EP0923291A1 - Agents for controlling harmful fungi - Google Patents

Agents for controlling harmful fungi

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Publication number
EP0923291A1
EP0923291A1 EP97944801A EP97944801A EP0923291A1 EP 0923291 A1 EP0923291 A1 EP 0923291A1 EP 97944801 A EP97944801 A EP 97944801A EP 97944801 A EP97944801 A EP 97944801A EP 0923291 A1 EP0923291 A1 EP 0923291A1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
methyl
compound
stands
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Withdrawn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
EP97944801A
Other languages
German (de)
French (fr)
Inventor
Ruth Müller
Herbert Bayer
Hubert Sauter
Karl Eicken
Frank Wetterich
Eberhard Ammermann
Gisela Lorenz
Siegfried Strathmann
Maria Scherer
Klaus Schelberger
Bernd Müller
Joachim Leyendecker
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from DE19634771A external-priority patent/DE19634771A1/en
Application filed by BASF SE filed Critical BASF SE
Publication of EP0923291A1 publication Critical patent/EP0923291A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof

Definitions

  • the present invention relates to agents for combating harmful fungi and in particular to fungicidal mixtures of certain carbamates or oxime ethers and valinamides.
  • the invention also relates to a method for controlling harmful fungi using these agents.
  • R 11 , R 12 , R 13 , R 14 , R 15 , m and n have different meanings and X represents an oxygen or ammonium group
  • X represents an oxygen or ammonium group
  • the preparation and use of which for controlling harmful fungi or animal pests is known from WO-A- 96/01256 known.
  • Corresponding t ⁇ azole derivatives are described in OA-96/01258.
  • X represents 0 or NH
  • Y represents CH, CHO or NO
  • Z represents 0, S, NH or, for example, N-alkyl
  • R a , R b and R c can have a number of different meanings.
  • DE-A-195 31 814 describes valinamide derivatives of the formula IIIc
  • R x and RV have different meanings and the two optically active centers are in (S) and (R) configuration.
  • R x and R ⁇ have different meanings, together with at least one further active ingredient, selected from dichlofluanide, tolylfluanid, chlorothalonil, propineb, thiram, mancozeb, dyrene, copper oxychloride, captan, dimetomorph, dithianon, phtan, cymoxanil, propamocarb , Fosetyl, Metalaxyl, Oxadixyl, Fluzzinam, Methoxyacrylaten, Methoximinoacetaten, Furalaxyl, Azolen, such as Triadimenol, Bitertanol, Triadimefon and Tebuconazol, Etidiazol and Pencycuron, contain.
  • at least one further active ingredient selected from dichlofluanide, tolylfluanid, chlorothalonil, propineb, thiram, mancozeb, dyrene, copper oxychloride, captan
  • the present invention was based on the object of providing novel active compound combinations for better combating harmful fungi.
  • mixtures should be made available which are distinguished by a synergistic effect, so that a reduction in the application rates for the active ingredients used is made possible.
  • X represents CH or N
  • radicals R a and R b independently of one another represent a hydrogen atom, a halogen atom, a C ⁇ -C 4 alkyl or -CC 4 ⁇ haloalkyl group;
  • R ' is C ⁇ -C 6 -alkyl, C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -CG-haloalkynyl,
  • C -Cg-cycloalkyl-methyl or benzyl which can be partially or completely halogenated and / or can carry one to three radicals, which are selected from cyano, C ⁇ -C 4 ⁇ alkyl, -C-C 4 haloalkyl, C ! -C 4 alkoxy, -C-C 4 -haloalkoxy and -C-C 4 alkylthio; and
  • X ' represents O or NH
  • Y is CH or N
  • R 1 represents C 3 -C 4 alkyl
  • R 2 is naphthyl or phenyl, the phenyl radical in the 4-position by a halogen atom, a C 1 -C 4 alkyl or
  • compositions according to the invention contain, as compounds of the formula I, in particular carbamates of the formula wherein
  • X ', Y, Z and R' have the meanings given above.
  • a combined application in the sense of the present invention comprises the simultaneous or sequential application of the compounds according to the invention in any order.
  • the connections can be made jointly or separately.
  • the above-mentioned object is also achieved by providing a method for combating harmful fungi, which is characterized in that the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free of them with an effective amount of an agent treated according to the above definition.
  • halogen represents fluorine, chlorine, bromine, iodine, preferably fluorine, chlorine or bromine.
  • C 1 -C 4 -alkyl radicals are saturated, straight-chain or branched hydrocarbon radicals having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl.
  • C 1 -C 4 -haloalkyl radicals are saturated, straight-chain or branched hydrocarbon chains with 1 to 4 carbon atoms as defined above, where in these groups the hydrogen atoms can be partially or completely replaced by halogen atoms, such as e.g.
  • C ⁇ -Cg-alkyl radicals are saturated, straight-chain or branched hydrocarbon radicals having 1 to 6 carbon atoms, such as the above-mentioned examples of C 1 -C 4 -alkyl, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpenty1, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-l-methylpropyl and
  • C 1 -C 2 -alkyl radicals are straight-chain or branched, saturated carbon chains with 1 to 20 carbon atoms.
  • Ci-C ß -alkyl radicals as defined above and longer-chain alkyl radicals such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, stearyl, nonadecyl and arachinyl , as well as the one or more branched analogues thereof.
  • Ci-Cg-haloalkyl radicals are saturated, straight-chain or branched hydrocarbon chains with 1 to 6 carbon atoms as defined above, it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms, such as, for example, the above-mentioned examples for C 1 ⁇ C 4- haloalkyl, and 1-fluoro- or 1-chloropentyl and 1-fluoro- or 1-chlorohexyl.
  • C 2 -Cg alkenyl radicals are unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position, such as, for example, ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2- Butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-wench hy1-2-propenyl,
  • C 2 -CG-haloalkenyl are straight-chain or branched carbon radicals having 2 to 6 carbon atoms and a double bond in any position, as defined above, wherein the hydrogen atoms are replaced partially or completely by halogen atoms such as 1-fluoro- or 1-chloroethenyl; 1-fluoro or 1-chloro-1-propenyl, 1-fluoro or 1-chloro-2-propenyl; 3-fluoro or 3-chloro-2-propenyl, or 2, 3, 3-trichloro-2-propenyl.
  • halogen atoms such as 1-fluoro- or 1-chloroethenyl; 1-fluoro or 1-chloro-1-propenyl, 1-fluoro or 1-chloro-2-propenyl; 3-fluoro or 3-chloro-2-propenyl, or 2, 3, 3-trichloro-2-propenyl.
  • C 3 -C 6 alkynyl radicals are straight-chain or branched hydrocarbon groups with 3 to 6 carbon atoms and a triple bond in any position, such as 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l -Methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3rd -Methyl-1-butynyl, 1, 1-Dirnethy1-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl -2-pent
  • C 3 -C 6 -haloalkynyl radicals are straight-chain or branched hydrocarbon groups with 3 to 6 carbon atoms and a triple bond in any position according to the above definition, the hydrogen atoms being partially or completely replaced by halogen atoms, such as 3-fluorine or 3- Chloro-l-propynyl, 1-fluoro or 1-chloro-2-propynyl.
  • C 3 -C 6 cycloalkyl groups include monocyclic alkyl groups having 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • C ⁇ -C 4 alkoxy groups are straight-chain or branched alkyl radicals having 1 to 4 carbon atoms as defined above, which are bonded to the molecule via an oxygen atom, such as methoxy, ethoxy, 1- or 2-propoxy and 1-butoxy.
  • C ⁇ -C 4 -haloalkoxy groups are straight-chain or branched alkoxy groups as defined above with 1 to 4 carbon atoms, in which the hydrogen atoms can be partially or completely replaced by halogen atoms, such as chloromethoxy, fluoromethoxy, 2-fluoro- or 2-chloroethoxy, 3 -Fluoro- or 3-chloropropoxy or 4-fluoro- or 4-chlorobutoxy.
  • halogen atoms such as chloromethoxy, fluoromethoxy, 2-fluoro- or 2-chloroethoxy, 3 -Fluoro- or 3-chloropropoxy or 4-fluoro- or 4-chlorobutoxy.
  • C 1 -C 4 -alkylthio radicals are straight-chain or branched alkyl radicals having 1 to 4 carbon atoms as defined above, which are bonded to the molecule via a sulfur atom, such as, for example, methylthio, ethylthio, 1- or 2-propylthio and 1-butylthio.
  • Preferred fungicidal agents contain oxime ethers of the formula IA or IB
  • R ' represents Ci-Cg-alkyl, -C-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -Cg cycloalkylmethyl, benzyl or ring-halogenated benzyl.
  • Particularly preferred compounds of the formulas IA and IB are those whose Z-R 'radicals have the meanings given in Table I below.
  • IA.3, IB.3 0-CH 2 CH 2 CH 2 CH3
  • Examples of particularly preferred compounds are IA.2 and IA.4.
  • either the pure E or Z isomers or E / Z isomer mixtures can be present.
  • the E / Z isomer mixture or the E isomer is preferably used in each case, the E isomer of the oxime ethers being particularly preferred.
  • oxime ethers with the following E / Z configuration in the side chain are preferred:
  • oxime ethers of the formula I contained in the agents according to the invention and their preparation are per se from the older one
  • Oxime ethers of the formula I can then be prepared, for example, by reacting a benzyl derivative of the formula IV
  • L 1 represents a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate and triflate,
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (for example sodium hydride, potassium hydroxide, potassium carbonate and triethylamine) in accordance with the methods described in Houben-Weyl, 4th edition, vol. E 14b, p. 370f and Houben -Weyl, vol. 10/1, p. 1189f.
  • a base for example sodium hydride, potassium hydroxide, potassium carbonate and triethylamine
  • the required hydroxyimine V is obtained, for example, by reacting an appropriate dihydroxyimine VI
  • nucleophilically substituted reagent H 3 CL 2 wherein L 2 stands for a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate and triflate.
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (for example potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine) in accordance with the methods described in Houben-Weyl, vol. E 14b, p. 307f, p. 370f and p . 385f; Houben-Weyl, 4th edition, vol. 10/4, pp. 55f, p. 180f and p. 217f; Houben-Weyl, vol. E 5, p. 780f.
  • a base for example potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine
  • the compounds of formula VI are known (DE-A-26 21 102) or can be prepared by known methods.
  • X has the meanings given above and at least one of the radicals R a and R b does not represent a hydrogen atom, and z. B. is selected from halogen and -CC 4 ⁇ alkyl.
  • carbamates used according to the invention are known per se. Their preparation is described, for example, in WO-A-96/01256 and WO-A-96/01258, which are hereby expressly incorporated by reference. Compounds IC.l to IC 52 listed in Table II below can be mentioned as examples of preferred carbamates.
  • the compounds IC.12, IC.23, IC.32 and IC.38, in particular IC.32 and IC.38, are particularly preferred.
  • a first preferred group of valiamide derivatives are compounds of the formula II '
  • R 1 is as defined above and X is halogen, -CC 4 alkyl or -CC 4 alkoxy.
  • valinamide derivatives are compounds of the formula II ′′
  • R 1 has the meanings given above.
  • Compounds of this type and their preparation are described for example in DE-A-43 21 897 and WO-A-96/07638, to which express reference is hereby made.
  • R 2 is ⁇ -naphthyl, ⁇ -naphthyl and phenyl, the phenyl radical in the 4-position being substituted by chlorine, bromine, C 1 -C 4 -alkyl or C 1 -C 4 alkoxy.
  • Valina ide which can be used according to the invention are summarized in Table III below.
  • compounds of the formula II are used in which the amino acid part is formed from alkoxycarbonyl-L-valine (S configuration) and the phenethylamine part or the naphthylethylamine part has the R configuration.
  • Such compounds can be represented by the general formula Ha
  • R 1 and R 2 have the meanings given for the compounds of the formula II.
  • the isomerically pure compounds of the formula Ha can be prepared in a manner known per se, starting from the corresponding L-valine-based carbamoylcarboxylic acids VII.
  • the compounds Ha are obtained by the processes described below, using a carbamoylcarboxylic acid VII with an amine VIII (the literature references "Houben-Weyl” refer to: Houben-Weyl, Methods of Organic Chemistry, 4th edition, Thieme Verlag, Stuttgart):
  • the carbamoylcarboxylic acids VII are known or can be prepared by known methods, especially starting from the amino acid L-valine (cf. "Houben-Weyl", volume 15/1, pp. 46-305, especially pp. 117-125) . 5
  • Amines VIII are also known or can easily be obtained (cf. Organikum, VEB German Publishing House of Sciences, 15th edition, Berlin, 1977, pp. 610 ff .; "Houben-Weyl", volume 15/1, p. 648 -665; Indian J. Chem. 10, p. 366 (1972); J. Am. Chem. Soc. 10 58, p. 1808-1811 (1936)).
  • the R-isomer can be separated from racemates of amines VIII in a manner known per se, for example by fractional crystallization with optically active tartaric acid or preferably by means of enzyme-catalyzed esterification and subsequent saponification (cf. for example WO-A-95/08636). .
