formyl-N-hydroxy-DL-alanine sodium salt O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,
  • Fenamiphos Fenazaquin, Fenbutatinoxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxanone Furathiocarb,
  • Halofenozide HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, Isazophos, Isofenphos, Isoxathion, Ivermectin, Kernpolyederviruses, Lambda-cyhalothrin, Lufenuron,
  • Mecarbam Metaldehyde, Methamidophos, Metharhilic anisopliae, Metharhilic flavoviride, Methidathion, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos, Naled, Nitenpyramo, Oxidomylonomidamyl, Oxitomyl, Oxitomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat,
  • Pirimiphos M Profenophos, Promecarb, Propoxur, Prothiophos, Prothoat,
  • Triazamates triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron,
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
  • the application rates can be varied within a relatively wide range, depending on the type of application.
  • the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha.
  • the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed.
  • the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
  • the agents used to protect industrial materials generally contain the active ingredients in an amount from 1 to 95% by weight, preferably from 10 to
  • the application concentrations of the active compounds according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected.
  • the optimal amount can be determined by test series.
  • the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.
  • the effectiveness and the spectrum of activity of the active substances to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be prepared therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active substances are used to increase the activity. Spectrum or achieving special effects such as the additional protection from
  • Insects can be added. These mixtures can have a broader spectrum of activity than the compounds according to the invention.
  • Emulsifier 3 parts by weight of alkyl aryl polyglycol ether
  • Evaluation is carried out 3 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
  • Emulsifier 3 parts by weight of alkyl aryl polyglycol ether

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

The invention relates to novel sulfonyl oxazolones of formula (I), wherein R1 represents alkyl or an optionally substituted heterocyclyl or a radical of formula (a) or (b), wherein R3 represents halogen, alkyl or phenyl, R4 represents hydrogen or alkyl and R5 represents alkyl or optionally substituted phenyl, and R2 represents alkyl, to a method for producing these substances and to their use for combating undesirable microorganisms. The invention also relates to novel intermediate products of formula (II) and to a method for producing the same.

Description

SULFONYLOXAZOLONE UND IHRE VERWENDUNG ZUR BEKÄMPFUNG VON UNERWÜNSCHTEN MIKROOGANISMENSULFONYLOXAZOLONE AND THEIR USE FOR COMBATING UNWANTED MICROOGANISMS
Die vorliegende Erfindung betrifft neue Sulfonyloxazolone, ein Verfahren zu deren Herstellung und der Verwendung zur Bekämpfung von unerwünschten Mikroorganismen.The present invention relates to new sulfonyloxazolones, a process for their preparation and their use for controlling unwanted microorganisms.
Es sind bereits bestimmte Sulfonyloxazolone, wie z.B. das 4-[(4-Chlorphenyl)sul- fonyl]-3-(2,4,6-trimethyl-phenyl)-l,2,4-oxadiazol-5(4H)-on, bekannt geworden (vgl. Zh. Org. Khim. 27 (1991), 1262-1270). Eine biologische Wirkung dieser Verbindungen wurde aber bisher noch nicht beschrieben.Certain sulfonyloxazolones, e.g. the 4 - [(4-chlorophenyl) sulfonyl] -3- (2,4,6-trimethyl-phenyl) -l, 2,4-oxadiazol-5 (4H) -one, became known (cf. Zh. Org. Khim. 27 (1991), 1262-1270). A biological effect of these compounds has not yet been described.
Es wurden nun neue Sulfonyloxazolone der FormelThere have now been new sulfonyloxazolones of the formula
in welcherin which
R1 für Alkyl oder für gegebenenfalls substituiertes Heterocyclyl steht oder für einen Rest der FormelR 1 represents alkyl or optionally substituted heterocyclyl or a radical of the formula
steht, worinstands in what
R3 für Halogen, Alkyl oder Phenyl steht, R4 für Wasserstoff oder Alkyl steht undR 3 represents halogen, alkyl or phenyl, R 4 represents hydrogen or alkyl and
R5 für Alkyl oder gegebenenfalls substituiertes Phenyl steht,R 5 represents alkyl or optionally substituted phenyl,
undand
R2 für Alkyl steht,R 2 represents alkyl,
gefunden.found.
Weiterhin wurde gefunden, daß man Sulfonyloxazolone der Formel (I) erhält, wenn man Oxazolone der FormelFurthermore, it was found that sulfonyloxazolones of the formula (I) can be obtained if oxazolones of the formula
in welcherin which
R2 die oben angegebene Bedeutung hat,R 2 has the meaning given above,
mit Sulfonsäurehalogeniden der Formelwith sulfonic acid halides of the formula
R1-SO2-Hal (III)R 1 -SO 2 -Hal (III)
in welcherin which
R1 die oben angegebene Bedeutung hat und Hal für Chlor oder Brom steht,R 1 has the meaning given above and Hal represents chlorine or bromine,
gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.
Schließlich wurde gefunden, daß die Sulfonyloxazolone der Formel (I) sehr gute mikrobizide Eigenschaften besitzen und zur Bekämpfung von unerwünschten Mikroorganismen im Pflanzenschutz und in der Landwirtschaft eingesetzt werden können.Finally, it was found that the sulfonyloxazolones of the formula (I) have very good microbicidal properties and can be used to combat unwanted microorganisms in crop protection and in agriculture.
Überraschenderweise zeigen die erfindungsgemäßen Sulfonyloxazolone derSurprisingly, the sulfonyloxazolones according to the invention show the
Formel (I) eine bessere Wirksamkeit gegen unerwünschte Mikroorganismen, insbesondere gegen Fungi, als die konstitutionell ähnlichsten, vorbekannten Stoffe gleicher Wirkungsrichtung.Formula (I) has a better activity against undesired microorganisms, in particular against fungi, than the structurally most similar, previously known substances with the same direction of action.
Die erfindungsgemäßen Stoffe sind durch die Formel (I) allgemein definiert.The substances according to the invention are generally defined by the formula (I).
R1 steht vorzugsweise für Alkyl mit 1 bis 4 Kohlenstoffatomen oder für einen Heterocyclyl-Rest mit 5 oder 6 Ringgliedern und 1 bis 3 Heteroatomen, wie Stickstoff, Sauerstoff und/oder Schwefel, wobei dieser Rest eine Keto- oder Imino-Gruppe enthalten kann und einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Halogen, Cyano, Nitro, Amino, Hydroxy, Alkyl mit 1 bis 4 Kohlenstoffatomen, Alkoxy mit 1 bis 4 Kohlenstoffatomen, Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 5 gleichen oder verschiedenen Halogenatomen, Halogenalkoxy mit 1 bis 4 Kohlenstoffatomen und 1 bis 5 gleichen oder verschiedenen Halogenatomen,R 1 preferably represents alkyl having 1 to 4 carbon atoms or a heterocyclyl radical with 5 or 6 ring members and 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, which radical can contain a keto or imino group and can be monosubstituted to trisubstituted, identical or different, by halogen, cyano, nitro, amino, hydroxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, Haloalkoxy with 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms,
Alkylcarbonyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil, Alkoxycarbonyl mit 1 bis 3 Kohlenstoffatomen im Alkoxyteil, Carbamoyl, Alkylamino- carbonyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil, Dialkylaminocarbonyl mit 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylteilen, Hydroximino- alkyl oder Alkoximinoalkyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylteilen oder Cycloalkyl mit 3 bis 6 Kohlenstoffatomen. R1 steht außerdem vorzugsweise für einen Rest der FormelAlkylcarbonyl with 1 to 4 carbon atoms in the alkyl part, alkoxycarbonyl with 1 to 3 carbon atoms in the alkoxy part, carbamoyl, alkylaminocarbonyl with 1 to 4 carbon atoms in the alkyl part, dialkylaminocarbonyl with 1 to 4 carbon atoms in the individual alkyl parts, hydroximinoalkyl or alkoximinoalkyl each with 1 up to 4 carbon atoms in the individual alkyl parts or cycloalkyl with 3 to 6 carbon atoms. R 1 also preferably represents a radical of the formula
R3 steht vorzugsweise für Fluor, Chlor, Brom, Alkyl mit 1 bis 6 Kohlenstoffatomen oder für Phenyl.R 3 preferably represents fluorine, chlorine, bromine, alkyl having 1 to 6 carbon atoms or phenyl.
R4 steht vorzugsweise für Wasserstoff oder Alkyl mit 1 bis 6 Kohlenstoffatomen.R 4 preferably represents hydrogen or alkyl having 1 to 6 carbon atoms.
R5 steht vorzugsweise für Alkyl mit 1 bis 6 Kohlenstoffatomen oder für Phenyl, das einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Halogen, Nitro, CrC6-Alkyl, CrC6-Alkoxy, CrC6-Alkylthio, CrC6- Halogenalkyl mit 1 bis 5 gleichen oder verschiedenen Halogenatomen, Cj- C6-Halogenalkoxy mit 1 bis 5 gleichen oder verschiedenen Halogenatomen,R 5 preferably represents alkyl having 1 to 6 carbon atoms or phenyl which can be monosubstituted to trisubstituted, identical or different, by halogen, nitro, C r C 6 alkyl, C r C 6 alkoxy, C r C 6 - Alkylthio, C r C 6 - haloalkyl with 1 to 5 identical or different halogen atoms, C j - C 6 haloalkoxy with 1 to 5 identical or different halogen atoms,
Ci-Cg-Halogenalkylthio mit 1 bis 5 gleichen oder verschiedenen Halogenatomen, Cyano und/oder Cycloalkyl mit 3 bis 6 Kohlenstoffatomen.Ci-Cg-haloalkylthio with 1 to 5 identical or different halogen atoms, cyano and / or cycloalkyl with 3 to 6 carbon atoms.
