WO2000035913A1 - 4-trifluoromethyl-3-oxadiazolyl pyridines, methods for the production thereof, agents containing these compounds, and their use as pesticides - Google Patents

4-trifluoromethyl-3-oxadiazolyl pyridines, methods for the production thereof, agents containing these compounds, and their use as pesticides Download PDF

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WO2000035913A1
WO2000035913A1 PCT/EP1999/009684 EP9909684W WO0035913A1 WO 2000035913 A1 WO2000035913 A1 WO 2000035913A1 EP 9909684 W EP9909684 W EP 9909684W WO 0035913 A1 WO0035913 A1 WO 0035913A1
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compounds
spp
formula
trifluoromethyl
alkyl
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PCT/EP1999/009684
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German (de)
French (fr)
Inventor
Sven Harmsen
Henricus Maria Martinus Bastiaans
Wolfgang Schaper
Jörg Tiebes
Uwe Döller
Daniela Jans
Ulrich Sanft
Waltraut Hempel
Maria-Theresia Thönessen
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Aventis Cropscience Gmbh
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Priority to EP99963446A priority Critical patent/EP1140922A1/en
Priority to AU19741/00A priority patent/AU1974100A/en
Priority to JP2000588173A priority patent/JP2002532497A/en
Publication of WO2000035913A1 publication Critical patent/WO2000035913A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • the invention relates to 4-trifluoromethyl-3-oxadiazolylpyridines, processes for their preparation, compositions containing them and their use for controlling animal pests, in particular insects, spider mites, ectoparasites and helminths.
  • the object of the present invention is to provide compounds having good insecticidal and acaricidal properties and, at the same time, low toxicity to mammals and aquatic organisms.
  • the invention therefore relates to 4-trifluoromethyl-3-oxadiazolylpyridine derivatives of the formula (I),
  • n 0 or 1
  • X is a single bond, a straight-chain alkylene group with 1, 2 or 3 C atoms or a branched alkylene group with 3 to 9 C atoms, where one or more H atoms can be replaced by F;
  • Y is -O-, -S-, -SO-, -SO 2 -, -O-CO-, -O-CO-O-, -SO 2 -O-, -O-SO 2 -, -NR 1 -, -NR 2 -CO-, -NR 3 -CO-O-, -NR 4 -CO-NR 5 -, -O-CO-CO-O-, -O-CO-NR 6 , -SO 2 - NR 7 , -NR 8 -SO 2 -;
  • R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are the same or different, independently of one another H, (C r C 10 ) alkyl, (C 2 -C 10 ) Alkenyl, (C 2 -C 10 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 4 -C 8 ) cycloalkenyl, (C 6 -C 8 ) cycloalkynyl, heterocyclyl or - (CH 2 ) 1 ⁇ l - heterocyclyl, where each of the eight last-mentioned groups is optionally substituted one or more times, and where appropriate R and R 1 , R and R 2 , R and R 5 , R and R 6 , R and R 7 , R and R 8 or R and X together can also form a ring system; with the proviso that the compounds in which
  • m is preferably 0.
  • n is preferably 2.
  • X is preferably a single bond, CH 2 , CH 2 -CH 2 , CH 2 -CH (CH 3 ) or
  • Y is preferably -O-, -S-, -SO-, -SO 2 -, -O-CO-, -O-CO-O, -O-CO-NR 6 -,
  • R, R, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are preferably the same or different, independently of one another H, (C r C 6 ) alkyl, (C 2 -C 6 ) Alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 4 -C 8 ) cycloalkenyl, (C 6 -C 8 ) cycloalkynyl, heterocyclyl, - (CH 2 ) 1 ⁇ -Heterocyclyl, the eight last-mentioned radicals optionally with one or more radicals from the group
  • R 6 , R and R 7 , R and R 8 or R and X together can also form a ring system.
  • Preferred for the construction of such ring systems are - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 2 -O- (CH 2 ) 2 -, - (CH 2 ) 2 -NR 3 - (CH 2 ) 2 -, - (thiophene-3,4-diyl) -C (O) -, CH (imidazolyl-) CF 2 C (O) -, -CH (Me) CH 2 C (O) -, -CMe 2 CH 2 C (O) -, -CH (Me) CH (Me) C (O) -, -CH 2 CH 2 CH 2 C (O) -, -CH (Me) CH 2 CH 2 C (O) -, -CH (Me) CH 2 CH 2 C (O) -, -CH 2 CH (Me) CH 2 C (O) -, -CH 2
  • W is O or S.
  • R 9 is hydrogen
  • R, R 1 -R 8 H, (C r C ⁇ ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, heterocyclyl are particularly preferred, the four last-mentioned radicals optionally with one or more, preferably one to four, radicals from the group halogen, preferably F, CN, SiMe 3 , -O- (C r C 6 ) -alkyl, -S- (C, -C 6 ) -alkyl or - 0-CO- (C 1 -C 6 ) alkyl are substituted.