  • This process is preferably carried out by first converting the carbamoylcarboxylic acids VII into carboxy-activated derivatives, especially acyl cyanides or anhydrides (cf. Tetrahedron Letters, Volume 18, pp. 1595-1598 (1973), or " Houben-Weyl ", volume 15/1, pp. 28-32). These derivatives are then reacted with the A in VI in the presence of bases.
  • carboxy-activated acyl cyanides e.g. the reaction of carbamoylcarboxylic acids VII with diethyl cyanophosphate, especially in an inert solvent such as tetrahydrofuran or toluene.
  • carboxy-activated anhydrides the reaction of carbamoylcarboxylic acid VII with carbonic acid chlorides, such as isobutyl chloroformate, in the presence of bases and, if appropriate, in an inert solvent, such as toluene or tetrahydrofuran, is preferred.
  • carbonic acid chlorides such as isobutyl chloroformate
  • reaction of the amines VIII with the carboxy-activated carbamoylcarboxylic acids VII is preferably carried out in a solvent such as dichloromethane, tetrahydrofuran or toluene.
  • the amines VIII can also serve as bases, usually being recovered from the crude product.
  • the carbamoylcarboxylic acid VII, the A in VIII, the reagent suitable for producing the carboxy-activated derivative of carbamoylcarboxylic acid VII and the base are reacted in a one-pot process, if appropriate in an inert solvent and the crude product is then worked up in a manner known per se for the isolation of the carboxylcarboxamide Ha.
  • the compounds of the formula I and II are capable of forming salts or adducts with inorganic or organic acids or with metal ions, which can likewise be used according to the invention.
  • inorganic acids examples include hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid.
  • suitable organic acids are formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids or sulfonic acid acids (sulfonic acid acids) branched alkyl radicals with 1 to 20 carbon atoms), arylsulfonic acids or disulfonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids with straight-chain or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonic acids or diphosphonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two phosphoric acid residues), where
  • the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main group, in particular aluminum, tin and lead, and also the first to eighth subgroup, in particular chromium, manganese, iron, cobalt, nickel, copper, come as metal ions. Zinc and others into consideration.
  • the metal ions of the elements of the subgroups of the fourth period are particularly preferred. The metals can be present in the various valences that they have.
  • the mixtures of the compounds I and II or the simultaneous, joint or separate, use of the compounds I and II are distinguished by an excellent activity against broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can therefore also be used as leaf and soil fungicides.
  • the compounds I and II are usually used in a weight ratio of 10: 1 to 0.1: 1, preferably 5: 1 to 0.2: 1, in particular 5: 1 to 1: 1.
  • At least one compound of formula IA or IB with at least one compound of formula II such as. B.
  • At least one compound of formula IC with at least one compound of formula II such as. B.
  • the application rates of the mixtures according to the invention are from 0.01 to 3 kg / ha, preferably 0.1 to 1.5 kg / ha, in particular 0.1 to 1.0 kg / ha.
  • the application rates for the compounds I are 0.01 to 0.5 kg / ha, preferably 0.05 to 0.5 kg / ha, in particular 0.05 to 0.4 kg / ha.
  • the application rates for the compounds II are accordingly from 0.01 to 0.5 kg / ha, preferably 0.05 to 0.5 kg / ha, in particular 0.05 to 0.4 kg / ha.
  • application rates of the mixture of from 0.001 to 50 g / kg of seed preferably 0.01 to 10 g / kg, in particular 0.01 to 8 g / kg, are generally used.
  • the compounds I and II or the mixtures of the compounds I and II are applied separately or together by spraying or dusting the seeds, the plants or the soil before or after the plants are sown or before or after the plants emerge.
  • the fungicidal synergistic mixtures according to the invention or the compounds I and II can be prepared, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-strength aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules and applied by spraying, atomizing, dusting, scattering or pouring.
  • the form of application depends on the intended use; in any case, it should ensure that the mixture according to the invention is as fine and uniform as possible.
  • the formulations are prepared in a manner known per se, e.g. by adding solvents and / or carriers. Inert additives such as emulsifiers or dispersants are usually added to the formulations.
  • the surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene 5-octylphenol ether, ethoxylated isooctyl, octyl or nonyl phenyl, alkyl phenol or tribol glycol,
  • Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds I or II or the mixture of the compounds I and II with a solid carrier.
  • Granules e.g. coated, impregnated or homogeneous granules
  • a solid carrier e.g., a wax
  • Mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, boluses, loess, clay, dolo-
  • diatomaceous earth calcium and magnesium sulfate, magnesium oxide, ground plastics, and fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and vegetable products, such as grain flour, tree bark, wood and nutshell flour, cellulose powder, or other solid carriers.
  • fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and vegetable products, such as grain flour, tree bark, wood and nutshell flour, cellulose powder, or other solid carriers.
  • the formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I or II or of the mixture of the compounds I and II.
  • the active ingredients are in a purity of 90% to 100%, preferably
  • the compounds I or II or the mixtures or the corresponding formulations are used by the fungi, the plants, seeds, soils, 40 areas, materials or spaces to be kept free of them with a fungicidally active
  • the application can take place before or after the infestation by the harmful fungi.
  • the active ingredients were separated or together as a 10% emulsion in a mixture of cyclohexanone and emulsifier (such as Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and Emulphor® EL (Emulan ® EL, emulsifier based on ethoxylated fatty alcohols)) and diluted with water to the desired concentration.
  • cyclohexanone and emulsifier such as Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and Emulphor® EL (Emulan ® EL, emulsifier based on ethoxylated fatty alcohols)
  • ⁇ corresponds to the fungal attack of the treated plants in%
  • ß corresponds to the fungal infection of the untreated (control) plants in%
  • Example 1 Activity against Phytophthora infestans on tomatoes
  • Leaves of potted plants of the variety Large meat tomatoes were sprayed to runoff point with an aqueous suspension which was prepared from a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. The following day, the leaves were infected with an aqueous suspension of zoospores from Phytophthora infestans. The plants were then placed in a steam-saturated chamber at temperatures between 16 and 18 ° C. After six days, the blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.
  • Leaves of pot vines of the Müller Thurgau variety were sprayed to runoff point with an aqueous suspension which was prepared from a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier.
  • the plants were placed in the greenhouse for 7 days after the spray coating had dried on. Only then were the leaves inoculated with an aqueous suspension of zoospores from Plasmopara viticola.
  • the vines were then left in a chamber saturated with water vapor for 48 hours and then in a greenhouse at temperatures between 20 and 5 days and set up at 30 ° C. After this time, the plants were again placed in a moist chamber for 16 h in order to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.

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

Abstract

Agents for controlling harmful fungi contain in a solid or liquid carrier (a) at least one compound of formula (I), in which M?1 and M2¿ have different meanings, and (b) at least one valine amide of formula (II), in which R1 stands for C¿3?-C4-alkyl and R?2¿ stands for naphthyl or phenyl, the phenyl radical being substituted at position 4 by a halogen atom, a C¿1?-C4-alkyl or C1-C4-alkoxy group. Also disclosed is a process for controlling harmful fungi by using these agents.

Description

Mittel zur Bekämpfung von SchadpilzenAgents for controlling harmful fungi
Beschreibungdescription
Die vorliegende Erfindung betrifft Mittel zur Bekämpfung von Schadpilzen und insbesondere fungizid wirkende Mischungen bestimmter Carbamate bzw. Oximether und Valinamide. Die Erfindung betrifft außerdem ein Verfahren zur Bekämpfung von Schadpilzen unter Verwendung dieser Mittel.The present invention relates to agents for combating harmful fungi and in particular to fungicidal mixtures of certain carbamates or oxime ethers and valinamides. The invention also relates to a method for controlling harmful fungi using these agents.
Verbindungen der allgemeinen Formel lilaCompounds of the general formula purple
worin R11, R12, R13, R14, R15, m und n unterschiedliche Bedeutungen besitzen und X für eine Sauerstoff- oder Ammgruppe steht, deren Herstellung und Verwendung zur Bekämpfung von Schadpilzen oder tierischen Schädlingen ist aus der WO-A-96/ 01256 bekannt. Entsprechende Tπazolderivate beschreibt die O-A-96/01258.in which R 11 , R 12 , R 13 , R 14 , R 15 , m and n have different meanings and X represents an oxygen or ammonium group, the preparation and use of which for controlling harmful fungi or animal pests is known from WO-A- 96/01256 known. Corresponding tπazole derivatives are described in OA-96/01258.
In der älteren Deutschen Patentanmeldung DE-A-195 28 651 sind Oximether der Formel IllbIn the older German patent application DE-A-195 28 651 oxime ethers of the formula Illb
beschrieben, worindescribed in what
X für 0 oder NH steht,X represents 0 or NH,
Y für CH, CHO oder NO steht,Y represents CH, CHO or NO,
Z für 0, S, NH oder z.B. N-Alkyl steht, und Ra, Rb und Rc eine Reihe von verschiedenen Bedeutungen be- sitzen können. Diese Verbindungen finden Verwendung bei derZ represents 0, S, NH or, for example, N-alkyl, and R a , R b and R c can have a number of different meanings. These compounds are used in the
Bekämpfung von Schadpilzen oder tierischen Schädlingen. Verbindungen des gleichen Typs werden auch in der WO-A-95/21153 und der O-A-95/2115 beschrieben.Control of harmful fungi or animal pests. Compounds of the same type are also described in WO-A-95/21153 and O-A-95/2115.
Außerdem beschreibt der Stand der Technik eine Reihe von Amino- saureamid-Verbindungen und deren Verwendung zur Bekämpfung von Schadpilzen. Hierzu sei beispielsweise verwiesen auf die EP- A-0 398 072, die O-A-96/07638 , die DE-A-43 21 897 sowie die ältere Deutsche Patentanmeldung DE-A-195 31 814.In addition, the prior art describes a number of amino acid amide compounds and their use for combating harmful fungi. For this, reference is made, for example, to the EP A-0 398 072, OA-96/07638, DE-A-43 21 897 and the older German patent application DE-A-195 31 814.
So beschreibt beispielsweise die DE-A-195 31 814 Valinamid-Deri- vate der Formel IIIcFor example, DE-A-195 31 814 describes valinamide derivatives of the formula IIIc
worin Rx und RV verschiedene Bedeutungen besitzen und die beiden optisch aktiven Zentren in (S)- bzw. (R) -Konfiguration vorliegen.wherein R x and RV have different meanings and the two optically active centers are in (S) and (R) configuration.
Weiterhin sind aus der EP-A-0 610 764 fungizide Wirkstoffkombina- tionen bekannt, die ein Valina id-Derivat der Formel IlldFurthermore, from EP-A-0 610 764 fungicidal combinations of active substances are known which contain a valina derivative of the formula IIld
worin Rx und R^ verschiedene Bedeutungen besitzen, zusammen mit wenigstens einem weiteren Wirkstoff, ausgewählt unter Dichloflua- nid, Tolylfluanid, Chlorothalonil , Propineb, Thiram, Mancozeb, Dyrene, Kupferoxychlorid, Captan, Dimetomorph, Dithianon, Phal- tan, Cymoxanil, Propamocarb, Fosetyl, Metalaxyl, Oxadixyl, Flua- zinam, Methoxyacrylaten, Methoximinoacetaten, Furalaxyl, Azolen, wie z.B. Triadimenol, Bitertanol, Triadimefon und Tebuconazol , Etidiazol und Pencycuron, enthalten.wherein R x and R ^ have different meanings, together with at least one further active ingredient, selected from dichlofluanide, tolylfluanid, chlorothalonil, propineb, thiram, mancozeb, dyrene, copper oxychloride, captan, dimetomorph, dithianon, phtan, cymoxanil, propamocarb , Fosetyl, Metalaxyl, Oxadixyl, Fluzzinam, Methoxyacrylaten, Methoximinoacetaten, Furalaxyl, Azolen, such as Triadimenol, Bitertanol, Triadimefon and Tebuconazol, Etidiazol and Pencycuron, contain.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, neuartige Wirkstoff ombinationen zur besseren Bekämpfung von Schadpilzen bereitzustellen. Insbesondere sollten solche Mischungen bereitgestellt werden, die sich durch einen synergistischen Effekt auszeichnen, so daß eine Senkung der Aufwandmengen für die einge- setzten Wirkstoffe ermöglicht wird.The present invention was based on the object of providing novel active compound combinations for better combating harmful fungi. In particular, mixtures should be made available which are distinguished by a synergistic effect, so that a reduction in the application rates for the active ingredients used is made possible.