R2 steht vorzugsweise für Alkyl mit 1 bis 6 Kohlenstoffatomen.R 2 preferably represents alkyl having 1 to 6 carbon atoms.
R1 steht besonders bevorzugt für Methyl, Ethyl, Propyl, Isopropyl oder für Furyl, Thienyl, Oxazolyl, Isoxazolyl, Pyrazolyl, Imidazolyl, Thiazolyl, Isothiazolyl, Oxadiazolyl, Thiadiazolyl, Pyridinyl, Pyrirnidinyl, Pyridazinyl, Pyrazinyl, 1,2,3-Triazinyl, 1,2,4-Triazinyl, 1,3,5-Triazinyl, Pyrrolidinyl, Piperidinyl oder Morpholinyl, wobei diese Reste einfach, zweifach oder dreifach, gleichartig oder verschieden substituiert sein können durch Fluor, Chlor, Brom, Cyano, Nitro, Amino, Hydroxy, Carbamoyl, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s-, oder t-Butyl, Cyclopropyl, Methoxy, Ethoxy, n- oder i-Propoxy, Trifluormethyl, Trifluorethyl, Difluormethoxy, Trifluormethoxy, Acetyl, Propionyl, Methoxy carbonyl, Ethoxy carbonyl, Hydroxyiminomethyl, Hydroximinoethyl, Methoximinomethyl, Ethoximinomethyl, Me hoximino- ethyl und Ethoxy iminoethyl.R 1 particularly preferably represents methyl, ethyl, propyl, isopropyl or furyl, thienyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrirnidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl , 1,2,4-triazinyl, 1,3,5-triazinyl, pyrrolidinyl, piperidinyl or morpholinyl, it being possible for these radicals to be substituted once, twice or three times, in the same or different manner, by fluorine, chlorine, bromine, cyano, nitro, amino , Hydroxyl, carbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, cyclopropyl, methoxy, ethoxy, n- or i-propoxy, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy Acetyl Propionyl, methoxy carbonyl, ethoxy carbonyl, hydroxyiminomethyl, hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl and ethoxyiminoethyl.
R1 steht außerdem besonders bevorzugt für einen Rest der FormelR 1 also particularly preferably represents a radical of the formula
R3 steht besonders bevorzugt für Fluor, Chlor, Brom, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, iso-Butyl, tert.-Butyl oder Phenyl.R 3 particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or phenyl.
R4 steht besonders bevorzugt für Wasserstoff, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, iso-Butyl oder tert.-Butyl.R 4 particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.
R5 steht besonders bevorzugt für Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, iso-Butyl oder tert.-Butyl, oder für Phenyl, das einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Nitro, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, Methylthio, Ethylthio, n- oder i-Propyl- thio, Trifluormethyl, Trifluorethyl, Difluormethoxy, Trifluormethoxy,R 5 particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl, or phenyl which can be monosubstituted to trisubstituted in the same or different manner by Fluorine, chlorine, bromine, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,
Difluorchlormethoxy, Trifluorethoxy, Cyano, Cyclopropyl, Cyclopentyl und/oder Cyclohexyl.Difluorochloromethoxy, trifluoroethoxy, cyano, cyclopropyl, cyclopentyl and / or cyclohexyl.
R2 steht besonders bevorzugt für Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, iso-Butyl oder tert.-Butyl.R 2 particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.
R1 steht ganz besonders bevorzugt für Methyl, Ethyl, Isopropyl oder für Furyl, Thienyl, Oxazolyl, Isoxazolyl, Pyrazolyl, Imidazolyl, Thiazolyl, Isothiazolyl, Oxadiazolyl, Thiadiazolyl, Pyridinyl, Pyrimidinyl, 1 ,2,4-Triazinyl, Pyrroli- dinyl, Piperidinyl oder Morpholinyl, wobei diese Reste einfach, zweifach oder dreifach, gleichartig oder verschieden substituiert sein können durch Fluor, Chlor, Brom, Cyano, Nitro, Amino, Hydroxy, Carbamoyl, Methyl, Ethyl, n- oder i-Propyl, Cyclopropyl, Methoxy, Ethoxy, Trifluormethyl, Di- fluormethoxy, Trifluormethoxy, Acetyl, Methoxycarbonyl, Ethoxycarbonyl, Hydroxyiminomethyl, Hydroxyiminoethyl, Methoximinomethyl, Ethoxy- iminomethyl, Methoximinoethyl und Ethoximinoethyl.R 1 very particularly preferably represents methyl, ethyl, isopropyl or furyl, thienyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, 1, 2,4-triazinyl, pyrroli- dinyl, piperidinyl or morpholinyl, where these radicals can be substituted once, twice or three times, in the same way or differently, by fluorine, chlorine, bromine, cyano, nitro, amino, hydroxyl, carbamoyl, methyl, ethyl, n- or i-propyl, cyclopropyl , Methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy, acetyl, methoxycarbonyl, ethoxycarbonyl, hydroxyiminomethyl, hydroxyiminoethyl, methoximinomethyl, ethoxyiminomethyl, methoximinoethyl and ethoximinoethyl.
R' steht außerdem ganz besonders bevorzugt für einen Rest der FormelR 'also very particularly preferably represents a radical of the formula
R3 steht ganz besonders bevorzugt für Fluor, Chlor, Brom, Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, tert.-Butyl oder Phenyl.R 3 very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or phenyl.
R4 steht ganz besonders bevorzugt für Wasserstoff, Methyl, Ethyl, n-Propyl,R 4 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl,
Isopropyl oder n-Butyl.Isopropyl or n-butyl.
R5 steht ganz besonders bevorzugt für Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, iso-Butyl oder tert.-Butyl, oder für Phenyl, das einfach bis dreifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Nitro, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, Methylthio, Trifluormethyl, Trifluorethyl, Difluormethoxy, Trifluormethoxy, Difluorchlormethoxy, Trifluorethoxy, Cyano, Cyclopropyl, Cyclopentyl und/oder Cyclohexyl.R 5 very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl, or phenyl, which can be monosubstituted to trisubstituted in the same or different manner by fluorine, chlorine, bromine, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy , Cyano, cyclopropyl, cyclopentyl and / or cyclohexyl.
R2 steht auch ganz besonders bevorzugt für Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, iso-Butyl oder tert.-Butyl. Die zuvor angegebenen Substituenten-Bedeutungen können untereinander in beliebiger Weise kombiniert werden. Außerdem können auch einzelne Definitionen entfallen.R 2 also very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl or tert-butyl. The substituent meanings given above can be combined with one another in any manner. In addition, individual definitions can also be omitted.
Verwendet man 5-Cyano-4-ethyl-3H-[l,3]-oxazol-2-on und 3,5-Dimethyl-isoxazol- 4-sulfonylchlorid als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens durch das folgende Formelschema veranschaulicht werden.If 5-cyano-4-ethyl-3H- [1,3] -oxazol-2-one and 3,5-dimethyl-isoxazole-4-sulfonyl chloride are used as starting materials, the course of the process according to the invention can be illustrated by the following formula become.
Die bei der Durchführung des erfindungsgemäßen Verfahrens als Ausgangstoffe benötigten Oxazolone sind durch die Formel (II) allgemein definiert. In dieser Formel hat R2 vorzugsweise diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Stoffe der Formel (I) für diesen Rest als bevorzugt genannt wurden.Formula (II) provides a general definition of the oxazolones required as starting materials when carrying out the process according to the invention. In this formula, R 2 preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention.
Die Oxazolone der Formel (II) sind bisher noch nicht bekannt. Sie lassen sich herstellen, indem man in einem ersten Schritt Hydroxyketone der FormelThe oxazolones of the formula (II) are hitherto unknown. They can be produced by using hydroxyketones of the formula in a first step
OO
(IV),(IV),
R 2— C ιι— CH^OHR 2—C ιι— CH ^ OH
in welcherin which
R2 die oben angegebene Bedeutung hat,R 2 has the meaning given above,
mit Harnstoff in Gegenwart von Eisessig umsetzt und die dabei entstehenden Produkte in einem zweiten Schritt mit Phosphoroxychlorid umsetzt.reacted with urea in the presence of glacial acetic acid and the resulting products are reacted with phosphorus oxychloride in a second step.
Die bei der Durchführung dieses Verfahrens als Ausgangsstoffe benötigten Hydroxyketone sind durch die Formel (IV) allgemein definiert. In dieser Formel hat R^ vorzugsweise diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Stoffe der Formel (I) für diesen Rest als bevorzugt genannt wurden.Formula (IV) provides a general definition of the hydroxy ketones required as starting materials for carrying out this process. In this formula, R ^ preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention.
Die Hydroxyketone der Formel (IV) sind bekannt oder lassen sich nach bekannten Methoden herstellen.The hydroxyketones of the formula (IV) are known or can be prepared by known methods.
Die Reaktionstemperaturen können bei der Durchführung des obigen Verfahrens zur Herstellung von Oxazolonen der Formel (II) innerhalb eines größeren Bereiches variiert werden. Im allgemeinen arbeitet man bei der Durchführung des ersten Schrittes bei Temperaturen zwischen 10°C und 160°C, vorzugsweise zwischen 20°C und 140°C. Bei der Durchführung des zweiten Schrittes arbeitet man im allgemeinen bei Temperaturen zwischen 10°C und 100°C, vorzugsweise zwischen 20°C und 80°C.The reaction temperatures can be varied within a substantial range when carrying out the above process for the preparation of oxazolones of the formula (II). In general, the first step is carried out at temperatures between 10 ° C. and 160 ° C., preferably between 20 ° C. and 140 ° C. The second step is generally carried out at temperatures between 10 ° C. and 100 ° C., preferably between 20 ° C. and 80 ° C.
