EP1001948A1 - Composes phenyliques a substitution bisimino et leur utilisation comme pesticides - Google Patents

Composes phenyliques a substitution bisimino et leur utilisation comme pesticides

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Publication number
EP1001948A1
EP1001948A1 EP98941366A EP98941366A EP1001948A1 EP 1001948 A1 EP1001948 A1 EP 1001948A1 EP 98941366 A EP98941366 A EP 98941366A EP 98941366 A EP98941366 A EP 98941366A EP 1001948 A1 EP1001948 A1 EP 1001948A1
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EP
European Patent Office
Prior art keywords
formula
compounds
alkyl
compound
alkoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP98941366A
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German (de)
English (en)
Inventor
Wassilios Grammenos
Herbert Bayer
Hubert Sauter
Thomas Grote
Andreas Gypser
Bernd Müller
Arne Ptock
Franz Röhl
Norbert Götz
Eberhard Ammermann
Volker Harries
Gisela Lorenz
Siegfried Strathmann
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BASF SE
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BASF SE
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Publication of EP1001948A1 publication Critical patent/EP1001948A1/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • the present invention relates to imino-substituted phenyl compounds of the formula I,
  • Z is a group A or B
  • R a for halogen, Cj . -C 4 alkyl or -CC 4 alkoxy
  • Y is halogen, C ⁇ -C 4 -alkyl, C 4 haloalkyl or C ⁇ ⁇ C 4 alkoxy;
  • R 1 halogen, C ⁇ -C 4 haloalkyl or -CC 4 alkoxy
  • R 2 C ⁇ -C 4 -alkyl, C 4 haloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 halo-alkenyl, C 3 -C 4 -alkynyl or C 3 -C 4 haloalkynyl;
  • R 3 cyano, Ci-Cg-alkyl, Ci-C ⁇ -haloalkyl, Ci-Cg-alkoxy, C 3 -C 6 -cycloalkoxy, C 2 -C 6 -alkoxyalkyl;
  • Cs-Ce cycloalkyl which can be partially or completely halogenated and / or can carry one to three C 1 -C 4 alkyl groups
  • Phenyl which in turn can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, nitro, C 1 -C 4 -alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C -Haloalkoxy;
  • Aryl, aryloxy or arylmethylene which can be partially or fully halogenated in the aryl moiety and / or may carry one to three of the following radicals: cyano, nitro, C 1 -C 4 alkyl -AI-, C ⁇ -C 4 haloalkyl, C ⁇ - C 4 alkoxy and Ci - ⁇ - haloalkoxy;
  • R 3a , R 3b , R 3c , R 3d independently of one another are hydrogen, C 1 -C 6 -alkyl or optionally substituted phenyl.
  • the invention relates to processes and intermediates for the preparation of the compounds I, and to agents and the use of the compounds I for controlling harmful fungi and animal pests.
  • ⁇ -phenylacrylic acid and ⁇ -phenyl- ⁇ -methoximinoacetic acid derivatives with an ortho-standing oxime ether group are described in DE-A 40 20 384, and those with a bisoxime ether group in WO-A 95 / 21,154.
  • the compounds described in the abovementioned documents are used as crop protection agents against harmful fungi and, for. Suitable against animal pests.
  • the compounds of the formula I differ from the compounds known from WO-A 97 / 02,255 mentioned above in the substitution of the oximino group by the specially designed radical R 1 which is bonded to a double bond.
  • the compounds of formula I have a comparison with the known compounds he ⁇ creased activity against harmful fungi and animal pests.
  • the compounds of the formula I per se can be obtained analogously to the methods described in WO-A 95 / 14,009, WO-A 97 / 02,255 or WO-A 95 / 21,153.
  • the compounds I can be obtained in various ways, it being irrelevant for the synthesis whether the group Z or the oxime ether group is built up first.
  • I # (R ⁇ halogen) R x in the formula purple represents the rest of a common leaving group.
  • the following groups are particularly to be understood: C 1 -C 4 -alkyl (especially methyl or ethyl) or phenyl.
  • L in formula IIa # stands for a nucleofugic leaving group.
  • halogen or alkyl or aryl sulfonate especially chlorine, bromine, iodine, mesylate, tosylate and triflate.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably alcohols such as methanol and ethanol. Mixtures of the solvents mentioned can also be used.
  • the bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal potassium carbonates such as lithium carbonate and alkaline earth metal carbonate and alkali metal carbonate and alkali metal carbonate such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, and also organic bases, for example Tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines.