Überraschenderweise konnte diese Aufgabe gelöst werden durch Bereitstellung von fungizid wirkenden Mischungen, enthaltend in einem festen oder flüssigen TrägerSurprisingly, this problem was solved by providing fungicidal mixtures containing in a solid or liquid carrier
a) wenigstens eine Verbindung der allgemeinen Formel I a) at least one compound of general formula I.
worinwherein
(al) M1 für eine Gruppe der Formel(al) M 1 for a group of the formula
x^ x ^
steht , worin stands in what
X für CH oder N steht, undX represents CH or N, and
die Reste Ra und Rb unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine Cχ-C4-Alkyl- oder Cι-C4~Halogenalkylgruppe stehen; undthe radicals R a and R b independently of one another represent a hydrogen atom, a halogen atom, a Cχ-C 4 alkyl or -CC 4 ~ haloalkyl group; and
M2 für eine Gruppe der FormelM 2 for a group of the formula
CH30-^^- \ CH 3 0 - ^^ - \
(I 0CH3 (I 0CH 3
OO
steht; oderstands; or
(a2)M1 für eine Gruppe der Formel(a2) M 1 for a group of the formula
Z-R'Z-R '
steht, worin Z für 0, S, NH oder N-Cι-C4-Alkyl steht;stands in what Z represents 0, S, NH or N -CC 4 alkyl;
R' für Cι-C6-Alkyl, Cι-C6-Halogenalkyl , C2-C6-Alkenyl , C2-C6-Halogenalkenyl , C3-C6-Alkinyl, C3-Cg-Halogenalkinyl ,R 'is Cι-C 6 -alkyl, C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -CG-haloalkynyl,
C -Cg-Cycloalkyl-methyl oder Benzyl steht, welches partiell oder vollständig halogeniert sein kann und/oder einen bis drei Reste tragen kann, die ausgewählt sind unter Cyano, Cχ-C4~Al- kyl, Cι-C4-Halogenalkyl, C!-C4-Alkoxy, Cι-C4-Ha- logenalkoxy und Cι-C4-Alkylthio; undC -Cg-cycloalkyl-methyl or benzyl, which can be partially or completely halogenated and / or can carry one to three radicals, which are selected from cyano, Cχ-C 4 ~ alkyl, -C-C 4 haloalkyl, C ! -C 4 alkoxy, -C-C 4 -haloalkoxy and -C-C 4 alkylthio; and
M2 für eine Gruppe der FormelM 2 for a group of the formula
steht, worinstands in what
X' für O oder NH steht; undX 'represents O or NH; and
Y für CH oder N steht;Y is CH or N;
undand
b) ein Valinamid der Formel IIb) a valinamide of the formula II
H3C CH CH3 o O CH, UI!H 3 C CH CH 3 o O CH, UI!
RlQ C NH CH C NH CH R2 RlQ C NH CH C NH CH R 2
worinwherein
R1 für C3-C4-Alkyl steht undR 1 represents C 3 -C 4 alkyl and
R2 Naphthyl oder Phenyl bedeutet, wobei der Phenylrest in 4-Stellung durch ein Halogenatom, eine Cι-C4-Alkyl- oderR 2 is naphthyl or phenyl, the phenyl radical in the 4-position by a halogen atom, a C 1 -C 4 alkyl or
Cι-C4~Alkoxygruppe substituiert ist.Cι-C 4 ~ alkoxy group is substituted.
Die erfindungsgemäßen Mittel enthalten als Verbindungen der Formel I, insbesondere Carbamate der Formel worinThe compositions according to the invention contain, as compounds of the formula I, in particular carbamates of the formula wherein
X, Ra und Rb die oben angegebenen Bedeutungen besitzen;X, R a and R b have the meanings given above;
oderor
Oximether der Formel,Oxime ethers of the formula
worin wherein
X', Y, Z und R' die oben angegebenen Bedeutungen besitzen.X ', Y, Z and R' have the meanings given above.
Überraschenderweise wurde insbesondere festgestellt, daß sich bei kombinierter Anwendung der Verbindungen der Formeln I und II Schadpilze besser bekämpfen lassen als mit den Einzelverbindungen.Surprisingly, it was found in particular that when the compounds of the formulas I and II are used in combination, harmful fungi can be controlled better than with the individual compounds.
Eine kombinierte Anwendung im Sinne der vorliegenden Erfindung umfaßt die gleichzeitige oder sequenzielle Anwendung der erfindungsgemäßen Verbindungen in beliebiger Reihenfolge. Für die gleichzeitige Anwendung können die Verbindungen gemeinsam oder getrennt voneinander ausgebracht werden.A combined application in the sense of the present invention comprises the simultaneous or sequential application of the compounds according to the invention in any order. For simultaneous use, the connections can be made jointly or separately.
Die oben genannte Aufgabe wird außerdem gelöst durch Bereitstellung eines Verfahrens zur Bekämpfung von Schadpilzen, das dadurch gekennzeichnet ist, daß man die Schadpilze, deren Lebensraum oder die von ihnen freizuhaltenden Pflanzen, Samen, Böden, Flächen, Materialien oder Räume mit einer wirksamen Menge eines Mittels gemäß obiger Definition behandelt.The above-mentioned object is also achieved by providing a method for combating harmful fungi, which is characterized in that the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free of them with an effective amount of an agent treated according to the above definition.
In den erfindungsgemäß verwendeten Verbindungen steht Halogen für Fluor, Chlor, Brom, Jod, vorzugsweise Fluor, Chlor oder Brom. Beispiele für Cι-C4-Alkylreste sind gesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 4 Kohlenstoffatomen, wie Methyl, Ethyl , n-Propyl, 1-Methylethyl , n-Butyl , 1-Methyl- propyl, 2-Methylpropyl , 1 , 1-Dimethylethyl .In the compounds used according to the invention, halogen represents fluorine, chlorine, bromine, iodine, preferably fluorine, chlorine or bromine. Examples of C 1 -C 4 -alkyl radicals are saturated, straight-chain or branched hydrocarbon radicals having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl.
Beispiele für Cι-C -Halogenalkylreste sind gesättigte, geradkettige oder verzweigte Kohlenwasserstoffketten mit 1 bis 4 Kohlenstoffatomen gemäß obiger Definition, wobei in diesen Gruppen teilweise oder vollständig die Wasserstoffatome durch Halogen- atome ersetzt sein können, wie z.B. Chlormethyl, Dichlormethyl , Trichlormethyl, Fluormethyl, Difluormethyl , Trifluormethyl , Chlorfluormethyl, Dichlorfluormethyl , Chlordifluormethyl, 1-Fluorethyl, 2-Fluorethyl , 2 , 2-Difluorethyl , 2 , 2 , 2-Trifluor- ethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2 , 2-difluorethyl, 2, 2-Dichlor-2-fluorethyl, 2 , 2 , 2-Trichlorethyl und Pentafluorethyl, 1-, 2- oder 3-Fluorpropyl , 1-, 2- oder 3-Chlorpropyl ; 1-Fluor- oder 1-Chlorbutyl .Examples of C 1 -C 4 -haloalkyl radicals are saturated, straight-chain or branched hydrocarbon chains with 1 to 4 carbon atoms as defined above, where in these groups the hydrogen atoms can be partially or completely replaced by halogen atoms, such as e.g. Chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl and pentafluoroethyl, 1-, 2- or 3-fluoropropyl, 1-, 2- or 3-chloropropyl; 1-fluorobutyl or 1-chlorobutyl.
Beispiele für Cχ-Cg-Alkylreste sind gesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 6 Kohlenstoffatomen, wie die oben genannten Beispiele für Cι~C4-Alkyl, sowie Pentyl, 1-Methylbutyl, 2-Methylbutyl , 3-Methylbutyl , 2 , 2-Dimethylpropyl , 1-Ethylpropyl , Hexyl, 1 , 1-Dimethylpropyl , 1 , 2-Dimethylpropyl , 1-Methylpentyl, 2-Methylpentyl , 3-Methylpenty1 , 4-Methylpentyl , 1, 1-Dimethylbutyl, 1 , 2-Dimethylbutyl , 1 , 3-Dimethylbutyl , 2,2-Di- methylbutyl, 2 , 3-Dimethylbutyl , 3 , 3-Dimethylbutyl , 1-Ethylbutyl , 2-Ethylbutyl, 1 , 1 , 2-Trimethylpropyl , 1 , 2 , 2-Trimethylpropyl , 1-Ethyl-l-methylpropyl und l-Ethyl-2-methylpropyl .Examples of Cχ-Cg-alkyl radicals are saturated, straight-chain or branched hydrocarbon radicals having 1 to 6 carbon atoms, such as the above-mentioned examples of C 1 -C 4 -alkyl, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpenty1, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-l-methylpropyl and l-ethyl-2-methylpropyl.
Beispiele für Cι-C2o-Alkylreste sind geradkettige oder verzweigte, gesättigte Kohlenstoff etten mit 1 bis 20 Kohlenstoffatomen . Beispielsweise können genannt werden Ci-Cß-Alkylreste gemäß obiger Definition sowie längerkettige Alkylreste, wie unverzweigtes Hep- tyl, Octyl, Nonyl , Decyl, Undecyl , Lauryl, Tridecyl, Myristyl, Pentadecyl , Palmityl, Heptadecyl , Stearyl, Nonadecyl und Arachi- nyl, sowie die ein- oder mehrfach verzweigten Analoga davon.Examples of C 1 -C 2 -alkyl radicals are straight-chain or branched, saturated carbon chains with 1 to 20 carbon atoms. For example, Ci-C ß -alkyl radicals as defined above and longer-chain alkyl radicals, such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, stearyl, nonadecyl and arachinyl , as well as the one or more branched analogues thereof.
Beispiele für Ci-Cg-Halogenalkylreste sind gesättigte, geradkettige oder verzweigte Kohlenwasserstoffketten mit 1 bis 6 Kohlen- stoffatomen gemäß obiger Definition, wobei in diesen Gruppen teilweise oder vollständig die Wasserstoffatome durch Halogenatome ersetzt sein können, wie z.B. die oben genannten Beispiele für Cι~C4-Halogenalkyl, sowie 1-Fluor- oder 1-Chlorpentyl und 1-Fluor- oder 1-Chlorhexyl . Beispiele für C2-Cg-Alkenylreste sind ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit 2 bis 6 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, wie z.B. Ethenyl , 1-Propenyl, 2-Propenyl, 1-Methylethenyl , 1-Butenyl, 2-Butenyl, 3-Butenyl, 1-Methyl-l-propenyl , 2-Methyl-l-propenyl , 1-Methyl-2-propenyl, 2-Methyl-2-propenyl , 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, 4-Pentenyl, 1-Methyl-l-butenyl, 2-Methyl-l-butenyl, 3-Methyl-l -butenyl, 1-Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2-butenyl, l-Methyl-3-butenyl , 2-Methyl-3-butenyl , 3-Methyl-3-butenyl, 1 , 1-Dirne hy1-2-propenyl , 1, 2-Dimethyl-l-pro- penyl , 1 , 2-Dimethyl-2-propenyl , 1-Ethyl-l-propenyl, 1-Ethy1-2-propenyl , 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Methyl-1-pentenyl , 2-Methyl-l-pentenyl , 3-Methyl-l-pentenyl, 4-Methyl-l-pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl , 4-Methyl-2-pentenyl, l-Methyl-3-pentenyl , 2-Methyl-3-pentenyl , 3-Methyl-3-pentenyl , 4-Methyl-3-pentenyl , l-Methyl-4-pentenyl , 2-Methyl-4-pentenyl , 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1, l-Dimethyl-2-butenyl , 1, l-Dimethyl-3-butenyl , 1 , 2-Dimethyl-l-butenyl , 1, 2-Dimethyl- 2-butenyl, 1 , 2-Dimethyl-3-butenyl , 1 , 3-Dimethyl-l-butenyl ,Examples of Ci-Cg-haloalkyl radicals are saturated, straight-chain or branched hydrocarbon chains with 1 to 6 carbon atoms as defined above, it being possible for some or all of the hydrogen atoms in these groups to be replaced by halogen atoms, such as, for example, the above-mentioned examples for C 1 ~ C 4- haloalkyl, and 1-fluoro- or 1-chloropentyl and 1-fluoro- or 1-chlorohexyl. Examples of C 2 -Cg alkenyl radicals are unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 6 carbon atoms and a double bond in any position, such as, for example, ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2- Butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2- butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-wench hy1-2-propenyl, 1, 2-dimethyl-l-propenyl, 1 , 2-Dimethyl-2-propenyl, 1-ethyl-l-propenyl, 1-Ethy1-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1 -pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl , 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3 -Methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l -Dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1, 2-dimethyl-l-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3 -Dimethyl-l-butenyl,
1, 3-Dimethyl-2-butenyl, 1 , 3-Dimethyl-3-butenyl , 2 , 2-Dimethyl- 3-butenyl, 2 , 3-Dimethyl-l-butenyl , 2 , 3-Dimethyl-2-butenyl , 2 , 3-Dimethyl-3-butenyl, 3 , 3-Dimethyl-l-butenyl , 3 , 3-Dimethyl- 2-butenyl, 1-Ethyl-l-butenyl , l-Ethyl-2-butenyl , l-Ethyl-3-bute- nyl, 2-Ethyl-1-butenyl , 2-Ethyl-2-butenyl , 2-Ethyl-3 -butenyl , 1,1, 2-Trimethyl-2-propenyl , l-Ethyl-l-methyl-2-propenyl , l-Ethyl-2-methyl-l-propenyl und l-Ethyl-2-methyl-2-proρenyl .1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-l-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-l-butenyl, l-ethyl-2-butenyl, l-ethyl 3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1, 2-trimethyl-2-propenyl, l-ethyl-l-methyl- 2-propenyl, l-ethyl-2-methyl-l-propenyl and l-ethyl-2-methyl-2-propenyl.
