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WO1997011065A1 - Phenylacetic acids, processes for their preparation and agents containing them - Google Patents

Phenylacetic acids, processes for their preparation and agents containing them Download PDF

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Publication number
WO1997011065A1
WO1997011065A1 PCT/EP1996/003937 EP9603937W WO9711065A1 WO 1997011065 A1 WO1997011065 A1 WO 1997011065A1 EP 9603937 W EP9603937 W EP 9603937W WO 9711065 A1 WO9711065 A1 WO 9711065A1
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Prior art keywords
formula
compounds
alkyl
methyl
halogen
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PCT/EP1996/003937
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German (de)
French (fr)
Inventor
Herbert Bayer
Ruth Müller
Hubert Sauter
Michael Rack
Albrecht Harreus
Eberhard Ammermann
Volker Harries
Gisela Lorenz
Siegfried Strathmann
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Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU70844/96A priority Critical patent/AU706982B2/en
Priority to BR9610592A priority patent/BR9610592A/en
Priority to JP9512354A priority patent/JPH11512446A/en
Priority to EP96931781A priority patent/EP0851863A1/en
Priority to NZ318771A priority patent/NZ318771A/en
Priority to EA199800308A priority patent/EA199800308A1/en
Priority to IL12342196A priority patent/IL123421A0/en
Priority to PL96325551A priority patent/PL325551A1/en
Publication of WO1997011065A1 publication Critical patent/WO1997011065A1/en

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    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
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    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen 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
    • A01N37/44—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 nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—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 nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • C07D233/72—Two oxygen atoms, e.g. hydantoin
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Definitions

  • Phenylacetic acids process for their preparation and compositions containing them Description
  • the present invention relates to phenylacetic acids of the formula I.
  • R is hydrogen and C 1 -C 4 alkyl
  • Z a possibly subst. a saturated or partially or completely unsaturated cyclic radical bonded via a nitrogen atom, which, in addition to the nitrogen atom via which it is bonded, can contain, in addition to carbon ring members, one to four heteroatoms from the group consisting of nitrogen, oxygen and sulfur;
  • R 1 is hydrogen and C 1 -C 4 alkyl; R 2 cyano, nitro, trif luormethyl, halogen, C 1 -C 4 alkyl and
  • R 3 is hydrogen, cyano, nitro, hydroxy, amino, cyclopropyl,
  • Halogen C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy,
  • R 4 is hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkylcarbonyl, C 2 -C 10 alkenylcarbonyl, C 2 -C 10 alkynylcarbonyl or C 1 -C 10 alkylsulfonyl, where these radicals can be partially or completely halogenated or can carry one to three of the following groups:
  • Halogen C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl,
  • Hetaryloxy and hetarylthio where the cyclic groups can in turn be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C 1 -C 6 alkyl ,
  • Halogen C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfonyl,
  • A represents oxygen, sulfur and nitrogen and the nitrogen carries hydrogen or C 1 -C 6 alkyl; n represents 0 or 1, and
  • R a , R b each represent hydrogen or C 1 -C 6 alkyl, and their salts.
  • the invention relates to processes and intermediates for the preparation of these compounds and compositions containing them for controlling animal pests and harmful fungi.
  • Phenylacetic acid derivatives for controlling animal pests and harmful fungi are known from the literature (EP-A 422 597, EP-A 463 488, EP-A 370 629, EP-A 460 575, EP-A 472 300, WO-A 90 / 07,493 , WO-A 92 / 13,830, WO-A 92 / 18,487).
  • the older German patent applications P 44 03 447.4 and P 44 03 448.2 describe phenylacetic acid derivatives with bis-oxime side chains with action against animal pests and harmful fungi.
  • the present invention was based on compounds with improved activity as an object.
  • L 1 in formula II stands for a nucleophilically interchangeable
  • Leaving group e.g. Halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate and triflate.
  • the reaction takes place in a manner known per se in an inert organic solvent in the presence of a base (for example sodium hydride, potassium hydroxide, potassium carbonate and triethylamine) in accordance with the methods described in Houben-Weyl, Vol. E 14b, p. 370f and Houben-Weyl, Vol. 10 / 1, p. 1189f described methods.
  • a base for example sodium hydride, potassium hydroxide, potassium carbonate and triethylamine
  • the required hydroxyimine III is obtained, for example, by reacting a corresponding purple dihydroxyimine with a nucleophilically substituted reagent V.
  • L 2 in formula V stands for a nucleophilically interchangeable
  • halogen or sulfonate groups preferably chlorine, bromine, iodine, mesylate, tosylate and triflate.
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (for example potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine) in accordance with the methods described in Houben-Weyl, vol. E 14b, p. 307f, p. 370f and p . 385f; Houben-Weyl, Vol. 10/4, p. 55f, p. 180f and p. 217f; Houben-Weyl, vol. E 5, p. 780f.
  • a base for example potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine
  • the compounds III can also be obtained by first converting the carbonylhydroxyimine IIIb with the sulfurization reagent into the corresponding thiocarbonylhydroxyimine IIIc and then IIIc either a) first with hydroxylamine or its salt and then with a compound of the formula V or
  • Q- in the formula VIIIb means the anion of an inorganic acid (in particular a halide such as chloride).
  • IIIb to IIIc takes place in a manner known per se [cf. Bull Soc. Chim. Belg. 87, 293 (1978)] at temperatures from 10 ° C to 150 ° C, preferably 20 ° C to 120 ° C in an inert organic 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, particularly preferably dioxane, toluene and xylene. Mixtures of the solvents mentioned can also be used.
  • P 4 S 10 or the Lawesson reagent [2,4-bis- (4-methoxyphenyl) -1,3-dithia-2,4-di-phosphetane-2,4-disulfide] are used as sulfurization reagents, for example.
  • the compounds I can also be obtained by first converting the benzyl derivative II with a dihydroxyimine IIIa into a corresponding benzyloxime IVa and then IVa with the nucleophilic substitution
  • Reagent V converts to I.
  • reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (e.g. potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine) according to the methods described in Houben-Weyl, Vol. 10/1, p. 1189f;
  • a base e.g. potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine
  • the compounds I can also be obtained by first converting the benzyl derivative II with a carbonylhydroxyimine IIIb into the corresponding benzyloxyimine VIa, VIa then converting the thio compound VIb with a sulfurization reagent and VIb either a) initially with hydroxylamine or its salt and then with a compound of formula V or
  • the reaction of the benzyl derivative II with the carbonylhydroxyimine IIIb is carried out as described in general and in particular for the reaction of II with III.
  • the sulfurization reaction and the oximation to I take place in general and in particular under the conditions described above.
  • the compounds VIa can also be obtained, for example, by a carboxylic acid VIc in a manner known per se [HouibenWeyl, Vol. E5, p. 941f] with a nitrogen-containing heterocycle IX.
  • the reaction is usually carried out at temperatures from -20 ° C to 100 ° C, preferably -10 ° C to 50 ° C, in an inert organic solvent, preferably in the presence of an activation reagent (eg phosgene, thionyl chloride, oxalyl chloride, N, N- Carbonyldiimidazole and triphenylphosphine / CCl 4 ).
  • an activation reagent eg phosgene, thionyl chloride, oxalyl chloride, N, N- Carbonyldiimidazole and triphenylphosphine / CCl 4 .
  • reaction is carried out in a manner known per se in an inert organic solvent according to that in EP-A 463 488 and
  • the required carbonyl compounds Villa are obtained, for example, by reacting the corresponding hydroxyiminocarbonyl compounds VIIIb with a nucleophilically substituted reagent V.
  • the compounds VIIIb can be obtained by reacting a hydroxamic acid VIIId in a manner known per se [cf.
  • the compounds I can also be obtained by first converting the benzylhydroxylamine Ha with the hydroxyimino derivative VIIIb into the corresponding benzyloxyimino derivative of the formula IVa and then reacting IVa to I with the nucleophilically substituted reagent V as described above.
  • the compounds I can also be obtained by first converting the benzylhydroxylamine IIa with the hydroxamic acid chloride VIIId into the corresponding compound IVb and then IVb first with IX in IVa and IVa then in I.
  • a further possibility for the preparation of the compounds I consists in converting the benzylhydroxylamine IIa with an ⁇ -keto acid VIIIe into the corresponding oximino-carboxylic acid VIc, converting VIc into the corresponding hydroxamic acid IVc by reaction with Vlla or Vllb, IVc to the hydroxamic acid halide IVd halogenated and IVd reacted with IX to I.
  • Molecule-bound are also obtained from the corresponding precursors in which the radical in question represents a hydroxyl group by methods known per se [cf. HoubenWeyl, Vol. E5, pp.826f; Aust. J. Chem. 27, 1341 (1974)].
  • the corresponding reactions to the alkoxy derivatives are preferably carried out at stages I and VIa.
  • corresponding ⁇ -ketocarboxamides XIIc can be obtained by reacting the ⁇ -ketocarboxylic acids XIIb or the esters XIIa [cf. Houben-Weyl, Vol. E5, p.
  • ⁇ -ketocarboxamides XIIc in which R is hydrogen, can also be obtained directly from the carboxylic acid halides XIb by reaction with isocyanides XIII (R 1 -NC) [cf. EP-A 547 825].
  • the E isomers of the compounds I are preferred in terms of their activity (configuration based on the CH 3 , CH 2 CH 3 or OCH 3 group to form the COYR 1 group).
  • the cis isomers of the compounds I are preferred in terms of their activity (configuration based on the radicals R 3 in relation to the OCH 2 grouping).
  • the configuration of the C (Z) NOR 4 double bond generally has only an insignificant influence on the biological activity of the compounds I. In cases in which an influence can be determined, the cis isomers (configuration based on the residues OR 4 in relation to the Z grouping).
  • isomer mixtures are formed in the synthesis, the separation into the individual compounds is generally not absolutely necessary, since the individual isomers partially convert into one another during preparation for use or during use (for example under the action of light, acid or base) can. Corresponding conversions can also take place after use, for example in the treatment of plants, fungi and animal pests in the treated organism.
  • Halogen fluorine, chlorine, bromine and iodine
  • Alkyl straight-chain or branched alkyl groups with 1 to 4, 6 or 10 carbon atoms, for example C 1 -C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl,
  • Dialkylamino an amino group which carries two independent, straight-chain or branched alkyl groups each having 1 to 4 or 6 carbon atoms as mentioned above;
  • Alkylcarbonyl straight-chain or branched alkyl groups with 1 to 6 or 10 carbon atoms, which are bonded to the skeleton via a carbonyl group (-CO-); Alkvisulfonyl; straight-chain or branched alkyl groups with 1 to 6 or 10 carbon atoms, which are bonded to the skeleton via a sulfonyl group (-SO 2 -); Alkyl sulfoxyl; straight-chain or branched alkyl groups with 1 to 6 carbon atoms, which have a sulfoxyl group
  • Alkylaminocarbonyl Alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the skeleton via a carbonyl group (-CO-);
  • Dialkylaminocarbonyl Dialkylamino groups each having 1 to 6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a carbonyl group (-CO-);
  • Alkylaminothiocarbonyl Alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-);
  • Dialkylaminothiocarbonyl Dialkylamino groups each having 1 to 6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-); Haloalkyl; straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms, in which case the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, for example C 1 -C 2 -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, Chlorofluoromethyl, dichlorofluoromethyl,
  • Chlorodifluoromethyl 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2,2-dichloro-2- fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
  • Alkoxy straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via an oxygen atom (-O-), e.g.
  • C 1 -C 6 alkoxy such as methyloxy, ethyloxy, propyloxy, 1-methylethyloxy, butyloxy, 1-methylpropyloxy, 2-methylpropyloxy, 1,1-dimethylethyloxy, pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy,
  • Haloalkoxy straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms, in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, and where these groups are bonded to the skeleton via an oxygen atom;
  • Alkylthio straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via a sulfur atom (-S-), e.g.
  • C 1 -C 6 alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2 2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio,
  • Cycloalkyl monocyclic alkyl groups with 3 to 6 carbon ring members, e.g. Cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
  • Alkenyl straight-chain or branched alkenyl groups with 2 to 6 or 10 carbon atoms and a double bond in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,
  • Alkenyloxy straight-chain or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in any position, which are bonded to the skeleton via an oxygen atom (-O-);
  • Alkynyl straight-chain or branched alkynyl groups with 2 to 10 carbon atoms and a triple bond in any position, for example C 2 -C 6 -alkynyl such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2- Pentinyl,
  • Heterocyclyl or heterocyclyloxy ; three- to six-membered, saturated or partially unsaturated mono- or polycyclic heterocycles, which contain one to three heteroatoms selected from a group consisting of oxygen, nitrogen and sulfur, and which are directly or (heterocyclyloxy) bonded to the skeleton via an oxygen atom are, such as 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazoldinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiaziazolidinyl, 4-isothiaziazolidinyl, 4 3-pyrazolidinyl,
  • Oxygen and sulfur can contain: three- to twelve-membered saturated or partially or completely unsaturated, mono- or polycyclic systems, which, in addition to the nitrogen atom via which they are attached, and in addition to carbon ring members, one to five further heteroatoms from a group consisting of nitrogen, oxygen and may contain sulfur, and in the event that the cycle contains more than one oxygen and / or sulfur ring member, these oxygen or sulfur atoms are not in an adjacent position to one another, for example
  • aromatic mono- or polycyclic hydrocarbon radicals which directly or (aryloxy) via an oxygen atom (-O-) or (arylthio) a sulfur atom (-S-), (arylcarbonyl) via a carbonyl group (-CO-) or (arylsulfonyl) via a Sulfonyl group (-SO 2 -) are bound to the skeleton, for example phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals; Hetaryl or hetaryloxy. Hetarylthio, hetarylcarbonyl and
  • Hetarylsulfonyl aromatic mono- or polycyclic radicals which in addition to carbon ring members additionally one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one
  • 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or may contain an oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl,
  • 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and / or one oxygen or sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four sticks atoms of matter or one to three nitrogen atoms and a sulfur or oxygen atom or an oxygen or
  • 5-membered heteroaryl bound via nitrogen. containing one to four nitrogen atoms. or nitrogen-bonded condensed 5-membered heteroaryl. containing one to five nitrogen atoms: 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 can be bridged to form an aromatic or heteroaromatic bi or polycycle, these rings being bridged one of the nitrogen ring members is bound to the frame: e.g.
  • 6-ring heteroaryl groups which, in addition to carbon atoms, contain one to three or one to four nitrogen may contain atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazine -2-yl, 1,2,4-triazin-3-yl and
  • C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylamino, di-C 1 -C 6 alkylamino, C 1 -C 6 alkylaminocarbonyl, Di-C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 alkylaminothiocarbonyl, di-C 1 -C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy or C ( NOR a ) -A n -R b ;
  • Hetaryl, hetaryloxy and hetarylthio where the cyclic groups can in turn be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C 1 -C 6 -Alkyl,
  • C 1 -C 6 haloalkyl C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylsulfoxyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl,
  • Oxy-C 1 -C 4 alkyleneoxy, the alkylene chains being partial or full can be constantly halogenated and / or one to three
  • C 1 -C 3 alkyl groups can carry.
  • substituted by conventional groups is intended to express that the radicals in question can be partially or completely halogenated and / or can carry one to three of the following substituents: cyano, nitro, C 1 -C 4 alkyl,
  • C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, phenyl, phenoxy, benzyl and benzyloxy, and / or a group C ( NOR a ) -A n -R b can carry.
  • R 1 is methyl.
  • R 3 is hydrogen, hydroxy, cyano, cyclopropyl, chlorine, methyl, ethyl,
  • compounds I are preferred in which R 3 is methoxy. In addition, compounds I are preferred in which R 3 is cyano.
  • R 3 represents chlorine.
  • R 3 represents methylthio.
  • R 4 is C 1 -C 6 alkyl.
  • R 4 represents methyl or ethyl.
  • R 4 represents aryloxyalkyl or hetaryloxyalkyl.
  • R 4 represents arylalkyl or heteroarylalkyl.
  • R 4 represents aryl or hetaryl.
  • R 4 is C 2 -C 6 alkenyl
  • the compounds I are suitable as fungicides.
  • the compounds I are notable for excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidiomycetes. Some of them are systemically effective and can be used as foliar and soil fungicides. They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetable plants such as cucumbers, beans and pumpkin family, as well as on the seeds of these plants.
  • crops such as wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetable plants such as cucumbers, beans and Pumpkin family, as well as on the seeds of these plants.
  • Erysiphe graminis in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species and Rhizoctonia Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species
  • Cereals Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and various plants , Plasmopara viticola on vines, Alternaria species
  • 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. It is used before or after the infection of the materials, plants or seeds by the fungi.
  • auxiliary agents come there The following are essentially considered: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g.
  • Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
  • Carriers such as natural stone powder (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates)
  • Emulsifiers such as non-ionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
  • the fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient. Depending on the type of effect desired, the application rates are between 0.01 and 2.0 kg of active ingredient per ha.
  • active ingredient 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
  • 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 with fertilizers are Fungicides or with fertilizers.
  • Sulfur, dithiocarbamates and their derivatives such as iron, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediamine bisdithiocarbamate min, Tetramethylthiuramdisulfide, ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate), ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis (thiocarbamoyl) disulfide;
  • Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-iso-propyl carbonate, 5-nitro -iso-phthalic acid di-iso-propyl ester; heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate,
  • Strobilurins such as methyl-E-methoximino- [ ⁇ - (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- ⁇ 2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl ⁇ - 3-methoxyacrylate, methyl-E-methoximino- [ ⁇ - (2-phenoxyphenyl)] acetamide, methyl-E-methoximino- [ ⁇ - (2,5-dimethylphenoxy) -o-tolyl] acetamide.
  • Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl-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. (2RS, 3SR) -1- [3- (2-chlorophenyl) -2- [4-fluorophenyl] oxiran-2-ylmethyl] -1H-1,2,4-triazole.
  • the compounds of the formula I are also suitable for effectively controlling pests from the class of the insects, arachnids and nematodes. You can in crop protection as well as on the
  • Hygiene storage protection and veterinary sector are used as pesticides.
  • the harmful insects from the order of the butterflies include, for example, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobisturaumumone, Cheimatobisturaumumone Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus,
  • Galleria mellonella Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,
  • brasiliensis Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus,
  • Leptinotarsa decemlineata Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,
  • Diptera From the order of the two-winged species (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropucitae, Cordylobia anthropucaga, brassylaciaacropucita, brassylaciaacropucita, brassylaciaacropucita, brassylaciaacropacea, brassylaciaacropaceacita, brassylaciaacropia , Fannia canicularis, Gasterophilus intestinalis,
  • Muscina stabulans Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa. From the order of the thrips (Thysanoptera) for example
  • Hoplocampa minuta Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.
  • Bugs Heteroptera
  • Acrosternum hilare Blissus leucopterus
  • Cyrtopeltis notatus From the order of the bugs (Heteroptera), for example Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps,
  • suckers for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypy, Dreianafiaisolumiaia, Dreianafusiaolaia, Dreianafusiaolaia, Dreyfusiaolaia Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida
  • Arachnoid for example, arachnids
  • Acarina such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyinommobusuncus, Iinoblus, I megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychuschusus, Tetranychuschuschusch.
  • Carina such as Amblyomma americanum, Am
  • root gall nematodes e.g. Meloidogyne hapla, Meloidogyne incognita
  • 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, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring can be used.
  • the application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Preparations can be varied in larger areas.
  • active ingredients 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
  • the application rate of active ingredient for controlling pests is 0.1 to 2.0, preferably 0.2 to 1.0 kg / ha under field conditions.
  • emulsions, pastes or old dispersions mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • Solvents e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water.
  • Aqueous application forms can be made from emulsion concentrates, pastes or wettable powders (wettable powders, old dispersions)
  • Water can be added.
  • 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.
  • Dispersants or emulsifiers and possibly solvents or oil existing concentrates are prepared which are suitable for dilution with water.
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • 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).
  • Castor oil consists (active ingredient content 9% by weight).
  • V. 80 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalenalphasulfonic 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 and in milled in a hammer mill (active ingredient content 80% by weight).
  • VIII.20 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene- ⁇ -sulfonic acid, 17 parts by weight of the sodium salt of lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and in one
  • 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, silicates, 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,
  • Mineral soils such as silica gel, silicas, silicates, talc, kaolin, attack clay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers
  • 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.
  • Example 7 Preparation of (Z, E, E) -2-methoxyimino-2- ⁇ 2 '- [(1 "-methyl, 1" - (1 "' - (1" "- piperidinyl), 1" '- methoxyiminomethyl)) - iminooxymethyl] phenyl ⁇ - methyl acetate (Example 1.002)
  • Dimethylformamide was first mixed with 2.0 g (5 mmol) of the compound from Example 4 and then with 4.3 g (50 mmol) of piperidine. After 60 h at room temperature (approx. 25 ° C), the reaction mixture was poured onto cooled, dilute hydrochloric acid. The product was tert with from the mixture thus obtained. -Butyl methyl ether extracted. After washing with water, drying and removing the solvent, 0.8 g (40%) of the title compound was obtained as a colorless oil from the ether phase.
  • the active ingredients were administered as a 20% 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.
  • % Emulphor® EL Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) prepared and diluted with water according to the desired concentration.
  • Tritici wheat flour dew
  • Leaves of wheat seedlings ("early gold” variety) were first treated with the aqueous preparation of the active ingredients (application rate: 63 ppm). After about 24 hours, the plants were dusted with spores of powdery mildew (Erysiphe graminis var. Tritici). The plants treated in this way were then incubated for 7 days at 20-22 ° C. and a relative atmospheric humidity of 75-80%. The extent of fungal development was then determined.
  • the no. 1,007, 1,011, 1,012, 1,014 and 1,016 treated plants had an infection of 15% and less, while the plants treated with the known active ingredients A. and B were 40% infected. The untreated (control) plants were 70% infected.
  • % Emulphor® EL Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) prepared and diluted with acetone in the case of a) or with water in the case of b) according to the desired concentration. After the end of the tests, the lowest concentration was determined at which the compounds still caused 80-100% inhibition or mortality compared to control tests (without treatment) (threshold of action or minimum concentration).

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Abstract

The invention concerns phenylacetic acids of formula (I) in which the substituents and the index have the following meanings: X is NOCH3, CHOCH3, CHCH3 and CHCH2CH3; Y = O and NR (R = hydrogen and alkyl); Z is an optionally substituted nitrogen atom-bonded heterocyclyl or heteroaryl; R1 = hydrogen and alkyl; R2 = cyano, nitro, trifluoromethyl, halogen, alkyl and alkoxy; m = 0, 1 or 2; R3 = hydrogen, cyano, nitro, hydroxy, amino, cyclopropyl, halogen, alkyl, alkyl halide, alkoxy, alkoxy halide, alkylthio, alkylamino and dialkylamino; R4 = hydrogen, optionally substituted alkyl, alkenyl, alkinyl, alkylcarbonyl, alkenylcarbonyl, alkinylcarbonyl, alkylsulphonyl, cycloalkyl, aryl, arylcarbonyl, arylsulphonyl, hetaryl, hetarylcarbonyl and hetarylsulphonyl. The invention further concerns salts thereof, processes for their preparation and agents containing them.

Description

Phenylessigsäuren, Verfahren zu ihrer Herstellung und sie enthaltende Mittel Beschreibung  Phenylacetic acids, process for their preparation and compositions containing them Description
Die vorliegende Erfindung betrifft Phenylessigsäuren der Formel I The present invention relates to phenylacetic acids of the formula I.