  • Alkali metal hydroxides such as sodium and potassium hydroxide and alkali metal alcohol
  • the bases are generally used in equimolar amounts or in excess.
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use hydroxylamine in an excess based on purple.
  • the carboxylic acid esters purple required for the preparation of the compounds I are known in the literature [DE-A 28 08 317; DE-A 22 65 234; J. Chem. Soc. PT 1, 2340 ff. (1975); Chem. Ber. 16, 2987 ff. (1883); J. Org. Chem. 37, 139 (1972)] or can be prepared according to the literature cited.
  • the reaction of the hydroxamic acid IIIb with the benzyl compound IIa # usually takes place at temperatures from 0 ° C. to 130 ° C., preferably 10 ° C. to 60 ° C., in an inert organic solvent in the presence of a base [cf. Liebigs Ann. Chem. 10, 997 ff. (1992); Synth. Commun. 19, 339 ff. (1989)].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, sodium hydride Alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate as well as alkali metal hydrogen carbonates such as sodium hydrogen carbonate, organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyllithium and methyl magnesium halide and lithium magnesium halide Alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert.
  • alkali metal and alkaline earth metal hydroxides such as lithium hydroxide
  • Butanolate and dimethoxymagnesium also organic bases, for example tertiary amines such as trimethylamine, triethylamine, Tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well as bicyclic amines.
  • tertiary amines such as trimethylamine, triethylamine, Tri-isopropylethylamine and N-methylpiperidine
  • pyridine substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well as bicyclic amines.
  • Sodium methoxide, potassium carbonate and sodium hydride are particularly preferred.
  • the bases are generally used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • the starting materials are generally reacted in equimolar amounts with each other ⁇ . It may be advantageous for the yield to use Illb in an excess based on Ha *.
  • This halogenation of the hydroxamic acid ester IVa # usually takes place at temperatures from -20 ° C to 100 ° C, preferably -10 ° C to 80 ° C, in an inert organic solvent [cf. Houben-Weyl, 4th ed., Vol. E5, p. 631 ff .; J. Org. Chem. 36, 233 (1971); Synthesis 9, 750 ff. (1991); Tetrahedron 52 (1), 233 ff. (1996)].
  • Suitable halogenating agents in this reaction are the customary inorganic and organic halogenating agents, for example thionyl chloride, oxalyl chloride, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, phosphorus triiodide, triphenylphosphine / CCl 4 , triphenylphosphine / CBr 4 , triphenylphosphinyl chloride or iodine Triphenylphosphine reagents.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • halogenating agents are generally used at least in equimolar amounts. It can be advantageous for the yield to use it in an excess of up to 10 mol based on 1 mol IVa #, preferably up to 5 mol, in particular up to 3 mol.
  • the compounds IVa * can also be obtained by reacting a carboxylic acid IIIc with a benzylhydroxylamine IIb #.
  • This reaction usually takes place at temperatures from -10 ° C. to 120 ° C., preferably 0 ° C. to 50 ° C., in an inert organic solvent in the presence of an activating reagent [cf. Houben-Weyl, 4th ed., Vol. E5, p. 1141 ff .; J. Antibiot. 39, 1382 (1986)].
  • an activating reagent cf. Houben-Weyl, 4th ed., Vol. E5, p. 1141 ff .; J. Antibiot. 39, 1382 (1986)].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ketone, diethyl ketone and tert. -Butylmethylketone, as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably tetrahydrofuran and methylene chloride. Mixtures of the solvents mentioned can also be used.
  • Suitable activating reagents are acid halide formers such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride or oxalyl chloride; Anhydride formers such as ethyl chloroformate or methanesulfonyl chloride; Carbodiimides such as N, N '-dicyclohexylcarbodiimide or other conventional agents such as N, N' -carbonyldiimidazole or triphenylphosphine in CC1 4 . Thionyl chloride, oxalyl chloride and N, N'-carbonyldiimidazole are particularly preferred.
  • acid halide formers such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, thion
  • the activation reagents are generally used in equimolar amounts or in excess.
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use IIIc in an excess based on Ilb *.
  • the carboxylic acids IIIc required for this reaction are known from the literature [J. Pharm. 57, 688 ff. (1968); DE-A 22 23 375; DE-A 22 65 234] or can be prepared according to the literature cited.
  • the compounds IVa * are also obtained by reacting a carboxylic acid ester of the formula lilac with the benzylhydroxylamine Ilb * under the conditions described above for the conversion of lilac to Illb.