Beispiele für C2-Cg-Halogenalkenylreste sind geradkettige oder verzweigte Kohlenstoffreste mit 2 bis 6 Kohlenstoffatomen und einer Doppelbindung in beliebiger Position gemäß obiger Definition, wobei die Wasserstoffatome teilweise oder ganz durch Halogenatome ersetzt sind, wie z.B. 1-Fluor- oder 1-Chlorethenyl ; 1-Fluor- oder 1-Chlor-l-propenyl , 1-Fluor- oder 1-Chlor-2-propenyl ; 3-Fluor- oder 3-Chlor-2-propenyl , oder 2 , 3 , 3-Trichlor-2-propenyl .Examples of C 2 -CG-haloalkenyl are straight-chain or branched carbon radicals having 2 to 6 carbon atoms and a double bond in any position, as defined above, wherein the hydrogen atoms are replaced partially or completely by halogen atoms such as 1-fluoro- or 1-chloroethenyl; 1-fluoro or 1-chloro-1-propenyl, 1-fluoro or 1-chloro-2-propenyl; 3-fluoro or 3-chloro-2-propenyl, or 2, 3, 3-trichloro-2-propenyl.
Beispiele für C3-C6-Alkinylreste sind geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 3 bis 6 Kohlenstoff tomen und einer Dreifachbindung in einer beliebigen Position, wie 1-Propinyl , 2-Propinyl, 1-Butinyl, 2-Butinyl, 3-Butinyl, l-Methyl-2-propinyl , 1-Pentinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, l-Methyl-2-buti- nyl, l-Methyl-3-butinyl, 2-Methyl-3-butinyl , 3-Methyl-l-butinyl , 1, 1-Dirnethy1-2-propinyl, l-Ethyl-2-propinyl , 1-Hexinyl, 2-Hexi- nyl , 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, 1-Methyl-2-pentinyl , l-Methyl-3-pentinyl , l-Methyl-4-pentinyl, 2-Methyl-3-pentinyl , 2-Methyl-4-pentinyl , 3-Methyl-l-pentinyl , 3-Methyl-4-pentinyl , 4-Methyl-1-pentinyl , 4-Methyl-2-pentinyl , 1 , l-Dimethyl-2-butinyl , 1, l-Dimethyl-3-butinyl, 1 , 2-Dimethyl-3-butinyl , 2 , 2-Dimethyl-3- butinyl, 3 , 3-Dimethyl-l-butinyl , l-Ethyl-2-butinyl , l-Ethyl-3-bu- tinyl , 2-Ethyl-3-butinyl und l-Ethyl-l-methyl-2-propinyl .Examples of C 3 -C 6 alkynyl radicals are straight-chain or branched hydrocarbon groups with 3 to 6 carbon atoms and a triple bond in any position, such as 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, l -Methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3rd -Methyl-1-butynyl, 1, 1-Dirnethy1-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl -2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-l-pentynyl, 3-methyl-4 pentinyl, 4-methyl-1-pentinyl, 4-methyl-2-pentinyl, 1, l-dimethyl-2-butinyl, 1, l-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2, 2-dimethyl-3-butynyl, 3, 3-dimethyl-l-butynyl, l-ethyl-2-butynyl, l- Ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-propynyl.
Beispiele für C3-C6-Halogenalkinylreste sind geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 3 bis 6 Kohlenstoff tomen und einer Dreifachbindung in beliebiger Position gemäß obiger Definition, wobei die Wasserεtoffatome teilweise oder ganz durch Halogenatome ersetzt sind, wie z.B. 3-Fluor- oder 3-Chlor-l-pro- pinyl, 1-Fluor- oder l-Chlor-2-propinyl .Examples of C 3 -C 6 -haloalkynyl radicals are straight-chain or branched hydrocarbon groups with 3 to 6 carbon atoms and a triple bond in any position according to the above definition, the hydrogen atoms being partially or completely replaced by halogen atoms, such as 3-fluorine or 3- Chloro-l-propynyl, 1-fluoro or 1-chloro-2-propynyl.
Beispiele für C3-C6-Cycloalkylgruppen umfassen monocyclische Alkylgruppen mit 3 bis 6 Kohlenstoffringgliedern wie Cyclopropyl, Cyclobutyl, Cyclopentyl und Cyclohexyl .Examples of C 3 -C 6 cycloalkyl groups include monocyclic alkyl groups having 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Beispiele für Cχ-C4-Alkoxygruppen sind geradkettige oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen gemäß obiger Definition, die über ein Sauerstoffatom an das Molekül gebunden sind, wie z.B. Methoxy, Ethoxy, 1- oder 2-Propoxy und 1-Butoxy.Examples of Cχ-C 4 alkoxy groups are straight-chain or branched alkyl radicals having 1 to 4 carbon atoms as defined above, which are bonded to the molecule via an oxygen atom, such as methoxy, ethoxy, 1- or 2-propoxy and 1-butoxy.
Beispiele für Cχ-C4-Halogenalkoxygruppen sind geradkettige oder verzweigte Alkoxygruppen gemäß obiger Definition mit 1 bis 4 Kohlenstoffatomen, worin die Wasserstoffatome teilweise oder ganz durch Halogenatome ersetzt sein können, wie z.B. Chlormethoxy , Fluormethoxy, 2-Fluor- oder 2-Chlorethoxy , 3-Fluor- oder 3-Chlor- propoxy oder 4-Fluor- oder 4-Chlorbutoxy .Examples of Cχ-C 4 -haloalkoxy groups are straight-chain or branched alkoxy groups as defined above with 1 to 4 carbon atoms, in which the hydrogen atoms can be partially or completely replaced by halogen atoms, such as chloromethoxy, fluoromethoxy, 2-fluoro- or 2-chloroethoxy, 3 -Fluoro- or 3-chloropropoxy or 4-fluoro- or 4-chlorobutoxy.
Beispiele für Cι-C4~Alkylthioreste sind geradkettige oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen gemäß obiger Definition, welche über ein Schwefelatom an das Molekül gebunden sind, wie z.B. Methylthio, Ethylthio, 1- oder 2-Propylthio und 1-Butylthio.Examples of C 1 -C 4 -alkylthio radicals are straight-chain or branched alkyl radicals having 1 to 4 carbon atoms as defined above, which are bonded to the molecule via a sulfur atom, such as, for example, methylthio, ethylthio, 1- or 2-propylthio and 1-butylthio.
Bevorzugte fungizide Mittel enthalten Oximether der Formel IA oder IB Preferred fungicidal agents contain oxime ethers of the formula IA or IB
worin jeweils where each
Z für 0 steht undZ stands for 0 and
R' für Ci-Cg-Alkyl, Cι-C6-Halogenalkyl , C2-C6-Alkenyl, C2-C6-Halo- genalkenyl, C3-Cg-Cycloalkylmethyl , Benzyl oder ringhaloge- niertes Benzyl steht.R 'represents Ci-Cg-alkyl, -C-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -Cg cycloalkylmethyl, benzyl or ring-halogenated benzyl.
Besonders bevorzugte Verbindungen der Formeln IA und IB sind solche, deren Reste Z-R' die in folgender Tabelle I angegebenen Bedeutungen besitzen.Particularly preferred compounds of the formulas IA and IB are those whose Z-R 'radicals have the meanings given in Table I below.
Tabelle I:Table I:
Nr. ZR'ZR '
IA.l, IB.l 0-CH2CH2CH3 IA.l, IB.l 0-CH 2 CH 2 CH 3
IA.2, IB.2 0-CH(CH3)2 IA.2, IB.2 0-CH (CH 3 ) 2
IA.3, IB.3 0-CH2CH2CH2CH3IA.3, IB.3 0-CH 2 CH 2 CH 2 CH3
IA.4, IB.4 0-CH(CH3)CH2CH3 IA.4, IB.4 0-CH (CH 3 ) CH 2 CH 3
IA.5, IB.5 0-CH2CH(CH3)2 IA.5, IB.5 0-CH 2 CH (CH 3 ) 2
IA.6, IB.6 0-CH(CH2CH3)CH2CH3 IA.6, IB.6 0-CH (CH 2 CH 3 ) CH 2 CH 3
IA.7, IB.7 O-CH2CH3 IA.7, IB.7 O-CH 2 CH 3
IA.8, IB.8 0-CH(CH3)CH2CH2CH3 IA.8, IB.8 0-CH (CH 3 ) CH 2 CH2CH 3
IA.9, IB.9 0-CH2C(CH3)3 IA.9, IB.9 0-CH 2 C (CH 3 ) 3
IA.10, IB.10 0-CH2CCl=CCl2 IA.10, IB.10 0-CH 2 CCl = CCl 2
IA.ll, IB.11 0-CH2CH=CH-Cl (trans)IA.ll, IB.11 0-CH 2 CH = CH-Cl (trans)
IA.12, IB.12 0-CH2-C(CH3)=CH2 IA.12, IB.12 0-CH 2 -C (CH 3 ) = CH 2
IA.13, IB.13 0-CH2- (cyclopropyl )IA.13, IB.13 0-CH 2 - (cyclopropyl)
IA.14, IB.14 0-CH2-C6H5 IA.14, IB.14 0-CH 2 -C 6 H 5
IA.15, IB.15 0-CH2-[4-F-C6H4]IA.15, IB.15 0-CH 2 - [4-FC 6 H 4 ]
Beispiele für besonders bevorzugte Verbindungen sind IA.2 und IA.4. In den Oximethern der Formel I kann die C=Y-Doppelbindung in der E- oder der Z-Konfiguration (in Bezug auf die Carbonsäurefunktion) vorliegen. In den erfindungsgemäßen Mischungen können jedoch entweder die reinen E- oder Z-Isomeren oder E/Z-Isomeren- gemische enthalten sein. Bevorzugt findet jeweils das E/Z-Isome- rengemisch oder das E-Isomere Anwendung, wobei das E-Isomere der Oximether besonders bevorzugt ist.Examples of particularly preferred compounds are IA.2 and IA.4. In the oxime ethers of the formula I, the C = Y double bond can be in the E or the Z configuration (with respect to the carboxylic acid function). In the mixtures according to the invention, however, either the pure E or Z isomers or E / Z isomer mixtures can be present. The E / Z isomer mixture or the E isomer is preferably used in each case, the E isomer of the oxime ethers being particularly preferred.
Die C=N-Doppelbindungen der Bisoximetherseitenkette der Oximether I können ebenfalls in reiner E- oder Z-Form oder als E/Z-Isome- rengemische vorliegen. In den erfindungsgemäßen Mischungen sind jedoch sowohl Isomerengemische als auch reine Isomere bezüglich der C=N-Doppelbindungen brauchbar. Insbesondere sind aber Oximether mit folgender E/Z-Konfiguration in der Seitenkette bevor- zugt:The C = N double bonds of the bisoximether side chain of the oxime ethers I can also be in pure E or Z form or as E / Z isomer mixtures. In the mixtures according to the invention, however, both isomer mixtures and pure isomers with regard to the C = N double bonds can be used. In particular, oxime ethers with the following E / Z configuration in the side chain are preferred:
Die in den erfindungsgemäßen Mitteln enthaltenen Oximether der Formel I und deren Herstellung sind an sich aus der älterenThe oxime ethers of the formula I contained in the agents according to the invention and their preparation are per se from the older one
Deutschen Patentanmeldung DE-A-195 28 651 bekannt, worauf hiermit vollinhaltlich Bezug genommen wird.German patent application DE-A-195 28 651 known, to which reference is hereby made in full.
Danach sind Oximether der Formel I beispielsweise herstellbar durch Umsetzung eines Benzylderivates der Formel IVOxime ethers of the formula I can then be prepared, for example, by reacting a benzyl derivative of the formula IV
worin L1 für eine nucleophil austauschbare Abgangsgruppe, z.B. Halogen oder Sulfonatgruppen, vorzugsweise Chlor, Brom, Iod, Mesylat, Tosylat und Triflat, steht, in which L 1 represents a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate and triflate,
mit einem Hydroxyimin der Formel Vwith a hydroxyimine of formula V
Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel in Gegenwart einer Base (z.B. Natriumhydrid, Kaliumhydroxid, Kaliumcarbonat und Triethyla in) gemäß den in Houben-Weyl, 4. Aufl., Bd. E 14b, S. 370f und Houben-Weyl , Bd. 10/1, S. 1189f beschriebenen Methoden. The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (for example sodium hydride, potassium hydroxide, potassium carbonate and triethylamine) in accordance with the methods described in Houben-Weyl, 4th edition, vol. E 14b, p. 370f and Houben -Weyl, vol. 10/1, p. 1189f.