Figure imgf000003_0001
in der die Substituenten und der Index die folgende Bedeutung haben: X NOCH3, CHOCH3, CHCH3 und CHCH2CH3 ;
Figure imgf000003_0001
in which the substituents and the index have the following meaning: X NOCH 3 , CHOCH 3 , CHCH 3 and CHCH 2 CH 3 ;
Y O und NR; Y O and NR;
R Wasserstoff und C1-C4-Alkyl; R is hydrogen and C 1 -C 4 alkyl;
Z ein ggf. subst. über ein Stickstoffatom gebundener gesättigter oder partiell oder vollständig ungesättigter cyclischer Rest, welcher neben dem Stickstoffatom, über den er gebunden ist, neben Kohlenstoff-Ringliedern ein bis vier Heteroatome aus der Gruppe Stickstoff, Sauerstoff und Schwefel enthalten kann; Z a possibly subst. a saturated or partially or completely unsaturated cyclic radical bonded via a nitrogen atom, which, in addition to the nitrogen atom via which it is bonded, can contain, in addition to carbon ring members, one to four heteroatoms from the group consisting of nitrogen, oxygen and sulfur;
R1 Wasserstoff und C1-C4-Alkyl; R2 Cyano, Nitro, Trif luormethyl, Halogen, C1-C4-Alkyl und R 1 is hydrogen and C 1 -C 4 alkyl; R 2 cyano, nitro, trif luormethyl, halogen, C 1 -C 4 alkyl and
C1-C4-Alkoxy; m 0, 1 oder 2, wobei die Reste R2 verschieden sein können, wenn m für 2 steht; C 1 -C 4 alkoxy; m is 0, 1 or 2, it being possible for the radicals R 2 to be different if m is 2;
R3 Wasserstoff, Cyano, Nitro, Hydroxy, Amino, Cyclopropyl, R 3 is hydrogen, cyano, nitro, hydroxy, amino, cyclopropyl,
Halogen, C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy, Halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy,
C1-C4-Halogenalkoxy, C1-C4-Alkylthio, C1-C4-Alkylamino und Di-C1-C4-alkylamino; C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino and di-C 1 -C 4 alkylamino;
R4 Wasserstoff, C1-C10-Alkyl, C2-C10-Alkenyl, C2-C10-Alkinyl, C1-C10-Alkylcarbonyl, C2-C10-Alkenylcarbonyl, C2-C10-Alkinylcarbonyl oder C1-C10-Alkylsulfonyl, wobei diese Reste partiell oder vollständig halogeniert sein können oder eine bis drei der folgenden Gruppen tragen können: R 4 is hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkylcarbonyl, C 2 -C 10 alkenylcarbonyl, C 2 -C 10 alkynylcarbonyl or C 1 -C 10 alkylsulfonyl, where these radicals can be partially or completely halogenated or can carry one to three of the following groups:
- Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, - cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl,
- Halogen, C1-C6-Halogenalkyl, C1-C6-Alkylsulfonyl, Halogen, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl,
C1-C6-Alkylsulfoxyl, C1-C6-Alkoxy, C1-C6-Halogenalkoxy, C1-C6-Alkoxycarbonyl, C1-C6-Alkylthio, C1-C6-Alkylamino, Di-C1-C6-alkylamino, C1-C6-Alkylaminocarbonyl, C 1 -C 6 alkylsulfoxyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylamino, di- C 1 -C 6 alkylamino, C 1 -C 6 alkylaminocarbonyl,
Di-C1-C6-alkylaminocarbonyl, C1-C6-Alkylaminothiocarbonyl, Di-C1-C6-alkylaminothiocarbonyl, C2-C6-Alkenyloxy, Di-C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 alkylaminothiocarbonyl, di-C 1 -C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyloxy,
- C3-C6-Cycloalkyl, C3-C6-Cycloalkoxy, Heterocyclyl, Heterocyclyloxy, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl,C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkoxy, heterocyclyl, heterocyclyloxy, benzyloxy, aryl, aryloxy, arylthio, hetaryl,
Hetaryloxy und Hetarylthio, wobei die cyclischen Gruppen ihrerseits partiell oder vollständig halogeniert sein können oder eine bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, C1-C6-Alkyl,Hetaryloxy and hetarylthio, where the cyclic groups can in turn be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C 1 -C 6 alkyl ,
C3-C6-Cycloalkyl, C1-C6-Halogenalkyl, C1-C6-Alkylsulfonyl, C1-C6-Alkylsulfoxyl, C1-C6-Alkoxy, C1-C6-Halogenalkoxy, C1-C6-Alkoxycarbonyl, C1-C6-Alkylthio, C1-C6-Alkylamino, Di-C1-C6-alkylamino, C1-C6-Alkylaminocarbonyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylsulfoxyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylthio, C 1 -C 6 -alkylamino, di-C 1 -C 6 -alkylamino, C 1 -C 6 -alkylaminocarbonyl,
Di-C1-C6-alkylaminocarbonyl, C1-C6-Alkylaminothiocarbonyl,Di-C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 alkylaminothiocarbonyl,
Di-C1-C6-alkylaminothiocarbonyl, C2-C6-Alkenyl, Di-C 1 -C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyl,
C2-C6-Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy, Hetarylthio und C 2 -C 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and
C(=NORa)-An-Rb; C (= NOR a ) -A n -R b ;
C3-C6-Cycloalkyl, Aryl, Arylcarbonyl, Arylsulfonyl, Hetaryl, Hetarylcarbonyl und Hetarylsulfonyl, wobei diese Reste partiell oder vollständig halogeniert sein können oder eine bis drei der folgenden Gruppen tragen können: C 3 -C 6 cycloalkyl, aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl and hetarylsulfonyl, where these radicals can be partially or completely halogenated or can carry one to three of the following groups:
- Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, - cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl,
- Halogen, C1-C6-Alkyl, C3-C6 -Cycloalkyl, C1-C6-Halogenalkyl, C1-C6-Alkylcarbonyl, C1-C6-Alkylsulfonyl, Halogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfonyl,
C1-C6-Alkylsulfoxyl, C1-C6-Alkoxy, C1-C6-Halogenalkoxy, C1-C6-Alkoxycarbonyl, C1-C6-Alkylthio, C1-C6-Alkylamino,C 1 -C 6 alkylsulfoxyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylamino,
Di-C1-C6-alkylamino, C1-C6-Alkylaminocarbonyl, Di-C 1 -C 6 alkylamino, C 1 -C 6 alkylaminocarbonyl,
Di-C1-C6-alkylaminocarbonyl, C1-C6-Alkylaminothiocarbonyl, Di-C1-C6-alkylaminothiocarbonyl, C2-C6-Alkenyl, Di-C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 alkylaminothiocarbonyl, di-C 1 -C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyl,
C2-C6-Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, C 2 -C 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy,
Hetaryl, Hetaryloxy und C (=NORa) -An-Rb; wobei Hetaryl, hetaryloxy and C (= NOR a ) -A n -R b ; in which
A für Sauerstoff, Schwefel und Stickstoff steht und wobei der Stickstoff Wasserstoff oder C1-C6-Alkyl trägt; n 0 oder 1 bedeutet, und A represents oxygen, sulfur and nitrogen and the nitrogen carries hydrogen or C 1 -C 6 alkyl; n represents 0 or 1, and
Ra, Rb jeweils für Wasserstoff oder C1-C6-Alkyl stehen, sowie deren Salze. R a , R b each represent hydrogen or C 1 -C 6 alkyl, and their salts.
Außerdem betrifft die Erfindung Verfahren und Zwischenprodukte zur Herstellung dieser Verbindungen sowie sie enthaltende Mittel zur Bekämpfung von tierischen Schädlingen und Schadpilzen. In addition, the invention relates to processes and intermediates for the preparation of these compounds and compositions containing them for controlling animal pests and harmful fungi.
Aus der Literatur sind Phenylessigsäurederivate zur Bekämpfung von tierischen Schädlingen und Schadpilzen bekannt (EP-A 422 597, EP-A 463 488, EP-A 370 629, EP-A 460 575, EP-A 472 300, WO-A 90/07,493, WO-A 92/13,830, WO-A 92/18,487). Außerdem werden in den älteren Deutschen Patentanmeldungen P 44 03 447.4 und P 44 03 448.2 Phenylessigsäurederivate mit Bis-Oxim Seitenketten mit Wirkung gegen tierische Schädlinge und Schadpilze beschrieben. Phenylacetic acid derivatives for controlling animal pests and harmful fungi are known from the literature (EP-A 422 597, EP-A 463 488, EP-A 370 629, EP-A 460 575, EP-A 472 300, WO-A 90 / 07,493 , WO-A 92 / 13,830, WO-A 92 / 18,487). In addition, the older German patent applications P 44 03 447.4 and P 44 03 448.2 describe phenylacetic acid derivatives with bis-oxime side chains with action against animal pests and harmful fungi.
Demgegenüber lagen der vorliegenden Erfindung Verbindungen mit verbesserter Wirkung als Aufgabe zugrunde. In contrast, the present invention was based on compounds with improved activity as an object.
Demgemäß wurden die eingangs definierten Phenylessigsäuren I gefunden. Außerdem wurden Verfahren und Zwischenprodukte zu ihrer Herstellung sowie sie enthaltende Mittel zur Bekämpfung von tierischen Schädlingen und Schadpilzen gefunden. We have found that this object is achieved by the phenylacetic acids I defined at the outset. In addition, processes and intermediates for their preparation and agents containing them for controlling animal pests and harmful fungi were found.
Die Verbindungen I sind auf verschiedenen Wegen nach an sich in der Literatur bekannten Verfahren erhältlich. Grundsätzlich ist es bei der Synthese der Verbindungen I unerheblich, ob zunächst die Gruppierung -C(=X)-COYR1 oder die Gruppe -CH2ON=CR3-C(Z) =NOR4 aufgebaut wird. Die verschiedenen Methoden zum Aufbau der C(=X) -CGYR1-Gruppierung (in den nachfolgenden Formeln z.T. mit dem Zeichen # verkürzt dargestellt) sind beispielsweise aus der eingangs zitierten Literatur bekannt. The compounds I can be obtained in various ways by processes known per se in the literature. Basically, it is irrelevant in the synthesis of the compounds I whether the grouping -C (= X) -COYR 1 or the group -CH 2 ON = CR 3 -C (Z) = NOR 4 is built up first. The various methods for building up the C (= X) -CGYR 1 grouping (sometimes abbreviated with the character # in the formulas below) are known, for example, from the literature cited at the beginning.
Die Art der Synthese der -CH2ON=CR3-C(Z)=NOR4 Seitenkette richtet sich im wesentlichen nach der Art des Substituenten R3. The type of synthesis of the -CH 2 ON = CR 3 -C (Z) = NOR 4 side chain depends essentially on the type of the substituent R 3 .
1. Für den Fall, daß R3 nicht Halogen bedeutet, geht man beim Aufbau der Gruppe -CH2ON=CR3-C(Z)=NOR4 im allgemeinen so vor, daß man ein Benzylderivat der Formel II mit einem Hydroxyimin der Formel III umsetzt.
Figure imgf000006_0001
1. In the event that R 3 is not halogen, the procedure for building the group -CH 2 ON = CR 3 -C (Z) = NOR 4 is generally such that a benzyl derivative of the formula II with a hydroxyimine Formula III implements.
Figure imgf000006_0001
L1 in der Formel II steht für eine nucleophil austauschbare L 1 in formula II stands for a nucleophilically interchangeable
Abgangsgruppe, z.B. Halogen oder Sulfonatgruppen, vorzugsweise Chlor, Brom, Iod, Mesylat, Tosylat und Triflat. Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel in Gegenwart einer Base (z.B. Natriumhydrid, Kaliumhydroxid, Kaliumcarbonat und Triethylamin) gemäß den in Houben-Weyl, Bd. E 14b, S. 370f und Houben-Weyl, Bd. 10/1, S. 1189f beschriebenen Methoden. Leaving group, e.g. Halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate and triflate. The reaction takes place in a manner known per se in an inert organic solvent in the presence of a base (for example sodium hydride, potassium hydroxide, potassium carbonate and triethylamine) in accordance with the methods described in Houben-Weyl, Vol. E 14b, p. 370f and Houben-Weyl, Vol. 10 / 1, p. 1189f described methods.
Das benötigte Hydroxyimin III erhält man beispielsweise durch Umsetzung eines entsprechenden Dihydroxyimins lila mit einem nucleophil substituierten Reagens V. The required hydroxyimine III is obtained, for example, by reacting a corresponding purple dihydroxyimine with a nucleophilically substituted reagent V.
Figure imgf000006_0002
Figure imgf000006_0002
L2 in der Formel V steht für eine nucleophil austauschbare L 2 in formula V stands for a nucleophilically interchangeable
Abgangsgruppe, z.B. Halogen oder Sulfonatgruppen, vorzugsweise Chlor, Brom, Iod, Mesylat, Tosylat und Triflat. Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel in Gegenwart einer Base (z.B. Kaliumcarbonat, Kaliumhydroxid, Natriumhydrid, Pyridin und Triethylamin) gemäß den in Houben-Weyl, Bd. E 14b, S. 307f, S. 370f und S. 385f; Houben-Weyl, Bd. 10/4, S. 55f, S. 180f und S. 217f; Houben-Weyl, Bd. E 5, S. 780f beschriebenen Methoden. Leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate and triflate. The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (for example potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine) in accordance with the methods described in Houben-Weyl, vol. E 14b, p. 307f, p. 370f and p . 385f; Houben-Weyl, Vol. 10/4, p. 55f, p. 180f and p. 217f; Houben-Weyl, vol. E 5, p. 780f.
Nach einem weiteren Verfahren können die Verbindungen III auch dadurch erhalten werden, daß man zunächst das Carbonylhydroxyimin IIIb mit dem Schwefelungsreagens in das entsprechende Thiocarbonylhydroxyimin IIIc überführt und IIIc anschließend entweder a) zunächst mit Hydroxylamin oder dessen Salz und danach mit einer Verbindung der Formel V oder According to a further process, the compounds III can also be obtained by first converting the carbonylhydroxyimine IIIb with the sulfurization reagent into the corresponding thiocarbonylhydroxyimine IIIc and then IIIc either a) first with hydroxylamine or its salt and then with a compound of the formula V or
b) mit einem Hydroxylamin oder einem Hydroxylammoniumsalz der Formel VIIa bzw. Vllb b) with a hydroxylamine or a hydroxylammonium salt of the formula VIIa or VIIIb
zu III umsetzt.
Figure imgf000007_0002
Figure imgf000007_0001
Q- in der Formel Vllb bedeutet das Anion einer anorganischen Säure (insbesondere ein Halogenid wie Chlorid). to III.
Figure imgf000007_0002
Figure imgf000007_0001
Q- in the formula VIIIb means the anion of an inorganic acid (in particular a halide such as chloride).
Weiterhin können die Verbindungen III wie in den Synthesebeispielen 9 und 10 gezeigt erhalten werden. Furthermore, the compounds III can be obtained as shown in Synthesis Examples 9 and 10.
Die Umsetzung von IIIb nach IIIc erfolgt in an sich bekannter Weise [vgl. Bull Soc. Chim. Belg. 87, 293 (1978)] bei Temperaturen von 10°C bis 150°C, vorzugsweise 20°C bis 120°C in einem inerten organischen Lösungsmittel. The conversion from IIIb to IIIc takes place in a manner known per se [cf. Bull Soc. Chim. Belg. 87, 293 (1978)] at temperatures from 10 ° C to 150 ° C, preferably 20 ° C to 120 ° C in an inert organic solvent.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert. -Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, besonders bevorzugt Dioxan, Toluol und Xylol. Es können auch Gemische der genannten Lösungsmittel verwendet werden. 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, particularly preferably dioxane, toluene and xylene. Mixtures of the solvents mentioned can also be used.
Als Schwefelungsreagentien finden beispielsweise P4S10 oder das Lawesson-Reagens [2,4-Bis-(4-methoxyphenyl)-1,3-dithia-2,4-di- phosphetan-2,4-disulfid] Verwendung. P 4 S 10 or the Lawesson reagent [2,4-bis- (4-methoxyphenyl) -1,3-dithia-2,4-di-phosphetane-2,4-disulfide] are used as sulfurization reagents, for example.
Die Oximierung von IIIc mit Vlla bzw. Vllb erfolgt in an sich bekannter Weise [vgl. J. Heterocycl. Chem. 17, 819 (1980); Houben- Weyl Bd. VIII, S. 694f] in einem inerten organischen Lösungsmittel. The oximation of IIIc with Vlla or Vllb takes place in a manner known per se [cf. J. Heterocycl. Chem. 17: 819 (1980); Houben-Weyl Vol. VIII, pp. 694f] in an inert organic solvent.
1.1 Alternativ können die Verbindungen I auch dadurch erhalten werden, daß man das Benzylderivat II zunächst mit einem Dihydroxyimin IIIa in ein entsprechendes Benzyloxim IVa überführt und IVa anschließend mit dem nucleophil substituierten 1.1 Alternatively, the compounds I can also be obtained by first converting the benzyl derivative II with a dihydroxyimine IIIa into a corresponding benzyloxime IVa and then IVa with the nucleophilic substitution
Reagens V zu I umsetzt.  Reagent V converts to I.
Figure imgf000008_0001
Figure imgf000008_0001
Figure imgf000008_0002
Figure imgf000008_0002
Figure imgf000008_0003
Figure imgf000008_0003
Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel in Gegenwart einer Base (z.B. Kaliumcarbonat, Kaliumhydroxid, Natriumhydrid, Pyridin und Triethylamin) gemäß den in Houben-Weyl, Bd. 10/1, S. 1189f;The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (e.g. potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine) according to the methods described in Houben-Weyl, Vol. 10/1, p. 1189f;
Houben-Weyl, Bd. E 14b, S. 307f, S. 370f und S. 385f; Houben- Weyl, Bd. 10/4, S. 55f, S. 180f und S. 217f; Houben-Weyl, Bd. E 5, S. 780f beschriebenen Methoden. Houben-Weyl, vol. E 14b, p. 307f, p. 370f and p. 385f; Houben Weyl, vol. 10/4, p. 55f, p. 180f and p. 217f; Houben-Weyl, vol. E 5, p. 780f.
1.2 In entsprechender Weise können die Verbindungen I auch da durch erhal ten werden , daß man das Benzylderivat II zunächst mit einem Carbonylhydroxyimin IIIb in das entsprechende Benzyloxyimin VIa überführt, VIa anschließend mit einem Schwefelungsreagens in die Thioverbindung VIb überführt und VIb entweder a) zunächst mit Hydroxylamin oder dessen Salz und danach mit einer Verbindung der Formel V oder 1.2 Correspondingly, the compounds I can also be obtained by first converting the benzyl derivative II with a carbonylhydroxyimine IIIb into the corresponding benzyloxyimine VIa, VIa then converting the thio compound VIb with a sulfurization reagent and VIb either a) initially with hydroxylamine or its salt and then with a compound of formula V or
b) mit einem Hydroxylamin oder einem Hydroxylammoniumsalz der Formel Vlla bzw. Vllb  b) with a hydroxylamine or a hydroxylammonium salt of the formula VIII or VIIIb
zu I umsetzt. converts to I.
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0003
Figure imgf000010_0003
Die Umsetzung des Benzylderivats II mit dem Carbonylhydroxyimin IIIb erfolgt im wie im allgemeinen und im besonderen für die Umsetzung von II mit III beschrieben. Die Schwefelungsreaktion und die Oximierung zu I erfolgen im allgemeinen und im besonderen unter den vorstehend beschriebenen Bedingungen. Die Verbindungen VIa sind beispielsweise auch dadurch erhältlich, daß man eine Carbonsäure VIc in an sich bekannter Weise [HouibenWeyl , Bd . E5, S . 941f] mit einem Stickstoff-haltigen Heterocyclus IX umsetzt.
Figure imgf000011_0001
The reaction of the benzyl derivative II with the carbonylhydroxyimine IIIb is carried out as described in general and in particular for the reaction of II with III. The sulfurization reaction and the oximation to I take place in general and in particular under the conditions described above. The compounds VIa can also be obtained, for example, by a carboxylic acid VIc in a manner known per se [HouibenWeyl, Vol. E5, p. 941f] with a nitrogen-containing heterocycle IX.
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0002
Die Umsetzung erfolgt in der Regel bei Temperaturen von -20°C bis 100°C, vorzugsweise -10°C bis 50°C, in einem inerten organischen Lösungsmittel bevorzugt in Gegenwart eines Aktivierungsreagens (z.B. Phosgen, Thionylchlorid, Oxalylchlorid, N,N-Carbonyldiimidazol und Triphenylphosphin/CCl4). 1.3 Eine weitere Möglichkeit zur Herstellung der Verbindungen I ist die Umsetzung des Benzylderivats II mit N-Hydroxyphthalimid und nachfolgender Hydrazinolyse zum Benzylhydroxylamin Ha und die weitere Umsetzung von Ha mit einer Carbonylverbindung Villa. The reaction is usually carried out at temperatures from -20 ° C to 100 ° C, preferably -10 ° C to 50 ° C, in an inert organic solvent, preferably in the presence of an activation reagent (eg phosgene, thionyl chloride, oxalyl chloride, N, N- Carbonyldiimidazole and triphenylphosphine / CCl 4 ). 1.3 Another possibility for the preparation of the compounds I is the reaction of the benzyl derivative II with N-hydroxyphthalimide and subsequent hydrazinolysis to give the benzylhydroxylamine Ha and the further reaction of Ha with a carbonyl compound Villa.
Figure imgf000012_0001
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0002
Die Umsetzung erfolgt in an sich bekannter Weise in einem inerten organischen Lösungsmittel gemäß den in EP-A 463 488 und The reaction is carried out in a manner known per se in an inert organic solvent according to that in EP-A 463 488 and
EP-A 585 751 beschriebenen Methoden. Methods described in EP-A 585 751.
Die benötigten Carbonylverbindungen Villa erhält man beispielsweise durch Umsetzung der entsprechenden Hydroxyiminocarbonylverbindungen VIIIb mit einem nucleophil substituierten Reagens V. The required carbonyl compounds Villa are obtained, for example, by reacting the corresponding hydroxyiminocarbonyl compounds VIIIb with a nucleophilically substituted reagent V.
Figure imgf000012_0003
Die Verbindungen VIIIb können dadurch erhalten werden, daß man ein Hydroxamsäurechlorid VIIId in an sich bekannter Weise [vgl.
Figure imgf000012_0003
The compounds VIIIb can be obtained by reacting a hydroxamic acid VIIId in a manner known per se [cf.
J. Heterocycl. Chem. 21, 1029 (1984); Coll, Czech. Chem. Comm.J. Heterocycl. Chem. 21, 1029 (1984); Coll, Czech. Chem. Comm.
41, 3085 (1976)] mit einem Stickstoffhaltigen Heterocyclus (IX) umsetzt. 41, 3085 (1976)] with a nitrogen-containing heterocycle (IX).
Figure imgf000013_0001
Figure imgf000013_0001
1.4 Entsprechend können die Verbindungen I auch dadurch erhalten werden, daß man das Benzylhydroxylamin Ha zunächst mit dem Hydroxyiminoderivat VIIIb in das entsprechende Benzyloxyiminoderivat der Formel IVa überführt und IVa anschließend mit dem nucleophil substituierten Reagens V wie vorstehend beschrieben zu I umsetzt. 1.4 Correspondingly, the compounds I can also be obtained by first converting the benzylhydroxylamine Ha with the hydroxyimino derivative VIIIb into the corresponding benzyloxyimino derivative of the formula IVa and then reacting IVa to I with the nucleophilically substituted reagent V as described above.
Figure imgf000014_0001
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0002
Figure imgf000014_0003
Figure imgf000014_0004
1.5 Analog können die Verbindungen I auch dadurch erhalten
Figure imgf000014_0003
Figure imgf000014_0004
1.5 Analogously, the compounds I can also obtain
werden, daß das Benzylhydroxylamin der Formel Ha zunächst mit einem α-Dicarbonyl VIIIc in das Benzyloxyiminoderivat VIa überführt wird und VIa anschließend wie vorstehend beschrieben zu I umgesetzt wird.
Figure imgf000015_0001
be that the benzylhydroxylamine of the formula Ha is first converted into the benzyloxyimino derivative VIa with an α-dicarbonyl VIIIc and then VIa is converted to I as described above.
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000015_0002
Figure imgf000015_0003
Figure imgf000015_0003
Figure imgf000015_0004
Figure imgf000015_0004
1.6 Nach einem weiteren Verfahren können die Verbindungen I auch dadurch erhalten werden, daß man das Benzylhydroxylamin IIa zunächst mit dem Hydroxamsäurechlorid VIIId in die entsprechende Verbindung IVb überführt und IVb anschließend zunächst mit IX in IVa und IVa dann in I überführt.
Figure imgf000016_0001
1.6 According to a further process, the compounds I can also be obtained by first converting the benzylhydroxylamine IIa with the hydroxamic acid chloride VIIId into the corresponding compound IVb and then IVb first with IX in IVa and IVa then in I.
Figure imgf000016_0001
Figure imgf000016_0002
Figure imgf000016_0002
Figure imgf000016_0003
Figure imgf000016_0004
1.7 Eine weitere Möglichkeit zur Herstellung der Verbindungen I besteht darin, daß man das Benzylhydroxylamin IIa mit einer α-Ketosäure VIIIe in die entsprechende Oximino-Carbonsäure VIc überführt, VIc durch Umsetzung mit Vlla bzw. Vllb in die entsprechende Hydroxamsäure IVc überführt, IVc zum Hydroxamsäurehalogenid IVd halogeniert und IVd mit IX zu I umsetzt.
Figure imgf000017_0001
Figure imgf000016_0003
Figure imgf000016_0004
1.7 A further possibility for the preparation of the compounds I consists in converting the benzylhydroxylamine IIa with an α-keto acid VIIIe into the corresponding oximino-carboxylic acid VIc, converting VIc into the corresponding hydroxamic acid IVc by reaction with Vlla or Vllb, IVc to the hydroxamic acid halide IVd halogenated and IVd reacted with IX to I.