  • the compounds I are advantageously obtained by converting an amidoxime Illd with a benzyl compound Ila * into the corresponding compound of the formula IVb * and replacing the amino group of IVb * with halogen by diazoation.
  • the reaction of the amidoxime Illd with the benzyl compound Ila * usually takes place at temperatures from 0 ° C. to 130 ° C., preferably 10 ° C. to 60 ° C., in an inert organic solvent in the presence of a base [cf. Lit. Heterocycles 36, 1027 ff. (1993)].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • Dirnethylacetamide particularly preferably tetrahydrofuran, acetonitrile and dimethylformamide. Mixtures of the solvents mentioned can also be used.
  • Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride and calcium hydride, sodium hydride, sodium hydride, sodium hydride, sodium hydride, Alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate as well as alkali metal hydrogen carbonates such as sodium hydrogen carbonate, organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyllithium and phenomagnesium magnesium chloride, and methyl lithium magnesium chloride Alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert.
  • Butanolate and dimethoxy magnesium also organic bases, e.g. Tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines.
  • Tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine
  • pyridine substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines.
  • Sodium methoxide, potassium carbonate and sodium hydride are particularly preferred.
  • the bases are generally used in equimolar amounts or in excess.
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use Illd in an excess based on Ila *.
  • the amide oximes IIld required for this preparation of the compounds I are known in the literature [DE-A 44 42 732; Gazz. Chim. Italian 55, 327 (1925)] or can be prepared according to the literature cited.
  • the diazotization and halogenation of IVb * to I * is usually carried out at temperatures from -20 ° C to 50 ° C, preferably 0 ° C to 20 ° C, in water or in an aqueous inert organic solvent [cf. Lit. J. Org. Chem. 45, 4144 ff. (1980); Chem. Ber. 26, 1567 ff. (1893)].
  • the halogenating agents are generally used in excess or, if appropriate, as a solvent.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • -Butyl methyl ketone alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert.
  • -Butanol as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferred besides water are mixtures of dioxane and water and / or tetrahydrofuran and water.
  • benzyl compounds Ila * required for the preparation of the compounds I are known from the literature [cf. WO-A 97 / 02,255]. They can be obtained by the following synthetic route:
  • benzyl compounds IIB * required for the preparation of the compounds IB in which R a is halogen or alkoxy are known from the literature [cf. WO-A 97 / 02,255], or are accessible analogously to the literature cited. They can be obtained by the following synthetic route:
  • benzyl compounds IIB * required for the preparation of the compounds IB in which R a is alkyl are known from the literature [cf. WO-A 96 / 36.229] and are analogous to the cited Li ⁇ erature accessible. They are accessible by reacting the carbamates of the formula II ⁇ with orthoesters:
  • This route is not only suitable for the preparation of the benzyl compounds Ila *, but in principle for the synthesis of groups A and B at each synthesis stage of the oxime ether group E *.
  • Be ⁇ Sonders preferably carried out the construction of the group X on the stage of the compounds Il ⁇ or Il ⁇ where E * is hydrogen.
  • R 3a , R 3b independently of one another are hydrogen, C 1 -C 6 -alkyl or optionally substituted phenyl, for example by reacting a benzyl compound of the formula Ila * with an oxime of the formula V and the oxime ether of the formula obtained VI * converted into the halogen compound of the formula VII * by halogenation, VII * reacted with a hydroxylamine ether of the formula VIII 'to the bisoxime ether of the formula IX *, IX * oxidized to the carbonyl compound of the formula X * and X * with a hydroxylamine ether of the formula VIII implements.
  • the reaction of the benzyl compound Ila * with the oxime of the formula V is carried out in a manner known per se at temperatures from -10 ° C. to 100 ° C., preferably 10 ° C. to 85 ° C., in an inert organic solvent in the presence of a base [cf. . WO-A 97 / 02,255].
  • Suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol , Ethanol, n-propanol, isopropanol, n-butanol and tert.
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran
  • nitriles such as acetonitrile and propionitrile
  • ketones such as acetone, methyl ethyl ketone, diethyl
  • Suitable bases are, generally, inorganic compounds such as kalimetall- Al and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali - metal and alkaline earth metal hydrides such as lithium hydride, Natri ⁇ hydride, potassium hydride and calcium hydride, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, , and alkali metal bicarbonates, such as sodium bicarbonate, alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethoxide, potassium ethanolate, potassium tert.