Das benötigte Hydroxyimin V erhält man beispielsweise durch Umsetzung eines entsprechenden Dihydroxyimins VIThe required hydroxyimine V is obtained, for example, by reacting an appropriate dihydroxyimine VI
Z-R'Z-R '
mit dem nucleophil substituierten Reagens H3CL2, worin L2 für eine nucleophil austauschbare Abgangsgruppe, z.B. Halogen oder Sulfo- natgruppen, vorzugsweise Chlor, Brom, Iod, Mesylat, Tosylat und Triflat, steht.with the nucleophilically substituted reagent H 3 CL 2 , wherein L 2 stands for a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate and triflate.
Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel in Gegenwart einer Base (z.B. Kaliumcarbonat, Kaliumhydroxid, Natriumhydrid, Pyridin und Triethylamin) gemäß den in Houben-Weyl, Bd. E 14b, S. 307f , S. 370f und S. 385f; Houben-Weyl, 4. Aufl., Bd. 10/4, S. 55f, S. 180f und S. 217f ; Houben-Weyl, Bd. E 5, S. 780f beschriebenen Methoden.The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (for example potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine) in accordance with the methods described in Houben-Weyl, vol. E 14b, p. 307f, p. 370f and p . 385f; Houben-Weyl, 4th edition, vol. 10/4, pp. 55f, p. 180f and p. 217f; Houben-Weyl, vol. E 5, p. 780f.
Die Verbindungen der Formel VI sind bekannt (DE-A-26 21 102) oder können nach bekannten Methoden hergestellt werden.The compounds of formula VI are known (DE-A-26 21 102) or can be prepared by known methods.
Weitere erfindungsgemäß bevorzugte Mittel enthalten Carbamate der Formel ICOther agents preferred according to the invention contain carbamates of the formula IC
worin wherein
X die oben angegebenen Bedeutungen besitzt und wenigstens einer der Reste Ra und Rb nicht für ein Wasserstoffatom steht, und z. B. ausgewählt ist unter Halogen und Cι-C4~Alkyl .X has the meanings given above and at least one of the radicals R a and R b does not represent a hydrogen atom, and z. B. is selected from halogen and -CC 4 ~ alkyl.
Die erfindungsgemäß verwendeten Carbamate sind an sich bekannt. Deren Herstellung ist beispielsweise beschrieben in der WO-A-96/01256 und der WO-A-96/01258 , worauf hiermit ausdrücklich Bezug genommen wird. Als Beispiele für bevorzugte Carbamate können die in der folgenden Tabelle II aufgeführten Verbindungen IC.l bis IC 52 genannt werden.The carbamates used according to the invention are known per se. Their preparation is described, for example, in WO-A-96/01256 and WO-A-96/01258, which are hereby expressly incorporated by reference. Compounds IC.l to IC 52 listed in Table II below can be mentioned as examples of preferred carbamates.
Tabelle IITable II
Nr. X Ra R*>No.XR a R *>
IC.l N 2-F HIC.l N 2-F H
IC.2 N 3-F HIC.2 N 3-F H
IC 3 N 4-F HIC 3 N 4-F H
IC.4 N 2-C1 HIC.4 N 2-C1 H
IC 5 N 3-C1 HIC 5 N 3-C1 H
IC.6 N 4-C1 HIC.6 N 4-C1 H
IC 7 N 2-Br HIC 7 N 2-Br H
IC.8 N 3-Br HIC.8 N 3-Br H
IC.9 N 4-Br HIC.9 N 4-Br H
IC.10 N 2-CH3 HIC.10 N 2-CH 3 H
ICH N 3-CH3 HI N 3-CH 3 H
IC.12 N 4-CH3 HIC.12 N 4-CH 3 H
IC.13 N 2-CH2CH3 HIC.13 N 2-CH 2 CH3 H
IC 14 N 3-CH2CH3 HIC 14 N 3-CH 2 CH 3 H
IC 15 N 4-CH2CH3 HIC 15 N 4-CH 2 CH 3 H
IC.16 N 2-CH(CH3)2 HIC.16 N 2-CH (CH 3 ) 2 H
IC 17 N 3-CH(CH3)2 HIC 17 N 3-CH (CH 3 ) 2 H
IC 18 N 4-CH(CH3)2 HIC 18 N 4-CH (CH 3 ) 2 H
IC.19 N 2-CF3 HIC.19 N 2-CF 3 H
IC.20 N 3-CF3 HIC.20 N 3-CF 3 H
IC.21 N 4-CF3 HIC.21 N 4-CF 3 H
IC.22 N 2-F 4-FIC.22 N 2-F 4-F
IC.23 N 2-C1 4-C1IC.23 N 2-C1 4-C1
IC.24 N 3-C1 4-C1IC.24 N 3-C1 4-C1
IC.25 N 2-C1 4-CH3IC.25 N 2-C1 4-CH3
IC26 N 3-C1 4-CH3 IC26 N 3-C1 4-CH 3
IC.27 CH 2-F HIC.27 CH 2-F H
IC.28 CH 3-F HIC.28 CH 3-F H
IC29 CH 4-F HIC29 CH 4-F H
IC30 CH 2-C1 HIC30 CH 2-C1 H
IC.31 CH 3-C1 HIC.31 CH 3-C1 H
IC.32 CH 4-C1 HIC.32 CH 4-C1 H
IC.33 CH 2-Br HIC.33 CH 2-Br H
IC.34 CH 3-Br H Nr. X Ra R*>IC.34 CH 3-Br H No.XR a R *>
IC.35 CH 4-Br HIC.35 CH 4-Br H
IC.36 CH 2-CH3 HIC.36 CH 2-CH 3 H
IC.37 CH 3-CH3 HIC.37 CH 3-CH 3 H
IC.38 CH 4-CH3 HIC.38 CH 4-CH 3 H
IC.39 CH 2-CH2CH3 HIC.39 CH 2-CH 2 CH 3 H
IC.40 CH 3-CH2CH3 HIC.40 CH 3-CH 2 CH 3 H
IC.41 CH 4-CH2CH3 HIC.41 CH 4-CH 2 CH 3 H
IC.42 CH 2-CH(CH3)2 HIC.42 CH 2-CH (CH 3 ) 2 H
IC.43 CH 3-CH(CH3)2 HIC.43 CH 3-CH (CH 3 ) 2 H
IC.44 CH 4-CH(CH3)2 HIC.44 CH 4-CH (CH 3 ) 2 H
IC.45 CH 2-CF3 HIC.45 CH 2-CF 3 H
IC.46 CH 3-CF3 HIC.46 CH 3-CF 3 H
IC.47 CH 4-CF3 HIC.47 CH 4-CF 3 H
IC.48 CH 2-F 4-FIC.48 CH 2-F 4-F
IC.49 CH 2-C1 4-C1IC.49 CH 2-C1 4-C1
IC.50 CH 3-C1 4-C1IC.50 CH 3-C1 4-C1
IC.51 CH 2-C1 4-CH3 IC.51 CH 2-C1 4-CH 3
IC 52 CH 3-C1 4-CH3 IC 52 CH 3-C1 4-CH 3
Besonders bevorzugt werden die Verbindungen IC.12, IC.23, IC.32 und IC.38, insbesondere IC.32 und IC.38.The compounds IC.12, IC.23, IC.32 and IC.38, in particular IC.32 and IC.38, are particularly preferred.
Die erfindungsgemäß verwendeten Verbindungen der Formel II sind ebenfalls an sich bekannt. Eine erste bevorzugte Gruppe von Vali- namidderivaten sind Verbindungen der Formel II'The compounds of formula II used according to the invention are also known per se. A first preferred group of valiamide derivatives are compounds of the formula II '
worin R1 wie oben definiert ist und X für Halogen, Cι-C4-Alkyl oder Cι-C4-Alkoxy steht. Verbindungen dieses Typs und deren Herstellung sind beispielsweise beschrieben in der EP-A-0 610 764 und der EP-A-0 398 072, worauf hiermit ausdrücklich Bezug genommen wird.wherein R 1 is as defined above and X is halogen, -CC 4 alkyl or -CC 4 alkoxy. Compounds of this type and their preparation are described, for example, in EP-A-0 610 764 and EP-A-0 398 072, to which express reference is hereby made.
Eine weitere bevorzugte Gruppe von Valinamidderivaten sind Verbindungen der Formel II ' ' Another preferred group of valinamide derivatives are compounds of the formula II ″
worin R1 die oben angegebenen Bedeutungen besitzt. Verbindungen dieses Typs und deren Herstellung sind beispielsweise beschrieben in der DE-A-43 21 897 und der WO-A-96/07638 , worauf hiermit aus- drücklich Bezug genommen wird.wherein R 1 has the meanings given above. Compounds of this type and their preparation are described for example in DE-A-43 21 897 and WO-A-96/07638, to which express reference is hereby made.
Bevorzugt sind Verbindungen der Formel II, in denen R1 iso-Propyl, sec. -Butyl und tert.-Butyl bedeutet.Compounds of the formula II in which R 1 is isopropyl, sec-butyl and tert-butyl are preferred.
Gleichermaßen werden Verbindungen der Formel II bevorzugt, in denen R2 α-Naphthyl, ß-Naphthyl und Phenyl bedeutet, wobei der Phenylrest in 4-Stellung substituiert ist durch Chlor, Brom, Cι-C -Alkyl oder Cι-C4-Alkoxy .Likewise, compounds of the formula II are preferred in which R 2 is α-naphthyl, β-naphthyl and phenyl, the phenyl radical in the 4-position being substituted by chlorine, bromine, C 1 -C 4 -alkyl or C 1 -C 4 alkoxy.
Insbesondere bevorzugt sind Verbindungen der Formel II, in denen R2 für ß-Naphthyl, 4-Chlorphenyl , 4-Methylphenyl und 4-Methoxy- phenyl steht .Compounds of the formula II in which R 2 is β-naphthyl, 4-chlorophenyl, 4-methylphenyl and 4-methoxyphenyl are particularly preferred.
Bevorzugte Beispiele für erfindungsgemäß verwendbare Valina ide sind in folgender Tabelle III zusammengefaßt.Preferred examples of Valina ide which can be used according to the invention are summarized in Table III below.
Tabelle IIITable III
Nr. Ri R2 No. R i R 2
II.1 iso-Propyl ß-NaphthylII.1 iso-propyl ß-naphthyl
II.2 iso-Propyl 4-ChlorphenylII.2 iso-propyl 4-chlorophenyl
II.3 iso-Propyl 4-MethylphenylII.3 iso-propyl 4-methylphenyl
II.4 iso-Propyl 4-MethoxyphenylII.4 iso-propyl 4-methoxyphenyl
II.5 sec .-Butyl ß-NaphthylII.5 sec. -Butyl ß-naphthyl
II.6 sec . -Butyl 4-ChlorphenylII.6 sec. -Butyl 4-chlorophenyl
II.7 sec . -Butyl 4-MethylphenylII.7 sec. -Butyl 4-methylphenyl
II.8 sec . -Butyl 4-MethoxyphenylII.8 sec. -Butyl 4-methoxyphenyl
II.9 tert . -Butyl ß-NaphthylII.9 tert. -Butyl ß-naphthyl
11.10 tert. -Butyl 4-Chlorphenyl11.10 tert. -Butyl 4-chlorophenyl
11.11 tert . -Butyl 4-Methylphenyl11.11 tert. -Butyl 4-methylphenyl
11.12 tert.-Butyl 4-Methoxyphenyl11.12 tert-butyl 4-methoxyphenyl
Besonders bevorzugt werden die Verbindungen II.1, II.2 und II.9, insbesondere II.1 und II.2. Aus der Strukturformel für die Verbindungen der Formel II ist ersichtlich, daß diese Verbindungen zwei asymmetrisch substituierte Kohlenstoffatome aufweisen. Die Verbindungen können daher in der erfindungsgemäßen Mischung entweder als Gemische von verschiede- nen Isomeren oder als reine Isomere Verwendung finden.Compounds II.1, II.2 and II.9, in particular II.1 and II.2, are particularly preferred. It can be seen from the structural formula for the compounds of the formula II that these compounds have two asymmetrically substituted carbon atoms. The compounds can therefore be used in the mixture according to the invention either as mixtures of different isomers or as pure isomers.
Gemäß einer weiteren bevorzugten Ausführungsform verwendet man Verbindungen der Formel II, in denen der Aminosäureteil aus Alkoxycarbonyl-L-valin (S-Konfiguration) gebildet wird und der Phenethylaminteil oder der Naphthylethylaminteil die R-Konfigura- tion aufweist. Solche Verbindungen sind darstellbar durch die allgemeine Formel HaAccording to a further preferred embodiment, compounds of the formula II are used in which the amino acid part is formed from alkoxycarbonyl-L-valine (S configuration) and the phenethylamine part or the naphthylethylamine part has the R configuration. Such compounds can be represented by the general formula Ha
(S) (R) (S) (R)
worin R1 und R2 die für die Verbindungen der Formel II genannten Bedeutungen besitzen.wherein R 1 and R 2 have the meanings given for the compounds of the formula II.
