EP1487786A2 - Acrylamides z-substitues, procede de production et agents contenant lesdits acrylamides - Google Patents

Acrylamides z-substitues, procede de production et agents contenant lesdits acrylamides

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Publication number
EP1487786A2
EP1487786A2 EP03709773A EP03709773A EP1487786A2 EP 1487786 A2 EP1487786 A2 EP 1487786A2 EP 03709773 A EP03709773 A EP 03709773A EP 03709773 A EP03709773 A EP 03709773A EP 1487786 A2 EP1487786 A2 EP 1487786A2
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EP
European Patent Office
Prior art keywords
formula
compounds
alkyl
methyl
weight
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Withdrawn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
EP03709773A
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German (de)
English (en)
Inventor
Wassilios Grammenos
Thomas Grote
Carsten Blettner
Markus Gewehr
Andreas Gypser
Bernd Müller
Joachim Rheinheimer
Peter Schäfer
Anja Schwögler
Jordi Tormo I Blasco
Norbert Götz
Gisela Lorenz
Eberhard Ammermann
Siegfried Strathmann
Reinhard Stierl
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BASF SE
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BASF SE
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Publication date
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Publication of EP1487786A2 publication Critical patent/EP1487786A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C235/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/22—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to an acyclic carbon atom of a carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to Z-substituted acrylamides of the formula I.
  • X is hydrogen, halogen, Ci-Q-alkyl, C 1 -C 4 -haloalkyl,
  • n 1 or 2, where X can be different if n is 2;
  • R 1 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 5 cycloalkyl, C ⁇ -C 4 -alk- oxy, C ⁇ -C4-haloalkoxy, aziridine and oxirane; and
  • R 2 is hydrogen, -CC 4 alkyl, -C-C 2 haloalkyl, allyl, propargyl or CH 2 C ⁇ C -CC 4 -alkyl.
  • the invention relates to processes for their preparation and compositions containing them, and to their use for controlling phytopathogenic harmful fungi.
  • ⁇ -Oximinophenylacetic acid arylamides are described in WO-A 96/17825 and WO-A 96/23763 as fungicides and in JP 02/200 658 as herbicides.
  • Arylacrylamides are only covered by the general disclosure in WO-A 96/17825.
  • WO-A 01/95721 discloses acrylamides with a fungicidal action.
  • the invention was an object to find 'compounds having improved activity. We have found that this object is achieved by the Z-substituted acrylamides and agents containing them.
  • Carboxylic acids of the formula II can be amidated directly in a known manner with phenethylamines of the formula III to give compounds of the formula IV [cf. Houben-Weyl, Methods of Organic Chemistry, Vol. E5, pp. 941-972, Georg Thie e Verlag Stuttgart and New York 1985].
  • the starting materials are generally reacted with one another in equimolar amounts. It can be advantageous for the yield to use III in an excess based on II.
  • carboxylic acids of the formula II can first be activated before amidation with III, for example by conversion into acid halides, in particular into the acid chlorides.
  • Phenethylamides of formula IV are converted with a trialkyltin hydride, wherein R is Ci-C ⁇ -alkyl, for example tributyltin hydride or triphenyltin hydride in the organotin compounds of the formula V
  • This reaction is usually carried out at temperatures from -20 ° C to 80 ° C, preferably 0 ° C to 60 ° C, in an inert organic solvent in the presence of a catalyst [cf. Tetrahedron 49 (21), 4677 (1993); ibid. 33 (31), 4495 (1992); ibid. 48 (40), 8801 (1992); Synth. Commun. 23 (2), 143 (1993)].
  • a catalyst cf. Tetrahedron 49 (21), 4677 (1993); ibid. 33 (31), 4495 (1992); ibid. 48 (40), 8801 (1992); Synth. Commun. 23 (2), 143 (1993)].
  • Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, and also dimethyl sulfoxide, diethyl formamide and dirnethylacetamide, particularly preferably tetrahydrofuran and dimethylacetamide. Mixtures of the solvents mentioned can also be used.
  • a catalyst e.g. B. a transition metal.
  • Suitable transition metal catalysts are iron, cobalt, nickel, rhodium, palladium or platinum compounds, particularly nickel (0), nickel (II) and palladium (O) and palladium (II) compounds. Salts such as nickel chloride, palladium chloride, palladium acetate or even complexes can be used. The only requirement is that the ligands on the palladium can be displaced from the substrate under the reaction conditions.
  • Phosphine ligands such as. B. aryl alkyl phosphines such as u. a.