  • inorganic compounds such as kalimetall- Al and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide
  • alkali - metal and alkaline earth metal hydrides such as lithium hydride, Natri ⁇ hydride, potassium hydride and calcium
  • -Butanolat and Dimethoxymagnesium in addition ⁇ the organic bases, for example tertiary amines such as trimethylamine, t ⁇ ethylamine, tri-isopropylethylamm and N-methylpiperidm, pyridine, substituted pyridme, we Collidm, utidin and 4-dimethylammopyr ⁇ d ⁇ n, and bicyclic amines into consideration.
  • tertiary amines such as trimethylamine, t ⁇ ethylamine, tri-isopropylethylamm and N-methylpiperidm
  • pyridine substituted pyridme
  • we Collidm utidin and 4-dimethylammopyr ⁇ d ⁇ n
  • bicyclic amines into consideration.
  • Sodium hydride, potassium carbonate and sodium methoxide are particularly preferred.
  • the bases are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.
  • the starting materials are generally reacted with one another in aquimolar amounts. It may be advantageous for the yield to use V in an excess based on Ila *.
  • the oximes of the formula V are also known from the literature [cf. WO-A 95 / 21,153] or can be prepared according to the literature cited.
  • the halogenation of the oxime ether VI * is usually carried out at temperatures from -10 ° C to 80 ° C, preferably 0 ° C to
  • Suitable halogenating agents are bromine, chlorine, pyridine HBr 3 , CuBr and S0C1 2, in particular bromine, CuBr and S0C1. They are generally reacted with one another in aquimolar amounts. It can be advantageous for the yield to use them in a 1.2- to 2.5-fold excess, based on the compound IV *.
  • Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbon ⁇ such as methylene chloride, chloroform and chlorobenzene, and alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert Butanol, particularly preferably cyclohexane, methylene chloride, chloroform, chlorobenzene and methanol. Mixtures of the solvents mentioned can also be used.
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • halogenated hydrocarbon ⁇ such as methylene chloride, chloroform and chlorobenzene
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert Butanol, particularly preferably cyclohexane,
  • acids and acidic catalysts there are inorganic acids such as hydrochloric acid, hydrobromic acid and sulfuric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin IV chloride, titanium IV chloride and zinc II chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid use.
  • inorganic acids such as hydrochloric acid, hydrobromic acid and sulfuric acid
  • Lewis acids such as boron trifluoride, aluminum trichloride, iron III chloride, tin IV chloride, titanium IV chloride and zinc II chloride
  • organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid use.
  • the acids are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use an excess of the halogenating agent, based on IV *.
  • reaction of the oxime ether VII * with the hydroxylamine ether of the formula VIII 'to the bisoxime ether IX * is carried out in a known manner at temperatures from 0 ° C. to 85 ° C., preferably at 20 ° C. to 65 ° C., in an inert organic solvent .
  • Suitable oxidizing agents are N-methylmorpholine-N-oxide, 2-benzoyl-1-trifluoromethanesulfonyl-hydrazine, trimethylamine-N-oxide and pyridine-N-oxide, in particular N-methylmorpholine-N-oxide, trimethylamine-N -Oxide and pyridine-N-oxide.
  • inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, Ka ⁇ liumcarbonat and calcium carbonate, and also alkali metal hydrogen ⁇ carbonates, such as sodium bicarbonate, moreover organic bases, for example tertiary amines such as trimethylamine, triethylamine, 5 triisopropylethylamine and N-methylpiperidine, pyridine, substi ⁇ -substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, and bicyclic amines into consideration. Especially before ⁇ be Trains t sodium hydroxide, sodium bicarbonate and potassium carbonate. 10
  • the bases are set, a ⁇ generally used in catalytic amounts, but they may also equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in aquimolar amounts. It may be advantageous for the yield to use the oxidizing agent in an excess based on IX *.
  • the conversion of the carbonyl compound X * into the trisoxime ether 1.1 * usually takes place at temperatures from 10 ° C. to 120 ° C., preferably 20 ° C. to 85 ° C., in an inert organic solvent, if appropriate in the presence of a base [cf. EP-A 386 561].
  • Suitable solvents are ethers such as diethyl ether, diisopropyl ether, tert. -Butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-Bu-
  • Bases generally include inorganic compounds such as alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, and alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium
  • organic bases e.g. tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine, and bicycli-
  • amines Sodium hydrogen carbonate, pyridine and triethylamine are particularly preferred.
  • the bases are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • the starting materials are generally reacted with one another in aquimolar amounts. It may be advantageous for the yield to use VIII in an excess based on X *.
  • the Wittig reaction takes place in a known manner at temperatures from -78 ° C to 85 ° C, preferably -10 ° C to 65 ° C, in an inert organic solvent in the presence of a base [cf. EP-A 513 580].