Bei der Herstellung von Oxazolonen der Formel (II) nach dem obigen Verfahren arbeitet man sowohl bei der Durchführung des ersten Schrittes als auch des zweiten Schrittes im allgemeinen unter Atmosphärendruck. Es ist aber auch möglich, unter erhöhtem Druck zu arbeiten.In the preparation of oxazolones of the formula (II) by the above process, both the first step and the second step are generally carried out under atmospheric pressure. But it is also possible to work under increased pressure.
Bei der Synthese von Oxazolonen der Formel (II) setzt man bei der Durchführung des ersten Schrittes auf 1 mol an Hydroxyketon der Formel (IV) im allgemeinen 1,5 bis 3 Mol an Harnstoff in Gegenwart von Eisessig ein. Die Aufarbeitung erfolgt nach üblichen Methoden. Im allgemeinen verfährt man in der Weise, daß man dasIn the synthesis of oxazolones of the formula (II), when carrying out the first step, 1 to 3 moles of hydroxyketone of the formula (IV) are generally employed from 1.5 to 3 moles of urea in the presence of glacial acetic acid. The processing takes place according to usual methods. In general, one proceeds in such a way that one
Reaktionsgemisch einengt, den verbleibenden Rückstand über ein adsorbierendes Material filtriert, den nach dem Einengen des Eluates erhaltenen Rückstand mit Wasser verrührt und den dabei anfallenden Niederschlag absaugt und trocknet. Im zweiten Schritt des Verfahrens setzt man das Zwischenprodukt mit einem Überschuß an Phosphoroxychlorid um. Die Aufarbeitung erfolgt nach üblichen Methoden. Im allgemeinen verfährt man in der Weise, daß man das Reaktionsgemisch über ein adsorbierendes Material absaugt, das Filtrat in Wasser gibt, das entstehende Gemisch mit einem in Wasser wenig löslichen organischen Solvens extrahiert und die vereinigten organischen Phasen trocknet und unter vermindertem Druck einengt.The reaction mixture is concentrated, the remaining residue via an adsorbent Filtered material, the residue obtained after concentrating the eluate is stirred with water and the resulting precipitate is suction filtered and dried. In the second step of the process, the intermediate is reacted with an excess of phosphorus oxychloride. The processing takes place according to usual methods. In general, the procedure is such that the reaction mixture is suctioned off through an adsorbent material, the filtrate is added to water, the resulting mixture is extracted with a water-insoluble organic solvent and the combined organic phases are dried and concentrated under reduced pressure.
Die zur Durchführung des erfindungsgemäßen Verfahrens als Reaktionskomponenten benötigten Sulfonsäurehalogenide sind durch die Formel (III) allgemein definiert. In dieser Formel hat R1 vorzugsweise diejenige Bedeutung, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) als bevorzugt für R1 angegeben wurde. X steht vorzugsweise für Chlor.Formula (III) provides a general definition of the sulfonic acid halides required as reaction components for carrying out the process according to the invention. In this formula, R 1 preferably has the meaning which has already been stated as preferred for R 1 in connection with the description of the compounds of the formula (I) according to the invention. X preferably represents chlorine.
Die Sulfonsäurehalogenide der Formel (III) sind bekannt oder können nach bekannten Verfahren hergestellt werden (vgl. J. Heterocyclic Chem. 1981, 997-1006 und EP-A 0 238 824).The sulfonic acid halides of the formula (III) are known or can be prepared by known processes (cf. J. Heterocyclic Chem. 1981, 997-1006 and EP-A 0 238 824).
Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens kommen alle inerten organischen Lösungsmittel in Betracht. Vorzugsweise verwendbar sind aliphatische, alicyclische oder aromatische Kohlenwasserstoffe, wie Petrolether, Hexan, Heptan, Cyclohexan, Methylcyclohexan, Benzol, Toluol, Xylol oder Decalin; halogenierte Kohlenwasserstoffe, wie Chlorbenzol, Dichlorbenzol, Dichlormethan, Chloroform, Tetrachlormethan, Dichlorethan oder Trichlorethan; Ether, wie Diethyl- ether, Diisopropylether, Methyl-t-butylether, Methyl-t-Amylether, Dioxan, Tetrahy- drof ran, 1 ,2-Dimethoxyethan, 1 ,2-Diethoxyethan oder Anisol; Ketone, wie Aceton, Butanon, Methyl-isobutylketon oder Cyclohexanon; Nitrile, wie Acetonitril, Propio- nitril, n- oder i-Butyronitril oder Benzonitril; Ester wie Essigsäuremethylester oder Essigsäureethylester. Als Säurebindemittel kommen bei der Durchführung des erfindungsgemäßen Verfahrens alle üblichen anorganischen oder organischen Basen infrage. Vorzugsweise verwendbar sind Erdalkalimetall- oder Alkalimetallhydride, -hydroxide, -amide, -alko- holate, -acetate, -carbonate oder -hydrogencarbonate, wie Natriumhydrid, Natrium- amid, Natrium-methylat, Natrium-ethylat, Kalium-tert.-butylat, Natriumhydroxid,Suitable diluents for carrying out the process according to the invention are all inert organic solvents. Aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Esters such as methyl acetate or ethyl acetate. Suitable acid binders for carrying out the process according to the invention are all customary inorganic or organic bases. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, are preferably usable. Sodium hydroxide,
Kaliumhydroxid, Natriumacetat, Kaliumacetat, Calciumacetat, Natriumcarbonat, Kaliumcarbonat, Kaliumhydrogencarbonat oder Natriumhydrogencarbonat, ferner Ammonium- Verbindungen, wie Ammoniumhydroxid, Ammoniumacetat oder Ammoniumcarbonat, sowie tertiäre Amine, wie Trimethylamin, Triethylamin, Tri- butylamin, N,N-Dimethylanilin, N,N-Dimethyl-benzylamin, Pyridin, N-Methyl- piperidin, N-Methylmorpholin, N,N-Dimethylaminopyridin, Diazabicyclooctan (DABCO), Diazabicyclononen (DBN) oder Diazabicycloundecen (DBU).Potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate, furthermore ammonium compounds, such as ammonium hydroxide, ammonium acetate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tri-butylamine, N, N-dimethylaniline, N, N -Dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0°C und 150°C, vorzugsweise zwischen 20°C und 120°C.The reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C.
Das erfindungsgemäße Verfahren wird im allgemeinen unter Atmosphärendruck durchgeführt. Es ist jedoch auch möglich, unter erhöhtem oder vermindertem DruckThe process according to the invention is generally carried out under atmospheric pressure. It is also possible, however, under increased or reduced pressure
- im allgemeinen zwischen 0,1 bar und 10 bar - zu arbeiten.- generally between 0.1 bar and 10 bar - to work.
Zur Durchführung des erfindungsgemäßen Verfahrens setzt man pro Mol an Oxazo- lon der Formel (II) im allgemeinen 1 bis 2 Mol, vorzugsweise 1 bis 1,3 Mol, an Sul- fonsäurehalogenid der Formel (III) und gegebenenfalls 1,0 bis 2,0 Mol, vorzugsweiseTo carry out the process according to the invention, generally 1 to 2 mol, preferably 1 to 1.3 mol, of sulfonic acid halide of the formula (III) and, if appropriate, 1.0 to 2, are used per mol of oxazolone of the formula (II), 0 moles, preferably
1,0 bis 1,3 Mol an Säureakzeptor ein.1.0 to 1.3 moles of acid acceptor.
Die Aufarbeitung erfolgt nach üblichen Methoden. Im allgemeinen verfährt man in der Weise, daß man das Reaktionsgemisch in Wasser gießt, das entstehende Gemisch mehrfach mit einem in Wasser wenig löslichen organischen Solvens extrahiert, die vereinigten organischen Phasen trocknet und unter vermindertem Druck einengt. Der verbleibende Rückstand kann gegebenenfalls nach üblichen Reinigungsmethoden von eventuell noch vorhandenen Verunreinigungen befreit werden.The processing takes place according to usual methods. In general, the procedure is such that the reaction mixture is poured into water, the resulting mixture is extracted several times with an organic solvent which is sparingly soluble in water, and the combined organic phases are dried and concentrated under reduced pressure. The Any remaining residue can, if necessary, be freed of any impurities that may still be present using customary cleaning methods.
Die erfindungsgemäßen Stoffe weisen eine starke mikrobizide Wirkung auf und kön- nen zur Bekämpfung von unerwünschten Mikroorganismen, wie Fungi und Bakterien, im Pflanzenschutz und im Material schütz eingesetzt werden.The substances according to the invention have a strong microbicidal action and can be used to protect against undesired microorganisms, such as fungi and bacteria, in crop protection and in the material.