Figure imgf000017_0001
Figure imgf000017_0002
Figure imgf000017_0002
Figure imgf000017_0003
Figure imgf000017_0003
Figure imgf000017_0004
Figure imgf000017_0004
Figure imgf000017_0005
Figure imgf000017_0005
1.8 Verbindungen, in denen R3 für ein Halogenatom steht, erhält man aus den entsprechenden Vorstufern, in denen der entsprechende Rest für eine Hydroxygruppe steht nach an sich bekannten Methoden [vgl. Houben-Weyl, Vol. E5, S. 631; J. Org. 1.8 Compounds in which R 3 represents a halogen atom are obtained from the corresponding precursors in which the corresponding radical represents a hydroxy group by methods known per se [cf. Houben-Weyl, Vol. E5, p. 631; J. Org.
Chem. 36, 233 (1971); J. Org. Chem. 57, 3245 (1992)] . Vorzugsweise werden die entsprechenden Umsetzungen zum Halogenderivat auf den Stufen I und VIa vorgenommen. 1.9 Verbindungen, in denen R3 über ein O-, S- oder N-Atom an das Molekülgerüst gebunden ist, erhält man aus den entsprechenden Vorstufern, in denen der entsprechende Rest für ein Halogenatom steht nach an sich bekannten Methoden [vgl. Houben-Weyl, Vol. E5, S. 826f. und S. 1280f.; J. Org. Chem. 36., 233 Chem. 36, 233 (1971); J. Org. Chem. 57, 3245 (1992)]. The corresponding reactions to the halogen derivative are preferably carried out at stages I and VIa. 1.9 Compounds in which R 3 is bonded to the molecular structure via an O, S or N atom are obtained from the corresponding precursors in which the corresponding radical represents a halogen atom by methods known per se [cf. Houben-Weyl, Vol. E5, pp. 826f. and p. 1280f .; J. Org. Chem. 36, 233
(1971); J. Org. Chem. 4£, 3623 (1981)]. Vorzugsweise werden die entsprechenden Umsetzungen zum Halogenderivat auf den Stufen I und VIa vorgenommen. 2. Verbindungen I, in denen R3 über ein Sauerstoffatom an das(1971); J. Org. Chem. 4 £, 3623 (1981)]. The corresponding reactions to the halogen derivative are preferably carried out at stages I and VIa. 2. Compounds I in which R 3 has an oxygen atom attached to the
Molekül gebunden sind, erhält man auch aus den entsprechenden Vorstufen, in denen der betreffende Rest für eine Hydroxygruppe steht nach an sich bekannten Verfahren [vgl. HoubenWeyl, Bd. E5, S.826f; Aust. J. Chem. 27, 1341 (1974)]. Vor- zugsweise werden die entsprechenden Umsetzungen zu den Alko- xyderivaten auf den Stufen I und VIa vorgenommen. Molecule-bound are also obtained from the corresponding precursors in which the radical in question represents a hydroxyl group by methods known per se [cf. HoubenWeyl, Vol. E5, pp.826f; Aust. J. Chem. 27, 1341 (1974)]. The corresponding reactions to the alkoxy derivatives are preferably carried out at stages I and VIa.
3. Verbindungen I, in denen R3 nicht Halogen bedeutet, erhält man bevorzugt dadurch, daß man eine Verbindung der Formel III gemäß den in EP-A 493 711 beschriebenen Methoden mit einem3. Compounds I in which R 3 is not halogen are preferably obtained by using a compound of the formula III according to the methods described in EP-A 493 711
Lacton X zunächst in die entsprechende Benzoesäure XIa überführt und XIa über das entsprechende Halogenid (XIb; Hai = Halogen) in die Cyanocarbonsäure XIc überführt, welche dann im Wege der Pinner-Reaktion [Angew. Chem. 94, 1 (1982)] in den α-Ketoester Xlla übergeführt wird [vgl. EP-A 348 766, EP-A 178 826, DE-A 37 05 389, DE-A 36 23 921] . Lactone X is first converted into the corresponding benzoic acid XIa and XIa is converted via the corresponding halide (XIb; Hai = halogen) into the cyanocarboxylic acid XIc, which is then converted by the Pinner reaction [Angew. Chem. 94, 1 (1982)] is converted into the α-ketoester Xlla [cf. EP-A 348 766, EP-A 178 826, DE-A 37 05 389, DE-A 36 23 921].
Figure imgf000019_0001
Figure imgf000019_0001
Figure imgf000019_0002
Figure imgf000019_0003
Figure imgf000019_0004
Figure imgf000019_0002
Figure imgf000019_0003
Figure imgf000019_0004
Figure imgf000019_0005
Figure imgf000019_0005
Die α-Ketoester XIIa beziehungsweise die entsprechenden α-Ketocarbonsäuren (R1 = Wasserstoff); erhältlich durch an sich bekannte Hydrolyse der Ester) stellen zentrale Zwischenprodukte zur Herstellung der verschiedenen Gruppierungen - C(=X)COYR1 dar. The α-keto esters XIIa or the corresponding α-ketocarboxylic acids (R 1 = hydrogen); obtainable by known hydrolysis of the esters) represent central intermediates for the preparation of the various groupings - C (= X) COYR 1 .
Beispielsweise können entsprechende α-Ketocarbonsäureamide XIIc durch Umsetzung der α-Ketocarbonsäuren XIIb bzw. der Ester XIIa erhalten werden [vgl. Houben-Weyl , Bd. E5, S. For example, corresponding α-ketocarboxamides XIIc can be obtained by reacting the α-ketocarboxylic acids XIIb or the esters XIIa [cf. Houben-Weyl, Vol. E5, p.
941f] . 4. In Abwandlung des vorstehend geschilderten Verfahrens können α-Ketocarbonsäureamide XIIc, in denen R für Wasserstoff steht, auch direkt aus den Carbonsäurehalogeniden XIb durch Umsetzung mit Isocyaniden XIII (R1-NC) erhalten werden [vgl. EP-A 547 825]. 941f]. 4. In a modification of the process described above, α-ketocarboxamides XIIc, in which R is hydrogen, can also be obtained directly from the carboxylic acid halides XIb by reaction with isocyanides XIII (R 1 -NC) [cf. EP-A 547 825].
Figure imgf000020_0002
Figure imgf000020_0001
Figure imgf000020_0002
Figure imgf000020_0001
5. In einer weiteren Variante erhält man Verbindungen XIIc 5. In a further variant, compounds XIIc are obtained
dadurch, daß man ortho-Halogenbenzylderivate Xld zunächst metalliert und die erhaltene Organo-Metallverbindung mit Oxalylchlorid in das entsprechende α-Ketocarbonsäurechlorid Xlld überführt, welches anschließend mit einem Amin in das entsprechende Amid XIIc überführt wird [ vgl . J. Org. Chem . 46. 212 (1981) ; DE-A 40 42 280; Houben-Weyl , Bd. E5 , S.  by first metalizing ortho-halogenobenzyl derivatives Xld and converting the organometallic compound obtained with oxalyl chloride to the corresponding α-ketocarboxylic acid chloride Xlld, which is then converted into the corresponding amide XIIc with an amine [cf. J. Org. Chem. 46: 212 (1981); DE-A 40 42 280; Houben-Weyl, Vol. E5, p.
972f] . 972f].
Figure imgf000021_0001
Figure imgf000021_0001
Figure imgf000021_0002
Figure imgf000021_0002
Figure imgf000021_0003
Figure imgf000021_0003
Die Umsetzung der α-Ketocarbonsäurederivate XII in die entsprechenden Verbindungen I sowie die Herstellung der  The implementation of the α-ketocarboxylic acid derivatives XII in the corresponding compounds I and the preparation of
Verbindungen II ist in der eingangs zitierten Literatur sowie in EP-A 585 751, EP-A 513 580, EP-A 477 631, EP-A 400 417, DE 37 05 389, EP-A 348 766, EP-A 251 082, EP-A 398 692, EP-A 178 826 und DE-A 36 23 921 beschrieben. Die Verbindungen I können bei der bei der Herstellung aufgrund ihrer C=C- und C=N-Doppelbindungen als E/Z-Isomerengemische anfallen, die z.B. durch Kristallisation oder Chromatographie in üblicher Weise in die Einzelverbindungen aufgetrennt werden können.  Compounds II is in the literature cited at the beginning and in EP-A 585 751, EP-A 513 580, EP-A 477 631, EP-A 400 417, DE 37 05 389, EP-A 348 766, EP-A 251 082 , EP-A 398 692, EP-A 178 826 and DE-A 36 23 921. The compounds I can be obtained as E / Z isomer mixtures in the preparation due to their C = C and C = N double bonds, which e.g. can be separated into the individual compounds by crystallization or chromatography in a conventional manner.
In Bezug auf die C=X-Doppelbindung werden hinsichtlich ihrer Wirksamkeit die E-Isomere der Verbindungen I bevorzugt (Konfiguration bezogen auf die CH3, CH2CH3 bzw. OCH3 Gruppe zur COYR1 Gruppe). With regard to the C = X double bond, the E isomers of the compounds I are preferred in terms of their activity (configuration based on the CH 3 , CH 2 CH 3 or OCH 3 group to form the COYR 1 group).
In Bezug auf die CH2ON=CR3-Doppelbindung werden hinsichtlich ihrer Wirksamkeit die cis-Isomere der Verbindungen I bevorzugt (Konfiguration bezogen auf die Reste R3 im Verhältnis zur OCH2-Grup- pierung). Die Konfiguration der C(Z) NOR4-Doppelbindung hat im allgemeinen nur einen unwesentlichen Einfluß auf die biologische Wirksamkeit der Verbindungen I. In Fällen, in denen ein Einfluß feststellbar ist, kommt üblicherweise den cis-Isomeren (Konfiguration bezogen auf die Reste OR4 im Verhältnis zur Z-Gruppierung) eine größere Bedeutung zu. With regard to the CH 2 ON = CR 3 double bond, the cis isomers of the compounds I are preferred in terms of their activity (configuration based on the radicals R 3 in relation to the OCH 2 grouping). The configuration of the C (Z) NOR 4 double bond generally has only an insignificant influence on the biological activity of the compounds I. In cases in which an influence can be determined, the cis isomers (configuration based on the residues OR 4 in relation to the Z grouping).
Sofern bei der Synthese Isomerengemische gebildet werden, ist die Trennung in die Einzelverbindungen im allgemeinen jedoch nicht unbedingt erforderlich, da sich die einzelnen Isomere teilweise während der Aufbereitung für die Anwendung oder bei der Anwendung (z.B. unter Licht-, Säure- oder Baseneinwirkung) ineinander umwandeln können. Entsprechende Umwandlungen können auch nach der Anwendung, beispielsweise bei der Behandlung von Pflanzen, Pilzen und tierischen Schädlingen im behandelten Organismus erfolgen. If isomer mixtures are formed in the synthesis, the separation into the individual compounds is generally not absolutely necessary, since the individual isomers partially convert into one another during preparation for use or during use (for example under the action of light, acid or base) can. Corresponding conversions can also take place after use, for example in the treatment of plants, fungi and animal pests in the treated organism.
Bei der eingangs angegebenen Definition der Verbindungen I wurden Sammelbegriffe verwendet, die allgemein repräsentativ für die folgenden Gruppen stehen: In the definition of compounds I given at the outset, collective terms were used which are generally representative of the following groups:
Halogen : Fluor, Chlor, Brom und Jod; Halogen: fluorine, chlorine, bromine and iodine;
Alkyl : geradkettige oder verzweigte Alkylgruppen mit 1 bis 4, 6 oder 10 Kohlenstoffatomen, z.B. C1-C6-Alkyl wie Methyl, Ethyl, Propyl, 1-Methylethyl, Butyl, 1-Methyl-propyl, 2-Methylpropyl, 1,1-Dimethylethyl, Pentyl, 1-Methylbutyl, 2-Methylbutyl, Alkyl: straight-chain or branched alkyl groups with 1 to 4, 6 or 10 carbon atoms, for example C 1 -C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl,
3-Methylbutyl, 2, 2-Di-methylpropyl, 1-Ethylpropyl, Hexyl, 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, 1,1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl,
1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-Dimethylbutyl, 3 ,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl und 1- Ethyl-2-methylpropyl; Alkylamino; eine Aminogruppe, welche eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 4 oder 6 Kohlenstoffatomen wie vorstehend genannt trägt;  2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2- methylpropyl; Alkylamino; an amino group which carries a straight-chain or branched alkyl group having 1 to 4 or 6 carbon atoms as mentioned above;
Dialkylamino: eine Aminogruppe, welche zwei voneinander unabhängige, geradkettige oder verzweigte Alkylgruppen mit jeweils 1 bis 4 oder 6 Kohlenstoffatomen wie vorstehend genannt, trägt; Dialkylamino: an amino group which carries two independent, straight-chain or branched alkyl groups each having 1 to 4 or 6 carbon atoms as mentioned above;
Alkylcarbonyl : geradkettige oder verzweigte Alkylgruppen mit 1 bis 6 oder 10 Kohlenstoffatomen, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind; Alkvisulfonyl; geradkettige oder verzweigte Alkylgruppen mit 1 bis 6 oder 10 Kohlenstoffatomen, welche über eine Sulfonylgruppe (-SO2-) an das Gerüst gebunden sind; Alkylsulfoxyl; geradkettige oder verzweigte Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, welche über eine Sulfoxylgruppe Alkylcarbonyl: straight-chain or branched alkyl groups with 1 to 6 or 10 carbon atoms, which are bonded to the skeleton via a carbonyl group (-CO-); Alkvisulfonyl; straight-chain or branched alkyl groups with 1 to 6 or 10 carbon atoms, which are bonded to the skeleton via a sulfonyl group (-SO 2 -); Alkyl sulfoxyl; straight-chain or branched alkyl groups with 1 to 6 carbon atoms, which have a sulfoxyl group
(-S(=O)-) an das Gerüst gebunden sind;  (-S (= O) -) are bound to the framework;
Alkylaminocarbonyl; Alkylaminogruppen mit 1 bis 6 Kohlenstoffatomen wie vorstehend genannt, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind; Alkylaminocarbonyl; Alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the skeleton via a carbonyl group (-CO-);
Dialkylaminocarbonyl; Dialkylaminogruppen mit jeweils 1 bis 6 Kohlenstoffatomen pro Alkylrest wie vorstehend genannt, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind; Dialkylaminocarbonyl; Dialkylamino groups each having 1 to 6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a carbonyl group (-CO-);
Alkylaminothiocarbonyl; Alkylaminogruppen mit 1 bis 6 Kohlenstoffatomen wie vorstehend genannt, welche über eine Thiocarbonylgruppe (-CS-) an das Gerüst gebunden sind; Alkylaminothiocarbonyl; Alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-);
Dialkylaminothiocarbonyl; Dialkylaminogruppen mit jeweils 1 bis 6 Kohlenstoffatomen pro Alkylrest wie vorstehend genannt, welche über eine Thiocarbonylgruppe (-CS-) an das Gerüst gebunden sind; Halogenalkyl; geradkettige oder verzweigte Alkylgruppen mit 1 bis4 oder 6 Kohlenstoffatomen, wobei in diesen Gruppen teilweise oder vollständig die Wasserstoffatome durch Halogenatome wie vorstehend genannt ersetzt sein können, z.B. C1-C2-Halogenalkyl wie Chlormethyl, Dichlormethyl, Trichlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl,Dialkylaminothiocarbonyl; Dialkylamino groups each having 1 to 6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-); Haloalkyl; straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms, in which case the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, for example C 1 -C 2 -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, Chlorofluoromethyl, dichlorofluoromethyl,
Chlordifluormethyl, 1-Fluorethyl, 2-Fluorethyl, 2,2-Difluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2, 2-difluorethyl, 2,2-Dichlor-2-fluorethyl, 2,2,2-Trichlorethyl und Pentafluorethyl; Chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2,2-dichloro-2- fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
Alkoxy: geradkettige oder verzweigte Alkylgruppen mit 1 bis 4 oder 6 Kohlenstoffatomen wie vorstehend genannt, welche über ein Sauerstoffatom (-O-) an das Gerüst gebunden sind, z.B. Alkoxy: straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via an oxygen atom (-O-), e.g.
C1-C6-Alkoxy wie Methyloxy, Ethyloxy, Propyloxy, 1-Methylethyloxy, Butyloxy, 1-Methyl-propyloxy, 2-Methylpropyloxy, 1,1-Dimethylethyloxy, Pentyloxy, 1-Methylbutyloxy, 2-Methylbutyloxy, C 1 -C 6 alkoxy such as methyloxy, ethyloxy, propyloxy, 1-methylethyloxy, butyloxy, 1-methylpropyloxy, 2-methylpropyloxy, 1,1-dimethylethyloxy, pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy,
3-Methylbutyloxy, 2,2-Di-methylpropyloxy, 1-Ethylpropyloxy, 3-methylbutyloxy, 2,2-dimethylpropyloxy, 1-ethylpropyloxy,
Hexyloxy, 1,1-Dimethylpropyloxy, 1,2-Dimethylpropyloxy, 1-Methylpentyloxy, 2-Methylpentyloxy, 3-Methylpentyloxy, 4-Methylpentyloxy, 1,1-Dimethylbutyloxy, 1,2-Dimethylbutyloxy, 1,3-Dimethylbutyloxy, 2,2-Dimethylbutyloxy, 2,3-Dimethylbutyloxy, Hexyloxy, 1,1-dimethylpropyloxy, 1,2-dimethylpropyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutyloxy, 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2, 2-dimethylbutyloxy, 2,3-dimethylbutyloxy,
3,3-Dimethylbutyloxy, 1-Ethyl-butyloxy, 2-Ethylbutyloxy, 1,1,2-Trimethylpropyloxy, 1,2,2-Trimethylpropyloxy, 3,3-dimethylbutyloxy, 1-ethylbutyloxy, 2-ethylbutyloxy, 1,1,2-trimethylpropyloxy, 1,2,2-trimethylpropyloxy,
1-Ethyl-1-methylpropyloxy und 1-Ethyl-2-methylpropyloxy; 1-ethyl-1-methylpropyloxy and 1-ethyl-2-methylpropyloxy;
Alkoxycarbonyl: geradkettige oder verzweigte Alkylgruppen mit 1 bis 6 Kohlenstoffatomen, welche über eine Oxycarbonylgruppe (-OC(=O)-) an das Gerüst gebunden sind; Alkoxycarbonyl: straight-chain or branched alkyl groups with 1 to 6 carbon atoms, which are bonded to the skeleton via an oxycarbonyl group (-OC (= O) -);
Halogenalkoxy; geradkettige oder verzweigte Alkylgruppen mit 1 bis 4 oder 6 Kohlenstoffatomen, wobei in diesen Gruppen teilweise oder vollständig die Wasserstoffatome durch Halogenatome wie vorstehend genannt ersetzt sein können, und wobei diese Gruppen über ein Sauerstoffatom an das Gerüst gebunden sind; Haloalkoxy; straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms, in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, and where these groups are bonded to the skeleton via an oxygen atom;
Alkylthio; geradkettige oder verzweigte Alkylgruppen mit 1 bis 4 oder 6 Kohlenstoffatomen wie vorstehend genannt, welche über ein Schwefelatom (-S-) an das Gerüst gebunden sind, z.B. Alkylthio; straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via a sulfur atom (-S-), e.g.