  • Triphenylphosphine tritolylphosphine
  • trixylylphosphine trixylylphosphine
  • trihetarylphosphines such as trifurylphosphine or di
  • the complex used can be used directly in the reaction. So you can z. B. with bis (triphenylphosphine) nickel (I ⁇ ) bromide, bis (triphenylphosphine) nickel (II) chloride, [1, 3-bis (diphenylphosphine) propane] nickel (II) chloride, [1,2-bis (di - phenylphosphine) ethane] nickel (II) chloride, tetrakistriphenylphosphine palladium (O), bistriphenylphosphine palladium dichloride, bistriphenylphosphine palladium diacetate, a dibenzylideneacetone palladium (0) complex, tetrakismethyl bisphenylphosphine (diphenylphosphine) diphenylphosphine (diphenylphosphine) diphenylphosphine (diphenylphosphine) diphenylphosphine (dip
  • a nickel or palladium salt and, in addition, a suitable ligand can also be used, which then only form the catalytically active complex in situ.
  • This procedure offers z. B. in the above salts and phosphine ligands such.
  • Nickel or palladium complexes such as. B. tris (dibenzylidene acetone) dipalladium, bis (dibenzylidene acetone) palladium or 1, 5-cyclooctadienpal- ladium dichloride by the addition of ligands such as. B. trifurylphosphine or tritolylphosphine can be activated further.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • This reaction usually takes place at temperatures from 0 ° C. to 80 ° C., preferably 20 ° C. to 60 ° C., in an inert organic solvent in the presence of a transition metal catalyst [UM] [cf. Tetrahedron 50 (41), 12029 (1994); Org. Lett. 2 (8), 1121 (2000)].
  • UM transition metal catalyst
  • Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, and also dimethyl sulfoxide, dimethyl formamide and dimethylacetamide, particularly preferably tetrahydrofuran, dimethylacetamide and dimethylformamide. Mixtures of the solvents mentioned can also be used.
  • a catalyst e.g. B. a transition metal.
  • Suitable transition metal catalysts are iron, cobalt, nickel, rhodium, palladium or platinum compounds, particularly nickel (0), nickel (II) and palladium (O) and palladium (II) compounds. Salts such as nickel chloride, palladium chloride, palladium acetate or even complexes can be used. The only requirement is that the ligands on the palladium can be displaced from the substrate under the reaction conditions. Phosphine ligands such as. B.
  • aryl-alkylphosphines such as methyldiphenylphosphine, isopropyldiphenylphosphine, triarylphosphines such as triphenylphosphine, tritolylphosphine, trixylylphosphine, trihetarylphosphines such as trifurylphosphine or dimeric phosphines.
  • olefinic ligands such as dibenzylidene acetone or its salts, cycloocta-1,5-diene or amines such as trialkylamines (e.g. triethylamine, tetramethylethylene diamine, N-methylmorpholine) or pyridine.
  • the complex used can be used directly in the reaction. So you can z. B. with bis (triphenylphosphine) nickel (I ⁇ ) bromide, bis (triphenylphosphine) nickel (II) chloride, [1, 3-bis (diphenylphosphine) propane] nickel (II) chloride, [1,2-bis (di - phenylphosphine) ethane] nickel (II) chloride, tetrakistriphenylphosphine palladium (O), bistriphenylphosphine palladium dichloride, bistriphenylphosphine palladium diacetate, a dibenzylideneacetone palladium (0) complex, tetrakismethyl bisphenylphosphine (diphenylphosphine) diphenylphosphine (diphenylphosphine) diphenylphosphine (diphenylphosphine) diphenylphosphine (dip
  • a nickel or palladium salt and, in addition, a suitable ligand can also be used, which then only form the catalytically active complex in situ.
  • This procedure offers z. B. in the above salts and phosphine ligands such.
  • Nickel or palladium complexes such as. B. tris (dibenzylidene acetone) dipalladium, bis (dibenzylidene acetone) palladium or 1, 5-cyclooctadiene palladium dichloride by adding ligands such as. B. trifurylphosphine or tritolylphosphine can be activated further.
  • the reaction is advantageously carried out in the presence of copper (I) salts, such as. B. Cu (I) J as an additional catalyst.
  • the starting materials are generally reacted with one another in aluolar amounts. It may be advantageous for the yield to use VI in an excess based on V.
  • reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, purifying the crude products by chromatography.
  • the intermediate and end products are obtained in the form of colorless or slightly brownish, viscous oils, which are freed or purified of volatile components under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, they can also be purified by recrystallization or digesting. If individual compounds I are not accessible in the ways described above, they can be prepared by derivatizing other compounds I.