Fungizide lassen sich Pflanzenschutz zur Bekämpfung von Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes und Deuteromycetes einsetzen.Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
Bakterizide lassen sich im Pflanzenschutz zur Bekämpfung von Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae und Streptomycetaceae einsetzen.Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
Beispielhaft aber nicht begrenzend seien einige Erreger von pilzlichen und bakteriellen Erkrankungen, die unter die oben aufgezählten Oberbegriffe fallen, genannt:Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas-Arten, wie beispielsweise Xanthomonas campestris pv. oryzae;Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;
Pseudomonas-Arten, wie beispielsweise Pseudomonas syringae pv. lachrymans;Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans;
Erwinia-Arten, wie beispielsweise Erwinia amylovora;Erwinia species, such as, for example, Erwinia amylovora;
Pythium-Arten, wie beispielsweise Pythium ultimum;Pythium species, such as, for example, Pythium ultimum;
Phytophthora-Arten, wie beispielsweise Phytophthora infestans; Pseudoperonospora-Arten, wie beispielsweise Pseudoperonospora humuli oderPhytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or
Pseudoperonospora cubensis;Pseudoperonospora cubensis;
Plasmopara- Arten, wie beispielsweise Plasmopara viticola;Plasmopara species, such as, for example, Plasmopara viticola;
Bremia-Arten, wie beispielsweise Bremia lactucae;Bremia species, such as, for example, Bremia lactucae;
Peronospora-Arten, wie beispielsweise Peronospora pisi oder P. brassicae; Erysiphe-Arten, wie beispielsweise Erysiphe graminis;Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca-Arten, wie beispielsweise Sphaerotheca fuliginea; Podosphaera-Arten, wie beispielsweise Podosphaera leucotricha;Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia-Arten, wie beispielsweise Venturia inaequalis;Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora- Arten, wie beispielsweise Pyrenophora teres oder P. gramineaPyrenophora species, such as, for example, Pyrenophora teres or P. graminea
(Konidienform: Drechslera, Syn: Helminthosporium); Cochliobolus-Arten, wie beispielsweise Cochliobolus sativus(Conidial form: Drechslera, Syn: Helminthosporium); Cochliobolus species, such as, for example, Cochliobolus sativus
(Konidienform: Drechslera, Syn: Helminthosporium);(Conidial form: Drechslera, Syn: Helminthosporium);
Uromyces-Arten, wie beispielsweise Uromyces appendiculatus;Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia- Arten, wie beispielsweise Puccinia recondita;Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia-Arten, wie beispielsweise Sclerotinia sclerotiorum; Tilletia- Arten, wie beispielsweise Tilletia caries;Sclerotinia species, such as, for example, Sclerotinia sclerotiorum; Tilletia species, such as, for example, Tilletia caries;
Ustilago-Arten, wie beispielsweise Ustilago nuda oder Ustilago avenae;Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia-Arten, wie beispielsweise Pellicularia sasakii;Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia-Arten, wie beispielsweise Pyricularia oryzae;Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium-Arten, wie beispielsweise Fusarium culmorum; Botrytis-Arten, wie beispielsweise Botrytis cinerea;Fusarium species, such as, for example, Fusarium culmorum; Botrytis species, such as, for example, Botrytis cinerea;
Septoria-Arten, wie beispielsweise Septoria nodorum;Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria-Arten, wie beispielsweise Leptosphaeria nodorum;Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora- Arten, wie beispielsweise Cercospora canescens;Cercospora species, such as, for example, Cercospora canescens;
Alternaria-Arten, wie beispielsweise Alternaria brassicae; Pseudocercosporella-Arten, wie beispielsweise Pseudocercosporella herpotrichoides.Alternaria species, such as, for example, Alternaria brassicae; Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
Die gute Pflanzenverträglichkeit der Wirkstoffe in den zur Bekämpfung von Pflanzenkrankheiten notwendigen Konzentrationen erlaubt eine Behandlung von oberirdischen Pflanzenteilen, von Pflanz- und Saatgut, und des Bodens.The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.
Dabei lassen sich die erfindungsgemäßen Wirkstoffe mit besonders gutem Erfolg zur Bekämpfung von Krankheiten im Wein-, Obst- und Gemüseanbau, wie beispielsweise gegen Phytophthora- Arten, einsetzen. Die erfindungsgemäßen Wirkstoffe eignen sich auch zur Steigerung des Ernteertrages. Sie sind außerdem mindertoxisch und weisen eine gute Pflanzenverträglichkeit auf.The active compounds according to the invention can be used with particularly good success to combat diseases in wine, fruit and vegetable cultivation, such as, for example, against Phytophthora species. The active compounds according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.
Im Materialschutz lassen sich die erfindungsgemäßen Stoffe zum Schutz von technischen Materialien gegen Befall und Zerstörung durch unerwünschte Mikroorganismen einsetzen.In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
Unter technischen Materialien sind im vorliegenden Zusammenhang nichtlebende Materialien zu verstehen, die für die Verwendung in der Technik zubereitet worden sind. Beispielsweise können technische Materialien, die durch erfindungsgemäße Wirkstoffe vor mikrobieller Veränderung oder Zerstörung geschützt werden sollen, Klebstoffe, Leime, Papier und Karton, Textilien, Leder, Holz, Anstrichmittel und Kunststoffartikel, Kühlschmierstoffe und andere Materialien sein, die von Mikroor- ganismen befallen oder zersetzt werden können. Im Rahmen der zu schützendenIn the present context, technical materials are to be understood as non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected from microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which attack or decompose from microorganisms can be. As part of the to be protected
Materialien seien auch Teile von Produktionsanlagen, beispielsweise Kühlwasserkreisläufe, genannt, die durch Vermehrung von Mikroorganismen beeinträchtigt werden können. Im Rahmen der vorliegenden Erfindung seien als technische Materialien vorzugsweise Klebstoffe, Leime, Papiere und Kartone, Leder, Holz, Anstrichmittel, Kühlschmiermittel und Wärmeübertragungsflüssigkeiten genannt, besonders bevorzugt Holz.Materials are also parts of production systems, such as cooling water circuits, that can be affected by the proliferation of microorganisms. In the context of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.
Als Mikroorganismen, die einen Abbau oder eine Veränderung der technischen Materialien bewirken können, seien beispielsweise Bakterien, Pilze, Hefen, Algen und Schleimorganismen genannt. Vorzugsweise wirken die erfindungsgemäßenBacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The ones according to the invention preferably act
Wirkstoffe gegen Pilze, insbesondere Schimmelpilze, holzverfärbende und holzzerstörende Pilze (Basidiomyceten) sowie gegen Schleimorganismen und Algen.Active substances against fungi, in particular mold, wood-staining and wood-destroying fungi (Basidiomycetes) as well as against slime organisms and algae.
Es seien beispielsweise Mikroorganismen der folgenden Gattungen genannt: Alternaria, wie Alternaria tenuis,For example, microorganisms of the following genera may be mentioned: Alternaria, such as Alternaria tenuis,
Aspergillus, wie Aspergillus niger, Chaetomium, wie Chaetomium globosum, Coniophora, wie Coniophora puetana, Lentinus, wie Lentinus tigrinus, Penicillium, wie Penicillium glaucum, Polyporus, wie Polyporus versicolor,Aspergillus, such as Aspergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetana, Lentinus, such as Lentinus tigrinus, Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor,
Aureobasidium, wie Aureobasidium pullulans, Sclerophoma, wie Sclerophoma pityophila, Trichoderma, wie Trichoderma viride, Escherichia, wie Escherichia coli, Pseudomonas, wie Pseudomonas aeruginosa,Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, wie Staphylococcus aureus.Staphylococcus, such as Staphylococcus aureus.
Die Wirkstoffe können in Abhängigkeit von ihren jeweiligen physikalischen und/oder chemischen Eigenschaften in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Pasten,Depending on their respective physical and / or chemical properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes,
Granulate, Aerosole, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, sowie ULV-Kalt- und Warmnebel-Formulierungen.Granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm mist formulations.
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel ver- wendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aro- maten, wie Xylol, Toluol oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polareThese formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, are strongly polar
Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser. Mit verflüssigten gasformigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid. Als feste Trägerstoffe kommen in Frage: z.B. natürliche Ge- steinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmo- rillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate. Als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und orga- nischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengel. Als Emulgier und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäureester, Polyoxyethylen-Fettalkoholether, z.B. Alkylaryl- polyglycolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydroly- säte. Als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methyl- cellulose.Solvents such as dimethylformamide and dimethyl sulfoxide, and water. With Liquefied gaseous extenders or carriers are those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. The following are suitable as solid carriers: for example, natural rock powders such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Possible emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates. Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholi- pide, wie Kephaline und Lecithine, und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferro- cyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyanin- farbstoffe und Spurennährstoffe, wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. 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.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %. Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Fungiziden, Bakteriziden, Akariziden, Nematiziden oder Insektiziden verwendet werden, um so z.B. das Wirkungsspektrum zu verbreitern oder Resistenzentwicklungen vorzubeugen. In vielen Fällen erhält man dabei synergistische Effekte, d.h. die Wirksamkeit der Mischung ist größer als dieThe formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%. The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In many cases synergistic effects are obtained, ie the effectiveness of the mixture is greater than that
Wirksamkeit der Einzelkomponenten.Effectiveness of the individual components.