C1-C6-Alkylthio wie Methylthio, Ethylthio, Propylthio, 1-Methylethylthio, Butylthio, 1-Methylpropylthio, 2-Methylpropylthio, 1,1-Dimethylethylthio, Pentylthio, 1-Methylbutylthio, 2-Methylbutylthio, 3-Methylbutylthio, 2, 2-Di-methylpropylthio, 1-Ethylpropylthio, Hexylthio, 1, 1-Dimethylpropylthio, 1, 2-Dimethyl- propylthio, 1-Methylpentylthio, 2-Methylpentylthio, 3-Methylpentylthio, 4-Methylpentylthio, 1,1-Dimethylbutylthio, C 1 -C 6 alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2 2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio,
1, 2-Dimethylbutylthio, 1, 3-Dimethylbutylthio, 2, 2-Dimethylbutylthio, 2, 3-Dimethylbutylthio, 3 , 3-Dimethylbutylthio, 1-Ethylbutyl thio, 2-Ethylbutylthio, 1, 1, 2-Trimethylpropylthio, 1,2,2-Trimethylpropylthio, 1-Ethyl-1-methylpropylthio und 1, 2-dimethylbutylthio, 1, 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2, 3-dimethylbutylthio, 3, 3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1, 1, 2-trimethylpropylthio, 1,2 , 2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and
1-Ethyl-2-methylpropylthio; Cycloalkyl; monocyclische Alkylgruppen mit 3 bis 6 Kohlenstoffringgliedern, z.B. Cyclopropyl, Cyclobutyl, Cyclopentyl und Cyclohexyl; 1-ethyl-2-methylpropylthio; Cycloalkyl; monocyclic alkyl groups with 3 to 6 carbon ring members, e.g. Cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
Alkenyl; geradkettige oder verzweigte Alkenylgruppen mit 2 bis 6 oder 10 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, z.B. C2-C6-Alkenyl wie Ethenyl, 1-Propenyl, 2-Propenyl, 1-Methylethenyl, 1-Butenyl, 2-Butenyl, 3-Butenyl, 1-Methyl-1-propenyl, 2-Methyl-1-propenyl, 1-Methyl-2-propenyl, 2-Methyl-2-propenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, Alkenyl; straight-chain or branched alkenyl groups with 2 to 6 or 10 carbon atoms and a double bond in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,
4-Pentenyl, 1-Methyl-1-butenyl, 2-Methyl-1-butenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,
3-Methyl-1-butenyl, 1-Methyl-2-butenyl, 2-Methyl-2-butenyl, 3-Methyl-2-butenyl, 1-Methyl-3-butenyl, 2-Methyl-3-butenyl, 3-Methyl-3-butenyl, 1, 1-Dimethyl-2-propenyl,  3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3- Methyl-3-butenyl, 1, 1-dimethyl-2-propenyl,
1,2-Dimethyl-1-propenyl, 1,2-Dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,
1-Ethyl-1-propenyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Methyl-1-pentenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,
2-Methyl-1-pentenyl, 3-Methyl-1-pentenyl, 4-Methyl-1-pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2-pentenyl, 1-Methyl-3-pentenyl, 2-Methyl-3-pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pentenyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1,1-Dimethyl-2-butenyl, 1 ,1-Di-methyl-3-butenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3- Methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1- Dimethyl-2-butenyl, 1, 1-dimethyl-3-butenyl,
1,2-Dimethyl-1-butenyl, 1,2-Dimethyl-2-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,
1,2-Dimethyl-3-butenyl, 1,3-Dimethyl-1-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,
1,3-Dimethyl-2-butenyl, 1,3-Dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,
2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,
2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
3,3-Dimethyl-1-butenyl, 3,3-Dimethyl-2-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,
1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,
2-Ethyl-1-butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,
1,1,2-Trimethyl-2-propenyl, 1- Ethyl-1-methyl-2-propenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,
1-Ethyl-2-methyl-1-propenyl und 1-Ethyl-2-methyl-2-propenyl; 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
Alkenyloxy; geradkettige oder verzweigte Alkenylgruppen mit 2 bis 6 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, welche über ein Sauerstoffatom (-O-) an das Gerüst gebunden sind; Alkenyloxy; straight-chain or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in any position, which are bonded to the skeleton via an oxygen atom (-O-);
Alkenylcarbonyl; geradkettige oder verzweigte Alkenylgruppen mitAlkenylcarbonyl; straight-chain or branched alkenyl groups with
2 bis 10 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind; 2 to 10 carbon atoms and a double bond in any position which are bonded to the skeleton via a carbonyl group (-CO-);
Alkinyl; geradkettige oder verzweigte Alkinylgruppen mit 2 bis 10 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, z.B. C2-C6-Alkinyl wie Ethinyl, 2-Propinyl, 2-Butinyl, 3-Butinyl, 1-Methyl-2-propinyl, 2-Pentinyl, Alkynyl; straight-chain or branched alkynyl groups with 2 to 10 carbon atoms and a triple bond in any position, for example C 2 -C 6 -alkynyl such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2- Pentinyl,
3-Pentinyl, 4-Pentinyl, 1-Methyl-2-butinyl, 1-Methyl-3-butinyl, 2-Methyl-3-butinyl, 1,1-Dimethyl-2-propinyl, 1-Ethyl-2-propinyl, 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, 1-Methyl-2-pentinyl, 1-Methyl-3-pentinyl, 1-Methyl-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4-pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-2-pentinyl, 1,1-Dimethyl-2-butinyl, 1,1-Dimethyl-3-butinyl, 1, 2-Dimethyl-3-butinyl, 2,2-Dimethyl-3-butinyl, 1-Ethyl-2-butinyl, 1-Ethyl-3-butinyl, 2-Ethyl-3-butinyl und 1-Ethyl-1-methyl-2-propinyl; Alkinylcarbonyl; geradkettige oder verzweigte Alkinylgruppen mit 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2- Methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3- butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl; Alkynylcarbonyl; straight-chain or branched alkynyl groups with
3 bis 10 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, welche über eine Carbonylgruppe (-CO-) an das Gerüst gebunden sind; Cvcloalkoxy; monocyclische Alkenylgruppen mit 3 bis 6 Kohlenstoffringgliedern, welche über ein Sauerstoffatom an das Gerüst gebunden sind, z.B. Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl; 3 to 10 carbon atoms and a triple bond in any position which are bonded to the skeleton via a carbonyl group (-CO-); Cvcloalkoxy; monocyclic alkenyl groups with 3 to 6 carbon ring members which are bonded to the skeleton via an oxygen atom, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
Heterocyclyl bzw. Heterocyclyloxy; drei- bis sechsgliedrige, gesättigte oder partiell ungesättigte mono- oder polycyclische Heterocyclen, die ein bis drei Heteroatome ausgewählt aus einer Gruppe bestehend aus Sauerstoff, Stickstoff und Schwefel enthalten, und welche direkt bzw. (Heterocyclyloxy) über ein Sauer-Stoffatom an das Gerüst gebunden sind, wie z.B. 2-Tetrahydrofuranyl, Oxiranyl, 3-Tetrahydrofuranyl, 2-Tetrahydrothienyl, 3-Tetrahydrothienyl, 2-Pyrrolidinyl, 3-Pyrrolidinyl, 3-Isoxazoldinyl, 4-Isoxazolidinyl, 5-Isoxazolidinyl, 3-Isothiazolidinyl, 4-Isothiazolidinyl, 5-Isothiazolidinyl, 3-Pyrazolidinyl, Heterocyclyl or heterocyclyloxy; three- to six-membered, saturated or partially unsaturated mono- or polycyclic heterocycles, which contain one to three heteroatoms selected from a group consisting of oxygen, nitrogen and sulfur, and which are directly or (heterocyclyloxy) bonded to the skeleton via an oxygen atom are, such as 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazoldinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiaziazolidinyl, 4-isothiaziazolidinyl, 4 3-pyrazolidinyl,
4-Pyrazolidinyl, 5 -Pyrazolidinyl, 2-Oxazolidinyl, 4 -Oxazolidinyl, 5-Oxazolidinyl, 2-Thiazolidinyl, 4-Thiazolidinyl, 5-Thiazolidinyl, 2-Imidazolidinyl, 4-Imidazolidinyl, 1,2,4-Oxadiazolidin-3-yl, 1,2,4-Oxadiazolidin-5-yl, 1,2,4-Thiadiazolidin-3-yl, 1,2,4-Thiadiazolidin-5-yl, 1,2,4-Triazolidin-3-yl,  4-pyrazolidinyl, 5 -pyrazolidinyl, 2-oxazolidinyl, 4 -oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3- yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,
1,3,4-Oxadiazolidin-2-yl, 1,3,4-Thiadiazolidin-2-yl, 1,3,4-Triazolidin-2-yl, 2,3-Dihydrofur-2-yl, 2,3-Dihydrofur-3-yl,  1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3- Dihydrofur-3-yl,
2,3-Dihydro-fur-4-yl, 2,3-Dihydro-fur-5-yl, 2,5-Dihydro-fur-2-yl, 2, 5-Dihydro-fur-3-yl, 2,3-Dihydrothien-2-yl, 2,3-Dihydrothien-3-yl, 2,3-Dihydrothien-4-yl, 2,3-Dihydrothien-5-yl,  2,3-dihydro-fur-4-yl, 2,3-dihydro-fur-5-yl, 2,5-dihydro-fur-2-yl, 2,5-dihydro-fur-3-yl, 2, 3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl,
2,5-Dihydrothien-2-yl, 2,5-Dihydrothien-3-yl, 2,3-Dihydropyrrol-2-yl, 2,3-Dihydropyrrol-3-yl, 2,3-Dihydropyrrol-4-yl, 2,3-Dihydropyrrol-5-yl, 2,5-Dihydropyrrol-2-yl, 2,5-Dihydropyrrol-3-yl, 2,3-Dihydroisoxazol-3-yl, 2 ,3-Dihydroisoxazol-4-yl, 2,3-Dihydroisoxazol-5-yl, 4,5-Dihydroisoxazol-3-yl, 4,5-Dihydroisoxazol-4-yl, 4,5-Dihydroisoxazol-5-yl, 2,5-Dihydroisothiazol-3-yl, 2,5-Dihydroisothiazol-4-yl, 2,5-Dihydroisothiazol-5-yl, 2,3-Dihydropyrazol-3-yl, 2,3-Dihydropyrazol-4-yl, 2,3-Dihydropyrazol-5-yl, 4,5-Dihydropyrazol-3-yl, 4,5-Dihydropyrazol-4-yl, 4,5-Dihydropyrazol-5-yl, 2,5-Dihydropyrazol-3-yl, 2,5-Dihydropyrazol-4-yl, 2,5-Dihydropyrazol-5-yl, 2,3,Dihydrooxazol-2-yl, 2,3-Dihydrooxazol-4-yl, 2,3-Dihydrooxazol-5-yl, 4,5-Dihydrooxazol-2-yl, 4,5-Dihydrooxazol-4-yl, 4,5-Dihydrooxazol-5-yl, 2,5-Dihydrooxazol-2-yl, 2,5-Dihydrooxazol-4-yl, 2,5-Dihydrooxazol-5-yl, 2,3-Dihydrothiazol-2-yl, 2,3-Dihydrothiazol-4-yl, 2,3-Dihydrothiazol-5-yl, 4,5-Dihydrothiazol-2-yl, 4,5-Dihydrothiazol-4-yl, 4,5-Dihydrothiazol-5-yl, 2,5-Dihydrothiazol-2-yl, 2,5-Dihydro- thiazol-4-yl, 2,5-Dihydrothiazol-5-yl, 2,3-Dihydroimidazol-2-yl, 2,3-Dihydroimidazol-4-yl, 2,3-Dihydroimidazol-5-yl, 4,5-Dihydroimidazol-2-yl, 4,5-Dihydroimidazol-4-yl, 4,5-Dihydroimidazol-5-yl, 2,5-Dihydroimidazol-2-yl, 2,5-Dihydroimidazol-4-yl, 2,5-Dihydroimidazol-5-yl, 2 -Morpholinyl, 3-Morpholinyl, 2-Piperidinyl, 3-Piperidinyl, 4-Piperidinyl, 3 -Hexahydropyridazinyl, 4-Hexahydropyridazinyl, 2-Hexahydropyrimidinyl, 4 -Hexahydropyrimidinyl, 5-Hexahydropyrimidinyl, 2-Hexahydropyrazinyl, 1,3,5-Hexahydrotriazin-2-yl, 1,2,4-Hexahydrotriazin-3-yl, 1,3-Dihydrooxazin-2-yl, 1,3-Dithian-2-yl, 2-Tetrahydropyranyl, 1,3-Dioxolan-2-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,5-dihydropyrazol-3-yl, 2,5-dihydropyrazol-4-yl, 2,5-dihydropyrazol-5-yl, 2,3, dihydrooxazol-2-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazol-2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4.5 -Dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydro-thiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2 , 3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2 , 5-dihydroimidazol-2-yl, 2,5-dihydroimidazol-4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-hexahydropyrazinyl, 1,3,5-hexahydrotriazin-2-yl Hexahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyranyl, 1,3-dioxolan-2-yl,
3,4,5,6-Tetrahydropyridin-2-yl, 4H-1,3-Thiazin-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl,
4H-3,1-Benzothiazin-2-yl, 1,1-Dioxo-2, 3,4,5-tetrahydrothien-2-yl, 2H-1,4-Benzothiazin-3-yl, 2H-1,4-Benzoxazin-3-yl, 1,3-Dihydrooxazin-2-yl, 1 ,3-Dithian-2-yl, ggf. subst. über ein Stickstoffatom gebundene gesättigte oder partiell oder vollständig ungesättigte Cyclen, welche neben dem Stickstoffatom, über den sie gebunden sind, neben Kohlenstoff-Ringliedern ein bis fünf Heteroatome aus der Gruppe Stickstoff. Sauerstoff und Schwefel enthalten können: drei- bis zwölfgliedrige gesättigte oder partiell oder vollständig ungesättigte, mono- oder polycyclische Systeme, welche neben dem Stickstoffatom, über das sie gebunden sind, und neben Kohlenstoffringgliedern ein bis fünf weitere Heteroatome aus einer Gruppe bestehend aus Stickstoff, Sauerstoff und Schwefel enthalten können, wobei für den Fall, daß der Cyclus mehr als ein Sauerstoff- und/ oder Schwefelringglied enthält, diese Sauerstoff- bzw. Schwefelatome nicht in benachbarter Position zueinander stehen, z.B. 4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2, 3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4- Benzoxazin-3-yl, 1,3-dihydrooxazin-2-yl, 1, 3-dithian-2-yl, optionally subst. Saturated or partially or completely unsaturated cycles which are bonded via a nitrogen atom and which, in addition to the nitrogen atom via which they are bonded, in addition to carbon ring members, contain one to five heteroatoms from the group consisting of nitrogen. Oxygen and sulfur can contain: three- to twelve-membered saturated or partially or completely unsaturated, mono- or polycyclic systems, which, in addition to the nitrogen atom via which they are attached, and in addition to carbon ring members, one to five further heteroatoms from a group consisting of nitrogen, oxygen and may contain sulfur, and in the event that the cycle contains more than one oxygen and / or sulfur ring member, these oxygen or sulfur atoms are not in an adjacent position to one another, for example
1-Aziridinyl, 1-Diaziridinyl, 1-Azetidinyl, 1-Pyrrolidinyl, 2-Isoxazolidinyl, 2-Isothiazolidinyl, 1-Pyrazolidinyl, 3-Oxazolidinyl, 3-Thiazolidinyl, 1-Imidazolidinyl, 1,2,4-Oxadiazolidin-2-yl, 1,2,4-Oxadiazolidin-4-yl, 1,2,4-Thiadiazolidin-2-yl, 1,2,4-Thiadiazolidin-4-yl, 1-Triazolidinyl, 1-aziridinyl, 1-diaziridinyl, 1-azetidinyl, 1-pyrrolidinyl, 2-isoxazolidinyl, 2-isothiazolidinyl, 1-pyrazolidinyl, 3-oxazolidinyl, 3-thiazolidinyl, 1-imidazolidinyl, 1,2,4-oxadiazolidin-2- yl, 1,2,4-oxadiazolidin-4-yl, 1,2,4-thiadiazolidin-2-yl, 1,2,4-thiadiazolidin-4-yl, 1-triazolidinyl,
1,3,4-Oxadiazolidin-3-yl, 1,3,4-Thiadiazolidin-3-yl, 2,3-Dihydropyrrol-1-yl, 2,5-Dihydropyrrol-1-yl, 2,3-Dihydroisoxazol-2-yl, 1,3,4-oxadiazolidin-3-yl, 1,3,4-thiadiazolidin-3-yl, 2,3-dihydropyrrol-1-yl, 2,5-dihydropyrrol-1-yl, 2,3-dihydroisoxazole 2-yl,
2,5-DiDydroisoxazol-2-yl, 2,3-Dihydroisothiazol-2-yl, 2,5-Dihydroisothiazol-2-yl, 2,3-Dihydropyrazol-1-yl, 2,3-Dihydropyrazol-2-yl, 4,5-Dihydropyrazol-1-yl, 2,3-Dihydrooxazol-3-yl, 2,3-Dihydrothiazol-3-yl, 2,3-Dihydroimidazol-1-yl, 4,5-Dihydroimidazol-1-yl, 2,5-Dihydroimidazol-1-yl, 1-Piperidinyl, 2,5-diDydroisoxazol-2-yl, 2,3-dihydroisothiazol-2-yl, 2,5-dihydroisothiazol-2-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 4,5-dihydropyrazol-1-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrothiazol-3-yl, 2,3-dihydroimidazol-1-yl, 4,5-dihydroimidazol-1-yl, 2,5-dihydroimidazol-1-yl, 1-piperidinyl,
4-Morpholinyl, 1-Piperazinyl, 1-Hexahydropyridazinyl, 1-Hexahydropyrimidinyl, 2,3-Dihydroindol-1-yl, 4-Thiomorpholinyl,  4-morpholinyl, 1-piperazinyl, 1-hexahydropyridazinyl, 1-hexahydropyrimidinyl, 2,3-dihydroindol-1-yl, 4-thiomorpholinyl,
1,2,4-Hexahydrotriazin-1-yl, 2,3-Dihydroisoindol-2-yl, 1,2,4-hexahydrotriazin-1-yl, 2,3-dihydroisoindol-2-yl,
1-Pyrrolyl, 1-Imidazolyl, 1-Pyrazolyl, 1-Triazolyl, 1-Tetrazolyl, 2-Tetrazolyl, 1-Indolyl, 1-Indazolyl, Benzimidazol-1-yl, Benztriazol-1-yl, Pyrrolopyridin-1-yl, Pyrrolopyridazin-1-yl, Pyrro- lopyrimidin-1-yl, Pyrrolopyrazin-1-yl, Pyrrolotriazin-1-yl, Imidazopyridin-1-yl, Imidazopyridazin-1-yl, Imidazopyrimidin-1-yl, Imidazopyrazin-1-yl, Pyrazolopyridin-1-yl, Pyrazolopyridazin-1-yl, Pyrazolopyrimidin-1-yl, Pyrazolopyrazin-1-yl und Pyrazolotriazin-1-yl. Aryl bzw. Aryloxy, Arylthio, Arylcarbonyl und Arylsulfonyl; 1-pyrrolyl, 1-imidazolyl, 1-pyrazolyl, 1-triazolyl, 1-tetrazolyl, 2-tetrazolyl, 1-indolyl, 1-indazolyl, benzimidazol-1-yl, benztriazol-1-yl, pyrrolopyridin-1-yl, Pyrrolopyridazin-1-yl, pyrrolopyrimidin-1-yl, pyrrolopyrazin-1-yl, pyrrolotriazin-1-yl, imidazopyridin-1-yl, imidazopyridazin-1-yl, imidazopyrimidin-1-yl, imidazopyrazin-1-yl Pyrazolopyridin-1-yl, pyrazolopyridazin-1-yl, pyrazolopyrimidin-1-yl, pyrazolopyrazin-1-yl and pyrazolotriazin-1-yl. Aryl or aryloxy, arylthio, arylcarbonyl and arylsulfonyl;
aromatische mono- oder polycyclische Kohlenwasserstoffreste welche direkt bzw. (Aryloxy) über ein Sauerstoffatom (-O-) oder (Arylthio) ein Schwefelatom (-S-), (Arylcarbonyl) über eine Carbonylgruppe (-CO-) oder (Arylsulfonyl) über eine Sulfonylgruppe (-SO2-) an das Gerüst gebunden sind, z.B. Phenyl, Naphthyl und Phenanthrenyl bzw. Phenyloxy, Naphthyloxy und Phenanthrenyloxy und die entsprechenden Carbonyl- und Sulfonylreste; Hetaryl bzw. Hetaryloxy. Hetarylthio, Hetarylcarbonyl und aromatic mono- or polycyclic hydrocarbon radicals which directly or (aryloxy) via an oxygen atom (-O-) or (arylthio) a sulfur atom (-S-), (arylcarbonyl) via a carbonyl group (-CO-) or (arylsulfonyl) via a Sulfonyl group (-SO 2 -) are bound to the skeleton, for example phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals; Hetaryl or hetaryloxy. Hetarylthio, hetarylcarbonyl and
Hetarylsulfonyl; aromatische mono- oder polycyclische Reste welche neben Kohlenstoffringgliedern zusätzlich ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Sauerstoff- oder ein Schwefelatom oder ein Sauerstoff- oder ein Hetarylsulfonyl; aromatic mono- or polycyclic radicals which in addition to carbon ring members additionally one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one
Schwefelatom enthalten können und welche direkt bzw. (Hetaryloxy) über ein Sauerstoffatom (-O-) oder (Hetarylthio) ein Schwefelatom (-S-), (Hetarylcarbonyl) über eine Carbonylgruppe (-CO-) oder (Hetarylsulfonyl) über eine Sulfonylgruppe (-SO2-) an das Gerüst gebunden sind, z.B. - 5-gliedriges Heteroaryl, enthaltend ein bis drei Stickstoffatome: 5-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis drei Stickstoffatome als Ringglieder enthalten können, z.B. 2-Pyrrolyl, 3-Pyrrolyl, 3-Pyrazolyl, Can contain sulfur atom and which directly or (hetaryloxy) via an oxygen atom (-O-) or (hetarylthio) a sulfur atom (-S-), (hetarylcarbonyl) via a carbonyl group (-CO-) or (hetarylsulfonyl) via a sulfonyl group ( -SO 2 -) are bound to the skeleton, for example - 5-membered heteroaryl containing one to three nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three nitrogen atoms as ring members, for example 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl,
4-Pyrazolyl, 5-Pyrazolyl, 2-Imidazolyl, 4-Imidazolyl,  4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl,
1,2,4-Triazol-3-yl und 1,3,4-Triazol-2-yl;  1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl;
- 5-gliedriges Heteroaryl, enthaltend ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefeloder Sauerstoffatom oder ein Sauerstoff oder ein Schwefelatom: 5-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom oder ein Sauerstoff- oder Schwefelatom als Ringglieder enthalten können, z.B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, - 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or may contain an oxygen or sulfur atom as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl,
2-Pyrrolyl, 3-Pyrrolyl, 3-Isoxazolyl, 4-Isoxazolyl,  2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl,
5-Isoxazolyl, 3-Isothiazolyl, 4-Isothiazolyl, 5-Isothiazolyl, 3-Pyrazolyl, 4-Pyrazolyl, 5-Pyrazolyl, 2-Oxazolyl,  5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl,
4-Oxazolyl, 5-Oxazolyl, 2-Thiazolyl, 4-Thiazolyl,  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-yl, 1,2,4-Thiadiazol-3-yl,  5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,
1,2,4-Thiadiazol-5-yl, 1,2,4-Triazol-3-yl,  1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl,
1,3,4-Oxadiazol-2-yl, 1,3,4-Thiadiazol-2-yl,  1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl,
1,3,4-Triazol-2-yl;  1,3,4-triazol-2-yl;
- kondensiertes 5-gliedriges Heteroaryl, enthaltend ein bis vier Stickstoffatome oder ein bis drei Stickstoffatome und/ oder ein Sauerstoff- oder Schwefelatom: 5-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis vier Stick stoffatome oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom oder ein Sauerstoff- oder ein - Condensed 5-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and / or one oxygen or sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four sticks atoms of matter or one to three nitrogen atoms and a sulfur or oxygen atom or an oxygen or
Schwefelatom als Ringglieder enthalten können, und in welchen zwei benachbarte Kohlenstoffringglieder oder ein Stickstoff- und ein benachbartes Kohlenstoffringglied zu einem aromatischen oder heteroaromatischen Bi- oder Polycyclus verbrückt sein können: z.B. Benzofuranyl, Isobenzofuranyl, Benzothienyl, Isobenzothienyl, Indolyl, Isoindolyl, Benzisoxazolyl, Benzoxazolyl, Benzoisothiazolyl, Benzothiazolyl, indazolyl, Benzimidazolyl, Pyrrolopyridinyl, Pyrrolopyridazinyl, Pyrrolopyrimidinyl, Pyrrolopyrazinyl, Pyrrolotriazinyl, Furopyridinyl, Furopyridazinyl, Furopyrimidyl, Furopyrazinyl, Furotriazinyl, Thienopyridinyl, Thienopyridazinyl, Thienopyrimidyl, Thienopyrazinyl, Thienotriazinyl, Imidazopyridinyl, Imidazopyridazinyl, Imidazopyrimidyl, Imidazopyrazinyl, Imidazotriazinyl, Pyrazolopyridinyl, Pyrazolopyridazinyl, Pyrazolopyrimidyl, Pyrazolopyrazinyl, Pyrazolotriazinyl, Isoxazolopyridinyl, Isoxazolopyridazinyl, Isoxazolopyrimidyl, Isoxazolopyrazinyl, Isoxazolotriazinyl, Oxazolopyridinyl, Oxazolopyridazinyl, Oxazolopyrimidyl, Oxazolopyrazinyl, Oxazolotriazinyl, Isothiazolopyridinyl, Isothiazolopyridazinyl, Isothiazolopyrimidyl, Isothiazolopyrazinyl, Isothiazolotriazinyl, Thiazolopyridinyl, Thiazolopyridazinyl, Thiazolopyrimidyl, Thiazolopyrazinyl, Thiazolotriazinyl, Triazolopyridinyl, Triazolopyridazinyl, Triazolopyrimidyl, Triazolopyrazinyl und Triazolotriazinyl;  Can contain sulfur atom as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member can be bridged to form an aromatic or heteroaromatic bi- or polycycle: e.g. Benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, indolyl, isoindolyl, benzisoxazolyl, benzoxazolyl, benzoisothiazolyl, benzothiazolyl, indazolyl, benzimidazolyl, pyrrolopyridinyl, Pyrrolopyridazinyl, pyrrolopyrimidinyl, Pyrrolopyrazinyl, Pyrrolotriazinyl, furopyridinyl, Furopyridazinyl, Furopyrimidyl, Furopyrazinyl, Furotriazinyl, thienopyridinyl, Thienopyridazinyl, thienopyrimidyl, Thienopyrazinyl, Thienotriazinyl, imidazopyridinyl, Imidazopyridazinyl, Imidazopyrimidyl, Imidazopyrazinyl, Imidazotriazinyl, Pyrazolopyridinyl, Pyrazolopyridazinyl, Pyrazolopyrimidyl, Pyrazolopyrazinyl, Pyrazolotriazinyl, Isoxazolopyridinyl, Isoxazolopyridazinyl, Isoxazolopyrimidyl, Isoxazolopyrazinyl, Isoxazolotriazinyl, oxazolopyridinyl, Oxazolopyridazinyl, Oxazolopyrimidyl, Oxazolopyrazinyl, Oxazolotriazinyl, Isothiazolopyridinyl, Isothiazolopyridazinyl, Isothiazolopyrimidyl, Isothiazolopyrazinyl, isothiazolotriazinyl, thiazolopyridinyl, thiazolopyridazinyl, thiazolopyrimidyl, thiazolopyraz inyl, thiazolotriazinyl, triazolopyridinyl, triazolopyridazinyl, triazolopyrimidyl, triazolopyrazinyl and triazolotriazinyl;
- über Stickstoff gebundenes 5-gliedriges Heteroaryl. enthaltend ein bis vier Stickstoffatome. oder über Stickstoff gebundenes kondensiertes 5-gliedriges Heteroaryl. enthaltend ein bis fünf Stickstoffatome: 5-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis vier Stickstoffatome bzw. ein bis drei Stickstoffatome als Ringglieder enthalten können, und in welchen zwei benachbarte Kohlenstoffringglieder zu einem aromatischen oder heteroaromatischen Bioder Polycyclus verbrückt sein können, wobei diese Ringe über eines der Stickstoffringglieder an das Gerüst gebunden sind: z.B. 1-Pyrrolyl, 1-Imidazolyl, 1-Pyrazolyl, 1-Triazolyl, 1-Tetrazolyl, 2-Tetrazolyl, 1-Indolyl, 1-Indazolyl, Benzimidazol -1-yl, Pyrrolopyridin-1-yl, Benzotriazol -1 -yl, Pyrrolopyridazin-1-yl, Pyrrolopyrimidin-1-yl, Pyrrolopyrazin-1-yl, Pyrolotriazin-1-yl, lmidazopyridin-1-yl, Imidazopyridazin-1-yl, Imidazopyrimidin-1-yl, Imidiazopyrazin-1-yl, Pyrazolopyridin-1-yl, Pyrazolopyridazin-1-yl, Pyrazoloprimi- din-1-yl, Pyrazolopyrazin-1-yl und Pyrazolotriazin-1-yl; - 5-membered heteroaryl bound via nitrogen. containing one to four nitrogen atoms. or nitrogen-bonded condensed 5-membered heteroaryl. containing one to five nitrogen atoms: 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 can be bridged to form an aromatic or heteroaromatic bi or polycycle, these rings being bridged one of the nitrogen ring members is bound to the frame: e.g. 1-pyrrolyl, 1-imidazolyl, 1-pyrazolyl, 1-triazolyl, 1-tetrazolyl, 2-tetrazolyl, 1-indolyl, 1-indazolyl, benzimidazol -1-yl, pyrrolopyridin-1-yl, benzotriazol -1 -yl, Pyrrolopyridazin-1-yl, pyrrolopyrimidin-1-yl, pyrrolopyrazin-1-yl, pyrolotriazin-1-yl, imidazopyridin-1-yl, imidazopyridazin-1-yl, imidazopyrimidin-1-yl, imidiazopyrazin-1-yl 1-yl, pyrazolopyridazin-1-yl, pyrazoloprimidine-1-yl, pyrazolopyrazin-1-yl and pyrazolotriazin-1-yl;
- 6-gliedriges Heteroaryl, enthaltend ein bis drei bzw. ein bis vier Stickstoffatome: 6-Ring Heteroarylgruppen, welche neben Kohlenstoffatomen ein bis drei bzw. ein bis vier Stickstoff atome als Ringglieder enthalten können, z.B. 2-Pyridinyl, 3-Pyridinyl, 4-Pyridinyl, 3-Pyridazinyl, 4-Pyridazinyl, 2-Pyrimidinyl, 4-Pyrimidinyl, 5-Pyrimidinyl, 2-Pyrazinyl, 1,3,5-Triazin-2-yl, 1,2,4-Triazin-3-yl und - 6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups which, in addition to carbon atoms, contain one to three or one to four nitrogen may contain atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazine -2-yl, 1,2,4-triazin-3-yl and
1,2,4,5-Tetrazin-3-yl;  1,2,4,5-tetrazin-3-yl;
- benzokondensiertes 6-gliedriges Heteroaryl, enthaltend ein bis vier Stickstoffatome: 6-Ring Heteroarylgruppen in - Benzo-fused 6-membered heteroaryl, containing one to four nitrogen atoms: 6-ring heteroaryl groups in
welchen zwei benachbarte Kohlenstoffringglieder durch eine Buta-1,3-dien-1,4-diylgruppe verbrückt sein können, z.B.  which two adjacent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group, e.g.