  • the reaction is usually carried out at temperatures from 20 to 120 ° C., preferably at 20 to 80 ° C., in an inert organic solvent [cf. J. Org. Chem., 50, p. 993 (1985); Tetrahedron Lett. , 35, p. 15 (1994)].
  • Suitable solvents are ethers, such as dioxane or tetrahydro ⁇ drofuran, nitriles, such as acetonitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol or tert-butanol and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide. Mixtures of the solvents mentioned can also be used.
  • the starting materials are generally reacted with one another in aquimolar amounts. It may be advantageous for the yield to use XII in an excess based on I *.
  • the starting materials are generally reacted with one another in aquimolar amounts. It may be advantageous for the yield to use Ille in an excess based on Ila *.
  • the oximes of the formula IIle are obtained, for example, by reacting an oxime of the formula Ulf, in which R 1 is halogen, with an alcoholate of the formula XII under the conditions described in Section 12 [cf. EP-A 158 153; US 4,339,444] or can be prepared according to the literature cited.
  • the oximes of the formula Ulf are obtained, for example, by reacting a ketoxime of the formula Ulf with a hydroxylamine ether of the formula VIII '.
  • ketoximes of the Ulf formula are known in the literature [cf. Ber. German Chem. Ges. 88, p. 130 (1955); J. Org. Chem., P. 4570 (1987)], or can be prepared according to the literature cited.
  • reaction mixtures are worked up in a conventional manner, e.g. by mixing with water, separating the phases and, if necessary, purifying the crude products by chromatography.
  • the intermediate and end products fall partly in the form of colorless or slightly brownish, viscous oils, which are freed from volatile components or cleaned 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.
  • the compounds I can be obtained as E / Z isomer mixtures which, for example, can be separated into the individual compounds by crystallization or chromatography in the usual way.
  • isomer mixtures are obtained during the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (e.g. under the action of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be controlled.
  • Halogen fluorine, chlorine, bromine and iodine
  • Alkyl saturated, straight-chain or branched hydrocarbon ⁇ hydrocarbon radicals having 1 to 4 or 6 carbon atoms, for example, C ⁇ -C 6 alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbuty
  • Haloalkyl straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms (as mentioned above), it being possible in these groups for the hydrogen atoms to be partially or completely replaced by halogen atoms as mentioned above, for example C 1 -C 2 -haloalkyl such as chloromethyl, bromomethyl, dichlorme - thyl, 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
  • Alkoxy straight-chain or branched alkyl groups with 1 to 6 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-0-);
  • Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals with 3 to 4 carbon atoms and a double bond in any position, for example C 3 -C 4 alkenyl such as 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl and 2-methyl-2-propenyl;
  • Haloalkenyl unsaturated, straight-chain or branched hydrocarbon radicals with 3 to 4 carbon atoms and a double bond in any position (as mentioned above), whereby partially full ⁇ constantly replaced by halogen atoms called the hydrogen atoms in these groups or above, in particular fluorine, chlorine and bromine, may be replaced;
  • Alkynyl straight-chain or branched hydrocarbon groups with 3 to 4 carbon atoms and a triple bond in any position, for example C 3 -C 4 -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and l-methyl-2-propynyl;
  • Haloalkynyl unsaturated straight-chain or branched Koh ⁇ radicals having 3 to 4 carbon atoms and a triple bond in any position (as mentioned ge ⁇ Nannt), whereby partially to completely by halogen atoms called the hydrogen atoms in these groups or above, in particular fluorine, Chlorine and bromine, can be replaced;
  • Aryl a mono- to trinuclear aromatic ring system contained ⁇ tend 6 to 14 carbon ring members, for example phenyl, naphthyl and anthracenyl;
  • Aryloxy a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded to the skeleton via an oxygen atom (-0-).
  • this radical can be partially or completely halogenated [ie the hydrogen atoms of this radical can be partially or completely replaced by the same or different halogen atoms as mentioned above (preferably fluorine, be replaced is chlorine or bromine, in particular fluorine or chlorine)] and / or a (especially to four may have one to three wear) of the following radicals: halogen, cyano, nitro, C ⁇ -C 4 -alkyl, C 4 haloalkyl, C 1 -C 4 -AI- koxy, -C-C 4 -haloalkoxy, -C-C 4 -alkylamino, di-C ⁇ -C 4 -alkylamino and C ⁇ -C 4 ⁇ alkylthio;
  • 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3- Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-oxadiazol-3-yl, 1, 2, 4-oxadiazol-5-
  • benzo-fused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulfur atom 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group; - 5- ⁇ liedri ⁇ es heteroaryl bound via nitrogen. containing one to four nitrogen atoms, or nitrogen-bonded benzo-fused 5-membered heteroaryl.