Als Mischpartner kommen zum Beispiel folgende Verbindungen in Frage:The following connections can be considered as mixed partners:
Fungizide:Fungicides:
Aldimorph, Ampropylfos, Ampropylfos-Kalium, Andoprim, Anilazin, Azaconazol, Azoxystrobin,Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, Bendicar, Benodanil, Benomyl, Benzamacril, Benzamacryl-isobutyl, Bialaphos, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazol,Benalaxyl, bendicar, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole,
Bupirimat, Buthiobat,Bupirimate, buthiobate,
Calciumpolysulfid, Capsimycin, Captafol, Captan, Carbendazim, Carboxin, Carvon, Chinomethionat (Quinomethionat), Chlobenthiazon, Chlorfenazol, Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinat, Clozylacon, Cufraneb, Cymoxanil, Cypro- conazol, Cyprodinil, Cyprofuram,Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanilol, cyofuraminil, cyproamaminol, cypro- aminol, cyproaminol, cyproinamol
Debacarb, Dichlorophen, Diclobutrazol, Diclofluanid, Diclomezin, Dicloran, Dietho- fencarb, Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Diniconazol-M, Dinocap, Diphenylamin, Dipyrithione, Ditalimfos, Dithianon, Dodemorph, Dodine,Debacarb, dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dorphianon, dithianon, dithianon,
Drazoxolon,Drazoxolon,
Ediphenphos, Epoxiconazol, Etaconazol, Ethirimol, Etridiazol,Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadon, Fenapanil, Fenarimol, Fenbuconazol, Fenfuram, Fenitropan,Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan,
Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Flurprimidol, Flusilazol, Flusulfamid, Flutolanil, Flutriafol, Folpet, Fosetyl-Alminium, Fosetyl- Natrium, Fthalid, Fuberidazol, Furalaxyl, Furametpyr, Furcarbonil, Furconazol, Furconazol-cis, Furmecyclox,Fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Flurprimidol, Flusilazol, Flusulfamid, Flutolanil, Flutriafol, Folpet, Fosetyl-Alminium, Fosetyl-Sodium, Fthalid, Fuberidazol, Furalaxyl, Furametpyr, Furcarboniloxol, Furcarbonil, Furcarbonil, Furcarbonil, Furcarbonil
Guazatin,Guazatin,
Hexachlorobenzol, Hexaconazol, Hymexazol,Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat,Imazalil, imibenconazole, iminoctadine, iminoctadineal besilate, iminoctadine triacetate,
Iodocarb, Ipconazol, Iprobenfos (IBP), Iprodione, Irumamycin, Isoprothiolan, Iso- valedione,Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovededione,
Kasugamycin, Kresoxim-methyl, Kupfer-Zubereitungen, wie: Kupferhydroxid, Kupfernaphthenat, Kupferoxychlorid, Kupfersulfat, Kupferoxid, Oxin-Kupfer und Bordeaux-Mischung,Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel-dimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol,Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazol, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin,Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin,
Piperalin, Polyoxin, Polyoxorim, Probenazole, Prochloraz, Procymidon, Propamocarb, Propanosine-Natrium, Propiconazol, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon, Pyroxyfur,Piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,
Quinconazol, Quintozen (PCNB), Quinoxyfen, Schwefel und Schwefel-Zubereitungen,Quinconazole, quintozen (PCNB), quinoxyfen, Sulfur and sulfur preparations,
Tebuconazol, Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazol, Thiabendazol, Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutil, Triazoxid, Trichlamid,Tebuconazole, Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazole, Thiabendazole, Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutichlamidid, Triazoxid, Triazoxid
Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazol,Tricyclazole, tridemorph, triflumizole, triforin, triticonazole,
Uniconazol,Uniconazole,
Validamycin A, Vinclozolin, Viniconazol,Validamycin A, vinclozolin, viniconazole,
Zarilamid, Zineb, Ziram sowie Dagger G, OK-8705, OK-8801, α-( 1 , 1 -Dimethylethyl)-ß-(2-phenoxyethyl)- 1 H- 1 ,2,4-triazol- 1 -ethanol, α-(2,4-Dichlorphenyl)-ß-fluor-b-propyl- 1 H- 1 ,2,4-triazol- 1 -ethanol, α-(2,4-Dichlorphenyl)-ß-methoxy-a-methyl- 1 H- 1 ,2,4-triazol- 1 -ethanol, α-(5-Methyl-l ,3-dioxan-5-yl)-ß-[[4-(trifluormethyl)-phenyl]-methylen]- 1 H- 1 ,2,4- triazol-1 -ethanol, (5RS,6RS)-6-Hydroxy-2,2,7,7-tetramethyl-5-(lH-l,2,4-triazol-l-yl)-3-octanon,Zarilamide, Zineb, Ziram and Dagger G, OK-8705, OK-8801, α- (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H- 1, 2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) -ß-fluoro-b-propyl-1 H-1, 2,4-triazole-1-ethanol, α- (2,4-dichlorophenyl) -ß-methoxy-a-methyl - 1 H- 1, 2,4-triazole-1-ethanol, α- (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] - 1 H- 1, 2,4-triazole-1-ethanol, (5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (lH-l, 2,4-triazole-l- yl) -3-octanon,
(E)-a-(Methoxyimino)-N-methyl-2-phenoxy-phenylacetamid,(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
{2-Methyl-l-[[[l-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbaminsäure- 1-isopropylester{2-Methyl-l - [[[l- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester
1 -(2,4-Dichlorphenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-ethanon-O-(phenylmethyl)-oxim, 1 -(2-Methyl- 1 -naphthalenyl)- 1 H-pyrrol-2,5-dion, l-(3,5-Dichlorphenyl)-3-(2-propenyl)-2,5-pyrrolidindion, l-[(Diiodmethyl)-sulfonyl]-4-methyl-benzol, l-[[2-(2,4-Dichlorphenyl)-l,3-dioxolan-2-yl]-methyl]-lH-imidazol, l-[[2-(4-Chlorphenyl)-3-phenyloxiranyl]-methyl]-lH-l,2,4-triazol, l-[l-[2-[(2,4-Dichloφhenyl)-methoxy]-phenyl]-ethenyl]-lH-imidazol, l-Methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol, 2',6'-Dibrom-2-methyl-4'-trifluormethoxy-4'-trifluor-methyl-l,3-thiazol-5- carboxanilid,1 - (2,4-dichlorophenyl) -2- (1 H- 1, 2,4-triazole-1-yl) -ethanone-O- (phenylmethyl) -oxime, 1 - (2-methyl-1-naphthalenyl) - 1 H-pyrrole-2,5-dione, l- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione, l - [(diiodomethyl) sulfonyl] -4-methyl- benzene, l - [[2- (2,4-dichlorophenyl) -1, 3-dioxolan-2-yl] methyl] -IH-imidazole, l - [[2- (4-chlorophenyl) -3-phenyloxiranyl] -methyl] -lH-l, 2,4-triazole, l- [l- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -lH-imidazole, l-methyl-5- nonyl-2- (phenylmethyl) -3-pyrrolidinol, 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-l, 3-thiazole-5-carboxanilide,
2,2-Dichlor-N-[l-(4-chloφhenyl)-ethyl]-l-ethyl-3-methyl-cyclopropancarboxamid,2,2-dichloro-N- [1- (4-chloro-phenyl) -ethyl] -l-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-Dichlor-5-(methylthio)-4-pyrimidinyl-thiocyanat, 2,6-Dichlor-N-(4-trifluormethylbenzyl)-benzamid,2,6-dichloro-5- (methylthio) -4-pyrimidinyl-thiocyanate, 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide,
2,6-Dichlor-N-[[4-(trifluormethyl)-phenyl]-methyl]-benzamid,2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,
2-(2,3,3-Triiod-2-propenyl)-2H-tetrazol,2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2-[(l-Methylethyl)-sulfonyl]-5-(trichlormethyl)-l,3,4-thiadiazol,2 - [(l-methylethyl) sulfonyl] -5- (trichloromethyl) -1, 3,4-thiadiazole,
2-[[6-Deoxy-4-O-(4-O-methyl-ß-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4- methoxy- 1 H-pyrrolo [2,3 -d]pyrimidin-5-carbonitril,2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -aD-glucopyranosyl] amino] -4-methoxy-1 H-pyrrolo [2,3-d] pyrimidine -5-carbonitrile,
2-Aminobutan,2-aminobutane,
2-Brom-2-(brommethyl)-pentandinitril,2-bromo-2- (bromomethyl) pentandinitrile,
2-Chlor-N-(2,3-dihydro-l,l,3-trimethyl-lH-inden-4-yl)-3-pyridincarboxamid,2-chloro-N- (2,3-dihydro-l, l, 3-trimethyl-lH-inden-4-yl) -3-pyridinecarboxamide,
2-Chlor-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamid, 2-Phenylphenol(OPP),2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide, 2-phenylphenol (OPP),
3 ,4-Dichlor- 1 -[4-(difluormethoxy)-phenyl]- 1 H-pyrrol-2,5-dion,3,4-dichloro-1 - [4- (difluoromethoxy) phenyl] -1 H-pyrrole-2,5-dione,
3,5-Dichlor-N-[cyan[(l-methyl-2-propynyl)-oxy]-methyl]-benzamid,3,5-dichloro-N- [cyan [(1-methyl-2-propynyl) oxy] methyl] benzamide,
3 -( 1 , 1 -Dimethylpropy 1- 1 -oxo- 1 H-inden-2-carbonitril,3 - (1, 1-dimethylpropy 1- 1 -oxo-1 H-indene-2-carbonitrile,
3-[2-(4-Chloφhenyl)-5-ethoxy-3-isoxazolidinyl]-pyridin, 4-Chlor-2-cyan-N,N-dimethyl-5-(4-methylphenyl)-lH-imidazol-l-sulfonamid,3- [2- (4-chloro-phenyl) -5-ethoxy-3-isoxazolidinyl] pyridine, 4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -lH-imidazole-l- sulfonamide,
4-Methyl-tetrazolo[l,5-a]quinazolin-5(4H)-on,4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,
8-(l,l-Dimethylethyl)-N-ethyl-N-propyl-l,4-dioxaspiro[4.5]decan-2-methanamin,8- (l, l-dimethylethyl) -N-ethyl-N-propyl-l, 4-dioxaspiro [4.5] decane-2-methanamine,
8-Hydroxychinolinsulfat,8-hydroxyquinoline sulfate,
9H-Xanthen-9-carbonsäure-2-[(phenylamino)-carbonyl]-hydrazid, bis-(l-Methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophendicarboxylat, eis- 1 -(4-Chlθφhenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-cycloheptanol, cis-4-[3-[4-(l,l-Dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholin- hydrochlorid,9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide, bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate, ice-1 - (4-Chlθφhenyl) -2- (1 H- 1, 2,4-triazol-1-yl) cycloheptanol, cis-4- [3- [4- (l, l-dimethylpropyl) phenyl -2-methylpropyl] -2,6-dimethyl-morpholine hydrochloride,
Ethyl-[(4-chlθφhenyl)-azo]-cyanoacetat, Kaliumhydrogencarbonat,Ethyl - [(4-chlθφhenyl) azo] cyanoacetate, potassium hydrogen carbonate,
Methantetrathiol-Natriumsalz, Methyl- 1 -(2,3 -dihydro-2,2-dimethyl- 1 H-inden- 1 -y 1)- 1 H-imidazol-5 -carboxy lat,Methane tetrathiol sodium salt, Methyl 1 - (2,3-dihydro-2,2-dimethyl-1 H-inden-1-y 1) - 1 H-imidazole-5-carboxy lat,
Methyl-N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninat,Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl-N-(chloracetyl)-N-(2,6-dimethylphenyl)-DL-alaninat,Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N-(2,3-Dichlor-4-hydroxyphenyl)-l-methyl-cyclohexancarboxamid. N-(2,6-Dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamid,N- (2,3-dichloro-4-hydroxyphenyl) -l-methyl-cyclohexane carboxamide. N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N-(2,6-Dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamid,N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N-(2-Chlor-4-nitrophenyl)-4-methyl-3-nitro-benzolsulfonamid,N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N-(4-Cyclohexylphenyl)- 1 ,4,5 ,6-tetrahydro-2-pyrimidinamin,N- (4-cyclohexylphenyl) - 1, 4,5, 6-tetrahydro-2-pyrimidinamine,