Chinolin, Isochinolin, Chinazolin und Chinoxalin, bzw. die entsprechenden Oxy-, Thio-, Carbonyl- oder Sulfonylgruppen. Die Angabe "ggf . subs t . " in Bezug auf die Gruppe Z soll zum Ausdruck bringen, daß die betreffenden Gruppen partiell oder vollständig halogeniert sein können und/oder eine bis drei der folgenden Gruppen tragen können: - Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl,  Quinoline, isoquinoline, quinazoline and quinoxaline, or the corresponding oxy, thio, carbonyl or sulfonyl groups. The indication "if necessary subs." In relation to group Z is intended to express that the groups in question can be partially or completely halogenated and / or can carry one to three of the following groups: - cyano, nitro, hydroxy, mercapto , Amino, carboxyl, aminocarbonyl, aminothiocarbonyl,
- C1-C6-Alkyl, C1-C6-Halogenalkyl, C1-C6-Alkylcarbonyl, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylcarbonyl,
C1-C6-Alkylsulfonyl, C1-C6-Alkylsulfoxyl, C1-C6-Alkoxy, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylsulfoxyl, C 1 -C 6 alkoxy,
C1-C6-Halogenalkoxy, C1-C6-Alkoxycarbonyl, C1-C6-Alkylthio, C1-C6-Alkylamino, Di-C1-C6-alkylamino, C1-C6-Alkylaminocarbonyl, Di-C1-C6-alkylaminocarbonyl, C1-C6-Alkylaminothio- carbonyl, Di-C1-C6-alkylaminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Alkenyloxy oder C(=NORa) -An-Rb; C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylamino, di-C 1 -C 6 alkylamino, C 1 -C 6 alkylaminocarbonyl, Di-C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 alkylaminothiocarbonyl, di-C 1 -C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy or C (= NOR a ) -A n -R b ;
- C3-C6-Cycloalkyl, C3-C6-Cycloalkoxy, Heterocyclyl, Heterocyclyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, - C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkoxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio,
Hetaryl, Hetaryloxy und Hetarylthio, wobei die cyclischen Gruppen ihrerseits partiell oder vollständig halogeniert sein können oder eine bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, C1-C6-Alkyl, Hetaryl, hetaryloxy and hetarylthio, where the cyclic groups can in turn be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C 1 -C 6 -Alkyl,
C1-C6-Halogenalkyl, C1-C6-Alkylsulfonyl, C1-C6-Alkylsulfoxyl, C1-C6-Alkoxy, C1-C6-Halogenalkoxy, C1-C6-Alkoxycarbonyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylsulfoxyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl,
C1-C6"Alkylthio, C1-C6-Alkylamino, Di-C1-C6-alkylamino, C 1 -C 6 "alkylthio, C 1 -C 6 alkylamino, di-C 1 -C 6 alkylamino,
C1-C6-Alkylaminocarbonyl, Di-Cx-C6-alkylaminocarbonyl, C 1 -C 6 alkylaminocarbonyl, di-Cx-C 6 alkylaminocarbonyl,
C1-C6-Alkylaminothiocarbonyl, Di-C1-C6-alkylaminothiocarbonyl, C2-C6-Alkenyl, C2-C6-Alkenyloxy, C (=NORa) -An-Rb, oder durch übliche Gruppen substituiertes Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy und Hetarylthio, und/oder daß diese Gruppen durch einen der folgenden Reste Verbrückt sein können: C1-C5-Alkylen, Oxy-C1-C4-alkylen und C 1 -C 6 alkylaminothiocarbonyl, di-C 1 -C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C2 -C 6 alkenyloxy, C (= NOR a ) -A n -R b , or by conventional groups substituted benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, and / or that these groups can be bridged by one of the following radicals: C 1 -C 5 alkylene, oxy-C 1 -C 4 alkylene and
Oxy-C1-C4-alkylenoxy, wobei die Alkylenketten partiell oder voll ständig halogeniert sein können und/oder eine bis drei Oxy-C 1 -C 4 alkyleneoxy, the alkylene chains being partial or full can be constantly halogenated and / or one to three
C1-C3-Alkylgruppen tragen können. C 1 -C 3 alkyl groups can carry.
Die Angabe "durch übliche Gruppen substi tuiert" soll zum Ausdruck bringen, daß die betreffenden Reste partiell oder vollständig halogeniert sein können und/oder einen bis drei der folgenden Substituenten tragen können: Cyano, Nitro, C1-C4-Alkyl, The expression "substituted by conventional groups" is intended to express that the radicals in question can be partially or completely halogenated and / or can carry one to three of the following substituents: cyano, nitro, C 1 -C 4 alkyl,
C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy, C1-C4-Alkylthio, C1-C4-Halogenalkylthio, C1-C4-Alkylcarbonyl, C1-C4-Alkoxycarbonyl, Phenyl, Phenoxy, Benzyl und Benzyloxy, und/oder eine Gruppe C (=NORa)-An-Rb tragen können. C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, phenyl, phenoxy, benzyl and benzyloxy, and / or a group C (= NOR a ) -A n -R b can carry.
Die Angabe "partiell oder vollständig halogeniert" soll zum Ausdruck bringen, daß in den derart charakterisierten Gruppen die Wasserstoffatome zum Teil oder vollständig durch gleiche oder verschiedene Halogenatome wie vorstehend genannt ersetzt sein können. The expression "partially or fully halogenated" is intended to express that the hydrogen atoms in the groups characterized in this way can be replaced in part or in full by the same or different halogen atoms as mentioned above.
Im Hinblick auf ihre biologische Wirkung sind Verbindungen der Formel I bevorzugt, in denen m für 0 steht. With regard to their biological action, preference is given to compounds of the formula I in which m is 0.
Gleichermaßen bevorzugt sind Verbindungen der Formel I, in denen R1 für Methyl steht. Daneben werden Verbindungen I bevorzugt, in denen R3 für Wasserstoff, Hydroxy, Cyano, Cyclopropyl, Chlor, Methyl, Ethyl, Likewise preferred are compounds of formula I in which R 1 is methyl. In addition, compounds I are preferred in which R 3 is hydrogen, hydroxy, cyano, cyclopropyl, chlorine, methyl, ethyl,
1-Methylethyl, Methoxy, Methylthio oder Phenyl steht. 1-methylethyl, methoxy, methylthio or phenyl.
Außerdem werden Verbindungen I bevorzugt, in denen R3 für Methyl steht. In addition, compounds I are preferred in which R 3 is methyl.
Des weiteren werden Verbindungen I bevorzugt, in denen R3 für Methoxy steht. Außerdem werden Verbindungen I bevorzugt, in denen R3 für Cyano steht. Furthermore, compounds I are preferred in which R 3 is methoxy. In addition, compounds I are preferred in which R 3 is cyano.
Außerdem werden Verbindungen I bevorzugt, in denen R3 für Tri- fluormethyl steht. In addition, compounds I are preferred in which R 3 represents trifluoromethyl.
Außerdem werden Verbindungen I bevorzugt, in denen R3 für Hydroxy steht. In addition, compounds I are preferred in which R 3 is hydroxy.
Des weiteren werden Verbindungen I bevorzugt, in denen R3 für Chlor steht. Außerdem werden Verbindungen I bevorzugt, in denen R3 für Methylthio steht. Furthermore, compounds I are preferred in which R 3 represents chlorine. In addition, compounds I are preferred in which R 3 represents methylthio.
Außerdem werden Verbindungen I bevorzugt, in denen R4 für In addition, compounds I are preferred in which R 4 is
Wasserstoff, Cχ-C6-Alkyl, Arylalkyl, Hetarylalkyl, Aryloxyalkyl, Hetaryloxyalkyl, Aryl, Hetaryl, C2-C6-Alkenyl oder C2-C6-Alkinyl steht. Is hydrogen, Cχ-C6-alkyl, arylalkyl, hetarylalkyl, aryloxyalkyl, hetaryloxyalkyl, aryl, hetaryl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl.
Des weiteren werden Verbindungen I bevorzugt, in denen R4 für C1-C6-Alkyl steht. Furthermore, compounds I are preferred in which R 4 is C 1 -C 6 alkyl.
Außerdem werden Verbindungen I bevorzugt, in denen R4 für Methyl oder Ethyl steht. Außerdem werden Verbindungen I bevorzugt, in denen R4 für Aryloxyalkyl oder Hetaryloxyalkyl steht. In addition, compounds I are preferred in which R 4 represents methyl or ethyl. In addition, compounds I are preferred in which R 4 represents aryloxyalkyl or hetaryloxyalkyl.
Daneben werden Verbindungen I bevorzugt, in denen R4 für Arylalkyl oder Heteroarylalkyl steht. In addition, compounds I are preferred in which R 4 represents arylalkyl or heteroarylalkyl.
Außerdem werden Verbindungen I bevorzugt, in denen R4 für Aryl oder Hetaryl steht. In addition, compounds I are preferred in which R 4 represents aryl or hetaryl.
Des weiteren werden Verbindungen I bevorzugt, in denen R4 für C2 - C6 -Alkenyl steht . Furthermore, compounds I are preferred in which R 4 is C 2 -C 6 alkenyl.
Außerdem werden Verbindungen I bevorzugt, in denen R4 für In addition, compounds I are preferred in which R 4 is
C2-C6-Alkinyl steht. Daneben werden Verbindungen der Formel I bevorzugt, in denen X für NOCH3 steht. C 2 -C 6 alkynyl. In addition, preference is given to compounds of the formula I in which X represents NOCH 3 .
Daneben werden Verbindungen der Formel I bevorzugt, in denen X für CHOCH3 steht. In addition, preference is given to compounds of the formula I in which X represents CHOCH 3 .
Daneben werden Verbindungen der Formel I bevorzugt, in denen X für CHCH3 oder CHCH2CH3 steht. In addition, preference is given to compounds of the formula I in which X represents CHCH 3 or CHCH 2 CH 3 .
Außerdem werden Verbindungen der Formel I bevorzugt, in denen Y für O steht. Compounds of the formula I in which Y is O are also preferred.
Des weiteren werden Verbindungen der Formel I bevorzugt, in denen Y für NH oder N-CH3 steht. Gleichermaßen bevorzugt sind Verbindungen der Formel I, in denen R1 für Wasserstoff steht. Besonders bevorzugt sind Verbindungen der Formel I, in denen Y für NH und R1 für Methyl steht. Furthermore, compounds of formula I are preferred in which Y represents NH or N-CH 3 . Likewise preferred are compounds of formula I in which R 1 represents hydrogen. Compounds of the formula I in which Y is NH and R 1 is methyl are particularly preferred.
Besonders bevorzugt sind auch Verbindungen der Formel I, in denen Y für NH und R1 für Wasserstoff steht. Compounds of the formula I in which Y is NH and R 1 is hydrogen are also particularly preferred.
Besonders bevorzugt sind ebenso Verbindungen der Formel I, in denen Y für O und R1 für Methyl steht. Außerdem werden Verbindungen der Formel I bevorzugt, in denen Z für ggf. substituiertes, über Stickstoff gebundenes Heterocyclyl bedeutet. Compounds of the formula I in which Y is O and R 1 is methyl are also particularly preferred. In addition, preference is given to compounds of the formula I in which Z denotes optionally substituted heterocyclyl bonded via nitrogen.
Daneben werden Verbindungen der Formel I bevorzugt, in denen Zfür ggf. substituiertes, über Stickstoff gebundenes Heteroaryl bedeutet. In addition, preference is given to compounds of the formula I in which Z denotes heteroaryl which is substituted and which is bonded via nitrogen.
Besonders bevorzugt sind Verbindungen der Formel I, in denen Z für ggf. subst. 1-Pyrrolyl, 1-Pyrazolyl, 1-Imidazolyl, 1-Triazolyl oder 1-Tetrazolyl steht. Compounds of the formula I in which Z is optionally substituted are particularly preferred. 1-pyrrolyl, 1-pyrazolyl, 1-imidazolyl, 1-triazolyl or 1-tetrazolyl.
Insbesondere sind im Hinblick auf ihre Verwendung die in den folgenden Tabellen zusammengestellten Verbindungen I bevorzugt. Die in den Tabellen für einen Substituenten genannten Gruppen stellen außerdem für sich betrachtet (unabhängig von der Kombination, in der sie genannt sind) eine besonders bevorzugte Ausgestaltung des betreffenden Substituenten dar. In particular, in view of their use, the compounds I compiled in the tables below are preferred. The groups mentioned for a substituent in the tables also represent a particularly preferred embodiment of the substituent in question (regardless of the combination in which they are mentioned).
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Die Verbindungen I eignen sich als Fungizide. The compounds I are suitable as fungicides.
Die Verbindungen I zeichnen sich durch eine hervorragende Wirk- samkeit gegen ein breites Spektrum von pflanzenpathogenen Pilzen, insbesondere aus der Klasse der Ascomyceten und Basidiomyceten, aus. Sie sind zum Teil systemisch wirksam und können als Blatt- und Bodenfungizide eingesetzt werden. Besondere Bedeutung haben sie für die Bekämpfung einer Vielzahl von Pilzen an verschiedenen Kulturpflanzen wie Weizen, Roggen, Gerste, Hafer, Reis, Mais, Gras, Baumwolle, Soja, Kaffee, Zuckerrohr, Wein, Obst- und Zierpflanzen und Gemüsepflanzen wie Gurken, Bohnen und Kürbisgewächsen, sowie an den Samen dieser Pflanzen. The compounds I are notable for excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes and Basidiomycetes. Some of them are systemically effective and can be used as foliar and soil fungicides. They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetable plants such as cucumbers, beans and Pumpkin family, as well as on the seeds of these plants.
Speziell eignen sie sich zur Bekämpfung folgender Pflanzenkrankheiten: Erysiphe graminis (echter Mehltau) in Getreide, Erysiphe cichoracearum und Sphaerotheca fuliginea an Kürbisgewächsen, Podosphaera leucotricha an Äpfeln, Uncinula necator an Reben, Puccinia-Arten an Getreide, Rhizoctonia-Arten an Baumwolle und Rasen, Ustilago-Arten an Getreide und Zuckerrohr, Venturia inaequalis (Schorf) an Äpfeln, Helminthosporium-Arten an They are particularly suitable for combating the following plant diseases: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species and Rhizoctonia Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species
Getreide, Septoria nodorum an Weizen, Botrytis cinerea (Grauschimmel) an Erdbeeren, Reben, Cercospora arachidicola an Erdnüssen, Pseudocercosporella herpotrichoides an Weizen, Gerste, Pyricularia oryzae an Reis, Phytophthora infestans an Kartoffeln und Tomaten, Fusarium- und Verticillium-Arten an verschiedenen Pflanzen, Plasmopara viticola an Reben, Alternaria-Arten an Cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and various plants , Plasmopara viticola on vines, Alternaria species
Gemüse und Obst. Vegetables and fruit.
Die Verbindungen I werden angewendet, indem man die Pilze oder die vor Pilzbefall zu schützenden Pflanzen, Saatgüter, Materialien oder den Erdboden mit einer fungizid wirksamen Menge der Wirkstoffe behandelt. Die Anwendung erfolgt vor oder nach der Infektion der Materialien, Pflanzen oder Samen durch die Pilze. 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. It is used before or after the infection of the materials, plants or seeds by the fungi.
Sie können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Die Anwendungsform richtet sich nach dem jeweiligen Verwendungszweck; sie soll in jedem Fall eine feine und gleichmäßige Verteilung der erfindungsgemäßen Verbindungen gewährleisten. Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gewünschtenfalls unter Verwendung von Emulgiermittein und Dispergiermitteln, wobei im Falle von Wasser als Verdünnungsmittel auch andere organische Lösungsmittel als Hilfslösungsmittel verwendet werden können. Als Hilfsstoffe kommen da für im wesentlichen in Betracht: Lösungsmittel wie Aromaten (z.B. Xylol), chlorierte Aromaten (z.B. Chlorbenzole), Paraffine (z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Butanol), Ketone (z.B. Cyclohexanon), Amine (z.B. Ethanolamin, Dimethylformamid) und Wasser; Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, Silikate); Emulgiermittel wie nicht- ionogene und anionische Emulgatoren (z.B. Polyoxyethylen-Fettalkohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergiermittel wie Lignin-Sulfitablaugen und Methylcellulose. They can be converted into the usual formulations, such as 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 compounds according to the invention. The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and if organic diluents are used, other organic solvents can also be used as auxiliary solvents. As auxiliary agents come there The following are essentially considered: 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 (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.
Die fungiziden Mittel enthalten im allgemeinen zwischen 0,1 und 95, vorzugsweise zwischen 0,5 und 90 Gew.% Wirkstoff. Die Aufwandmengen liegen je nach Art des gewünschten Effektes zwischen 0,01 und 2,0 kg Wirkstoff pro ha. The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient. Depending on the type of effect desired, the application rates are between 0.01 and 2.0 kg of active ingredient per ha.
Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 0,1 g, vorzugsweise 0,01 bis 0,05 g je Kilogramm Saatgut benötigt. In the case of seed treatment, amounts of active ingredient of 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.
Die erfindungsgemäßen Mittel können in der Anwendungsform als Fungizide auch zusammen mit anderen Wirkstoffen vorliegen, der z.B. mit Herbiziden, Insektiziden, Wachstumsregulatoren, 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,
Fungiziden oder auch mit Düngemitteln. Fungicides or with fertilizers.
Beim Vermischen mit Fungiziden erhält man dabei in vielen Fällen eine Vergrößerung des fungiziden Wirkungsspektrums. Die folgende Liste von Fungiziden, mit denen die erfindungs- gemäßen Verbindungen gemeinsam angewendet werden können, soll die Kombinationsmöglichkeiten erläutern, nicht aber einschränken: When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases. The following list of fungicides with which the compounds according to the invention can be used together is intended to explain the possible combinations, but not to limit it:
Schwefel, Dithiocarbamate und deren Derivate wie Ferridimethyldithiocarbamat, Zinkdimethyldithiocarbamat, Zinkethylenbisdithiocarbamat, Manganethylenbisdithiocarbamat, Mangan-Zink-ethylendia- min-bis-dithiocarbamat, Tetramethylthiuramdisulfide, Ammoniak-Komplex von Zink-(N,N-ethylen-bis-dithiocarbamat), Ammoniak-Komplex von Zink-(N,N'-propylen-bis-dithiocarbamat), Zink-(N,N'-propylen-bis-dithiocarbamat), N,N'-Polypropylen-bis- (thiocarbamoyl)disulfid; Sulfur, dithiocarbamates and their derivatives such as iron, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediamine bisdithiocarbamate min, Tetramethylthiuramdisulfide, ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate), ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis (thiocarbamoyl) disulfide;
Nitroderivate wie Dinitro- (1-methylheptyl)phenylcrotonat, 2-sec.- Butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylat, 2-sec.-Butyl-4, 6-dinitrophenyl-iso-propylcarbonat, 5-Nitro-iso-phthalsäure-di-iso-propylester; heterocyclische Substanzen wie 2-Heptadecyl-2-imidazolin-acetat,Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-iso-propyl carbonate, 5-nitro -iso-phthalic acid di-iso-propyl ester; heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate,
2,4-Dichlor-6-(o-chloranilino)-s-triazin, O,O-Diethyl-phthalimidophosphonothioat, 5-Amino-1-[bis-(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazol, 2,3-Dicyano-1,4-dithioanthrachinon, 2-Thio-1,3-dithiolo-[4,5-b]-chinoxalin, 1-(Butylcarbamoyl)-2-benzimidazol-carbaminsäuremethylester, 2-Methoxycarbonylamino-benzimidazol, 2-(Furyl-(2))benzimidazol, 2-(Thiazolyl-(4))benzimidazol, N-(1,1,2,2-Tetrachlorethylthio)tetrahydrophthalimid, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1,2,4 -triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo- [4,5-b] -quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino -benzimidazole, 2- (furyl- (2)) benzimidazole, 2- (thiazolyl- (4)) benzimidazole, N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide,
N-Trichlormethylthio-tetrahydrophthalimid, N-Trichlor-methylthiophthalimid,  N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthiophthalimide,
N-Dichlorfluormethylthio-N',N'-dimethyl-N-phenyl-schwefelsäurediamid, 5-Ethoxy-3-trichlormethyl-1,2,4-thiadiazol, 2-Rhodanmethylthiobenzthiazol, 1,4-Dichlor-2,5-dimethoxybenzol, 4-(2-Chlorphenylhydrazono)-3-methyl-5-isoxazolon, Pyridin-2-thio-1-oxid, 8-Hydroxychinolin bzw. dessen Kupfersalz, 2,3-Dihydro-5-carboxanilido-6-methyl-1,4-oxathiin, 2,3-Dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxid, 2-Methyl-5, 6-dihydro-4H-pyran-3-carbonsäure-anilid, 2-Methyl-furan-3-carbonsäureanilid, 2,5-Dimethyl-furan-3-carbonsäureanilid, 2,4,5-Trimethyl-furan-3-carbonsäureanilid, 2,5-Dimethyl-furan-3-carbonsäurecyclohexylamid, N-Cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carbonsäureamid, 2-Methyl-benzoesäure-anilid, 2-Iod-benzoesäure-anilid, N-Formyl-N-morpholin-2,2,2-trichlor-ethylacetal, Piperazin-1,4-diylbis-(1-(2,2,2-trichlor-ethyl)formamid, 1-(3,4-Dichloranilino)-1-formylamino-2,2,2-trichlorethan, 2,6-Dimethyl-N-tridecyl-morpholin bzw. dessen Salze, 2,6-Dimethyl-N-cyclododecylmorpholin bzw. dessen Salze, N-[3-(p-tert.-Butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholin, N-[3-(p-tert.-Butylphenyl)-2-methylpropyl]-piperidin, 1-[2-(2,4-Dichlorphenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazol, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyl-sulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2-rhodanmethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1, 4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2-methyl-5, 6-dihydro-4H-pyran-3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide, N- Cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2,2-trichloro- ethyl acetal, piperazin-1,4-diylbis- (1- (2,2,2-trichloro-ethyl) formamide, 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2, 6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecylmorph oline or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl] cis-2,6-dimethylmorpholine, 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-Dichlorphenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazol, N-(n-Propyl)-N-(2,4,6-trichlor-phenoxyethyl)-N'-imidazol-yl-harnstoff, 1-(4-Chlorphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanon, (2-Chlorphenyl)-(4-chlorphenyl)-5-pyrimidin-methanol, 5-Butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidin, Bis-(p-chlorphenyl)-3-pyridinmethanol, 1,2-Bis-(3-ethoxycarbonyl-2-thioureido)benzol, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) - N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl-urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazole- 1-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p- chlorphenyl) -3-pyridinemethanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene,
1,2-Bis-3-methoxycarbonyl-2-thioureido)benzol, [2-(4-Chlorphenyl)ethyl]-(1,1-dimethylethyl)-1H-1,2,4-triazol-1-ethanol sowie verschiedene Fungizide wie Dodecylguanidinacetat, 3-[3-(3,5-Dimethyl-2-oxycyclohexyl)-2-hydroxyethyl)]glutarimid, Hexachlorbenzol, DL-Methyl-N-(2,6-dimethyl-phenyl)-N-furoyl(2)alaninat, DL-N-(2,6-Dimethyl-phenyl)-N-(2'-methoxyacetyl)alanin-methylester, N-(2,6-Dimethylphenyl)-N-chloracetyl-D,L-2-aminobutyrolacton, DL-N- (2,6-Dimethylphenyl)-N-(phenylacetyl)alaninmethylester, 5-Methyl-5-vinyl-3-(3,5-dichlorphenyl)-2,4-dioxo-1,3-oxazolidin, 3-(3,5-Dichlorphenyl)-5-methyl-5-methoxymethyl-1,3-oxazolidin-2,4-dion, 3-(3,5-Dichlorphenyl)-1-isopropylcarbamoylhydantoin, N-(3,5-Dichlorphenyl)-1,2-dimethylcyclopropan-1,2-dicarbonsäureimid, 2-Cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamid, 1-[2-(2,4-Dichlorphenyl)pentyl]-1H-1,2,4-triazol, 2,4-Difluor-α-(1H-1,2,4-triazolyl-1-methyl)benzhydrylalkohol, 1,2-bis-3-methoxycarbonyl-2-thioureido) benzene, [2- (4-chlorophenyl) ethyl] - (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol and various Fungicides such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl)] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl ( 2) alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2- aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 3- (3,5-dichlorophenyl) -5-methyl-5-methoxymethyl-1, 3-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H- 1,2,4-triazolyl-1-methyl) benzhydryl alcohol,
N-(3-Chlor-2,6-dinitro-4-trifluormethyl-phenyl)-5-trifluormethyl-3-chlor-2-aminopyridin, 1-((bis-(4-Fluorphenyl)methylsilyl)methyl)-1H-1,2,4-triazol. N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methylsilyl) methyl) -1H- 1,2,4-triazole.