Die Herstellung der bevorzugten Isomere der Formel Ha erfolgt in Analogie zu den in der älteren Deutschen Patentanmeldung DE-A-195 31 814 beschriebenen Methoden. Auf die Offenbarung dieser Anmeldung wird hiermit ausdrücklich Bezug genommen.The preferred isomers of the formula Ha are prepared in analogy to the methods described in the earlier German patent application DE-A-195 31 814. Reference is hereby expressly made to the disclosure of this application.
Die isomerenreinen Verbindungen der Formel Ha können in an sich bekannter Weise ausgehend von den entsprechenden, auf L-Valin basierenden, Carbamoylcarbonsäuren VII hergestellt werden. Beispielsweise erhält man die Verbindungen Ha nach den im folgenden beschriebenen Verfahren, bei dem man ein Carbamoylcarbonsäure VII mit einem Amin VIII einsetzt (die Literaturzitate "Houben-Weyl" beziehen sich auf: Houben-Weyl, Methoden der Organischen Chemie, 4. Auflage, Thieme Verlag, Stuttgart):The isomerically pure compounds of the formula Ha can be prepared in a manner known per se, starting from the corresponding L-valine-based carbamoylcarboxylic acids VII. For example, the compounds Ha are obtained by the processes described below, using a carbamoylcarboxylic acid VII with an amine VIII (the literature references "Houben-Weyl" refer to: Houben-Weyl, Methods of Organic Chemistry, 4th edition, Thieme Verlag, Stuttgart):
(VII) <VI11) Die Carbamoylcarbonsäuren VII sind bekannt oder können nach bekannten Methoden, vor allem ausgehend von der Aminosäure L-Valin hergestellt werden (vgl. "Houben-Weyl", Band 15/1, S.46-305, vor allem S. 117-125) . 5(VII) < VI11 ) The carbamoylcarboxylic acids VII are known or can be prepared by known methods, especially starting from the amino acid L-valine (cf. "Houben-Weyl", volume 15/1, pp. 46-305, especially pp. 117-125) . 5
Die Amine VIII sind ebenfalls bekannt oder können leicht erhalten werden (vgl. Organikum, VEB Deutscher Verlag der Wissenschaften, 15. Auflage, Berlin, 1977, S. 610 ff.; "Houben-Weyl", Band 15/1, S. 648-665; Indian J. Chem. 10, S. 366 (1972); J. Am. Chem. Soc . 10 58, S. 1808-1811 (1936)).Amines VIII are also known or can easily be obtained (cf. Organikum, VEB German Publishing House of Sciences, 15th edition, Berlin, 1977, pp. 610 ff .; "Houben-Weyl", volume 15/1, p. 648 -665; Indian J. Chem. 10, p. 366 (1972); J. Am. Chem. Soc. 10 58, p. 1808-1811 (1936)).
Aus Racematen der Amine VIII kann das R-Isomere in an sich bekannter Weise, etwa durch fraktionierte Kristallisation mit optisch aktiver Weinsäure oder vorzugsweise mittels enzymkataly- 15 sierter Veresterung und anschließender Verseifung separiert werden (vgl. z.B. die WO-A-95/08636) .The R-isomer can be separated from racemates of amines VIII in a manner known per se, for example by fractional crystallization with optically active tartaric acid or preferably by means of enzyme-catalyzed esterification and subsequent saponification (cf. for example WO-A-95/08636). .
Vorzugsweise arbeitet man in diesem Verfahren so, daß man zunächst die Carbamoylcarbonsäuren VII in carboxyaktivierte Deri- 20 vate, vor allem in Acylcyanide oder Anhydride, überführt (vgl. Tetrahedron Letters, Band 18, S. 1595-1598 (1973), bzw. "Houben- Weyl", Band 15/1, S. 28-32) . Diese Derivate werden dann mit den A inen VI in Gegenwart von Basen zur Reaktion gebracht.This process is preferably carried out by first converting the carbamoylcarboxylic acids VII into carboxy-activated derivatives, especially acyl cyanides or anhydrides (cf. Tetrahedron Letters, Volume 18, pp. 1595-1598 (1973), or " Houben-Weyl ", volume 15/1, pp. 28-32). These derivatives are then reacted with the A in VI in the presence of bases.
25 Zur Herstellung der carboxyaktivier en Acylcyanide eignet sich z.B. die Reaktion der Carbamoylcarbonsäuren VII mit Cyanphoεphon- säurediethylester, vor allem in einem inerten Lösungsmittel wie Tetrahydrofuran oder Toluol .25 For the production of the carboxy-activated acyl cyanides, e.g. the reaction of carbamoylcarboxylic acids VII with diethyl cyanophosphate, especially in an inert solvent such as tetrahydrofuran or toluene.
30 Zur Herstellung der carboxyaktivierten Anhydride ist die Umsetzung der Carbamoylcarbonsäure VII mit Kohlensaurechloriden, wie Chlorameisensäure-iso-butylester , in Gegenwart von Basen und gegebenenfalls in einem inerten Lösungsmittel, wie Toluol oder Tetrahydrofuran, bevorzugt.30 To prepare the carboxy-activated anhydrides, the reaction of carbamoylcarboxylic acid VII with carbonic acid chlorides, such as isobutyl chloroformate, in the presence of bases and, if appropriate, in an inert solvent, such as toluene or tetrahydrofuran, is preferred.
3535
Die Umsetzung der Amine VIII mit den carboxyaktivierten Carbamoylcarbonsäuren VII erfolgt vorzugsweise in einem Lösungsmittel wie Dichlormethan, Tetrahydrofuran oder Toluol .The reaction of the amines VIII with the carboxy-activated carbamoylcarboxylic acids VII is preferably carried out in a solvent such as dichloromethane, tetrahydrofuran or toluene.
40 Als Basen können auch die Amine VIII dienen, wobei man sie üblicherweise aus dem Rohprodukt zurückgewinnt.The amines VIII can also serve as bases, usually being recovered from the crude product.
In einer bevorzugten Ausführungsform dieser Verfahrensstufe werden die Carbamoylcarbonsäure VII, das A in VIII, das zur Erzeu- 45 gung des carboxyaktivierten Derivates der Carbamoylcarbonsäure VII geeignete Reagens und die Base im Eintopfverfahren, gegebenenfalls in einem inerten Lösungsmittel, zur Reaktion gebracht und das Rohprodukt anschließend in an sich bekannter Weise zur Isolierung des Carba oylcarbonsäureamids Ha aufgearbeitet.In a preferred embodiment of this process step, the carbamoylcarboxylic acid VII, the A in VIII, the reagent suitable for producing the carboxy-activated derivative of carbamoylcarboxylic acid VII and the base are reacted in a one-pot process, if appropriate in an inert solvent and the crude product is then worked up in a manner known per se for the isolation of the carboxylcarboxamide Ha.
Die Verbindungen der Formel I und II sind wegen des basischen Charakters in der Lage, mit anorganischen oder organischen Säuren oder mit Metallionen Salze oder Addukte zu bilden, die ebenfalls erfindungsgemäß anwendbar sind.Because of their basic character, the compounds of the formula I and II are capable of forming salts or adducts with inorganic or organic acids or with metal ions, which can likewise be used according to the invention.
Beispiele für anorganische Säuren sind Halogenwasserstoffsäuren wie Fluorwasserstoff, Chlorwasserstoff, Bromwasserstoff und Jodwasserstoff, Schwefelsäure, Phosphorsäure und Salpetersäure.Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and nitric acid.
Als organischen Säuren kommen beispielsweise in Frage Ameisensäure, Kohlensäure und Alkansäuren, wie Essigsäure, Trifluor- essigsaure, Trichloressigsäure und Propionsäure sowie Glycol- säure, Thiocyansäure, Milchsäure, Bernsteinsäure, Zitronensäure, Benzoesäure, Zimtsäure, Oxalsäure, Alkylsulfonsäuren (Sulfon- säuren mit geradkettigen oder verzweigten Alkylresten mit 1 bis 20 Kohlenstoffatomen) , Arylsulfonsäuren oder -disulfonsäuren (aromatische Reste wie Phenyl und Naphthyl welche eine oder zwei Sulfonsäuregruppen tragen) , Alkylphosphonsäuren (Phosphonsäuren mit geradkettigen oder verzweigten Alkylresten mit 1 bis 20 Kohlenstoffatomen) , Arylphosphonsäuren oder -diphosphonsäuren (aromatische Reste wie Phenyl und Naphthyl welche eine oder zwei Phosphorsäurereste tragen) , wobei die Alkyl- bzw. Arylreste weitere Substituenten tragen können, z.B. p-Toluolsulfonsäure, Salizylsäure, p-Aminosalizylsäure, 2-Phenoxybenzoesäure, 2-Ace- toxybenzoesäure etc.Examples of suitable organic acids are formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids or sulfonic acid acids (sulfonic acid acids) branched alkyl radicals with 1 to 20 carbon atoms), arylsulfonic acids or disulfonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids with straight-chain or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonic acids or diphosphonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two phosphoric acid residues), where the alkyl or aryl residues can carry further substituents, for example p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-ace-toxybenzoic acid etc.
Als Metallionen kommen insbesondere die Ionen der Elemente der zweiten Hauptgruppe, insbesondere Calziu und Magnesium, der dritten und vierten Hauptgruppe, insbesondere Aluminium, Zinn und Blei, sowie der ersten bis achten Nebengruppe, insbesondere Chrom, Mangan, Eisen, Kobalt, Nickel, Kupfer, Zink und andere in Betracht. Besonders bevorzugt sind die Metallionen der Elemente der Nebengruppen der vierten Periode. Die Metalle können dabei in den verschiedenen ihnen zukommenden Wertigkeiten vorliegen.In particular, the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main group, in particular aluminum, tin and lead, and also the first to eighth subgroup, in particular chromium, manganese, iron, cobalt, nickel, copper, come as metal ions. Zinc and others into consideration. The metal ions of the elements of the subgroups of the fourth period are particularly preferred. The metals can be present in the various valences that they have.
Bevorzugt setzt man bei der Bereitstellung der Mischungen die reinen Wirkstoffe I und II ein, denen man je nach Bedarf weitere Wirkstoffe gegen Schadpilze oder andere Schädlinge wie Insekten, Spinntiere oder Nematoden, oder auch Herbizide oder wachstumsregulierende Wirkstoffe oder Düngemittel beimischen kann.When preparing the mixtures, preference is given to using the pure active ingredients I and II, to which, as required, further active ingredients against harmful fungi or other pests such as insects, arachnids or nematodes, or else herbicides or growth-regulating active ingredients or fertilizers can be admixed.
Die Mischungen der Verbindungen I und II bzw. die gleichzeitige, und zwar gemeinsame oder getrennte, Verwendung der Verbindungen I und II zeichnen sich durch eine hervorragende Wirkung gegen ein breites Spektrum von pflanzenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten, Deuteromyceten, Phycomyceten und Basidiomyceten, aus. Sie sind z.T. systemisch wirksam und können daher auch als Blatt- und Bodenfungizide eingesetzt werden.The mixtures of the compounds I and II or the simultaneous, joint or separate, use of the compounds I and II are distinguished by an excellent activity against broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can therefore also be used as leaf and soil fungicides.
Besondere Bedeutung haben sie für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen, wie Baumwolle, Gemüsepflanzen (z.B. Gurken, Bohnen und Kürbisgewächse), Gerste, Gras, Hafer, Kaffee, Mais, Obstpflanzen, Reis, Roggen, Soja, Wein, Weizen, Zierpflanzen, Zuckerrohr, Bananen und einer Vielzahl von Samen.They are of particular importance for combating a large number of fungi on various crops, such as cotton, vegetables (for example cucumbers, beans and squashes), barley, grass, oats, coffee, corn, fruit plants, rice, rye, soybeans, wine, wheat, Ornamental plants, sugar cane, bananas and a variety of seeds.
Insbesondere eignen sie sich zur Bekämpfung der folgenden pflanzenpathogenen Pilze: Erysiphe graminis (echter Mehltau) an Getreide, Erysiphe cichoracearum und Sphaerotheca fuliginea an Kürbisgewächsen, Podosphaera leucotricha an Äpfeln, Puccinia- Arten an Getreide, Rhizoctonia-Arten an Baumwolle, Reis und Rasen, Ustilago-Arten an Getreide und Zuckerrohr, Venturia inaequalis (Schorf) an Äpfeln, Helminthosporium-Arten an Ge- treide, Septoria nodorum an Weizen, Botrytis cinerea (Grauschimmel) an Erdbeeren, Gemüse, Zierpflanzen und Reben, Cercospora arachidicola an Erdnüssen, Pseudocercosporella herpotrichoides an Weizen und Gerste, Pyricularia oryzae an Reis, Phytophthora infestans an Kartoffeln und Tomaten, Pseudoperonospora-Arten an Kürbisgewächsen und Hopfen, Plasmopara viticola an Reben, Alternaria-Arten an Gemüse und Obst, Mycosphaerella-Arten in Bananen sowie Fusarium- und Verticillium-Arten.They are particularly suitable for combating the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Puccinia species on cereals, Rhizoctonia species on cotton, rice and lawn Species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotricho Wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora species on pumpkin plants and hops, Plasmopara viticola on vines, Alternaria species on vegetables and fruit, Mycosphaerella species in bananas and Fusarium and Verticillium species.