N-(4-Hexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidinamin, N-(5 -Chlor-2-methylphenyl)-2-methoxy-N-(2-oxo-3 -oxazolidiny l)-acetamid,N- (4-hexylphenyl) -l, 4,5,6-tetrahydro-2-pyrimidinamine, N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidiny l) -acetamide,
N-(6-Methoxy)-3-pyridinyl)-cyclopropancarboxamid,N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,
N-[2,2,2-Trichlor-l-[(chloracetyl)-amino]-ethyl]-benzamid,N- [2,2,2-trichloro-l - [(chloroacetyl) amino] ethyl] benzamide,
N-[3-Chlor-4,5-bis-(2-propinyloxy)-phenyl]-N'-methoxy-methanimidamid,N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide,
N-Formyl-N-hydroxy-DL-alanin -Natriumsalz, O,O-Diethyl-[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioat,N-formyl-N-hydroxy-DL-alanine sodium salt, O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,
O-Methyl-S-phenyl-phenylpropylphosphoramidothioat,O-methyl-S-phenyl-phenylpropylphosphoramidothioat,
S-Methyl-l,2,3-benzothiadiazol-7-carbothioat, spiro[2H]-l-Benzopyran-2,l'(3'H)-isobenzofuran]-3'-on,S-methyl-l, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] -l-benzopyran-2, l '(3'H) -isobenzofuran] -3'-one,
Bakterizide:Bactericides:
Bromopol, Dichlorophen, Nitrapyrin, Nickel-dimethyldithiocarbamat, Kasugamycin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.Bromopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insektizide / Akarizide / Nematizide:Insecticides / acaricides / nematicides:
Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviren, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomethrin, Biopermethrin, BPMC, Bromophos A, Bufencarb, Buprofezin, Butathiofos, Buto- carboxim, Butylpyridaben,Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomefufenol, Bifenthrin, Bioethanomofufenhrin - carboxim, butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloφyrifos, Chlorpyrifos M, Chlovaphorthrin, Cis-Resmethrin, Cispermethrin, Clocythrin, Cloethocarb, Clofentezine, Cyanophos, Cycloprene, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloφyrifos, Chlorpyrifos M, Chlovaphorthrin, Cis-Resmethrin, Clocytermochrhrine, Clocytermochrhrine, Clispyrethrin Clin, Cispermethrin Clin , Cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn, Elfusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimphos,Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn, Elfusilanate, Emamectin, Empentanate, Espentan, Entphrine, Endof. Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxuron, Flucythrinate, Flufenoxuron, Flutenzine, Fluvalinate, Fonophos, Fosmethilan, Fosthiazate, Fubfenprox, Furathiocarb,Fenamiphos, Fenazaquin, Fenbutatinoxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxanone Furathiocarb,
Granuloseviren,Granulosis viruses,
Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, Isazophos, Isofenphos, Isoxathion, Ivermectin, Kernpolyederviren, Lambda-cyhalothrin, Lufenuron,Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, Isazophos, Isofenphos, Isoxathion, Ivermectin, Kernpolyederviruses, Lambda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Metaldehyd, Methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, Methidathion, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos, Naled, Nitenpyram, Nithiazine, Novaluron, Omethoat, Oxamyl, Oxydemethon M, Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat,Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhilic anisopliae, Metharhilic flavoviride, Methidathion, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos, Naled, Nitenpyramo, Oxidomylonomidamyl, Oxitomyl, Oxitomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl, Oxidomyl Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat,
Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A,Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A,
Pirimiphos M, Profenophos, Promecarb, Propoxur, Prothiophos, Prothoat,Pirimiphos M, Profenophos, Promecarb, Propoxur, Prothiophos, Prothoat,
Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridathion, Pyrimidifen, Pyriproxifen,Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridathion, Pyrimidifen, Pyriproxifen,
Quinalphos,Quinalphos,
Ribavirin,Ribavirin,
Salithion, Sebufos, Silafluofen, Spinosad, Sulfotep, Sulprofos,Salithion, Sebufos, Silafluofen, Spinosad, Sulfotep, Sulprofos,
Tau-fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Thetacyper- methrin, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate.Tau fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Thetacypermethrin, Thiamethoxam, Thiapronil, Thiatriphos hydrogen, Thiocyclos.
Thiodicarb, Thiofanox, Thuringiensin, Tralocythrin, Tralomethrin, Triarathene,Thiodicarb, Thiofanox, Thuringiensin, Tralocythrin, Tralomethrin, Triarathene,
Triazamate, Triazophos, Triazuron, Trichlophenidine, Trichlorfon, Triflumuron,Triazamates, triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron,
Trimethacarb, Vamidothion, Vaniliprole, Verticillium lecaniiTrimethacarb, vamidothione, vaniliprole, verticillium lecanii
YI 5302YI 5302
Zeta-Cypermethrin, ZolaprofosZeta-cypermethrin, zolaprofos
(lR-cis)-[5-(Phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)- furanyliden)-methyl]-2,2-dimethylcyclopropancarboxylat, (3-Phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylat, l-[(2-Chlor-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-l,3,5-triazin-2(lH)- imin,(lR-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) - furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate, (3- Phenoxyphenyl) methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, l - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-l, 3,5-triazine-2 (lH) - imin,
2-(2-Chlor-6-fluoφhenyl)-4-[4-(l,l-diemthylethyl)phenyl]-4,5-dihydro-oxazol,2- (2-chloro-6-fluorophene) -4- [4- (l, l-dimethylethyl) phenyl] -4,5-dihydro-oxazole,
2-(Acetlyoxy)-3-docecyl- 1 ,4-naphthalinidion, 2-Chlor-N-[[[4-(l-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamid,2- (acetyloxy) -3-docecyl-1,4-naphthalenide ion, 2-chloro-N - [[[4- (l-phenylethoxy) phenyl] amino] carbonyl] benzamide,
2-Chlor-N-[[[4-(2,2-dichlor-l,l-difluorethoxy)-phenyl]-amino]-carbonyl]-benzamid,2-chloro-N - [[[4- (2,2-dichloro-l, l-difluoroethoxy) phenyl] amino] carbonyl] benzamide,
3 -Methylpheny 1-propylcarbamat,3-methylpheny 1-propyl carbamate,
4-[4-(4-Ethoxyphenyl)-4-methylpentyl]-l-fluor-2-phenoxy-benzol,4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene,
4-Chlor-2-(l,l-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]- 3(2H)-pyridazinon, 4-Chlor-2-(2-chlor-2-methylpropyl)-5-[(6-iod-3-pyridinyl)methoxy]-3(2H)- pyridazinon,4-chloro-2- (l, l-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] - 3 (2H) -pyridazinone, 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone,
4-Chlor-5[(6-chlor-3-pyridinyl)methoxy]-2-(3,4-dichloφhenyl)-3(2H)-pyridazinon,4-chloro-5 [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichloφhenyl) -3 (2H) -pyridazinone,
Bacillus thuringiensis strain EG-2348, Benzoesäure (2-benzoyl-l-(l,l-dimethylethyl)-hydrazid,Bacillus thuringiensis strain EG-2348, benzoic acid (2-benzoyl-l- (l, l-dimethylethyl) hydrazide,
Butan 2,2-dimethyl-3-(2,4-dichloφhenyl)-2-oxo-l-oxaspiro[4.5]dec-3-en-4-yl-ester,Butane 2,2-dimethyl-3- (2,4-dichloφhenyl) -2-oxo-l-oxaspiro [4.5] dec-3-en-4-yl ester,
[3-[(6-Chlor-3-pyridinyl)methyl]-2-thiazolidinyliden]-cyanamid,[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] cyanamide,
Dihydro-2-(nitromethylen)-2H-l,3-thiazine-3(4H)-carboxaldehyd,Dihydro-2- (nitromethylene) -2H-l, 3-thiazine-3 (4H) -carboxaldehyde,
Ethyl-[2-[[l,6-dihydro-6-oxo-l-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamat, N-(3 ,4,4-Trifluor- 1 -oxo-3 -buteny l)-glycin,Ethyl [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate, N- (3,4,4-trifluoro-1-oxo-3 -buteny l) -glycine,
N-(4-Chloφhenyl)-3-[4-Difluormethoxy)phenyl]-4,5-dihydro-4-phenyl-lH-pyrazol-N- (4-chloro-phenyl) -3- [4-difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-
1 -carboxamid,1-carboxamide,
N-[(2-Chlor-5-thiazolyl)methyl]-N'-methyl-N"-nitro-guanidin,N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine,
N-Methyl-N'-( 1 -methyl-2-propenyl)- 1 ,2-hydrazindicarbothioamid, N-Methyl-N'-2-propenyl- 1 ,2-hydrazindicarbothioamid,N-methyl-N '- (1-methyl-2-propenyl) -1, 2-hydrazinedicarbothioamide, N-methyl-N'-2-propenyl-1, 2-hydrazinedicarbothioamide,
O,O-Diethyl-[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioat.O, O-Diethyl- [2- (dipropylamino) -2-oxoethyl] ethyl phosphoramidothioate.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Herbiziden oder mit Düngemitteln und Wachstumsregulatoren ist möglich.A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Suspensionen, Spritzpulver, Pasten, lösliche Pulver, Stäubemittel und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Verspritzen, Versprü- hen, Verstreuen, Verstäuben, Verschäumen, Bestreichen usw. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low-Volume-Verfahren auszubringen oder die Wirkstoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. Es kann auch das Saatgut der Pflanzen behandelt werden.The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients using the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
Beim Einsatz der erfindungsgemäßen Wirkstoffe als Fungizide können die Aufwandmengen je nach Applikationsart innerhalb eines größeren Bereiches variiert werden. Bei der Behandlung von Pflanzenteilen liegen die Aufwandmengen an Wirkstoff im allgemeinen zwischen 0,1 und 10.000 g/ha, vorzugsweise zwischen 10 und 1.000 g/ha. Bei der Saatgutbehandlung liegen die Aufwandmengen an Wirkstoff im allgemeinen zwischen 0,001 und 50 g pro Kilogramm Saatgut, vorzugsweise zwischen 0,01 und 10 g pro Kilogramm Saatgut. Bei der Behandlung des Bodens liegen die Aufwandmengen an Wirkstoff im allgemeinen zwischen 0,1 und 10.000 g/ha, vorzugsweise zwischen 1 und 5.000 g/ha.When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
Die zum Schutz technischer Materialien verwendeten Mittel enthalten die Wirkstoffe im allgemeinen in einer Menge von 1 bis 95 Gewichts-%, bevorzugt von 10 bisThe agents used to protect industrial materials generally contain the active ingredients in an amount from 1 to 95% by weight, preferably from 10 to