Strobilurine wie Methyl-E-methoximino-[α-(o-tolyloxy)-o-tolyl]acetat, Methyl-E-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylat, Methyl-E-methoximino-[α-(2-phenoxyphenyl)]acetamid, Methyl-E-methoximino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamid. Strobilurins such as methyl-E-methoximino- [α- (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} - 3-methoxyacrylate, methyl-E-methoximino- [α- (2-phenoxyphenyl)] acetamide, methyl-E-methoximino- [α- (2,5-dimethylphenoxy) -o-tolyl] acetamide.
Anilinopyrimidine wie N-(4,6-Dimethylpyrimidin-2-yl)anilin, N-[4-Methyl-6-(1-propinyl)pyrimidin-2-yl]anilin, N-(4-Methyl-6-cyclopropyl-pyrimidin-2-yl)anilin. Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl-6-cyclopropyl- pyrimidin-2-yl) aniline.
Phenylpyrrole wie 4-(2,2-difluor-1,3-benzodioxol-4-yl)pyrrol-3-carbonitril. Zimtsäureamide wie 3-(4-Chlorphenyl)-3-(3,4-dimethoxyphenyl)acrylsäuremorpholid. (2RS, 3SR)-1-[3-(2-Chlorphenyl)-2-[4-fluorphenyl]oxiran-2-ylmethyl]-1H-1,2,4-triazol. 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. (2RS, 3SR) -1- [3- (2-chlorophenyl) -2- [4-fluorophenyl] oxiran-2-ylmethyl] -1H-1,2,4-triazole.
Die Verbindungen der Formel I sind außerdem geeignet, Schädlinge aus der Klasse der Insekten, Spinnentiere und Nematoden wirksam zu bekämpfen. Sie können im Pflanzenschutz sowie auf dem The compounds of the formula I are also suitable for effectively controlling pests from the class of the insects, arachnids and nematodes. You can in crop protection as well as on the
Hygiene-, Vorratsschutz- und Veterinärsektor als Schädlingsbekämpfungsmittel eingesetzt werden. Hygiene, storage protection and veterinary sector are used as pesticides.
Zu den schädlichen Insekten gehören aus der Ordnung der Schmetterlinge (Lepidoptera) beispielsweise Agrotis ypsilon, Agrotis segetum, Alabama argillacea, 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, The harmful insects from the order of the butterflies (Lepidoptera) include, for example, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobisturaumumone, Cheimatobisturaumumone Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus,
Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea,Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea,
Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,
Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege
sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeiraphera canadensis. sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephella, Piercellaella phylocellaella phyllocellella phthalica phylocellella phthalica phylocellella phthalica phylocellella phthalica phylocellella phylloxia Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia niad, Zeirisheraphera.
Aus der Ordnung der Käfer (Coleoptera) beispielsweise Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Byus Bruchus pisorusum , Cassida nebulosa, Cerotoma trifurcata,
Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera,
Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus
brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus,
Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,
Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon
cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., cochleariae, Phyllotreta chrysocephala, Phyllophaga sp.,
Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta
striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria. striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.
Aus der Ordnung der Zweiflügler (Diptera) beispielsweise Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, From the order of the two-winged species (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropucitae, Cordylobia anthropucaga, brassylaciaacropucita, brassylaciaacropucita, brassylaciaacropacea, brassylaciaacropaceacita, brassylaciaacropia , Fannia canicularis, Gasterophilus intestinalis,
Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica,
Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa. Aus der Ordnung der Thripse (Thysanoptera) beispielsweise Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa. From the order of the thrips (Thysanoptera) for example
Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci. Aus der Ordnung der Hautflügler (Hymenoptera) beispielsweise Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana,  Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci. From the order of the hymenoptera, for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana,
Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta. Aus der Ordnung der Wanzen (Heteroptera) beispielsweise Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta. From the order of the bugs (Heteroptera), for example Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps,
Euschistus impictiventris, Leptoglossus phyllopus, Lygus Euschistus impictiventris, Leptoglossus phyllopus, Lygus
lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor. lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor.
Aus der Ordnung der Pflanzensauger (Homoptera) beispielsweise Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nord- mannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus From the order of the plant suckers (Homoptera), for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypy, Dreianafiaisolumiaia, Dreianafusiaolaia, Dreianafusiaolaia, Dreyfusiaolaia Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Psorylomyidalid, Psorylomyidalid, Psorylomyidis malic, Phorodlaid mali, Psorylomidis malic, Phorodlaid mali, Phorodlais malic, Phorodlais malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malic, Phorodlausi malical, Psoryllaid malicum , Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus
vitifolii. vitifolii.
Aus der Ordnung der Termiten (Isoptera) beispielsweise Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus, Termes natalensis. Aus der Ordnung der Geradflügler (Orthoptera) beispielsweise Acheta domestica, Blatta orientalis, Blattella germanica, From the order of the termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus, Termes natalensis. From the order of the straight wing (Orthoptera), for example Acheta domestica, Blatta orientalis, Blattella germanica,
Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana. Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus. Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana. Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.
Aus der Klasse der Arachnoidea beispielsweise Spinnentiere Arachnoid, for example, arachnids
(Acarina) wie Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius, Tetranychus urticae. (Acarina) such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyinommobusuncus, Iinoblus, I megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychuschusus, Tetranychuschusch.
Aus der Klasse der Nematoden beispielsweise Wurzelgallen- nematoden, z.B. Meloidogyne hapla, Meloidogyne incognita, From the class of nematodes, for example, root gall nematodes, e.g. Meloidogyne hapla, Meloidogyne incognita,
Meloidogyne javanica, Zysten bildende Nematoden, z.B. Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, Stock- und Blattälchen, z.B. 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 multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchususususususususususususususususususchusususususususchusatus, Pratchylenate, Prat.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder 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
Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln, Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten. Dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, atomizing, dusting, scattering or pouring can be used. The application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Die Wirkstoffkonzentrationen in den anwendungsfertigen The drug concentrations in the ready-to-use
Zubereitungen können in größeren Bereichen variiert werden. Preparations can be varied in larger areas.
Im allgemeinen liegen sie zwischen 0,0001 und 10 %, vorzugsweise zwischen 0,01 und 1 %. Die Wirkstoffe können auch mit gutem Erfolg im Ultra-Low-Volume-Verfahren (ULV) verwendet werden, wobei es möglich ist, Formulierungen mit mehr als 95 Gew.% Wirkstoff oder sogar den Wirkstoff ohne Zusätze auszubringen. 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.
Die Aufwandmenge an Wirkstoff zur Bekämpfung von Schädlingen beträgt unter Freilandbedingungen 0,1 bis 2,0, vorzugsweise 0,2 bis 1,0 kg/ha. Zur Herstellung von direkt versprühbaren Lösungen, Emulsionen, Pasten oder Oldispersionen kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Benzol, Toluol, Xylol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Chloroform, Tetrachlorkohlenstoff, Cyclohexanol, Cyclohexanon, Chlorbenzol, Isophoron, stark polare The application rate of active ingredient for controlling pests is 0.1 to 2.0, preferably 0.2 to 1.0 kg / ha under field conditions. For the production of directly sprayable solutions, emulsions, pastes or old dispersions, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils as well as 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
Lösungsmittel, z.B. Dimethylformamid, Dimethylsulfoxid, N-Methylpyrrolidon, Wasser, in Betracht. Solvents, e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver, Oldispersionen) durch Aqueous application forms can be made from emulsion concentrates, pastes or wettable powders (wettable powders, old dispersions)
Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Oldispersionen können die Substanzen als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermitttel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Water can be added. To prepare emulsions, pastes or old 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. However, wetting, adhesive,
Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind. Dispersants or emulsifiers and possibly solvents or oil existing concentrates are prepared which are suitable for dilution with water.
Als oberflächenaktive Stoffe kommen Alkali-, Erdalkali-, Alkali, alkaline earth,
Ammoniumsalze von Ligninsulfonsäure, Naphthalinsulfonsäure, Ammonium salts of lignosulfonic acid, naphthalenesulfonic acid,
Phenolsulfonsäure, Dibutylnaphthalinsulfonsäure, Alkylarylsulfonate, Alkylsulfate, Alkylsulfonate, Fettalkoholsulfate und Fettsäuren sowie deren Alkali- und Erdalkalisalze, Salze von sulfatiertem Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphtalinsulfon- säure mit Phenol und Formaldehyd, Polyoxyethylenoctylphenolether, ethoxyliertes Isooctylphenol, Octylphenol, Nonylphenol, Alkylphenylpolyglykolether, Tributylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethylenoxid- Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether, ethoxyliertes Polyoxypropylen, Laurylalkoholpolyglykolether acetal, Sorbitester, Ligninsulfitablaugen und Methylcellulose in Betracht. Phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids and their alkali and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde and naphthalenesulfonate with naphthalene, naphthalenethene with naphthalenesulfonate and naphthalenesulfonate, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol acetal, sorbitol esters, lignin sulfite liquors and methyl cellulose.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden. Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Die Formulierungen enthalten im allgemeinen zwischen 0,01 und 95 Gew.%, vorzugsweise zwischen 0,1 und 90 Gew.% des Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90 % bis 100 %, vorzugsweise 95 % bis 100 % (nach NMR-Spektrum) eingesetzt. 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).
Beispiele für Formulierungen sind: Examples of formulations are:
I. 5 Gew.-Teile einer erfindungsgemäßen Verbindung werden mitI. 5 parts by weight of a compound according to the invention
95 Gew.-Teilen feinteiligem Kaolin innig vermischt. Man erhält auf diese Weise ein Stäubemittel, das 5 Gew.% des95 parts by weight of finely divided kaolin intimately mixed. In this way a dusting agent is obtained which contains 5% by weight of the
Wirkstoffs enthält. Contains active ingredient.
II. 30 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit einer Mischung aus 92 Gew.-Teilen pulverförmigem Kieselsäuregel und 8 Gew.-Teilen Paraffinöl, das auf die Oberfläche dieses Kieselsäuregels gesprüht wurde, innig vermischt. Man erhält auf diese Weise eine Aufbereitung des Wirkstoffs mit guter Haftfähigkeit (Wirkstoffgehalt 23 Gew.%). II. 30 parts by weight of a compound according to the invention are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, a preparation of the active ingredient with good adhesion (active ingredient content 23% by weight) is obtained.
III. 10 Gew. -Teile einer erfindungsgemäßen Verbindung werden in einer Mischung gelöst, die aus 90 Gew.-Teilen Xylol, 6 Gew.- Teilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol Ölsäure-N-monoethanolamid, 2 Gew.-Teilen Calciumsalz der Dodecylbenzolsulfonsäure und 2 Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol III. 10 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight Calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole
Ricinusöl besteht (Wirkstoffgehalt 9 Gew.%).  Castor oil consists (active ingredient content 9% by weight).
IV. 20 Gew.-Teile einer erfindungsgemäßen Verbindung werden in einer Mischung gelöst, die aus 60 Gew.-Teilen Cyclohexanon,IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone,
30 Gew.-Teilen Isobutanol, 5 Gew.-Teilen des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Isooctylphenol und 5 Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht (Wirkstoffgehalt 16 Gew.%). 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (active ingredient content 16% by weight).
V. 80 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit 3 Gew.-Teilen des Natriumsalzes der Diisobutylnaphthalinalpha-sulfonsäure, 10 Gew.-Teilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfit-Ablauge und 7 Gew.-Teilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen (Wirkstoffgehalt 80 Gew.%). V. 80 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalenalphasulfonic 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 and in milled in a hammer mill (active ingredient content 80% by weight).
VI. Man vermischt 90 Gew. -Teile einer erfindungsgemäßen Verbindung mit 10 Gew. -Teilen N-Methyl-α-pyrrolidon und erhält eine Lösung, die zur Anwendung in Form kleinster Tropfen geeignet ist (Wirkstoffgehalt 90 Gew.%). VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution is obtained which is suitable for use in the form of tiny drops (active substance content 90% by weight).
VII. 20 Gew. -Teile einer erfindungsgemäßen Verbindung werden in einer Mischung gelöst, die aus 40 Gew.-Teilen Cyclohexanon, 30 Gew.-Teilen Isobutanol, 20 Gew.-Teilen des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Isooctylphenol undVII. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and
10 Gew.-Teilen des Anlagerungsproduktes von 40 Mol Ethylen oxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100 000 Gew. -Teilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.% des Wirkstoffs enthält. 10 parts by weight of the adduct of 40 moles of ethylene oxide on 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.
VIII.20 Gew.-Teile einer erfindungsgemäßen Verbindung werden mit 3 Gew.-Teilen des Natriumsalzes der Diisobutylnaphthalin-α- sulfonsäure, 17 Gew.-Teilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfit-Ablauge und 60 Gew. -Teilen pulverförmigem Kieselsäuregel gut vermischt und in einerVIII.20 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and in one
Hammermühle vermählen. Durch feines Verteilen der Mischung in 20 000 Gew. -Teilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew.% des Wirkstoffs enthält. Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate, können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind z.B. Mineralerden, wie Silicagel, Kieselsäuren, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie z.B. Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte, wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Grind the hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient. 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, silicates, 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,
Cellulosepulver und andere feste Trägerstoffe. Cellulose powder and other solid carriers.
Zu den Wirkstoffen können Öle verschiedenen Typs, Herbizide, Fungizide, andere Schädlingsbekämpfungsmittel, Bakterizide, gegebenenfalls auch erst unmittelbar vor der Anwendung (Tankmix), zugesetzt werden. Diese Mittel können zu den erfindungsgemäßen Mitteln im Gewichtsverhältnis 1:10 bis 10:1 zugemischt werden. 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.
Synthesebeispiele Synthesis examples
Die in den nachstehenden Synthesebeispielen wiedergegebenen Those reproduced in the synthesis examples below
Vorschriften wurden unter entsprechender Abwandlung der Ausgangsverbindungen zur Gewinnung weiterer Verbindungen I benutzt. Die so erhaltenen Verbindungen sind in den anschließenden Tabellen mit physikalischen Angaben aufgeführt. Beispiel 1 Regulations were used with a corresponding modification of the starting compounds to obtain further compounds I. The compounds thus obtained are listed in the tables below with physical details. example 1
Darstellung von E-2-Methoxyimino-2-[(2'-phthalimidooxymethyl)-phenyl]essigsäuremethylester Zu einer Lösung von 150 g (0,52 mol) E-2-Methoxyimino-2-[(2'-brommethyl)-phenyl]essigsäuremethylester und 85 g (0,52 mol) N-Hydroxyphthalimid in 350 ml N-Methylpyrrolidon tropft man 59 g (0,58 mol) Triethylamin und rührt 2 h bei 70°C. Man gießt das Reaktionsgemisch auf 2 1 Eiswasser, saugt die ausgefallenen Kristalle ab und nimmt sie in Methylenchlorid auf. Nach Waschen der organischen Phase mit Wasser, Trocknen über Natriumsulfat und Abrotieren des Lösungsmittels erhält man 168 g (88 % Ausbeute) E-2-Methoxyimino-2-[(2'-phthalimidooxymethyl) -phenyl] essigsäuremethylester als hellgraues Pulver vom Schmelzpunkt 152-153°C. 1H-NMR (CDCI3) : δ = 3,81 (s,3H); 3,95 (s,3H); 5,05(s,2H); Preparation of E-2-methoxyimino-2 - [(2'-phthalimidooxymethyl) phenyl] acetic acid methyl ester To a solution of 150 g (0.52 mol) of E-2-methoxyimino-2 - [(2'-bromomethyl) phenyl ] methyl acetate and 85 g (0.52 mol) of N-hydroxyphthalimide in 350 ml of N-methylpyrrolidone 59 g (0.58 mol) of triethylamine are added dropwise and the mixture is stirred at 70 ° C. for 2 h. The reaction mixture is poured onto 2 l of ice water, the crystals which have precipitated are filtered off and taken up in methylene chloride. After washing the organic phase with water, drying over sodium sulfate and spinning off the solvent, 168 g (88% yield) of E-2-methoxyimino-2 - [(2'-phthalimidooxymethyl) phenyl] acetic acid methyl ester as a light gray powder of melting point 152- 153 ° C. 1 H NMR (CDCI 3 ): δ = 3.81 (s, 3H); 3.95 (s, 3H); 5.05 (s. 2H);
7,12-7, 81(m,8H) ppm. 7.12-7.81 (m, 8H) ppm.
Beispiel 2 Darstellung von (E,E)-2-Methoxyimino-2-[2'-[(1"-methyl,1" Example 2 Preparation of (E, E) -2-methoxyimino-2- [2 '- [(1 "-methyl, 1"
-hydroxycarbonyl)-iminooxymethyl]phenyl]-essigsäuremethylester  -hydroxycarbonyl) -iminooxymethyl] phenyl] -acetic acid methyl ester
Zu einer Lösung von 100 g (0,27 mol) der Verbindung aus Beispiel 1 in 1000 ml Methanol gibt man 14 g (0,28 mol) Hydrazinhydrat und läßt 1 h bei Raumtemperatur nachrühren. Anschließend gibt man 30 g Molsieb (3 Å) und 24 g (0,27 mol) Brenztraubensäure zu und läßt erneut 1 h nachrühren. Das Reaktionsgemisch wird filtriert und das Filtrat eingeengt. Der Rückstand wird anschließend in gesättigter NaHCO3 - Lösung aufgenommen und mit Methylenchlorid extrahiert. Nach Ansäuren der wäßrigen Phase mit 2 M Salzsäure wird erneut mit Methylenchlorid extrahiert, die organische Phase mit Wasser gewaschen, über Natriumsulfat getrocknet und eingeengt. Man erhält so 71 g (86 % Ausbeute) der Titelverbindung. 1H-NMR (CDCl3) : δ = 2,20 (s,3H); 3,87 (s,3H); 4,04 (s,3H); 5,13 (s,2H); 7,15-7,46 (m,4H); 8,80 (s,br,1H) ppm. 14 g (0.28 mol) of hydrazine hydrate are added to a solution of 100 g (0.27 mol) of the compound from Example 1 in 1000 ml of methanol and the mixture is stirred at room temperature for 1 h. Then 30 g of molecular sieve (3 Å) and 24 g (0.27 mol) of pyruvic acid are added and the mixture is stirred again for 1 h. The reaction mixture is filtered and the filtrate is concentrated. The residue is then taken up in saturated NaHCO 3 solution and extracted with methylene chloride. After acidifying the aqueous phase with 2 M hydrochloric acid, the mixture is extracted again with methylene chloride, the organic phase is washed with water, dried over sodium sulfate and concentrated. This gives 71 g (86% yield) of the title compound. 1 H NMR (CDCl 3 ): δ = 2.20 (s, 3H); 3.87 (s, 3H); 4.04 (s, 3H); 5.13 (s, 2H); 7.15-7.46 (m, 4H); 8.80 (s, br, 1H) ppm.
Beispiel 3 Darstellung von (E, E)-2-Methoxyimino-2-[2'-[1"-methyl, 1"-methoxyaminocarbonyl)-iminooxymethyl]-phenyl]essigsäuremethylester Example 3 Preparation of (E, E) -2-methoxyimino-2- [2 '- [1 "-methyl, 1" -methoxyaminocarbonyl) -iminooxymethyl] -phenyl] acetic acid methyl ester
Zu einer Lösung von 71 g (0,23 mol) der Verbindung aus Beispiel 2 in 1000 ml Tetrahydrofuran werden 37 g (0,23 mol) Carbonyldiimidazol gegeben. Nach Beendigung der Gasentwicklung versetzt man portionsweise mit 38 g (0,46 mol) Methoxyaminhydrochlorid und läßt 16 h bei Raumtemperatur nachrühren. Anschließend wird eingeengt, der Rückstand in Methylenchlorid aufgenommen und die organische Phase zunächst mit gesättigter NaHCO3-Lösung extrahiert. Nach Waschen der organischen Phase mit 2 M Salzsäure und Wasser wird über Natriumsulfat getrocknet und eingeengt. Man erhält so 72,5 g (94 % Ausbeute) der TitelVerbindung als weißes Pulver vom Schmelzpunkt 105-108°C. 37 g (0.23 mol) of carbonyldiimidazole are added to a solution of 71 g (0.23 mol) of the compound from Example 2 in 1000 ml of tetrahydrofuran. When the evolution of gas has ended, 38 g (0.46 mol) of methoxyamine hydrochloride are added in portions and the mixture is stirred at room temperature for 16 h. The mixture is then concentrated, the residue is taken up in methylene chloride and the organic phase is first extracted with saturated NaHCO 3 solution. After washing the organic phase with 2 M hydrochloric acid and water, it is dried over sodium sulfate and concentrated. You get like that 72.5 g (94% yield) of the title compound as a white powder with a melting point of 105-108 ° C.
1H-NMR (CDCl3) : δ = 2,00 (s,3H); 3,77 (s,3H); 3,88 (s,3H); 4,03 (s,3H); 5,00 (s,2H); 7,13-7,42 (m, 4H) ; 9,19 (s,1H) ppm. 1 H NMR (CDCl 3 ): δ = 2.00 (s, 3H); 3.77 (s, 3H); 3.88 (s, 3H); 4.03 (s, 3H); 5.00 (s, 2H); 7.13-7.42 (m, 4H); 9.19 (s, 1H) ppm.
Beispiel 4: Darstellung von (Z, E, E)-2-Methoxyimino-2- {2'-[(1"-methyl,1"-(1"'-brom-, 1"'-methoxyiminomethyl))-iminooxymethyl]-phenyl}-essigsäuremethylester Example 4: Preparation of (Z, E, E) -2-methoxyimino-2- {2 '- [(1 "-methyl, 1" - (1 "' - bromo-, 1" '- methoxyiminomethyl)) - iminooxymethyl ] -phenyl} methyl acetate
Eine Mischung aus 50g (0.15 mol) der Verbindung aus Beispiel 3 und 117g (0.45 mol) Triphenylphosphin in 1000 ml Acetonitril wurde portionsweise mit 148g (0.45 mol) Tetrabrommethan versetzt. Die so erhaltene Mischung wurde für 100h refluxiert, anschließend ließ man auf Raumtemperatur (≈ 25°C) abkühlen. Die Reaktionsmischung wurde von Feststoffen befreit. Vom Filtrat wurde unter vermindertem Druck das Lösungsmittel abdestilliert und der so erhaltene Rückstand wurde säulenchromatographisch [Kieselgel; tert.-Butyl-methylether/Hexan] gereinigt. Zur weiteren Reinigung wurde das so erhaltene Produkt umkristallisiert [Methylenchlorid/ Hexan]. Man erhielt 34g (58%) der Titelverbindung als farbloses Pulver [Fp.: 103-105°C]. 1H-NMR (δ in ppm; CDCI3): 2.10 (s,3H); 3.86 (s,3H); 4.05 (s,3H); 4.10 (s,3H); 5.16 (s,2H); 7.16-7.51 (m, 4H) A mixture of 50 g (0.15 mol) of the compound from Example 3 and 117 g (0.45 mol) of triphenylphosphine in 1000 ml of acetonitrile was mixed in portions with 148 g (0.45 mol) of tetrabromomethane. The mixture thus obtained was refluxed for 100 h, then allowed to cool to room temperature (≈ 25 ° C). Solids were removed from the reaction mixture. The solvent was distilled off from the filtrate under reduced pressure and the residue thus obtained was subjected to column chromatography [silica gel; tert-butyl methyl ether / hexane] cleaned. For further purification, the product obtained in this way was recrystallized [methylene chloride / hexane]. 34 g (58%) of the title compound were obtained as a colorless powder [mp .: 103-105 ° C.]. 1H-NMR (δ in ppm; CDCI 3 ): 2.10 (s, 3H); 3.86 (s, 3H); 4.05 (s, 3H); 4.10 (s, 3H); 5.16 (s, 2H); 7.16-7.51 (m, 4H)
Beispiel 5: Darstellung von (Z,E,E)-2-Methoxyimino-2- {2'-[(1"-methyl, 1"-(1"'-brom-, 1"'-methoxyiminomethyl))-iminooxymethyl]-phenyl}-essigsäure-N-methylamid Example 5: Preparation of (Z, E, E) -2-methoxyimino-2- {2 '- [(1 "-methyl, 1" - (1 "' - bromo-, 1" '- methoxyiminomethyl)) - iminooxymethyl ] -phenyl} -acetic acid-N-methylamide
Eine Lösung von 8g (20 mmol) der Verbindung aus Beispiel 4 in 200 ml Tetrahydrofuran wurde mit 50 ml Methylamin-Lösung (40%-ig in Wasser) versetzt. Nach 20min bei Raumtemperatur (ca. 25°C) wurde das Reaktionsgemisch in gekühlte 2n Salzsäure gegossen. Das A solution of 8 g (20 mmol) of the compound from Example 4 in 200 ml of tetrahydrofuran was mixed with 50 ml of methylamine solution (40% in water). After 20 minutes at room temperature (approx. 25 ° C.), the reaction mixture was poured into cooled 2N hydrochloric acid. The
Produkt wurde aus der so erhaltenen Mischung mit tert.-Butyl-methylether extrahiert. Aus der Etherphase erhielt man nach Waschen mit Wasser, Trocknen und Entfernen des Lösungsmittels 7,7g (96%) der Titelverbindung als farbloses Pulver [Fp.: 135-137°C]. Product was extracted from the mixture thus obtained with tert-butyl methyl ether. After washing with water, drying and removal of the solvent, 7.7 g (96%) of the title compound were obtained from the ether phase as a colorless powder [mp: 135-137 ° C.].