Sie sind außerdem im Materialschutz (z.B. Holzschutz) anwendbar, beispielsweise gegen Paecilomyces variotii .They can also be used in material protection (e.g. wood protection), for example against Paecilomyces variotii.
Die Verbindungen I und II werden üblicherweise in einem Gewichtsverhältnis von 10:1 bis 0.1:1, vorzugsweise 5:1 bis 0.2:1, insbesondere 5:1 bis 1:1 angewendet.The compounds I and II are usually used in a weight ratio of 10: 1 to 0.1: 1, preferably 5: 1 to 0.2: 1, in particular 5: 1 to 1: 1.
Als nichtlimitierende Beispiele für erfindungsgemäß brauchbare Wirkstoffkombinationen können genannt werden:The following may be mentioned as non-limiting examples of active substance combinations which can be used according to the invention:
Wenigstens eine Verbindung der Formel IA oder IB mit wenigstens einer Verbindung der Formel II, wie z. B. Verbindungen gemäß Tabelle I, wie beispielsweise IA.2 oder IA.4, jeweils kombiniert mit Verbindungen gemäß Tabelle III, wie beispielsweise II.1.At least one compound of formula IA or IB with at least one compound of formula II, such as. B. Compounds according to Table I, such as IA.2 or IA.4, each combined with compounds according to Table III, such as II.1.
Wenigstens eine Verbindung der Formel IC mit wenigstens einer Verbindung der Formel II, wie z. B. Verbindungen gemäß Tabelle II, wie beispielsweise IC.32 oder IC.38, jeweils kombiniert mit Verbindungen gemäß Tabelle III, wie beispielsweise II.1 oder II.2.At least one compound of formula IC with at least one compound of formula II, such as. B. Compounds according to Table II, such as IC.32 or IC.38, each combined with Compounds according to Table III, such as II.1 or II.2.
Die Aufwandmengen der erfindungsgemäßen Mischungen liegen je nach Art des gewünschten Effekts bei 0,01 bis 3 kg/ha, vorzugsweise 0,1 bis 1,5 kg/ha, insbesondere 0,1 bis 1,0 kg/ha.Depending on the type of effect desired, the application rates of the mixtures according to the invention are from 0.01 to 3 kg / ha, preferably 0.1 to 1.5 kg / ha, in particular 0.1 to 1.0 kg / ha.
Die Aufwandmengen liegen dabei für die Verbindungen I bei 0,01 bis 0,5 kg/ha, vorzugsweise 0,05 bis 0,5 kg/ha, insbesondere 0,05 bis 0,4 kg/ha.The application rates for the compounds I are 0.01 to 0.5 kg / ha, preferably 0.05 to 0.5 kg / ha, in particular 0.05 to 0.4 kg / ha.
Die Aufwandmengen für die Verbindungen II liegen entsprechend bei 0,01 bis 0,5 kg/ha, vorzugsweise 0,05 bis 0,5 kg/ha, insbesondere 0, 05 bis 0,4 kg/ha.The application rates for the compounds II are accordingly from 0.01 to 0.5 kg / ha, preferably 0.05 to 0.5 kg / ha, in particular 0.05 to 0.4 kg / ha.
Bei der Saatgutbehandlung werden im allgemeinen Aufwandmengen an Mischung von 0,001 bis 50 g/kg Saatgut, vorzugsweise 0,01 bis 10 g/kg, insbesondere 0,01 bis 8 g/kg verwendet.In the case of seed treatment, application rates of the mixture of from 0.001 to 50 g / kg of seed, preferably 0.01 to 10 g / kg, in particular 0.01 to 8 g / kg, are generally used.
Sofern für Pflanzen pathogene Schadpilze zu bekämpfen sind, erfolgt die getrennte oder gemeinsame Applikation der Verbindungen I und II oder der Mischungen aus den Verbindungen I und II durch Besprühen oder Bestäuben der Samen, der Pflanzen oder der Böden vor oder nach der Aussaat der Pflanzen oder vor oder nach dem Auflaufen der Pflanzen.If pathogenic harmful fungi are to be combated for plants, the compounds I and II or the mixtures of the compounds I and II are applied separately or together by spraying or dusting the seeds, the plants or the soil before or after the plants are sown or before or after the plants emerge.
Die erfindungsgemäßen fungiziden synergistischen Mischungen bzw. die Verbindungen I und II können beispielsweise in Form von direkt versprühbaren Lösungen, Pulver und Suspensionen oder in Form von hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen, Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granulaten aufbereitet und durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsform ist abhängig vom Verwendungszweck; sie soll in jedem Fall eine möglichst feine und gleichmäßige Verteilung der erfindungsgemäßen Mischung gewährleisten.The fungicidal synergistic mixtures according to the invention or the compounds I and II can be prepared, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-strength aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules and applied by spraying, atomizing, dusting, scattering or pouring. The form of application depends on the intended use; in any case, it should ensure that the mixture according to the invention is as fine and uniform as possible.
Die Formulierungen werden in an sich bekannter Weise hergestellt, z.B. durch Zugabe von Lösungsmitteln und/oder Trägerstoffen. Den Formulierungen werden üblicherweise inerte Zusatzstoffe wie Emulgiermittel oder Dispergiermittel beigemischt.The formulations are prepared in a manner known per se, e.g. by adding solvents and / or carriers. Inert additives such as emulsifiers or dispersants are usually added to the formulations.
Als oberflächenaktive Stoffe kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin-, Phenol-, Naphthalin- und Dibutylnaphthalinsulfonsäure, sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octadecanole oder Fettalkoholglycolethern, Kondensationsprodukte von sulfoniertem Naphthalin und seinen Derivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethylen- 5 octylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonyl- phenol, Alkylphenol- oder Tributylphenylpolyglycolether , Alkyl- arylpolyetheralkohole, Isotridecylalkohol , Fettalkoholethylen- oxid- Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkyl- ether oder Polyoxypropylen, Laurylalkoholpolyglycoletheracetat , 10 Sorbitester, Lignin-Sulfitablaugen oder Methylcellulose in Betracht .The surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene 5-octylphenol ether, ethoxylated isooctyl, octyl or nonyl phenyl, alkyl phenol or tribol glycol, aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, 10 sorbitol esters, lignin sulfite waste liquors or methyl cellulose.
Pulver, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der Verbindungen I oder II oder der Mischung aus 15 den Verbindungen I und II mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compounds I or II or the mixture of the compounds I and II with a solid carrier.
Granulate (z.B. Umhüllungs-, Imprägnierungs- oder Homogengranulate) werden üblicherweise durch Bindung des Wirkstoffs oder 20 der Wirkstoffe an einen festen Trägerstoff hergestellt.Granules (e.g. coated, impregnated or homogeneous granules) are usually produced by binding the active ingredient or 20 of the active ingredients to a solid carrier.
Als Füllstoffe bzw. feste Trägerstoffe dienen beispielsweise Mineralerden, wie Silicagel, Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolo-Mineral earths, such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, boluses, loess, clay, dolo-
25 mit, Diatomeenerde, Kalzium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, sowie Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe, und pflanzliche Produkte, wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver , oder andere feste Trägerstoffe.25 with, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, and fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and vegetable products, such as grain flour, tree bark, wood and nutshell flour, cellulose powder, or other solid carriers.
3030
Die Formulierungen enthalten im allgemeinen 0,1 bis 95 Gew.-%, vorzugsweise 0,5 bis 90 Gew.-% einer der Verbindungen I oder II bzw. der Mischung aus den Verbindungen I und II. Die Wirkstoffe werden dabei in einer Reinheit von 90 % bis 100 %, vorzugsweiseThe formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I or II or of the mixture of the compounds I and II. The active ingredients are in a purity of 90% to 100%, preferably
35 95 % bis 100 % (nach NMR- oder HPLC-Spektrum) eingesetzt.35 95% to 100% (according to NMR or HPLC spectrum) used.
Die Verbindungen I oder II bzw. die Mischungen oder die entsprechenden Formulierungen werden angewendet, indem man die Schadpilze, die von ihnen freizuhaltenden Pflanzen, Samen, Böden, 40 Flächen, Materialien oder Räume mit einer fungizid wirksamenThe compounds I or II or the mixtures or the corresponding formulations are used by the fungi, the plants, seeds, soils, 40 areas, materials or spaces to be kept free of them with a fungicidally active
Menge der Mischung, bzw. der Verbindungen I und II bei getrennter Ausbringung, behandelt. Die Anwendung kann vor oder nach dem Befall durch die Schadpilze erfolgen.Amount of the mixture, or of the compounds I and II treated separately. The application can take place before or after the infestation by the harmful fungi.
45 Beispiele zur synergistischen Wirkung der erfindungsgemäßen Mischungen gegen Schadpilze. Die fungizide Wirkung der Verbindung und der Mischungen ließ sich durch folgende Versuche zeigen:45 examples of the synergistic effect of the mixtures according to the invention against harmful fungi. The fungicidal activity of the compound and the mixtures was demonstrated by the following tests:
Die Wirkstoffe wurden getrennt oder gemeinsam als 10 %ige Emulsion in einem Gemisch aus Cyclohexanon und Emulgiermittel (wie z. B. Nekanil® LN (Lutensol® AP6, Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxylierter Alkylphenole) und Emulphor® EL (Emulan® EL, Emulgator auf der Basis ethoxylierter Fettalkohole) ) aufbereitet und entsprechend der gewünsch- ten Konzentration mit Wasser verdünnt.The active ingredients were separated or together as a 10% emulsion in a mixture of cyclohexanone and emulsifier (such as Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and Emulphor® EL (Emulan ® EL, emulsifier based on ethoxylated fatty alcohols)) and diluted with water to the desired concentration.
Die Auswertung erfolgte durch Feststellung der befallenen Blattflächen in Prozent. Diese Prozent-Werte wurden in Wirkungsgrade umgerechnet. Die zu erwartenden Wirkungsgrade der Wirkstoff- mischungen wurden nach der Colby Formel [R.S. Colby, Weeds 15 , 20-22 (1967)] ermittelt und mit den beobachteten Wirkungsgraden verglichen.The evaluation was carried out by determining the affected leaf areas in percent. These percentages were converted into efficiencies. The expected efficacies of the active ingredient mixtures were calculated using the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies.
Colby Formel :Colby formula:
E = x + y -x-y/100E = x + y -x-y / 100
E zu erwartender Wirkungsgrad, ausgedrückt in % der unbehan- delten Kontrolle, beim Einsatz der Mischung aus den Wirk- Stoffen A und B in den Konzentrationen a und bE expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and b
x der Wirkungsgrad, ausgedrückt in % der unbehandelten Kontrolle, beim Einsatz des Wirkstoffs A in der Konzentration ax the efficiency, expressed in% of the untreated control, when using the active ingredient A in the concentration a
y der Wirkungsgrad, ausgedrückt in % der unbehandelten Kontrolle, beim Einsatz des Wirkstoffs B in der Konzentration by the efficiency, expressed in% of the untreated control, when using the active ingredient B in the concentration b
Der Wirkungsgrad (W) wurde nach der Formel von Abbot wie folgt berechnet :Efficiency (W) was calculated using Abbot's formula as follows:
W = (1 - α)«100/ßW = (1 - α) «100 / ß
α entspricht dem Pilzbefall der behandelten Pflanzen in % undα corresponds to the fungal attack of the treated plants in% and
ß entspricht dem Pilzbefall der unbehandelten (Kontroll-) Pflanzen in %ß corresponds to the fungal infection of the untreated (control) plants in%
Bei einem Wirkungsgrad von 0 entspricht der Befall der behandelten Pflanzen demjenigen der unbehandelten Kontrollpflanzen; bei einem Wirkungsgrad von 100 wiesen die behandelten Pflanzen keinen Befall auf. Beispiel 1: Wirksamkeit gegen Phytophthora infestans an TomatenWith an efficiency of 0, the infection of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants showed no infection. Example 1: Activity against Phytophthora infestans on tomatoes
Blätter von Topfpflanzen der Sorte Große Fleischtomate wurden mit einer wäßrigen Suspension, die aus einer Stammlösung aus 10 % Wirkstoff, 63 % Cyclohexanon und 27 % Emulgiermittel angesetzt wurde, bis zur Tropfnässe besprüht. Am folgenden Tag wurden die Blätter mit einer wäßrigen Zoosporenaufschwemmung von Phytophthora infestans infiziert. Anschließend wurden die Pflanzen in einer wasserdampfgesättigten Kammer bei Temperaturen zwischen 16 und 18 °C aufgestellt. Nach sechs Tagen hatte sich die Krautfäule auf den unbehandelten, jedoch infizierten Kontrollpflanzen so stark entwickelt, daß der Befall visuell in % ermittelt werden konnte .Leaves of potted plants of the variety Large meat tomatoes were sprayed to runoff point with an aqueous suspension which was prepared from a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. The following day, the leaves were infected with an aqueous suspension of zoospores from Phytophthora infestans. The plants were then placed in a steam-saturated chamber at temperatures between 16 and 18 ° C. After six days, the blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.