  • halogen includes fluorine, chlorine, bromine and iodine.
  • (C 1 -C 4 ) alkyl is an unbranched or branched
  • alkyl radicals with 1, 2, 3 or 4 carbon atoms such as the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical.
  • alkyl radicals with a larger range of carbon atoms are to be understood as an unbranched or branched saturated hydrocarbon radical which contains a number of carbon atoms which corresponds to this range specification.
  • the expression "(C 1 -C 6 ) alkyl” accordingly encompasses the abovementioned alkyl radicals and, for example, the pentyl, 2-methylbutyl, 1, 1-dimethylpropyl or hexyl radical.
  • (C 1 -C 10 ) alkyl means the aforementioned alkyl radicals and, for example, the nonyl, 1-decyl or 2-decyl radical.
  • alkyl group in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably chlorine or fluorine, such as the trifluoromethyl, the 1-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl -, Fluoromethyl, the difluoromethyl and the 1, 1, 2,2-tetrafluoroethyl group.
  • halogen atoms preferably chlorine or fluorine, such as the trifluoromethyl, the 1-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl -, Fluoromethyl, the difluoromethyl and the 1, 1, 2,2-tetrafluoroethyl group.
  • (C -, - C 4 ) alkoxy means an alkoxy group
  • Alkoxy groups are to be understood analogously, which comprise a larger range of carbon atoms.
  • alkenyl and alkynyl with a prefixed range of carbon atoms mean a straight-chain or branched hydrocarbon radical with a number of carbon atoms corresponding to this range, which contains at least one multiple bond, which can be located at any position of the unsaturated radical in question.
  • (C 2 -C 4 ) alkenyl thus stands for example for the vinyl, allyl, 2-methyl-2-propene or
  • Alkynyl stands for example for the ethynyl, propargyl, 2-methyl-2-propyne or 2-butynyl group.”
  • (C 2 -C 6 ) -alkynyl “includes the radicals mentioned above and, for example, the
  • 2-pentynyl or the 2-hexynyl group and “(C 2 -C 10 ) -alkynyl” means the radicals mentioned above and, for example, the 2-octynyl or the 2-decynyl group.
  • (C 3 -C 8 ) cycloalkyl stands for monocyclic alkyl radicals, such as the cyclopropyl
  • (C 3 -C 8 ) -cycloalkyl- (C r C 4 ) -alkyl is, for example, the cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylbutyl radical and the expression "(C 1 - C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkyl, for example 1-methyl-cyclopropyl-, 1-methyl-cyclopentyl-, 1-methyl-cyclohexyl-, 3-hexyl-cyclobutyl- and 4-tert.- To understand butyl-cyclohexyl radical.
  • "(C 1 -C 4 ) alkoxy- (C 1 -C 6 ) alkyloxy” means an alkoxy group as defined above which is substituted by a further alkoxy group, such as 1-ethoxyethoxy.
  • (C 3 -C 8 ) cycloalkoxy or "(C 3 -C 8 ) cycloalkylthio” is one of the (C 3 -C 8 ) cycloalkyl radicals mentioned above which is linked via an oxygen or sulfur atom , to understand.
  • (C 3 -C 8 ) cycloalkyl- (C 1 -C 6 ) alkoxy means, for example, cyclopropylmethoxy
  • (C 1 -C 4 ) alkyl (C 3 -C 8 ) cycloalkoxy stands for example for the methylcyclopropyloxy, methylcyclobutyloxy or the butylcyciohexyloxy group.
  • (CC 6 ) -Alkylthio stands for an alkylthio group whose hydrocarbon radical has the meaning given under the expression "(C-CgJ-alkyl).
  • (C -C 6 ) alkylsulfionyl means, for example, the methyl, ethyl, propyl, isopropyl
  • (d-CgJ-alkylamino) stands for a nitrogen atom which is substituted by one or two, identical or different alkyl radicals of the above definition.
  • (CC 6 ) mono- or dialkylcarbamoyl means a carbamoyl group having one or two hydrocarbon radicals which have the meaning given under the expression "(C 1 -C 6 alkyl)" and which, in the case of two hydrocarbon radicals, is identical or can be different.
  • (C 1 -C 6 ) -dihaloalkylcarbamoyl means a carbamoyl group, the two (CC 6 ) -haloalkyl radicals as defined above or one and carries a (CC 6 ) alkyl radical as defined above.
  • (CC 6 ) alkanoyl stands for example for the acetyl, propionyl, butyryl or 2-methylbutyryl group
  • aryl is a carbocyclic, i.e. aromatic radical composed of carbon atoms and preferably having 6 to 14, in particular 6 to 12, carbon atoms, such as phenyl, naphthyl or biphenylyl, preferably phenyl.