1H-NMR (δ in ppm; CDCI3) : 2.09 (s,3H); 2.88 (d,3H); 3.94 (s,3H); 4.08 (s,3H); 5.15 (s,2H); 6.74 (s,br,1H); 7.15-7.51 (m,4H) Beispiel 6: Darstellung von (Z,E,E)-2-Methoxyimino-2- {2'-[(1"-methyl, 1"-(1"'-(1""-pyrazolyl), 1"'-methoxyiminomethyl))-iminooxymethyl]-phenyl}-essigsäure- N-methylamid (Beispiel 1.011) 1H NMR (δ in ppm; CDCI 3 ): 2.09 (s, 3H); 2.88 (d. 3H); 3.94 (s, 3H); 4.08 (s, 3H); 5.15 (s, 2H); 6.74 (s, br, 1H); 7.15-7.51 (m, 4H) Example 6: Preparation of (Z, E, E) -2-methoxyimino-2- {2 '- [(1 "-methyl, 1" - (1 "' - (1""- pyrazolyl), 1"'- methoxyiminomethyl)) - iminooxymethyl] -phenyl} -acetic acid- N-methylamide (Example 1.011)
Eine Mischung von lg (40 mmol) Natriumhydrid und 100 ml Dimethylformamid wurde tropfenweise mit einer Lösung von 2.7g (40 mmol) Pyrazol in 50 ml Dimethylformamid versetzt. Nach 30min bei Raumtemperatur (ca. 25°C) wurde die so erhaltene Mischung mit einer Lösung von 7.7g (19mmol) der Verbindung aus Beispiel 5 in 100 ml Dimethylformamid versetzt. Die Reaktionsmischung wurde für 1h bei 100°C belassen. Nach dem Abkühlen gab man die Mischung auf Wasser. Das Produkt wurde aus der so erhaltenen Mischung mit tert.-Butylmethylether extrahiert. Aus der Etherphase erhielt man nach Wasehen mit verdünnter Salzsäure und Wasser, Trocknen und Entfernen des Lösungsmittels 5,7g (76%) der TitelVerbindung als farbloses Öl. A mixture of 1 g (40 mmol) sodium hydride and 100 ml dimethylformamide was added dropwise with a solution of 2.7 g (40 mmol) pyrazole in 50 ml dimethylformamide. After 30 minutes at room temperature (approx. 25 ° C.), the mixture thus obtained was mixed with a solution of 7.7 g (19 mmol) of the compound from Example 5 in 100 ml of dimethylformamide. The reaction mixture was left at 100 ° C for 1 h. After cooling, the mixture was poured into water. The product was extracted from the mixture thus obtained with tert-butyl methyl ether. After washing with dilute hydrochloric acid and water, drying and removal of the solvent, 5.7 g (76%) of the title compound were obtained from the ether phase as a colorless oil.
1H-NMR (δ in ppm; CDCI3) : 2.04 (s,3H); 2.87 (d, 3H); 3.91 (s,3H); 4.02 (s,3H); 5.05 (s,2H); 6.38 (t,1H); 7.01 (s,br,1H); 7.20-7.40 (m,4H); 7.65 (d,1H); 7.95 (d,1H) 1H-NMR (δ in ppm; CDCI 3 ): 2.04 (s, 3H); 2.87 (d, 3H); 3.91 (s, 3H); 4.02 (s, 3H); 5.05 (s, 2H); 6.38 (t, 1H); 7.01 (s, br, 1H); 7.20-7.40 (m, 4H); 7.65 (d. 1H); 7.95 (d, 1H)
Beispiel 7: Darstellung von (Z,E,E)-2-Methoxyimino-2-{2'-[(1"-methyl, 1"-(1"'-(1""-piperidinyl), 1"'-methoxyiminomethyl))-iminooxymethyl]-phenyl}- essigsäure-methylester (Beispiel 1.002) Example 7: Preparation of (Z, E, E) -2-methoxyimino-2- {2 '- [(1 "-methyl, 1" - (1 "' - (1" "- piperidinyl), 1" '- methoxyiminomethyl)) - iminooxymethyl] phenyl} - methyl acetate (Example 1.002)
Eine Mischung aus 1.0g (7 mmol) Kaliumcarbonat und 100 ml A mixture of 1.0g (7 mmol) potassium carbonate and 100 ml
Dimethylformamid wurde zunächst mit 2.0g (5 mmol) der Verbindung aus Beispiel 4 und anschließend mit 4.3g (50 mmol) Piperidin versetzt. Nach 60h bei Raumtemperatur (ca. 25°C) wurde das Reaktions- gemisch auf gekühlte, verdünnte Salzsäure gegossen. Das Produkt wurde aus der so erhaltenen Mischung mit tert. -Butyl-methylether extrahiert. Aus der Etherphase erhielt man nach Waschen mit Was- ser, Trocknen und Entfernen des Lösungsmittels 0.8g (40%) der Titelverbindung als farbloses Öl. Dimethylformamide was first mixed with 2.0 g (5 mmol) of the compound from Example 4 and then with 4.3 g (50 mmol) of piperidine. After 60 h at room temperature (approx. 25 ° C), the reaction mixture was poured onto cooled, dilute hydrochloric acid. The product was tert with from the mixture thus obtained. -Butyl methyl ether extracted. After washing with water, drying and removing the solvent, 0.8 g (40%) of the title compound was obtained as a colorless oil from the ether phase.
1H-NMR (δ in ppm; CDCI3) : 1.45-1.60 (m, 6H) ; 1.94 (s,3H); 3.04-3.11 (m,4H); 3.66 (s,3H); 3.86 (s,3H); 4.04 (s,3H); 5.06 (s,2H); 1H-NMR (δ in ppm; CDCI 3 ): 1.45-1.60 (m, 6H); 1.94 (s, 3H); 3.04-3.11 (m, 4H); 3.66 (s, 3H); 3.86 (s, 3H); 4.04 (s, 3H); 5.06 (s, 2H);
7.17-7.50 (m,4H) Beispiel 8: Darstellung von (Z, E, E)-2-Methoxyimino-2- {2'-[{1"-methyl, 1" -(1"'-(1""-piperidinyl), 7.17-7.50 (m, 4H) Example 8: Preparation of (Z, E, E) -2-methoxyimino-2- {2 '- [{1 "-methyl, 1" - (1 "' - (1""- piperidinyl),
1"'-methoxyiminomethyl))-iminooxymethyl]- phenyl}-essigsäure-N-methylamid (Beispiel 1.007)  1 "'- methoxyiminomethyl)) - iminooxymethyl] - phenyl} -acetic acid-N-methylamide (Example 1.007)
Eine Lösung aus 0.8g (2 mmol) der Verbindung aus Beispiel 7 in 100 ml Tetrahydrofuran wurde mit 10 ml Methylamin-Lösung (40%-ig in Wasser) versetzt. Nach 60h bei Raumtemperatur (ca. 25°C) wurde das Reaktionsgemisch in Wasser gegossen. Das Produkt wurde aus der so erhaltenen Mischung mit tert. -Butyl-methylether extrahiert. Aus der Etherphase erhielt man nach Waschen mit Wasser, Trocknen und Entfernen des Lösungsmittels 0.7g (87%) der Titelverbindung als farbloses Öl. 1H-NMR (δ in ppm; CDCI3): 1.41-1.62 (m, 6H) ; 1.93 (s,3H); 2.88 (d,3H); 2.98-3.06 (m,4H); 3.65 (s,3H); 3.94 (s,3H); 5.05 (s,2H); 6.80 (s,br,1H); 7.17-7.46 (m,4H) A solution of 0.8 g (2 mmol) of the compound from Example 7 in 100 ml of tetrahydrofuran was mixed with 10 ml of methylamine solution (40% in water). After 60 hours at room temperature (approx. 25 ° C) the reaction mixture was poured into water. The product was tert with from the mixture thus obtained. -Butyl methyl ether extracted. After washing with water, drying and removal of the solvent, 0.7 g (87%) of the title compound was obtained as a colorless oil from the ether phase. 1H-NMR (δ in ppm; CDCI 3 ): 1.41-1.62 (m, 6H); 1.93 (s, 3H); 2.88 (d. 3H); 2.98-3.06 (m, 4H); 3.65 (s, 3H); 3.94 (s, 3H); 5.05 (s, 2H); 6.80 (s, br, 1H); 7.17-7.46 (m, 4H)
Beispiel 9 Example 9
Darstellung von E-2-Benzyloxyimino, -N-methoxy-propionamid Preparation of E-2-benzyloxyimino, -N-methoxy-propionamide
Zu einer Lösung von 65 g (337 mmol) (E)-2-Benzyloxyiminopropionsäure (J. Org. Chem. 46 (1981), 3346-8) in 500 ml Tetrahydrofuran wurden portionsweise 55 g (337 mmol) Carbonyldiimidazol gegeben. Nach Beendigung der Gasentwicklung versetzte man portionsweise mit 43 g (510 mmol) Methoxyaminhydrochlorid und ließ 2 Stunden bei Raumtemperatur nachrühren. Der ausgefallene Niederschlag wurde abgesaugt und das Filtrat auf 2 M Salzsäure gegossen. Nach Extraktion mit tert.-Butylmethylether, Waschen der organischen Phase mit Wasser, Trocknen über Natriumsulfat und Entfernen des Lösungsmittels erhielt man 53,5 g (72 % Ausbeute) der Ti telverbindung als weißes Pulver vom Schmelzpunkt 59-62°C. 1H-NMR (δ in ppm; CDCI3) : 2,05 (s,3H); 3,78 (s,3H); 5,17 (s,2H); 7,25-7,40 (m,5H); 9,17 (s,1H). 55 g (337 mmol) of carbonyldiimidazole were added in portions to a solution of 65 g (337 mmol) of (E) -2-benzyloxyiminopropionic acid (J. Org. Chem. 46 (1981), 3346-8) in 500 ml of tetrahydrofuran. After the evolution of gas had ended, 43 g (510 mmol) of methoxyamine hydrochloride were added in portions and the mixture was stirred at room temperature for 2 hours. The precipitate was filtered off and the filtrate was poured onto 2 M hydrochloric acid. After extraction with tert-butyl methyl ether, washing the organic phase with water, drying over sodium sulfate and removal of the solvent, 53.5 g (72% yield) of the titanium compound were obtained as a white powder with a melting point of 59-62 ° C. 1 H NMR (δ in ppm; CDCI 3 ): 2.05 (s, 3H); 3.78 (s, 3H); 5.17 (s, 2H); 7.25-7.40 (m, 5H); 9.17 (s, 1H).
Beispiel 10 Darstellung von E-2-Benzyloxyimino, (Z)-N-methoxy-propanimidoylbromid Example 10 Preparation of E-2-benzyloxyimino, (Z) -N-methoxypropanimidoyl bromide
Eine Mischung aus 53,5 g (240 mmol) der Verbindung aus Beispiel 9 und 189 g (720 mmol) Triphenylphosphin in 1000 ml Acetonitril wurde portionsweise mit 240 g (720 mmol) Tetrabrommethan versetzt. Die so erhaltene Mischung wurde für 72 h refluxiert, anschließend ließ man auf Raumtemperatur (ca. 25°C) abkühlen. Die Reaktionsmischung wurde von Feststoffen befreit. Vom Filtrat wurde unter vermindertem Druck das Lösungsmittel abdestilliert und der so erhaltene Rückstand wurde säulenchromatographisch A mixture of 53.5 g (240 mmol) of the compound from Example 9 and 189 g (720 mmol) of triphenylphosphine in 1000 ml of acetonitrile was added in portions with 240 g (720 mmol) of tetrabromomethane. The mixture thus obtained was refluxed for 72 h, then allowed to cool to room temperature (approx. 25 ° C.). The Solids were removed from the reaction mixture. The solvent was distilled off from the filtrate under reduced pressure and the residue thus obtained was subjected to column chromatography
[Kieselgel; tert.-Butyl-methylether/Cyclohexan] gereinigt. Man erhielt so 59 g (87 % Ausbeute) der Titelverbindung als farbloses Öl.  [Silica gel; tert-butyl methyl ether / cyclohexane] cleaned. This gave 59 g (87% yield) of the title compound as a colorless oil.
1H-NMR (δ in ppm; CDCI3): 2,15 (s,3H); 4,08 (s,3H); 5,25 (s,2H); 7,26-7,45 (m,5H). 1 H NMR (δ in ppm; CDCI 3 ): 2.15 (s, 3H); 4.08 (s, 3H); 5.25 (s, 2H); 7.26-7.45 (m, 5H).
Beispiel 11 Example 11
Darstellung von 1-((E)-2-Benzyloxyimino, (Z)-N-methoxy-propanimidoyl)-4-methylpyrazol Preparation of 1 - ((E) -2-benzyloxyimino, (Z) -N-methoxy-propanimidoyl) -4-methylpyrazole
Zu einer Suspension von 4,8 g (200 mmol) Natriumhydrid in 200 ml Dimethylformamid wurden 16,4 g (200 mmol) 4-Methylpyrazol zugetropft. Nach 30 min bei Raumtemperatur (ca. 25°C) wurde die so erhaltene Mischung mit einer Lösung von 20 g (70 mmol) der Verbindung aus Beispiel 10 in 100 ml Dimethylformamid versetzt und der Reaktionsansatz 16 Stunden bei Raumtemperatur gerührt. Das Reaktionsgemisch wurde auf 2 M Salzsäure gegossen und mit tert.-Butylmethylether extrahiert. Aus der Etherphase erhielt man nach Waschen mit 2 M Salzsäure und Wasser, Trocknen und Entfernen des Lösungsmittels 11 g (55 % Ausbeute) der TitelVerbindung als hellbraunes Öl. 16.4 g (200 mmol) of 4-methylpyrazole were added dropwise to a suspension of 4.8 g (200 mmol) of sodium hydride in 200 ml of dimethylformamide. After 30 min at room temperature (approx. 25 ° C.), the mixture thus obtained was mixed with a solution of 20 g (70 mmol) of the compound from Example 10 in 100 ml of dimethylformamide and the reaction mixture was stirred for 16 hours at room temperature. The reaction mixture was poured onto 2 M hydrochloric acid and extracted with tert-butyl methyl ether. After washing with 2 M hydrochloric acid and water, drying and removal of the solvent, 11 g (55% yield) of the title compound were obtained from the ether phase as a light brown oil.
1H-NMR (δ in ppm; CDCI3): 2,08 (s,3H); 2,10 (s,3H); 4,00 (s,3H); 5,18 (s,2H); 7,25-7,40 (m,5H); 7,47 (s,1H); 7,80 (s,1H). 1 H NMR (δ in ppm; CDCI 3 ): 2.08 (s, 3H); 2.10 (s, 3H); 4.00 (s, 3H); 5.18 (s. 2H); 7.25-7.40 (m, 5H); 7.47 (s, 1H); 7.80 (s, 1H).
Beispiel 12 Example 12
Darstellung von 1- ((E)-2-Hydroxyimino, (Z)-N-methoxy-propanimidoyl)-4-methylpyrazol Preparation of 1- ((E) -2-hydroxyimino, (Z) -N-methoxypropanimidoyl) -4-methylpyrazole
11,0 g (38,6 mmol) der Verbindung aus Beispiel 11 wurden mit 250 ml Ethanol gelöst und unter Stickstoffatmosphäre mit 5 g Palladium auf Aktivkohle (10 %) versetzt. Nach Spülen der Reaktionsapparatur mit Wasserstoff wurde bei 60°C so lange gerührt, bis kein Wasserstoff mehr aufgenommen wurde. Nach Spülen der Apparatur mit Stickstoff wurde der Katalysator abfiltriert, das Filtrat eingeengt und der Rückstand in 10%iger Natronlauge aufgenommen. Nach Extraktion mit tert. -Butylmethylether wurde die wäßrige Phase mit 2 M Salzsäure angesäuert und mit tert.-Butylmethylether extrahiert. Die organische Phase wurde mit Wasser gewaschen, über hielt so 2,5 g (29 % Ausbeute) der Titelverbindung als hellgelbes Öl. 11.0 g (38.6 mmol) of the compound from Example 11 were dissolved with 250 ml of ethanol and 5 g of palladium on activated carbon (10%) were added under a nitrogen atmosphere. After flushing the reaction apparatus with hydrogen, the mixture was stirred at 60 ° C. until no more hydrogen was taken up. After flushing the apparatus with nitrogen, the catalyst was filtered off, the filtrate was concentrated and the residue was taken up in 10% sodium hydroxide solution. After extraction with tert. Butyl methyl ether, the aqueous phase was acidified with 2 M hydrochloric acid and extracted with tert-butyl methyl ether. The organic phase was washed with water, over thus held 2.5 g (29% yield) of the title compound as a light yellow oil.
1H-NMR (δ in ppm; CDCI3): 2,11 (s,6H); 3,99 (s,3H); 7,48 (s, 1H); 7,73 (s,1H). 1 H NMR (δ in ppm; CDCI 3 ): 2.11 (s, 6H); 3.99 (s, 3H); 7.48 (s, 1H); 7.73 (s, 1H).
Beispiel 13 Example 13
Darstellung von (Z,E,E)-2-{2'-[(1"-methyl,1"-(1'"-(1""-4-methylpyrazolyl),1"'-methoxyiminomethyl))-iminooxymethyl]-phenyl}-crotonsäuremethylester (Beispiel 1.022) Preparation of (Z, E, E) -2- {2 '- [(1 "-methyl, 1" - (1' "- (1" "- 4-methylpyrazolyl), 1" '- methoxyiminomethyl)) - iminooxymethyl ] -phenyl} -crotonic acid methyl ester (Example 1.022)
Zu 0,12 g (4 mmol) Natriumhydrid (80 %) in 10 ml Dimethylformamid gab man 0,8 g (3,6 mmol, der Verbindung aus Beispiel 12, gelöst in 10 ml Dimethylformamid. Man ließ 30 min nachrühren, gab anschließend 0,97 g (E)-3-Methyl-2-[(2'-brommethyl)phenyl]acrylsäuremethylester zu und ließ 16 Stunden bei Raumtemperatur rühren. Das Reaktionsgemisch wurde auf Wasser gegossen und mit tert.-Butylmethylether extrahiert. Die organische Phase wurde mit Natronlauge (10 %) und Wasser gewaschen, getrocknet und eingeengt. Nach Säulenchromatographie an Kieselgel (tert.-Butylmethylether/n-Hexan) erhielt man 1,2 g (51 % Ausbeute) der Titelverbindung als farbloses Öl. 1H-NMR (δ in ppm; CDCI3): 1,59 (d, 3H); 2,05 (s,3H); 2,11 (s,3H); 3,67 (s,3H); 4,01 (s,3H); 5,05 (s,br,2H); 7,02-7,51 (m, 6H); 7,80 (S,1H). 0.8 g (3.6 mmol, the compound from Example 12, dissolved in 10 ml of dimethylformamide) was added to 0.12 g (4 mmol) of sodium hydride (80%) in 10 ml of dimethylformamide. The mixture was allowed to stir for 30 minutes and then added 0.97 g of (E) -3-methyl-2 - [(2'-bromomethyl) phenyl] acrylic acid methyl ester and allowed to stir for 16 hours at room temperature The reaction mixture was poured into water and extracted with tert-butyl methyl ether The organic phase was washed with sodium hydroxide solution (10%) and water, dried and evaporated in. After column chromatography on silica gel (tert-butyl methyl ether / n-hexane), 1.2 g (51% yield) of the title compound were obtained as a colorless oil. 1 H-NMR (δ in ppm; CDCI 3 ): 1.59 (d, 3H); 2.05 (s, 3H); 2.11 (s, 3H); 3.67 (s, 3H); 4.01 (s , 3H); 5.05 (s, br, 2H); 7.02-7.51 (m, 6H); 7.80 (S, 1H).
Beispiel 14 Example 14
Darstellung von display of
(Z,E,E)-3-Methoxy-2-{2'-[(1"-methyl,1"-(1"'-(1""-4-methylpyrazolyl),1"'-methoxyiminomethyl))-iminooxymethyl]-phenyl}-acrylsäuremethylester (Beispiel 1.023) (Z, E, E) -3-methoxy-2- {2 '- [(1 "-methyl, 1" - (1 "' - (1" "- 4-methylpyrazolyl), 1" '- methoxyiminomethyl)) -iminooxymethyl] -phenyl} -acrylic acid methyl ester (Example 1.023)
Zu 0,12 g (4 mmol) Natriumhydrid (80 %) in 10 ml Dimethylformamid gab man 0,8 g (3,6 mmol) der Verbindung aus Beispiel 12, gelöst in 10 ml Dimethylformamid. Man ließ 30 min nachrühren, gab anschließend 1,0 g (3,6 mmol) (E)-3-Methoxy-2-[(2'-brommethyl)phenyl] acrylsäuremethylester zu und ließ 16 Stunden bei Raumtemperatur rühren. Das Reaktionsgemisch wurde auf Wasser gegossen und mit tert.-Butylmethylether extrahiert. Die organische Phase wurde mit Natronlauge (10 %) und Wasser gewaschen, getrocknet und eingeengt. Nach Säulenchromatographie an Kieselgel ( tert.-Butylmethylether/n-Hexan) erhielt man 1,0 g (65 % Ausbeute) der Titelverbindung als farbloses Öl. 1H-NMR (δ in ppm; CDCI3): 2,06 (s, 3H); 2,11 (s, 3H); 3,66 (s,3H); 3,79 (s, 3H); 4,02 (s, 3H); 5,14 (s, 2H); 7,10-7,55 (m, 6H); 7,83 (s,1H). 0.8 g (3.6 mmol) of the compound from Example 12, dissolved in 10 ml of dimethylformamide, was added to 0.12 g (4 mmol) of sodium hydride (80%) in 10 ml of dimethylformamide. The mixture was allowed to stir for 30 min, then 1.0 g (3.6 mmol) of (E) -3-methoxy-2 - [(2'-bromomethyl) phenyl] acrylic acid methyl ester was added and the mixture was stirred at room temperature for 16 hours. The reaction mixture was poured onto water and extracted with tert-butyl methyl ether. The organic phase was washed with sodium hydroxide solution (10%) and water, dried and concentrated. After column chromatography on silica gel (tert-butyl methyl ether / n-hexane), 1.0 g (65% yield) of the title compound was obtained as a colorless oil. 1 H NMR (δ in ppm; CDCI 3 ): 2.06 (s, 3H); 2.11 (s, 3H); 3.66 (s, 3H); 3.79 (s, 3H); 4.02 (s, 3H); 5.14 (s, 2H); 7.10 - 7.55 (m, 6H); 7.83 (s, 1H).