  • 5-ring heteroaryl groups which in addition to carbon atoms can contain one to four nitrogen atoms or one to three nitrogen atoms as ring members, and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member by a buta-1, 3 -diene-1,4-diyl group can be bridged, these rings being bound to the structure via one of the nitrogen ring members;
  • 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2- yl and 1, 2, 4-triazin-3-yl;
  • Heterocyclyl 5- or 6-membered heterocycles (heterocyclyl) containing, in addition to carbon ring members, one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms, for example 2-tetrahydrofurananyl, 3-tetrahydrofuranyl , 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl , 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl
  • R 1 is C 1 -C 4 -haloalkyl.
  • R 3 represents one of the following groups: phenyl or benzyl, which can be partially or completely halogenated in the aryl part and / or can carry one to three of the following radicals: cyano, C 1 -C 4 - alkyl, C ⁇ -C4-haloalkyl, C ⁇ -C4-alkoxy and halo-C ⁇ ⁇ C 4 alkoxy.
  • R 3 is phenoxy, which can be partially or completely halogenated and / or can carry one to three of the following radicals: cyano, C 1 -C 4 -alkyl, C 1 -C 4 haloalkyl, C ⁇ -C 4 alkoxy and Cj_-C 4 haloalkoxy.
  • R 3 is pyridyl.
  • compounds 1.2 are preferred in which R 3a and Y n are hydrogen and R 2 is methyl or ethyl.
  • compounds 1.2 are particularly preferred in which R 3a is hydrogen, R 2 is methyl or ethyl and Y n is 6-methyl.
  • Methyl and R 1 represents chlorine and the combination of the radicals R 3a ,
  • R 3c and R 3d for each connection corresponds to one row of Table C.
  • R 3a and R 3b for a compound corresponds in each case to one row of Table B.
  • R 1 is methoxy and the combination of the radicals R 3a ,
  • R 3c and R 3d for each connection corresponds to one row of Table C.
  • 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. They are of particular importance for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans, coffee , sugar cane, wine, fruit and ornamental plants and vegetable plants such as cucumbers, beans, tomatoes, potatoes and cucurbits, so ⁇ as the seeds of these plants.
  • crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans, coffee , sugar cane, wine, fruit and ornamental plants and vegetable plants such as cucumbers, beans, tomatoes, potatoes and cucurbits, so ⁇ as the seeds of these plants
  • Botrytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and grapevines ⁇
  • Rhizoctonia species on cotton, rice and lawn are Rhizoctonia species on cotton, rice and lawn.
  • Venturia species scab on apples and pears.
  • the compounds I are also suitable for combating harmful fungi such as Paecilomyces variotii in the protection of materials (for example wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • harmful fungi such as Paecilomyces variotii in the protection of materials (for example wood, paper, dispersions for painting, fibers or fabrics) and in the protection of stored products.
  • 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.
  • active ingredient 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
  • the amount of active ingredient applied depends on the type of application and the desired effect. Usual application rates in material protection 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 of the formula I are also suitable for effectively combating animal pests from the class of the insects, arachnids and nematodes. They can be used in crop protection as well as in the hygiene, storage protection and veterinary sectors to control animal pests. They are particularly suitable for controlling the following animal pests:
  • insects from the order of the butterflies (Lepidoptera) in ⁇ play Agrotis ypsilon, Agrotis segetum, Alabama argilla- cea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis , Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonothisis, Armolithiothaisella, Grapholithaiothaisana,
  • Beetles for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Bla- stophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bru- chus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus napimorri, heuthocnocysti, Ceuthorrhynchus naprimiibi, Ceuthorrhynchus naprimiibi, Ceuthorrhynchus assimili, Ceuthorrhynchus assimilisibi, Ceuthorrhynchus assimilisibi, Ceuthorrhynchus assimilisibi, Ce
  • Crioceris asparagi Diabrotica longicornis, Diabrotica 12-puncata, Diabrotica virgifera, Epilachna varivestis, Epitrix hir- tipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typineaopa, lemaanotinus, lemaanotanus, lema - cus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochlphretiae, Phyllophaala phyllophae , Phyl-lopertha
  • Two-winged e.g. Aedes aegypti, Aedes vexans, Anas - trepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macella- ria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pi piens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, fan- nia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina,
  • Thrips e.g. Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • Dermatoptera e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara quadrantulais, Pyanma viridula, Pies
  • Plant suckers for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Ceosipha gossypii, Dreyfusiafiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiaiausiaiaiausiaiaiausiaiaiaiaiaiaiausiaiaiaiaiaiaiaiausiaiaiaiaiaiaiaiaiaiaiausiaiaiaiaiaiaiaiaiaiaiausia
  • Termites e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus and Termes natalensis,
  • Straight wing aircraft e.g. Acheta domestica, Blatta orien- talis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguini- pes, Melanoplus spretus, Ameradococentina, Pericocarpeanus, Pericocarpus america, Nomadascacrata ameracerana, Periscus america, Pericocarpus nec , Stauronotus maroccanus and Tachycines asynamorus,
  • Orthoptera e.g. Acheta domestica, Blatta orien- talis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus
  • Arachnoid such as arachnids (Acarina), e.g. Amblyomma america - num, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Ialundusxusbodinus, Hyalommxxusbios, Hyalommxxusodusunc me- gnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllo- coptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabieus, Tetranychus c
  • Nematodes such as root gall nematodes, e.g. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming
  • Nematodes e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, stick and leaf wholes, e.g.