  • Aroyl therefore means an aryl radical as defined above which is bonded via a carbonyl group, such as e.g. the benzoyl group.
  • heterocyclyl preferably stands for a cyclic radical which can be completely saturated, partially unsaturated or completely unsaturated and which can be interrupted by at least one or more identical or different atoms from the group consisting of nitrogen, sulfur or oxygen, but not two Oxygen atoms may be directly adjacent and at least one carbon atom must be present in the ring, such as a residue of thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1, 3,4-oxadiazole, 1, 3 , 4-thiadiazole, 1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3 , 4-tetrazole, benzo [b] thiophene, benzo [b] furan, indole, benzo [c] thiophene,
  • Heterocyclyl particularly preferably means a saturated, partially saturated or aromatic ring system with 3 to 6 ring members and 1 to 4 heteroatoms from the group O, S and N, where at least one carbon atom must be present in the ring.
  • Heterocyclyl very particularly preferably denotes a radical of pyridine, pyrimidine, (1, 2,4) -oxadiazole, (1, 3,4) -oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1, 2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahydrofuran, tetrahydropyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine, oxirane and oxetane.
  • Aryl radical e.g. the benzyloxy, phenylethoxy, phenylbutoxy or naphthylmethoxy radical.
  • Arylthio means an aryl residue linked via a sulfur atom, e.g. the phenylthio or the 1- or 2-naphthylthio radical.
  • aryloxy means e.g. the phenoxy or 1- or 2-naphthyloxy radical.
  • Aryl- (C -C) alkylthio represents an aryl radical linked via an alkylthio radical, e.g. the benzylthio, naphthylmethylthio or the phenylethylthio radical.
  • the expression means a silicon atom bearing three identical or different alkyl radicals as defined above.
  • Stand analog C 6 dialkylsilyl "for a silicon atom which carries an aryl radical and two identical or different alkyl radicals as defined above," diaryi (C 1 -C 6 ) alkylsilyl "for a silicon atom which has one alkyl radical and two identical or different Carries aryl radicals as defined above, and "triarylsilyl" for a silicon atom bearing three identical or different aryl radicals as defined above.
  • the compounds of the general formula (I) have acidic or basic properties and can form salts. If the compounds of the general formula (I) carry, for example, groups such as hydroxyl, carboxy or other groups which induce acidic properties, these compounds can be reacted with bases to form salts.
  • bases are, for example, hydroxides, carbonates, hydrogen carbonates of the alkali and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines with (CC 4 ) alkyl radicals and mono-, di- and trialkanolamines of (CC 4 ) alkanols.
  • acids are, for example, mineral acids, such as hydrochloric, sulfuric and phosphoric acids, organic acids, such as acetic acid or oxalic acid, and acidic salts, such as NaHSO 4 and KHSO 4 .
  • the salts obtainable in this way also have insecticidal, acaricidal and nematicidal properties.
  • the compounds of the general formula (I) can have one or more asymmetric carbon atoms or stereoisomers on double bonds. Enantiomers or diastereomers can therefore occur.
  • the invention encompasses both the pure isomers and their mixtures.
  • the mixtures of diastereomers can be separated into the isomers by customary methods, for example by selective crystallization from suitable solvents or by chromatography. Racemates can be separated into the enantiomers by customary methods.
  • the compounds according to the invention are prepared by methods known per se from the literature, as are described in standard works on organic synthesis, for example Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart.
  • the preparation takes place under reaction conditions which are known and suitable for the reactions mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail.
  • the starting materials can also be formed in situ, in such a way that they are not isolated from the reaction mixture, but instead are immediately reacted further to give the compounds of the formula (I).
  • the radical XYR is as defined in formula (I) or corresponds to a precursor of such a radical.
  • an acid halide, an ester or an anhydride can be used as the activated derivative.
  • Suitable bases are amines, such as triethylamine, diisopropylethylamine, pyridine or lutidine, alkali metal hydroxides, alkali metal alcoholates, such as sodium ethanolate or potassium tert-butoxide, or alkyl metal compounds, such as butyllithium.
  • the reaction described can be carried out as a one-step process or as a two-step process, with compounds of the formula (IV) being run through:
  • Compounds of the formula (IV) can be cyclized by heating in an inert solvent to give the 1, 2,4-oxadiazoles at temperatures up to 180 ° C and by adding dehydrating reagents (e.g. Amberlyst).
  • dehydrating reagents e.g. Amberlyst
  • Compounds of the formula (IV) are also directly accessible from the acid of the formula (II) and amidoximes of the formula (III) by using a dehydrating reagent such as dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylamino-propyl) carbodiimide or N, N'-carbonyldiimidazole.