Die visuell ermittelten Werte für den Prozentanteil befallener Blattfläche wurde in Wirkungsgrade als % der unbehandelten Kontrolle umgerechnet. Die zu erwartenden Wirkungsgrade wurden nach der vorstehend beschriebenen Colby-Formel berechnet.The visually determined values for the percentage of leaf area affected were converted into efficiencies as% of the untreated control. The expected efficiencies were calculated using the Colby formula described above.
Wirkstoff bzw. Wirkungsgrad in % berechneter Wir-Active ingredient or efficiency in% of calculated active
Mischung der unbehandelten kungsgrad in % nachMix the untreated degree of efficiency in%
[Konz. ] Kontrolle Colby unbehandelt 93 % Befall -[Conc. ] Control Colby untreated 93% infestation -
IA.2 [5 ppm] 5 _IA.2 [5 ppm] 5 _
IA.4 [5 ppm] 5 _IA.4 [5 ppm] 5 _
II.1 [5 ppm] 5 -II.1 [5 ppm] 5 -
IA.2 + II.1 jeweils [5 ppm] 40 9IA.2 + II.1 each [5 ppm] 40 9
IA.4 + II.1 jeweils [5 ppm] 57 9IA.4 + II.1 each [5 ppm] 57 9
Beispiel 2 : Wirksamkeit gegen Plasmopara viticolaExample 2: Efficacy against Plasmopara viticola
Blätter von Topfreben der Sorte Müller Thurgau wurden mit einer wäßrigen Suspension, die aus einer Stammlösung aus 10 % Wirk- stoff, 63 % Cyclohexanon und 27 % Emulgiermittel angesetzt wurde, bis zur Tropfnässe besprüht. Um die Dauerwirkung der Substanzen beurteilen zu können, wurden die Pflanzen nach dem Antrocknen des Spritzbelags für 7 Tage im Gewächshaus aufgestellt. Erst dann wurden die Blätter mit einer wäßrigen Zoosporenaufschwemmung von Plasmopara viticola inokuliert. Danach wurden die Reben zunächst für 48 Stunden in einer wasserdampfgesättigten Kammer und anschließend für 5 Tage im Gewächshaus bei Temperaturen zwischen 20 und 30 °C aufgestellt. Nach dieser Zeit wurden die Pflanzen zur Beschleunigung des Sporangienträgerausbruchs abermals für 16 h in eine feuchte Kammer gestellt. Dann wurde das Ausmaß der Befallsentwicklung auf den Blattunterseiten visuell ermittelt.Leaves of pot vines of the Müller Thurgau variety were sprayed to runoff point with an aqueous suspension which was prepared from a stock solution of 10% active ingredient, 63% cyclohexanone and 27% emulsifier. In order to be able to assess the long-term effect of the substances, the plants were placed in the greenhouse for 7 days after the spray coating had dried on. Only then were the leaves inoculated with an aqueous suspension of zoospores from Plasmopara viticola. The vines were then left in a chamber saturated with water vapor for 48 hours and then in a greenhouse at temperatures between 20 and 5 days and set up at 30 ° C. After this time, the plants were again placed in a moist chamber for 16 h in order to accelerate the sporangium carrier outbreak. The extent of the development of the infestation on the undersides of the leaves was then determined visually.
Die visuell ermittelten Werte für den Prozentanteil befallener Blattfläche wurde in Wirkungsgrade als % der unbehandelten Kontrolle umgerechnet. Die zu erwartenden Wirkungsgrade wurden nach der vorstehend beschriebenen Colby-Formel berechnet.The visually determined values for the percentage of leaf area affected were converted into efficiencies as% of the untreated control. The expected efficiencies were calculated using the Colby formula described above.
Wirkstoff bzw. Wirkungsgrad in % berechneter Wir¬Active ingredient or efficiency in% of calculated Wir¬
Mischung der unbehandelten kungsgrad in % nachMix the untreated degree of efficiency in%
[Konz. ] Kontrolle Colby unbehandelt 93 % Befall -[Conc. ] Control Colby untreated 93% infestation -
IC.32 [0.32 ppm] 89 _IC.32 [0.32 ppm] 89 _
IC.32 [0.08 ppm] 25 _IC.32 [0.08 ppm] 25 _
IC.38 [0.32 ppm] 68 _IC.38 [0.32 ppm] 68 _
II.1 [0.32 ppm] 0 _II.1 [0.32 ppm] 0 _
II.2 [0.32 ppm] 0 _II.2 [0.32 ppm] 0 _
II.2 [0.08 ppm] 0 _II.2 [0.08 ppm] 0 _
IC.38 + II.1 95 68 jeweils [0,32 ppm]IC.38 + II.1 95 68 each [0.32 ppm]
IC.32 + II.2 100 89 jeweils [0,32 ppm]IC.32 + II.2 100 89 each [0.32 ppm]
IC.32 + II.2 46 25 jeweils [0,08 ppm]IC.32 + II.2 46 25 each [0.08 ppm]
Die Ergebnisse der vorstehenden Tabellen zeigen, daß für die erfindungsgemäßen Mischungen Wirkungsgrade erzielt werden, die deutlich über den nach der Colby-Formel berechneten Wirkungsgraden liegen. The results of the tables above show that efficiencies are achieved for the mixtures according to the invention which are significantly higher than the efficiencies calculated according to the Colby formula.

Claims

Patentansprücheclaims
1. Mittel zur Bekämpfung von Schadpilzen, enthaltend in einem festen oder flüssigen Träger1. Means for controlling harmful fungi, contained in a solid or liquid carrier
a) wenigstens eine Verbindung der allgemeinen Formel Ia) at least one compound of general formula I.
worinwherein
(al)M1 für eine Gruppe der Formel(al) M 1 for a group of the formula
\^X\ ^ X
steht, worin stands in what
X für CH oder N steht, undX represents CH or N, and
die Reste Ra und Rb unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, einethe radicals R a and R b independently of one another for a hydrogen atom, a halogen atom, a
Cι~C4-Alkyl- oder Cι-C4-Halogenalkylgruppe stehen,Cι ~ C 4 alkyl or Cι-C are 4 haloalkyl group,
M2 für eine Gruppe der FormelM 2 for a group of the formula
CH3O^^N^CH 3 O ^^ N ^
J| OCH3 J | OCH 3
00
steht; oderstands; or
(a2)Mi für eine Gruppe der Formel (a2) M i for a group of the formula
steht, worinstands in what
Z für 0, S, NH oder N-C1-C -Alkyl steht;Z represents 0, S, NH or NC 1 -C alkyl;
R' für Cι-C6-Alkyl, Cι-C6-Halogenalkyl , C2-C6-Alkenyl , C2-C6-Halogenalkenyl , C3-C6-Alkinyl , C3-Cg-Halogenalkinyl , C3-C6-Cycloalkyl-methyl oder Benzyl steht, welches partiell oder vollständig halogeniert sein kann und/oder einen bis drei Reste tragen kann, die ausgewählt sind unter Cyano, C1-C4-AI- kyl , Cχ-C4-Halogenalkyl, Cι-C4-Alkoxy, C-Cή-Ha- logenalkoxy und C!-C4-Alkylthio; undR 'is Cι-C 6 -alkyl, C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -CG haloalkynyl, C 3 -C 6 cycloalkyl-methyl or benzyl, which can be partially or completely halogenated and / or can carry one to three radicals which are selected from cyano, C 1 -C 4 -alkyl, Cχ-C 4 haloalkyl , -C-C 4 alkoxy, C-Cή-haloalkoxy and C ! -C 4 alkylthio; and
M2 für eine Gruppe der FormelM 2 for a group of the formula
steht, worinstands in what
X' für 0 oder NH steht; undX 'is 0 or NH; and
Y für CH oder N stehtY represents CH or N.
undand
wenigstens ein Valinamid der Formel IIat least one valinamide of the formula II
worin wherein
Ri für C3-C4-Alkyl steht und R2 Naphthyl oder Phenyl bedeutet, wobei der Phenylrest in 4-Stellung durch em Halogenatom, eine C1-C4-AI- kyl- oder Cχ-C4-Alkoxygruppe substituiert ist.R i is C 3 -C 4 alkyl and R 2 is naphthyl or phenyl, the phenyl radical in the 4-position being substituted by a halogen atom, a C 1 -C 4 -alkyl or Cχ-C 4 -alkoxy group.
2. Mittel nach Anspruch 1, enthaltend wenigstens einen Oximether der Formel IA oder IB2. Composition according to claim 1, containing at least one oxime ether of the formula IA or IB
worin jeweils where each
Z für O steht undZ stands for O and
R' für C-Cg-Alkyl, C-C-Halogenalkyl , C2-C6-Alkenyl ,R 'is C-Cg-alkyl, CC-haloalkyl, C 2 -C 6 alkenyl,
C2-C6-Halogenalkenyl , C3-Cg-Cycloalkylmethyl , Benzyl oder rmghalogeniertes Benzyl stehtC 2 -C 6 haloalkenyl, C 3 -Cg cycloalkylmethyl, benzyl or rmghalogenierter benzyl
Mittel nach Anspruch 1, enthaltend wenigstens e Carbamat der Formel ICAgent according to claim 1, containing at least e carbamate of formula IC
worin wherein
X die oben angegebenen Bedeutungen besitzt und wenigstens einer der Reste Ra und Rb nicht für em Wasserstoffatom steht.X has the meanings given above and at least one of the radicals R a and R b does not represent an hydrogen atom.
Mittel nach einem der vorhergehenden Ansprüche, enthaltend wenigstens ein Valmamid der Formel II, worin R1 für i-Propyl, sec . -Butyl oder tert.-Butyl steht und R2 für 4-Cl-, 4-Methyl- oder 4-Methoxyphenyl oder für 2-Naphthyl steht.Agent according to one of the preceding claims, containing at least one valmamide of formula II, wherein R 1 for i-propyl, sec. -Butyl or tert-butyl and R 2 represents 4-Cl-, 4-methyl- or 4-methoxyphenyl or 2-naphthyl.
Mittel nach einem der vorhergehenden Ansprüche, enthaltend wenigstens ein Valmamid der Formel Ha Agent according to one of the preceding claims, containing at least one valmamide of the formula Ha
worin R1 und R2 die oben angegebenen Bedeutungen besitzen.wherein R 1 and R 2 have the meanings given above.
6. Mittel nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Gewichtsverhältnis von Verbindung der Formel I zu Verbindung der Formel II 10:1 bis 1:10 beträgt.6. Composition according to one of the preceding claims, characterized in that the weight ratio of compound of formula I to compound of formula II is 10: 1 to 1:10.
7. Mittel nach einem der vorhergehenden Ansprüche, konditioniert in zwei Teilen, wobei der eine Teil die Verbindung der Formel I in einem festen oder flüssigen Träger enthält und der andere Teil die Verbindung der Formel II in einem festen oder flüssigen Träger enthält.7. Composition according to one of the preceding claims, conditioned in two parts, one part containing the compound of formula I in a solid or liquid carrier and the other part containing the compound of formula II in a solid or liquid carrier.
8. Verfahren zur Bekämpfung von Schadpilzen, dadurch gekenn- zeichnet, daß man die Schadpilze, deren Lebensraum oder die von ihnen freizuhaltenden Pflanzen, Samen, Böden, Flächen, Materialien oder Räume mit einer wirksamen Menge wenigstens eines Mittels gemäß einem der Ansprüche 1 bis 7 behandelt.8. A method for combating harmful fungi, characterized in that the harmful fungi, their habitat or the plants, seeds, soils, surfaces, materials or spaces to be kept free of them with an effective amount of at least one agent according to one of claims 1 to 7 treated.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß man wenigstens eine Verbindung der Formel I und wenigstens eine Verbindung der Formel II gleichzeitig, und zwar gemeinsam oder getrennt, oder nacheinander in beliebiger Reihenfolge ausbringt . 9. The method according to claim 8, characterized in that at least one compound of the formula I and at least one compound of the formula II are applied simultaneously, together or separately, or in succession in any order.
EP97944801A 1996-08-28 1997-08-27 Agents for controlling harmful fungi Withdrawn EP0923291A1 (en)

Applications Claiming Priority (5)

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DE19634771A DE19634771A1 (en) 1996-08-28 1996-08-28 Synergistic pesticidal especially fungicidal compositions
DE19634771 1996-08-28
DE19636752 1996-09-10
DE19636752 1996-09-10
PCT/EP1997/004679 WO1998008386A1 (en) 1996-08-28 1997-08-27 Agents for controlling harmful fungi

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UA70327C2 (en) * 1998-06-08 2004-10-15 Баєр Акціенгезельшафт Method of combating phytopathogenic diseases on crop plants and a fungicidal composition
JP2007533679A (en) * 2004-04-21 2007-11-22 ビーエーエスエフ　アクチェンゲゼルシャフト Sterilization mixture
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TW438575B (en) 2001-06-07
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JP2000516944A (en) 2000-12-19
CO4870748A1 (en) 1999-12-27
CA2264533A1 (en) 1998-03-05
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