  • Belonolaimus longicaudatus Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multi- ticinctus, Longidorus elongatus, Radopholus similis, Rotylen- chus robustus, Trichodorus primitivus, Tylenchorhynchus clay- toni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus and Pratylenchus goodeyi.
  • the application rate of active ingredient for controlling animal pests is 0.1 to 2.0, preferably 0.2 to 1.0 kg / ha under field conditions.
  • the compounds I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the application form depends according to 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, where, in the case of water as the 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 such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); 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.
  • Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfit
  • Mineral oil fractions from medium to high boiling points such as kerosene or diesel oil, are also used to produce directly sprayable solutions, emulsions, pastes or oil dispersions
  • Coal tar oils and oils of vegetable or animal origin aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene Isophorone, strongly polar solvents, e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water.
  • aliphatic, cyclic and aromatic hydrocarbons e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chlor
  • 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 silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, 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 silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomit
  • 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).
  • 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 and 10 parts by weight of the sodium salt
  • the active ingredients as such in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or Pouring can be applied.
  • the application forms depend entirely on the intended use; they should be in everyone As fine a distribution of the active substances according to the invention ⁇ guarantee.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions 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.
  • concentrates composed of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.
  • the active ingredient concentrations in the ready-prepared dishes ⁇ in larger areas can be varied. 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.
  • the agents according to the invention can also be present in the use form as fungicides together with other active ingredients, which e.g. with herbicides, insecticides, growth regulators, fungicides or even with fertilizers. Mixing the compounds I or the compositions containing them in the use form as fungicides with other fungicides results in an enlargement of the fungicidal spectrum of action in many cases.
  • fungicides with which the compounds according to the invention can be used together, is intended to explain, but not to limit, the possible combinations: • Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganarbambisbis Zinc ethylenediamine bis-dithiocarbamate, tetramethylthiuram disulfide, ammonia complex of zinc (N, N-ethylene bis-dithiocarbamate), am- monia complex of zinc (N, N '-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N' -polypropylene-bis- (thiocarbamoyl) disulfide;
  • Sulfur, dithiocarbamates and their derivatives such as ferridimethyldithiocarbamate, zinc
  • Nitroderivate such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-isopropyl carbonate, 5- Nitro-isophthalic acid-di-isopropyl ester;
  • Heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-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, l- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole , N- (1, 1, 2, 2-tetrachloro
  • Amines such as 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts,
  • 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 morpholide;
  • fungicides such as dodecylguanidine acetate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide,
  • 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
  • Example of use 1 Activity against powdery mildew Leaves of wheat seedlings of the "Schart" variety grown in pots were sprayed to runoff point with aqueous preparation of active compound, which was prepared from a stock solution consisting of 10% active compound, 63% cyclohexanone and 27% emulsifier, and 24 hours after the spray coating had dried on dusted with spores of powdery mildew (Erysiphe graminis forma specialis tritici). The test plants were then placed in the greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity. After 7 days, the extent of mildew development was determined visually in% infestation of the entire leaf area.
  • the active ingredients were a. as a 0.1% solution in acetone or b. 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) processed and in accordance with the desired concentration with acetone in the case of a. or with water in the case of b. diluted.