Figure imgf000322_0001
Figure imgf000322_0001
Figure imgf000323_0001
Figure imgf000324_0001
Figure imgf000323_0001
Figure imgf000324_0001
Figure imgf000325_0001
Beispiele zur Wirkung gegen Schadpilze
Figure imgf000325_0001
Examples of the action against harmful fungi
Die fungizide Wirkung der Verbindungen der Formel I ließ sich durch folgende Versuche zeigen: The fungicidal activity of the compounds of the formula I was demonstrated by the following tests:
Die Wirkstoffe wurden als 20 %-ige Emulsion in einem Gemisch aus 70 Gew.-% Cyclohexanon, 20 Gew.-% Nekanil® LN (Lutensol® AP6, Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxylierter Alkylphenole) und 10 Gew.-% Emulphor® EL (Emulan® EL, Emulgator auf der Basis ethoxylierter Fettalkohole) aufbereitet und entsprechend der gewünschten Konzentration mit Wasser verdünnt. Als Vergleichsverbindungen dienten die bekannten Wirkstoffe & (gemäß WO-A 95/21,154; X = NOCH3 ; YR1 = NHCH3 ; R2 m = H; R3 = R4 = CH3; Z' = 1-CH3-pyrazol-3-yl), B (gemäß WO-A 95/21,154; X = NOCH3 ; YR1 = NHCH3; R2 m = H; R3 = R4 = CH3 ; Z' = pyrimidin-2-yl) und C (gemäß WO-A 95/21,158; X = NOCH3 ; YR1 = OCH3 ; R2 m = H; R3 = R4 = CH3; Z' = pyridin-3-yl). The active ingredients were administered as a 20% 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. % Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) prepared and diluted with water according to the desired concentration. The known active ingredients & (according to WO-A 95 / 21,154; X = NOCH 3 ; YR 1 = NHCH 3 ; R 2 m = H; R 3 = R 4 = CH 3 ; Z '= 1-CH 3 - pyrazol-3-yl), B (according to WO-A 95 / 21,154; X = NOCH 3 ; YR 1 = NHCH 3 ; R 2 m = H; R 3 = R 4 = CH 3 ; Z '= pyrimidin-2- yl) and C (according to WO-A 95 / 21,158; X = NOCH 3 ; YR 1 = OCH 3 ; R 2 m = H; R 3 = R 4 = CH 3 ; Z '= pyridin-3-yl).
Wirkung gegen Erysiphe graminis var. tritici (Weizenmehl tau) Effect against Erysiphe graminis var. Tritici (wheat flour dew)
Blätter von Weizenkeimlingen (Sorte "Frühgold") wurden zunächst mit der wäßrigen Aufbereitung der Wirkstoffe behandelt (Aufwandmenge: 63 ppm). Nach ca. 24 h wurden die Pflanzen mit Sporen des Weizenmehltaus (Erysiphe graminis var. tritici) bestäubt. Die so behandelten Pflanzen wurden anschließend für 7 Tage bei 20-22°C und einer relativen Luftfeuchtigkeit von 75-80% inkubiert. An- schließend wurde das Ausmaß der Pilzentwicklung ermittlelt. Leaves of wheat seedlings ("early gold" variety) were first treated with the aqueous preparation of the active ingredients (application rate: 63 ppm). After about 24 hours, the plants were dusted with spores of powdery mildew (Erysiphe graminis var. Tritici). The plants treated in this way were then incubated for 7 days at 20-22 ° C. and a relative atmospheric humidity of 75-80%. The extent of fungal development was then determined.
In diesem Test zeigten die mit den erfindungsgemäßen Verbindungen Nrs. 1.007, 1.011, 1.012, 1.014 und 1.016 behandelten Pflanzen einen Befall von 15% und weniger während die mit den bekannten Wirkstoffen A. und B behandelten Pflanzen zu 40% befallen waren. Die unbehandelten (Kontroll-) Pflanzen waren zu 70% befallen. In this test, the no. 1,007, 1,011, 1,012, 1,014 and 1,016 treated plants had an infection of 15% and less, while the plants treated with the known active ingredients A. and B were 40% infected. The untreated (control) plants were 70% infected.
Wirkung gegen Puccinia recondita (Weizenbraunrost) Blätter von Weizensämlingen (Sorte "Kanzler") wurden mit Sporen des Braunrosts (Puccinia recondita) bestäubt. Die so behandelten Pflanzen wurden 24 h bei 20-22°C und einer relativen Luftfeuchtigkeit von 90-95% inkubiert und anschließend mit der wäßrigen Wirkstoffaufbereitung behandelt (Aufwandmenge: 63 ppm). Nach weiteren 8 Tagen bei 20-22°C und 65-70% relativer Luftfeuchtigkeit wurde das Ausmaß der Pilzentwicklung ermittlelt. Die Auswertung erfolgte visuell. Effect against Puccinia recondita (wheat brown rust) Leaves of wheat seedlings (variety "Chancellor") were dusted with spores of the brown rust (Puccinia recondita). The plants treated in this way were incubated for 24 hours at 20-22 ° C. and a relative atmospheric humidity of 90-95% and then treated with the aqueous preparation of active compound (application rate: 63 ppm). After another 8 days at 20-22 ° C and 65-70% relative humidity the extent of fungal development is determined. The evaluation was done visually.
In diesem Test zeigten die mit den erfindungsgemäßen Verbindungen Nrs. 1.007, 1.011, 1.013 bis 1.017 und 1.019 behandelten Pflanzen einen Befall von 25% und weniger, während die mit den bekannten Wirkstoffen A, B und C behandelten Pflanzen ebenso wie die unbe handel ten (Kontroll-) Pf lanzen zu 75% befallen waren. Beispiele zur Wirkung gegen tierische Schädlinge In this test, the no. Plants treated with 1.007, 1.011, 1.013 to 1.017 and 1.019 had an infection of 25% or less, while the plants treated with the known active compounds A, B and C and the untreated (control) plants were 75% infected. Examples of action against animal pests
Die Wirkung der Verbindungen der allgemeinen Formel I gegen tierische Schädlinge ließ sich durch folgende Versuche zeigen: Die Wirkstoffe wurden The activity of the compounds of the general formula I against animal pests was demonstrated by the following tests: The active compounds were
a) als 0,1 %-ige Lösung in Aceton oder a) as a 0.1% solution in acetone or
b) als 10 %-ige Emulsion in einem Gemisch aus 70 Gew.-% Cyclohexanon, 20 Gew.-% Nekanil® LN (Lutensol® AP6, Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxy- lierter Alkylphenole) und 10 Gew.-% Emulphor® EL (Emulan® EL, Emulgator auf der Basis ethoxylierter Fettalkohole) aufbereitet und entsprechend der gewünschten Konzentration mit Aceton im Fall von a) bzw. mit Wasser im Fall von b) verdünnt. Nach Abschluß der Versuche wurde die jeweils niedrigste Konzentration ermittelt, bei der die Verbindungen im Vergleich zu Kontrollversuchen (ohne Behandlung) noch eine 80 - 100 %-ige Hemmung bzw. Mortalität hervorriefen (Wirkschwelle bzw. Minimalkonzentration). 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. % Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) prepared and diluted with acetone in the case of a) or with water in the case of b) according to the desired concentration. After the end of the tests, the lowest concentration was determined at which the compounds still caused 80-100% inhibition or mortality compared to control tests (without treatment) (threshold of action or minimum concentration).

Claims

Patentansprüche claims
1. Phenylessigsäuren der Formel I 1. Phenylacetic acids of the formula I.
Figure imgf000328_0001
in der die Substituenten und der Index die folgende Bedeutung haben:
Figure imgf000328_0001
in which the substituents and the index have the following meaning:
X NOCH3, CHOCH3, CHCH3 und CHCH2CH3 ; X NOCH 3 , CHOCH 3 , CHCH 3 and CHCH 2 CH 3 ;
Y O und NR; R Wasserstoff und C1-C4-Alkyl; YO and NR; R is hydrogen and C 1 -C 4 alkyl;
Z ein ggf. subst. über ein Stickstoffatom gebundener gesättigter oder partiell oder vollständig ungesättigter cyclischer Rest, welcher neben dem Stickstoffatom, über den er gebunden ist, neben Kohlenstoff-Ringliedern ein bis vier Heteroatome aus der Gruppe Stickstoff, Sauerstoff und Schwefel enthalten kann; Z a possibly subst. a saturated or partially or completely unsaturated cyclic radical bonded via a nitrogen atom, which, in addition to the nitrogen atom via which it is bonded, can contain, in addition to carbon ring members, one to four heteroatoms from the group consisting of nitrogen, oxygen and sulfur;
R1 Wasserstoff und C1-C4-Alkyl; R 1 is hydrogen and C 1 -C 4 alkyl;
R2 Cyano, Nitro, Trifluormethyl, Halogen, C1-C4-Alkyl und C1-C4-Alkoxy; m 0, 1 oder 2, wobei die Reste R2 verschieden sein können, wenn m für 2 steht; R 2 cyano, nitro, trifluoromethyl, halogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy; m is 0, 1 or 2, it being possible for the radicals R 2 to be different if m is 2;
R3 Wasserstoff, Cyano, Nitro, Hydroxy, Amino, Cyclopropyl, Halogen, C1-C4-Alkyl, C1-C4-Halogenalkyl, C1-C4-Alkoxy, C1-C4-Halogenalkoxy, C1-C4-Alkylthio, C1-C4-Alkylamino und Di-C1-C4-alkylamino; R 3 is hydrogen, cyano, nitro, hydroxy, amino, cyclopropyl, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylamino and di-C 1 -C 4 alkylamino;
R4 Wasserstoff, C1-C10-Alkyl, C2-C10-Alkenyl, C2-C10-Alkinyl, C1-C10-Alkylcarbonyl, C2-C10-Alkenylcarbonyl, C2-C10-Alkinylcarbonyl oder C1-C10-Alkylsulfonyl, wobei diese Reste partiell oder vollständig halogeniert sein können oder eine bis drei der folgenden Gruppen tragen können: R 4 is hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 10 alkylcarbonyl, C 2 -C 10 alkenylcarbonyl, C 2 -C 10 alkynylcarbonyl or C 1 -C 10 alkylsulfonyl, where these radicals can be partially or completely halogenated or can carry one to three of the following groups:
- Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl,  - cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl,
- Halogen, C1-C6-Halogenalkyl, C1-C6-Alkylsulfonyl, Halogen, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl,
C1-C6-Alkylsulfoxyl, C1-C6-Alkoxy, C1-C6-Halogenalkoxy, C1-C6-Alkoxycarbonyl, C1-C6-Alkylthio, C 1 -C 6 alkyl sulfoxyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio,
C1-C6-Alkylamino, Di-C1-C6-alkylamino, C1-C6-Alkylaminocarbonyl, Di-C1-C6-alkylaminocarbonyl, C 1 -C 6 alkylamino, di-C 1 -C 6 alkylamino, C 1 -C 6 alkylaminocarbonyl, di-C 1 -C 6 alkylaminocarbonyl,
C1-C6-Alkylaminothiocarbonyl, Di-C1-C6-alkylaminothiocarbonyl, C2-C6-Alkenyloxy, C 1 -C 6 alkylaminothiocarbonyl, di-C 1 -C 6 alkylaminothiocarbonyl, C 2 -C 6 alkenyloxy,
- C3-C6-Cycloalkyl, C3-C6-Cycloalkoxy, Heterocyclyl,- C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkoxy, heterocyclyl,
Heterocyclyloxy, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy und Hetarylthio, wobei die cyclisehen Gruppen ihrerseits partiell oder vollständig halogeniert sein können oder eine bis drei der folgenden Gruppen tragen können: Cyano, Nitro, Hydroxy,Heterocyclyloxy, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, where the cyclic groups can in turn be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy,
Mercapto, Amino, Carboxyl, Aminocarbonyl, Aminothiocarbonyl, Halogen, C1-C6-Alkyl, C3-C6- Cycloalkyl, C1-C6-Halogenalkyl, C1-C6-Alkylsulfonyl, C1-C6-Alkylsulfoxyl, C1-C6-Alkoxy, C1-C6-Halogenalkoxy, Mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 - Alkylsulfoxyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy,
C1-C6-Alkoxycarbonyl, C1-C6-Alkylthio, C1-C6-Alkyl- amino, Di-C1-C6-alkylamino, C1-C6-Alkylaminocarbonyl, Di-C1-C6-alkylaminocarbonyl, C1-C6-Alkylaminothiocarbonyl, Di-C1-C6-alkylaminothiocarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylamino, di-C 1 -C 6 alkylamino, C 1 -C 6 alkylaminocarbonyl, di-C 1 -C 6- alkylaminocarbonyl, C 1 -C 6 -alkylaminothiocarbonyl, di-C 1 -C 6 -alkylaminothiocarbonyl,
C2-C6-Alkenyl, C2-C6-Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy, Hetarylthio und C(=NORa)-An-Rb; C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C (= NOR a ) -A n -R b ;
C3-C6-Cycloalkyl, Aryl, Arylcarbonyl, Arylsulfonyl, C 3 -C 6 cycloalkyl, aryl, arylcarbonyl, arylsulfonyl,
Hetaryl, Hetarylcarbonyl und Hetarylsulfonyl, wobei dieese Reste partiell oder vollständig halogeniert sein können oder eine bis drei der folgenden Gruppen tragen können: - Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Hetaryl, hetarylcarbonyl and hetarylsulfonyl, where these residues can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl,
Aminocarbonyl, Aminothiocarbonyl,  Aminocarbonyl, aminothiocarbonyl,
- Halogen, C1-C6-Alkyl, C1-C6-Halogenalkyl, C1-C6-Alkylcarbonyl, C1-C6-Alkylsulfonyl, C1-C6-Alkylsulfoxyl, C3-C6-Cycloalkyl, C1-C6-Alkoxy, C1-C6-Halogenalkoxy, C1-C6-Alkoxycarbonyl, C1-C6-Alkylthio, C1-C6-Alkylamino, Di-C1-C6-alkylamino, C1-C6-Alkylaminocarbonyl, Di-C1-C6-alkylaminocarbonyl, C1-C6-Alkylaminothiocarbonyl, Di-C1-C6-alkylaminothiocarbonyl, - Halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylsulfoxyl, C 3 -C 6 cycloalkyl , C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 alkylamino, di-C 1 -C 6 alkylamino , C 1 -C 6 alkylaminocarbonyl, di-C 1 -C 6 alkylaminocarbonyl, C 1 -C 6 alkylaminothiocarbonyl, di-C 1 -C 6 alkylaminothiocarbonyl,
C2-C6-Alkenyl, C2-C6-Alkenyloxy, Benzyl, Benzyloxy, Aryl, Aryloxy, Hetaryl, Hetaryloxy und C (=NORa) -An-Rb; wobei C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, benzyl, benzyloxy, Aryl, aryloxy, hetaryl, hetaryloxy and C (= NOR a ) -A n -R b ; in which
A für Sauerstoff, Schwefel und Stickstoff steht und wobei der Stickstoff Wasserstoff oder C1-C6-Alkyl trägt; n 0 oder 1 bedeutet, und A represents oxygen, sulfur and nitrogen and the nitrogen carries hydrogen or C 1 -C 6 alkyl; n represents 0 or 1, and
Ra,Rb jeweils für Wasserstoff oder C1-C6-Alkyl stehen, sowie deren Salze. R a , R b each represent hydrogen or C 1 -C 6 alkyl, and their salts.
2. Verbindungen der Formel I gemäß Anspruch 1, in denen m für 0 steht. 2. Compounds of formula I according to claim 1, in which m is 0.
3. Verbindungen der Formel I gemäß Anspruch 1, in denen R1 für Methyl steht. 3. Compounds of formula I according to claim 1, in which R 1 is methyl.
4. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1, in denen R3 nicht Halogen bedeutet, dadurch gekennzeichnet, daß man ein Benzylderivat der Formel II 4. A process for the preparation of the compounds of formula I according to claim 1, in which R 3 is not halogen, characterized in that a benzyl derivative of formula II
Figure imgf000330_0001
in der L1 für eine nucleophil austauschbare Abgangsgruppe steht, in an sich bekannter Weise mit einem Hydroxyimin der Formel III
Figure imgf000330_0002
umsetzt.
Figure imgf000330_0001
in which L 1 represents a nucleophilically exchangeable leaving group, in a manner known per se, with a hydroxyimine of the formula III
Figure imgf000330_0002
implements.
5. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1, in denen R3 nicht Halogen bedeutet, dadurch gekennzeichnet, daß man ein Benzylderivat der Formel II gemäß5. A process for the preparation of the compounds of formula I according to claim 1, in which R 3 is not halogen, characterized in that a benzyl derivative of the formula II according to
Anspruch 4 in an sich bekannter Weise mit einem Dihydroxyimin der Formel IIIa
Figure imgf000331_0001
zu einer Verbindung der Formel IVa Claim 4 in a manner known per se with a dihydroxyimine of the formula IIIa
Figure imgf000331_0001
to a compound of formula IVa
Figure imgf000331_0002
Figure imgf000331_0002
umsetzt und IVa anschließend mit einer Verbindung der implemented and IVa then with a compound of
Formel V
Figure imgf000331_0005
in der L2 für eine nucleophil austauschbare Abgangsgruppe steht, zu I umsetzt. Formula V
Figure imgf000331_0005
in which L 2 represents a nucleophilically exchangeable leaving group, converts to I.
6. Verfahren zur Herstellung der Verbindungen der Formel I gemäß Anspruch 1, in denen R3 nicht Halogen bedeutet, dadurch gekennzeichnet, daß man ein Benzylderivat der Formel II gemäß Anspruch 4 mit einem Carbonylhydroxyimin der Formel IIIb
Figure imgf000331_0003
zu einer Verbindung der Formel VIa 6. A process for the preparation of the compounds of formula I according to claim 1, in which R 3 is not halogen, characterized in that a benzyl derivative of formula II according to claim 4 with a carbonylhydroxyimine of formula IIIb
Figure imgf000331_0003
to a compound of formula VIa
Figure imgf000331_0004
umsetzt, VIa mit einem Schwefelungsreagenz in die Thioverbindung VIb
Figure imgf000332_0001
überführt und VIb anschließend entweder a) zunächst mit Hydroxylamin oder dessen Salz und danach mit einer Verbindung der Formel V (R4-L2) gemäß Anspruch 5 oder b) mit einem Hydroxylamin oder einem Hydroxylammoniumsalz der Formel Vlla bzw. VIIb
Figure imgf000332_0002
Figure imgf000331_0004
converts VIa with a sulfurization reagent into the thio compound VIb
Figure imgf000332_0001
transferred and VIb then either a) first with hydroxylamine or its salt and then with a compound of the formula V (R 4 -L 2 ) according to claim 5 or b) with a hydroxylamine or a hydroxylammonium salt of the formula VIIa or VIIb
Figure imgf000332_0002
in der Q- für das Anion einer Säure steht, zu I umsetzt.  in which Q- stands for the anion of an acid, converts to I.
7. Zur Bekämpfung von tierischen Schädlingen oder Schadpilzen geeignetes Mittel, enthaltend einen festen oder flüssigen Trägerstoff und eine Verbindung der allgemeinen Formel I gemäß Anspruch 1. 7. Suitable for controlling animal pests or harmful fungi, comprising a solid or liquid carrier and a compound of the general formula I according to claim 1.
8. Verfahren zur Bekämpfung von Schadpilzen, dadurch gekennzeichnet, daß man die Pilze oder die vor Pilzbefall zu schützenden Materialien, Pflanzen, Boden oder Saatgüter mit einer wirksamen Menge einer Verbindung der allgemeinen Formel I gemäß Anspruch 1 behandelt. 8. A method of combating harmful fungi, characterized in that the fungi or the materials, plants, soil or seeds to be protected against fungal attack are treated with an effective amount of a compound of the general formula I according to claim 1.
9. Verfahren zur Bekämpfung von tierischen Schädlingen, dadurch gekennzeichnet, daß man die Schädlingen oder die von ihnen zu schützenden Materialien, Pflanzen, Boden oder Saatgüter mit einer wirksamen Menge einer Verbindung der allgemeinen Formel I gemäß Anspruch 1 behandelt. 9. A method for controlling animal pests, characterized in that the pests or the materials, plants, soil or seeds to be protected by them are treated with an effective amount of a compound of the general formula I according to claim 1.
10. Verwendung der Verbindungen I gemäß Anspruch 1 zur Herstellung eines zur Bekämpfung von tierischen Schädlingen oder Schadpilzen geeigneten Mittels. 10. Use of the compounds I according to claim 1 for the preparation of an agent suitable for controlling animal pests or harmful fungi.
11. Verwendung der Verbindungen der Formel I gemäß Anspruch 1 zur Bekämpfung von tierischen Schädlingen oder Schadpilzen. 11. Use of the compounds of formula I according to claim 1 for controlling animal pests or harmful fungi.
12. Verbindungen der Formel VIa gemäß Anspruch 6. 12. Compounds of formula VIa according to claim 6.
13. Verbindungen der Formel VIb gemäß Anspruch 6. 13. Compounds of formula VIb according to claim 6.
14. Verwendung der Verbindungen der Formel VIa gemäß Anspruch 6 als Zwischenprodukte. 14. Use of the compounds of formula VIa according to claim 6 as intermediates.
15. Verwendung der Verbindungen der Formel VIb gemäß Anspruch 6 als Zwischenprodukte. 15. Use of the compounds of formula VIb according to claim 6 as intermediates.
16. Verbindungen der Formel III (R4 ≠ H) gemäß Anspruch 4. 16. Compounds of formula III (R 4 ≠ H) according to claim 4.
17. Verwendung der Verbindungen der Formel III (R4 ≠ H) gemäß Anspruch 4 als Zwischenprodukte. 17. Use of the compounds of formula III (R 4 ≠ H) according to claim 4 as intermediates.
PCT/EP1996/003937 1995-09-18 1996-09-09 Phenylacetic acids, processes for their preparation and agents containing them WO1997011065A1 (en)

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AU70844/96A AU706982B2 (en) 1995-09-18 1996-09-09 Phenylacetic acids, their preparation, and compositions comprising them
BR9610592A BR9610592A (en) 1995-09-18 1996-09-09 Compound process for preparing compost Useful composition and process for controlling pests and use of compost
JP9512354A JPH11512446A (en) 1995-09-18 1996-09-09 Phenylacetic acid, its preparation and compositions containing it
EP96931781A EP0851863A1 (en) 1995-09-18 1996-09-09 Phenylacetic acids, processes for their preparation and agents containing them
NZ318771A NZ318771A (en) 1995-09-18 1996-09-09 Phenylacetic acids, processes and intermediates for their preparation and agents compositions comprising them
EA199800308A EA199800308A1 (en) 1995-09-18 1996-09-09 PHENYLACETIC ACIDS, METHOD OF THEIR PRODUCTION AND CONTAINING THEIR MEANS
IL12342196A IL123421A0 (en) 1995-09-18 1996-09-09 Phenylacetic acids their preparation and compositions comprising them
PL96325551A PL325551A1 (en) 1995-09-18 1996-09-09 Phenylacetic acids, method of obtaining them and agent containing such acids

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US8895035B2 (en) 2010-06-24 2014-11-25 Kumiai Chemical Industry Co., Ltd Alkoxyimino derivative and pest control agent
US9745253B2 (en) 2015-03-13 2017-08-29 Forma Therapeutics, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US11691963B2 (en) 2020-05-06 2023-07-04 Ajax Therapeutics, Inc. 6-heteroaryloxy benzimidazoles and azabenzimidazoles as JAK2 inhibitors
US11970494B2 (en) 2021-11-09 2024-04-30 Ajax Therapeutics, Inc. 6-heteroaryloxy benzimidazoles and azabenzimidazoles as JAK2 inhibitors
US12043632B2 (en) 2020-12-23 2024-07-23 Ajax Therapeutics, Inc. 6-heteroaryloxy benzimidazoles and azabenzimidazoles as JAK2 inhibitors
US12162881B2 (en) 2021-11-09 2024-12-10 Ajax Therapeutics, Inc. Forms and compositions of inhibitors of JAK2

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Publication number Priority date Publication date Assignee Title
US8895035B2 (en) 2010-06-24 2014-11-25 Kumiai Chemical Industry Co., Ltd Alkoxyimino derivative and pest control agent
EP2594553A4 (en) * 2010-06-24 2016-01-20 Kumiai Chemical Industry Co ALCOXYIMINO DERIVATIVE AND PEST CONTROL AGENT
US9745253B2 (en) 2015-03-13 2017-08-29 Forma Therapeutics, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US10266487B2 (en) 2015-03-13 2019-04-23 Forma Therapeutics, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US10508077B2 (en) 2015-03-13 2019-12-17 Forma Therapeutics, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US10988441B2 (en) 2015-03-13 2021-04-27 Valo Early Discovery, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US11919839B2 (en) 2015-03-13 2024-03-05 Valo Health, Inc. Alpha-cinnamide compounds and compositions as HDAC8 inhibitors
US11691963B2 (en) 2020-05-06 2023-07-04 Ajax Therapeutics, Inc. 6-heteroaryloxy benzimidazoles and azabenzimidazoles as JAK2 inhibitors
US12275717B2 (en) 2020-05-06 2025-04-15 Ajax Therapeutics, Inc. 6-heteroaryloxy benzimidazoles and azabenzimidazoles as JAK2 inhibitors
US12043632B2 (en) 2020-12-23 2024-07-23 Ajax Therapeutics, Inc. 6-heteroaryloxy benzimidazoles and azabenzimidazoles as JAK2 inhibitors
US11970494B2 (en) 2021-11-09 2024-04-30 Ajax Therapeutics, Inc. 6-heteroaryloxy benzimidazoles and azabenzimidazoles as JAK2 inhibitors
US12162881B2 (en) 2021-11-09 2024-12-10 Ajax Therapeutics, Inc. Forms and compositions of inhibitors of JAK2

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CZ64598A3 (en) 1998-08-12
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