  • Halogen fluorine, chlorine, bromine and iodine
  • Alkyl saturated, straight-chain or branched hydrocarbon residues with 1 to 4 carbon atoms, e.g. Methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl;
  • Haloalkyl straight-chain or branched alkyl groups with 1 to 4 carbon atoms (as mentioned above), it being possible for part or all of the hydrogen atoms in these groups to be replaced by halogen atoms as mentioned above, for example C 1 -C 2 -haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl , Fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-di-fluoroethyl, 2, 2,2-trifluoroethyl, 2-chloro-2 -fluoroethyl, 2-chloro-2,2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2, 2, 2-trich
  • Alkoxy straight-chain or branched alkyl groups with 1 to 8 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-);
  • Haloalkoxy straight-chain or branched haloalkyl groups with 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via an acid atom (-0-);
  • R 1 is C 1 -C 4 -alk 1, halomethyl or C 3 -C 5 -cycloalkyl.
  • R 1 is methyl, ethyl, isopropyl, tert are particularly preferred.
  • Butyl, trifluoromethyl, cyclopropyl or cyclopentyl mean.
  • R 2 represents methyl, ethyl, propargyl, C 2 haloalkyl, in particular 2,2,2-trifluoroethyl, or allyl.
  • compounds I are particularly preferred in which n is 1 and X is in the 4-position.
  • compounds I are particularly preferred in which R 2 is hydrogen. They are valuable not only as active ingredients, but also as intermediates for the preparation of further compounds I.
  • Table 30 corresponds to compounds of the formula I in which R 1 represents cyclopropyl and R 2 is allyl and the radical X n for a compound 'corresponds to one row of Table A
  • the compounds I are suitable as fungicides. They are characterized by excellent activity against a 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 be used in plant protection as leaf and soil fungicides.
  • Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines
  • Venturia species scab on apples and pears.
  • the compounds I are also suitable for combating harmful fungi such as Paecilomyces variotii in the material protection (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the storage protection.
  • harmful fungi such as Paecilomyces variotii in the material protection (e.g. wood, paper, dispersions for painting, fibers or fabrics) and in the storage protection.
  • the compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds.
  • the application can take place both before and after the infection of the materials, plants or seeds by the fungi.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.
  • the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per ha.
  • active ingredients of from 0.001 to 0.1 g, preferably 0.01 to 0.05 g, are required per kg of seed.
  • the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in the material contactor are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of treated material.
  • the compounds I can be converted into the usual formulations, e.g. Solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as diluent other organic solvents can also be used as auxiliary solvents.
  • auxiliaries solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) ) and water;
  • Carriers such as natural stone powder (e.g.
  • Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • non-ionic and anionic emulsifiers e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates
  • dispersants such as lignin sulfite liquors and methyl cellulose.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are e.g. Mineral soils, such as silicas, silica gels, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • Mineral soils such as silicas, silica gels, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum). Examples of formulations are:
  • V. 80 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel well mixed and ground in a hammer mill (active ingredient content 80% by weight).
  • VIII.20 parts by weight of a compound according to the invention are mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene- ⁇ -sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel well mixed and ground in a hammer mill.
  • a spray liquor which contains 0.1% by weight of the active ingredient.
  • the active ingredients as such in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oldispersions, pastes, dusts, sprinkling agents, granules by spraying, atomizing, dusting, scattering or pouring.
  • the application forms depend entirely on the intended use; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, old dispersions) by adding water.
  • the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • wetting, adhesive wetting, adhesive,