  • 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

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  • 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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des composés phényliques à substitution imino de la formule (I) dans laquelle les substituants ont la signification suivante: Z désigne un groupe A ou B, où # caractérise la liaison avec le cycle phénylique et R<a> représente halogène, alkyle ou alcoxy; Y représente halogène, alkyle, halogénure d'alkyle ou alcoxy; n vaut 0, 1 ou 2, les restes Y pouvant être différents lorsque n = 2; R<1> représente halogène, halogénure d'alkyle ou alcoxy; R<2> désigne alkyle, halogénure d'alkyle, alcényle, halogénure d'alcényle, alcynyle ou halogénure d'alcynyle; R<3> représente cyano, alkyle, halogénure d'alkyle, alcoxy, cycloalcoxy, alcoxyalkyle, cycloalkyle éventuellement substitué, aryle, aryloxy ou arylméthylène, hétéroaryle, hétérocyclyle, C(R<3a>)=N-OR<3b> ou bien C(R<3a>)=CR<3c>R<3d>, où R<3a>, R<3b>, R<3c>, R<3d> représentent, indépendamment les uns des autres, hydrogène, alkyle ou bien phényle indépendamment substitué. L'invention concerne également leur procédé de préparation et leur utilisation pour lutter contre les champignons parasites et les parasites animaux.
EP98941366A 1997-07-30 1998-07-20 Composes phenyliques a substitution bisimino et leur utilisation comme pesticides Withdrawn EP1001948A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19732846 1997-07-30
DE19732846A DE19732846A1 (de) 1997-07-30 1997-07-30 Bisiminosubstituierte Phenylverbindungen
PCT/EP1998/004488 WO1999006379A1 (fr) 1997-07-30 1998-07-20 Composes phenyliques a substitution bisimino et leur utilisation comme pesticides

Publications (1)

Publication Number Publication Date
EP1001948A1 true EP1001948A1 (fr) 2000-05-24

Family

ID=7837390

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98941366A Withdrawn EP1001948A1 (fr) 1997-07-30 1998-07-20 Composes phenyliques a substitution bisimino et leur utilisation comme pesticides

Country Status (7)

Country Link
US (1) US6232317B1 (fr)
EP (1) EP1001948A1 (fr)
JP (1) JP2001512108A (fr)
AU (1) AU8977298A (fr)
DE (1) DE19732846A1 (fr)
WO (1) WO1999006379A1 (fr)
ZA (1) ZA986752B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GT199900107A (es) * 1998-07-23 2001-01-02 Derivados de dihidrotriazolona como pesticidas.
KR100311196B1 (ko) * 1999-08-16 2001-11-14 김충섭 옥심기를 가교로 하는, 불소화 프로페닐기가 치환된 프로페노익 에스테르 및 아미드 화합물, 이의 제조방법 및 이를 포함하는 살균제 조성물
GB9924692D0 (en) 1999-10-20 1999-12-22 Hoechst Schering Agrevo Gmbh Wood treatment
MX2010005953A (es) 2007-12-06 2010-07-30 Kyung Nong Corp Compuestos de metoxiimino y composicion fungicida que los comprende.
JP5923038B2 (ja) * 2010-06-24 2016-05-24 クミアイ化学工業株式会社 アルコキシイミノ誘導体及び節足動物防除剤

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
DK0669319T3 (da) 1990-06-27 1999-02-08 Basf Ag O-benzyloximethere og plantebeskyttelsesmidler indeholdende disse forbindelser
DE4020384A1 (de) 1990-06-27 1992-01-02 Basf Ag O-benzyl-oximether und diese verbindungen enthaltende pflanzenschutzmittel
ES2141262T3 (es) 1993-11-19 2000-03-16 Du Pont Amidas ciclicas fungicidas.
ATE236119T1 (de) 1994-02-04 2003-04-15 Basf Ag Phenylessigsäurederivate, verfahren und zwischenprodukte zu ihrer herstellung und sie enthaltende mittel
PL323311A1 (en) 1995-07-04 1998-03-16 Ciba Geigy Ag Bis-oximie derivatives of triazolin and isoxazolin and their application as pesticides
WO1998023155A1 (fr) * 1996-11-26 1998-06-04 E.I. Du Pont De Nemours And Company Amides cycliques arthropodicides et fongicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9906379A1 *

Also Published As

Publication number Publication date
AU8977298A (en) 1999-02-22
DE19732846A1 (de) 1999-02-04
ZA986752B (en) 2000-01-31
JP2001512108A (ja) 2001-08-21
US6232317B1 (en) 2001-05-15
WO1999006379A1 (fr) 1999-02-11

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