75 Gewichts-%.75% by weight.
Die Anwendungskonzentrationen der erfindungsgemäßen Wirkstoffe richten sich nach der Art und dem Vorkommen der zu bekämpfenden Mikroorganismen sowie nach der Zusammensetzung des zu schützenden Materials. Die optimale Einsatzmenge kann durch Testreihen ermittelt werden. Im allgemeinen liegen die Anwendungskonzentrationen im Bereich von 0,001 bis 5 Gewichts-%, vorzugsweise von 0,05 bis 1 ,0 Gewichts-% bezogen auf das zu schützende Material.The application concentrations of the active compounds according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal amount can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.
Die Wirksamkeit und das Wirkungsspektrum der erfindungsgemäß im Materialschutz zu verwendenden Wirkstoffe bzw. der daraus herstellbaren Mittel, Konzentrate oder ganz allgemein Formulierungen kann erhöht werden, wenn gegebenenfalls weitere antimikrobiell wirksame Verbindungen, Fungizide, Bakterizide, Herbizide, Insektizide oder andere Wirkstoffe zur Vergrößerung des Wirkungs- Spektrums oder Erzielung besonderer Effekte wie z.B. dem zusätzlichen Schutz vorThe effectiveness and the spectrum of activity of the active substances to be used according to the invention in the protection of materials or of the agents, concentrates or very generally formulations which can be prepared therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active substances are used to increase the activity. Spectrum or achieving special effects such as the additional protection from
Insekten zugesetzt werden. Diese Mischungen können ein breiteres Wirkungsspektrum besitzen als die erfindungsgemäßen Verbindungen.Insects can be added. These mixtures can have a broader spectrum of activity than the compounds according to the invention.
Die Herstellung und die Verwendung von erfindungsgemäßen Wirkstoffen werden durch die folgenden Beispiele veranschaulicht. HerstellungsbeispieleThe preparation and use of active compounds according to the invention are illustrated by the following examples. Manufacturing examples
Beispiel 1example 1
Eine Lösung von 2,8 g (20 mmol) 5-Cyano-4-ethyl-3H-[l,3]-oxazol-2-on in 50 ml Tetrahydrofuran wird bei Raumtemperatur unter Rühren mit 0,8 g (20 mmol) Natriumhydrid (60 %ig) in Öl versetzt und danach 10 Minuten bei Raumtemperatur gerührt. Anschließend fügt man 4,0 g (20 mmol) 3,5-Dimethyl-isoxazol-4-sulfonyl- chlorid hinzu und rührt weitere 20 Stunden bei Raumtemperatur. Zur Aufarbeitung wird das Reaktionsgemisch in 200 ml Wasser gegossen. Das dabei entstandene Gemisch wird dreimal mit je 50 ml Essigsäureethylester extrahiert. Die vereinigten organischen Phasen werden über Natriumsulfat getrocknet und unter vermindertem Druck eingeengt. Der verbleibende Rückstand wird mit Methylenchlorid als Laufmittel an Kieselgel chromatographiert. Man erhält auf diese Weise 0,9 g (16 % der Theorie) an 5-Cyano-4-ethyl-3-(3,5-dimethyl-isoxazol-4-sulfonyl)-3H-[l ,3]-oxazol- 2-on in Form einer farblosen Festsubstanz vom Schmelzpunkt 117 bis 122°C. log p: 2,87A solution of 2.8 g (20 mmol) of 5-cyano-4-ethyl-3H- [1,3] -oxazol-2-one in 50 ml of tetrahydrofuran is stirred at room temperature with 0.8 g (20 mmol) Sodium hydride (60%) in oil and then stirred for 10 minutes at room temperature. Then 4.0 g (20 mmol) of 3,5-dimethyl-isoxazole-4-sulfonyl chloride are added and the mixture is stirred for a further 20 hours at room temperature. For working up, the reaction mixture is poured into 200 ml of water. The resulting mixture is extracted three times with 50 ml of ethyl acetate. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The remaining residue is chromatographed on silica gel using mobile phase methylene chloride. In this way 0.9 g (16% of theory) of 5-cyano-4-ethyl-3- (3,5-dimethyl-isoxazole-4-sulfonyl) -3H- [1,3] -oxazole- 2-one in the form of a colorless solid with a melting point of 117 to 122 ° C. log p: 2.87
Herstellung von AusgangssubstanzenManufacture of starting substances
Erster Reaktionsschritt First reaction step
In ein Gemisch aus 10,2 g (0,17 mol) Harnstoff und 30 ml Eisessig werden unter Rühren bei Raumtemperatur 8,8 g (0,1 mol) 1 -Hydroxy-2-butanon gegeben. Das Ge- misch wird 4 Stunden unter Rückfluß erhitzt und dann unter vermindertem Druck eingeengt. Das verbleibende Produkt wird zunächst mit Diethylether und dann mit Methanol als Laufmittel an Kieselgel chromatographiert. Der nach dem Einengen der Methanol-Fraktion verbleibende Rückstand wird mit 100 ml Wasser verrührt. Der ausfallende Niederschlag wird abgesaugt und getrocknet. Man erhält auf diese Weise 3,9 g einer farblosen Festsubstanz vom Schmelzpunkt 160 bis 170°C.8.8 g (0.1 mol) of 1-hydroxy-2-butanone are added to a mixture of 10.2 g (0.17 mol) of urea and 30 ml of glacial acetic acid while stirring at room temperature. The mixture is heated under reflux for 4 hours and then concentrated under reduced pressure. The remaining product is first chromatographed on silica gel with diethyl ether and then with methanol as the eluent. The residue remaining after concentration of the methanol fraction is stirred with 100 ml of water. The precipitate is filtered off and dried. In this way, 3.9 g of a colorless solid substance with a melting point of 160 to 170 ° C.
Zweiter ReaktionsschrittSecond reaction step
Bei Raumtemperatur unter Rühren werden 30 g des nach dem ersten Reaktionsschritt hergestellten Produktes in 150 ml Phosphoroxychlorid eingetragen, wobei dieAt room temperature with stirring, 30 g of the product prepared after the first reaction step are introduced into 150 ml of phosphorus oxychloride, the
Temperatur des Gemisches auf 50°C ansteigt. Das Reaktionsgemisch wird 20 Stunden unter Rückfluß erhitzt und dann bei Raumtemperatur über Kieselgur abgesaugt. Das Filtrat wird unter vermindertem Druck eingeengt, und das verbleibende Produkt wird unter Kühlung auf 300 ml Wasser gegeben. Das entstehende Gemisch wird zweimal mit je 80 ml Essigsäureethylester extrahiert. Die vereinigten organischen Phasen werden über Natriumsulfat getrocknet und dann unter vermindertem Druck eingeengt. Man erhält auf diese Weise 2,2 g eines Produktes, das gemäß Gaschromatogramm zu 81 % aus 5-Cycano-4-ethyl-3H-[l,3]-oxazol-2-on besteht. Danach errechnet sich die Ausbeute zu 5 % der Theorie. log p: 0,88Temperature of the mixture rises to 50 ° C. The reaction mixture is heated under reflux for 20 hours and then suction filtered at room temperature over diatomaceous earth. The filtrate is concentrated under reduced pressure and the remaining product is added to 300 ml of water with cooling. The resulting mixture is extracted twice with 80 ml of ethyl acetate. The combined organic phases are dried over sodium sulfate and then concentrated under reduced pressure. 2.2 g of a product are obtained in this way, which according to the gas chromatogram consists of 81% 5-cycano-4-ethyl-3H- [1,3] -oxazol-2-one. Then the yield is 5% of theory. log p: 0.88
Nach der zuvor angegebenen Methode werden auch die in der folgenden Tabelle 1 aufgeführten Stoffe der Formel (I) hergestellt. Tabelle 1The substances of the formula (I) listed in Table 1 below are also prepared by the method given above. Table 1
VerwendungsbeispieleExamples of use
Beispiel AExample A
Phytophthora-Test (Tomate) / protektivPhytophthora test (tomato) / protective
Lösungsmittel: 47 Gewichtsteile AcetonSolvent: 47 parts by weight of acetone
Emulgator: 3 Gewichtsteile Alkyl-Aryl-PolyglykoletherEmulsifier: 3 parts by weight of alkyl aryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration.