  • Dispersants or emulsifiers and possibly solvents or oil existing concentrates are prepared which are suitable for dilution with water.
  • the active substance concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the active ingredients can also be used with great success in the ultra-low-volume process (ULV), it being possible to apply formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.
  • UUV ultra-low-volume process
  • Oils of various types, herbicides, fungicides, other pesticides, bactericides can be added to the active compounds, if appropriate also only immediately before use (tank mix). These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.
  • compositions according to the invention can also be present together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • other active compounds for example with herbicides, insecticides, growth regulators, fungicides or else with fertilizers.
  • Sulfur, dithiocarbamates and their derivatives such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethyl bisbisithithiocarbamate, manganese zinc ethylenediamine bis dithiocarbamate, tetramethylthiammonodiamide dithiodiamide sulfate , Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis (thiocarbamoyl) disulfide; Nitroderivate, such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-iso
  • heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2-chloro-N- (4'-chloro-biphenyl-2-yl) -nicotinamide, 2,4-di-chloro-6- (o -chloranilino) -s-triazine, 0, O-diethyl-phthalimidophosphonothioate, 5-amino-l- [bis- (dimethylamino) -phosphinyl] -3-phenyl-l, 2, 4-triazole, 2, 3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4,5-b] quinoxaline, methyl 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid, 2-methoxycarbonylamino benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thio
  • (2,2, 2-trichloroethyl) formamide 1- (3, 4-dichlorani ⁇ ino) -1-formylamino-2, 2, 2-trichloroethane, 2, 6-dimethyl-N-tridecyl-morpholine or the like Salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpro- pyl] -cis-2, 6-dimethyl-morpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2, 4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3 -dio
  • Anilinopyrimidines such as N- (4, 6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- [4-Me- thyl-6-cyclopropyl-pyrimidin-2-yl] aniline,
  • Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile,
  • Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acrylic acid morpholide, 3- (4-fluorophenyl) -3- (3,4-dimethoxyphenyl) acrylic acid morpholide,
  • the active ingredients were separated or together as a 10% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight .-% Wettol® EM (non-ionic emulsifier based on ethoxylated castor oil) prepared and diluted with water according to the desired concentration.
  • Nekanil® LN Litensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols
  • .-% Wettol® EM non-ionic emulsifier based on ethoxylated castor oil
  • aqueous active ingredient preparation which was prepared from a stock solution consisting of 10% active ingredient, 85% cyclohexanone and 5% 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 placed for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a moist chamber for 16 hours 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.
  • Leaves of potted plants of the "Large meat tomato St. Pierre" were treated with an aqueous suspension consisting of a stock solution consisting of 10% active ingredient, 85% cyclohexanone and 5% emulsifier was added, sprayed until dripping wet. The following day the leaves were infected with a cold aqueous zoospore suspension of Phytophthora infestans with a density of 0.25 x 10 6 spores / ml. The plants were then placed in a steam-saturated chamber at temperatures between 18 and 20 ° C. After 6 days, the blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.
  • Leaves of potted vines of the "Müller-Thurgau" variety were sprayed to runoff point with an aqueous suspension in the active ingredient concentration given below.
  • the suspension or emulsion was prepared from a stock solution with 10% active ingredient in a mixture consisting of 85% cyclohexanone and 5% emulsifier.
  • the following day the undersides of the leaves were inoculated with an aqueous zoospore suspension of Plasmopara viticola.
  • the vines were then placed for 48 hours in a steam-saturated chamber at 24 ° C and then for 5 days in a greenhouse at temperatures between 20 and 30 ° C. After this time, the plants were again placed in a humid chamber for 16 hours in order to accelerate the outbreak of sporangium carriers. 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)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Epoxy Compounds (AREA)

Abstract

L'invention concerne des acrylamides Z-substitués de formule (I), dans laquelle les substituants ont les significations suivantes : X désigne hydrogène, halogène, alkyle, halogène alkyle, alcoxy, halogène alcoxy, X se situant en position 3 ou 4 ; n représente 1 ou 2, X pouvant être différent si n signifie 2 ; R1 désigne alkyle, halogène alkyle, cycloalkyle, alcoxy, halogène alcoxy, aziridine et oxirane et R2 désigne hydrogène, alkyle, halogène alkyle, allyle, propargyle ou CH2C<u>=</u>C-alkyle. Ladite invention concerne également un procédé de production desdits acrylamides ainsi que des agents contenant ces derniers et leur utilisation dans la lutte contre les champignons parasites pathogènes des plantes.
EP03709773A 2002-03-14 2003-03-12 Acrylamides z-substitues, procede de production et agents contenant lesdits acrylamides Withdrawn EP1487786A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10211291 2002-03-14
DE10211291 2002-03-14
DE10218619 2002-04-25
DE10218619 2002-04-25
PCT/EP2003/002505 WO2003076392A2 (fr) 2002-03-14 2003-03-12 Acrylamides z-substitues, procede de production et agents contenant lesdits acrylamides

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EP1487786A2 true EP1487786A2 (fr) 2004-12-22

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US (1) US7186861B2 (fr)
EP (1) EP1487786A2 (fr)
JP (1) JP2005527517A (fr)
AR (1) AR038981A1 (fr)
AU (1) AU2003214116A1 (fr)
TW (1) TW200305367A (fr)
WO (1) WO2003076392A2 (fr)

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Publication number Priority date Publication date Assignee Title
AU2003216893A1 (en) * 2002-03-28 2003-10-13 Basf Aktiengesellschaft Phenethylacrylamide, methods for the production thereof and agents containing the same
NZ546829A (en) * 2003-11-26 2009-12-24 Syngenta Participations Ag Method for controlling fungi and mites in textile substrates
JP4941301B2 (ja) * 2005-04-14 2012-05-30 日産化学工業株式会社 α置換ビニルスズ化合物
DE102007018151A1 (de) 2007-04-16 2008-10-23 Günenthal GmbH Neue Vanilloid-Rezeptor Liganden und ihre Verwendung zur Herstellung von Arzneimitteln
WO2020032080A1 (fr) * 2018-08-07 2020-02-13 学校法人慶應義塾 Composé, sel de composé, agent de neuromodulation, procédé d'évaluation d'agent de neuromodulation, procédé de production de composé et procédé de production de sel de composé

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JPH02200658A (ja) * 1989-01-28 1990-08-08 Kumiai Chem Ind Co Ltd Ｎ―（置換）ベンジルカルボン酸アミド誘導体及び除草剤
DE4443641A1 (de) * 1994-12-08 1996-06-13 Bayer Ag Substituierte Carbonsäureamide
DE59608263D1 (de) * 1995-01-30 2002-01-03 Bayer Ag Alkoximinoessigsäureamide
EP1289365B1 (fr) * 2000-06-14 2004-09-08 Basf Aktiengesellschaft Utilisation de phenethylacrylamides, nouveaux phenethylacrylamides, leur procede de production et les produits les contenant

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Title
See references of WO03076392A2 *

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US20050107619A1 (en) 2005-05-19
WO2003076392A2 (fr) 2003-09-18
US7186861B2 (en) 2007-03-06
WO2003076392A3 (fr) 2004-01-08
AU2003214116A1 (en) 2003-09-22
JP2005527517A (ja) 2005-09-15
AR038981A1 (es) 2005-02-02
TW200305367A (en) 2003-11-01

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