Zur Prüfung auf protektive Wirksamkeit werden junge Pflanzen mit der Wirkstoffzu- bereitung in der angegebenen Aufwandmenge besprüht. Nach Antrocknen des Spritzbelages weerden die Pflanzen mit einer wäßrigen Sporensuspension von Phytophthora infestans inokuliert. Die Pflanzen werden dann in einer Inkubationskabine bei ca. 20°C und 100 % relativer Luftfeuchtigkeit aufgestellt.To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in an incubation cabin at approx. 20 ° C and 100% relative humidity.
3 Tage nach der Inokulation erfolgt die Auswertung. Dabei bedeutet 0 % ein Wirkungsgrad, der demjenigen der Kontrolle entspricht, während ein Wirkungsgrad von 100 % bedeutet, daß kein Befall beobachtet wird.Evaluation is carried out 3 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
Wirkstoffe, Aufwandmengen und Versuchsergebnisse gehen aus der folgenden Tabelle hervor. Tabelle AActive substances, application rates and test results are shown in the following table. Table A
Phytophthora-Test (Tomate) / protektivPhytophthora test (tomato) / protective
Beispiel BExample B
Plasmopara-Test (Rebe) / protektivPlasmopara test (vine) / protective
Lösungsmittel: 47 Gewichtsteile AcetonSolvent: 47 parts by weight of acetone
Emulgator: 3 Gewichtsteile Alkyl-Aryl-PolyglykoletherEmulsifier: 3 parts by weight of alkyl aryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration.
Zur Prüfung auf protektive Wirksamkeit werden junge Pflanzen mit der Wirkstoffzubereitung in der angegebenen Aufwandmenge besprüht. Nach Antrocknen des Spritzbelages werden die Pflanzen mit einer wäßrigen Sporensuspension von Plasmopara viticola inokuliert und verbleiben dann 1 Tag in einer Inkubationskabine bei ca. 20°C und 100 % relativer Luftfeuchtigkeit. Anschließend werden die Pflanzen 5 Tage im Gewächshaus bei ca. 21 °C und ca. 90 % Luftfeuchtigkeit aufgestellt. Die Pflanzen werden dann angefeuchtet und 1 Tag in eine Inkubationskabine gestellt.To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Plasmopara viticola and then remain in an incubation cabin at about 20 ° C. and 100% relative atmospheric humidity for 1 day. The plants are then placed in a greenhouse for 5 days at approx. 21 ° C and approx. 90% humidity. The plants are then moistened and placed in an incubation cabin for 1 day.
6 Tage nach der Inokulation erfolgt die Auswertung. Dabei bedeutet 0 % ein Wirkungsgrad, der demjenigen der Kontrolle entspricht, während ein Wirkungsgrad von 100 %> bedeutet, daß kein Befall beobachtet wird.Evaluation is carried out 6 days after the inoculation. 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infection is observed.
Wirkstoffe, Aufwandmengen und Versuchsergebnisse gehen aus der folgenden Tabelle hervor. Tabelle BActive substances, application rates and test results are shown in the following table. Table B
Plasmopara-Test (Rebe) / protektivPlasmopara test (vine) / protective

Claims

Patentansprüche claims
1. Sulfonyloxazolone der Formel1. Sulfonyloxazolones of the formula
in welcher in which
R1 für Alkyl oder für gegebenenfalls substituiertes Heterocyclyl steht oder für einen Rest der FormelR 1 represents alkyl or optionally substituted heterocyclyl or a radical of the formula
steht, worin stands in what
R3 für Halogen, Alkyl oder Phenyl steht,R 3 represents halogen, alkyl or phenyl,
R4 für Wasserstoff oder Alkyl steht undR 4 represents hydrogen or alkyl and
R5 für Alkyl oder gegebenenfalls substituiertes Phenyl steht,R 5 represents alkyl or optionally substituted phenyl,
undand
R2 für Alkyl steht.R 2 represents alkyl.
2. Verfahren zur Herstellung von Sulfonyloxazolonen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß man Oxazolone der Formel in welcher2. A process for the preparation of sulfonyloxazolones of the formula (I) according to claim 1, characterized in that oxazolones of the formula in which
R2 die oben angegebene Bedeutung hat,R 2 has the meaning given above,
mit Sulfonsäurehalogeniden der Formelwith sulfonic acid halides of the formula
R'-SO2-Hal (III)R'-SO 2 -Hal (III)
in welcherin which
R1 die oben angegebene Bedeutung hat undR 1 has the meaning given above and
Hai für Chlor oder Brom steht,Shark represents chlorine or bromine,
gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.
3. Mittel zur Bekämpfung von unerwünschten Mikroorganismen, gekenn- zeichnet durch einen Gehalt an mindestens einem Sulfonyloxazolon der3. Agents for combating undesirable microorganisms, characterized by a content of at least one sulfonyloxazolone
Formel (I) gemäß Anspruch 1 neben Streckmitteln und/oder oberflächenaktiven Stoffen.Formula (I) according to claim 1 in addition to extenders and / or surface-active substances.
4. Verwendung von Sulfonyloxazolonen der Formel (I) gemäß Anspruch 1 zur Bekämpfung von unerwünschten Mikroorganismen. 4. Use of sulfonyloxazolones of the formula (I) according to Claim 1 for combating undesired microorganisms.
5. Verfahren zur Bekämpfung von unerwünschten Mikroorganismen, dadurch gekennzeichnet, daß man Sulfonyloxazolone der Formel (I) auf die Mikroorganismen und/oder deren Lebensraum ausbringt.5. A method for controlling undesirable microorganisms, characterized in that sulfonyloxazolones of the formula (I) are applied to the microorganisms and / or their habitat.
6. Verfahren zur Herstellung von Mitteln zur Bekämpfung von unerwünschten6. Process for the preparation of agents for combating undesirable
Mikroorganismen, dadurch gekennzeichnet, daß man Sulfonyloxazolone der Formel (I) gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Stoffen vermischt.Microorganisms, characterized in that sulfonyloxazolones of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active substances.
7. Oxazolone der Formel7. Oxazolones of the formula
in welcher in which
R2 für Alkyl steht.R 2 represents alkyl.
8. Verfahren zur Herstellung von Oxazolonen der Formel (II) gemäß Anspruch8. A process for the preparation of oxazolones of the formula (II) according to claim
7, dadurch gekennzeichnet, daß man in einem ersten Schritt Hydroxyketone der Formel7, characterized in that in a first step hydroxyketones of the formula
(IV),(IV),
R— C— CH— OHR - C - CH - OH
in welcherin which
R2 die oben angegebene Bedeutung hat,R 2 has the meaning given above,
mit Harnstoff in Gegenwart von Eisessig umsetzt und die dabei entstehenden Produkte in einem zweiten Schritt mit Phosphoroxychlorid umsetzt.reacted with urea in the presence of glacial acetic acid and the resulting products are reacted with phosphorus oxychloride in a second step.
9. Sulfonyloxazolon gemäß Anspruch 1 , gekennzeichnet durch die Formel9. sulfonyloxazolone according to claim 1, characterized by the formula
10. Sulfonyloxazolon gemäß Anspruch 1, gekennzeichnet durch die Formel 10. sulfonyloxazolone according to claim 1, characterized by the formula
EP99969088A 1998-09-16 1999-09-09 Sulfonyl oxazolones and their use for combating undesirable microorganisms Withdrawn EP1114036A1 (en)

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DE19842353A DE19842353A1 (en) 1998-09-16 1998-09-16 New 4-alkyl-5-cyano-3-sulfonyl-oxazolones, used as microbicides, especially fungicides and bactericides, for protecting plants or materials such as wood
PCT/EP1999/006650 WO2000015620A1 (en) 1998-09-16 1999-09-09 Sulfonyl oxazolones and their use for combating undesirable microorganisms

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US3931213A (en) * 1974-12-18 1976-01-06 Interx Research Corporation 3-Chloro-2-oxazolidinones
US4097262A (en) * 1977-04-22 1978-06-27 E. I. Du Pont De Nemours And Company Herbicidal acetamides
US5223523A (en) * 1989-04-21 1993-06-29 E. I. Du Pont De Nemours And Company Fungicidal oxazolidinones
US4957933A (en) * 1989-04-21 1990-09-18 E. I. Du Pont De Nemours And Company Fungicidal oxazolidinones
ZW8594A1 (en) * 1993-08-11 1994-10-12 Bayer Ag Substituted azadioxacycbalkenes
DE19609060A1 (en) * 1995-08-10 1997-02-13 Bayer Ag Halobenzimidazoles
DE19623207A1 (en) * 1996-06-11 1997-12-18 Bayer Ag Imidazole derivatives
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