  • Haloalkyl-, hydroxyalkyl- and aminoalkyl-substituted oxadiazole derivatives of the formula (V) serve as central intermediates of ethers, thioethers and analogous derivatives,
  • Ethers of the formula (I) can be obtained by etherification of corresponding hydroxyl compounds, the hydroxyl compound advantageously first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3, into the corresponding alkali metal alcoholate. This can then be reacted with the corresponding alkyl halide, alkyl sulfonate or dialkyl sulfate, advantageously in an inert solvent such as acetone, 1, 2-dimethoxyethane, DMF or dimethyl sulfoxide, or with an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° C and 100 ° C.
  • the synthesis is accomplished by oxidation with an oxidizing agent, e.g. meta-chloroperbenzoic acid, by suitable choice of stoichiomethe and temperature.
  • an oxidizing agent e.g. meta-chloroperbenzoic acid
  • Collections of compounds of formula (I) which can be synthesized according to the above-mentioned scheme can also be produced in a parallelized manner, this being possible in a manual, partially automated or fully automated manner. It is possible, for example, to automate the reaction, the work-up or the cleaning of the products or intermediate stages. Overall, this is understood to mean a procedure as described, for example, by SH DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis", Volume 1, Escom 1997, pages 69 to 77.
  • a number of commercially available devices can be used for the parallel reaction and processing, for example from the companies Stern Corporation, Woodrolfe road, Tollesbury, Essex, CM9 8SE, England or H + P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleissheim, Germany or the company Radleys, Shirehill, Saffron Waiden, Essex, England.
  • Chromatography apparatus for example from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA, is available for the parallelized purification of compounds of the general formula (I) or of intermediate products obtained in the preparation.
  • Automation systems of this type can be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA.
  • compounds of the general formula (I) can be prepared completely or partially by methods supported by solid phases.
  • individual intermediates or all intermediates in the synthesis or a synthesis adapted for the corresponding procedure are bound to a synthetic resin.
  • Solid-phase-assisted synthesis methods are adequately described in the specialist literature, for example Barry A. Bunin in "The Combinatorial Index", published by Academic Press, 1998.
  • the use of solid-phase-supported synthesis methods allows a number of literature-known protocols, which in turn are carried out manually or automatically can. For example, the "Tea bag method” (Houghten, US 4,631,211; Houghten et al., Proc. Natl. Acad.
  • the preparation according to the processes described here provides compounds of the formula (I) in the form of substance collections which are called libraries.
  • the present invention also relates to libraries which contain at least two compounds of the formula (I).
  • the compounds of the formula (I) are suitable, with good plant tolerance and favorable warm-blood toxicity, for combating animal pests, in particular insects, arachnids, helminths and molluscs, very particularly preferably for combating insects and arachnids which are in the
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp.
  • Rhipicephalus spp. Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,
  • Chorioptes spp. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp., Eutetranychus spp ..
  • Symphyla for example, Scutigerella immaculata.
  • Thysanura for example Lepisma saccharina.
  • Collembola for example Onychiurus armatus.
  • Orthoptera for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Isoptera for example Reticulitermes spp .
  • Eurygaster spp. Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius proiixus, Triatoma spp .. From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phoralonosiphum, spp.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae,
  • Nephotettix cincticeps Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp ..
  • Heliothis spp. Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Cauleria Capellaella, Galleria mellononeella, Galleria mellononeella fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp ..
  • Oestrus spp. Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
  • Siphonaptera e.g. Xenopsylla cheopsis, Ceratophyllus spp ..
  • Arachnida e.g. Scorpio maurus
  • Latrodectus mactans From the class of the helminths e.g. Haemonchus, Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis as well as Fasciola.
  • Gastropoda e.g. Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphala a spp., Bulinus spp., Oncomelania spp ..
  • the plant-parasitic nematodes which can be controlled according to the invention include, for example, the root-parasitic soil nematodes such as, for example, those of the genera Meloidogyne (root-bile nematodes, such as Meloidogyne incognita, Meloidogyne hapla and Meloidogyne javanica), heterodera and Globodera (cyst-forming nematodes such as Globodera rostochiensis, Globodera pallida, Heterodera trifolii) and the genera Radopholus such as Radopholus similis, Pratylenchus such as Pratyglenchus neglectus, Pratylenchus penetrans and Pratylenchus curvitatus;
  • the root-parasitic soil nematodes such as, for example, those of the genera Meloidogyne (root-bile nematodes, such as Meloidogy
  • Tylenchulus such as Tylenchulus semipenetrans, Tylenchorhynchus, such as Tylenchorhynchus dubius and Tylenchorhynchus claytoni, Rotylenchus such as Rotylenchus robustus, Heliocotylenchus such as Haiiocotylenchus multicinctus, Belonoaimus such as Belonoaimus Trachususus longusus x longus.
  • the compounds of the invention can also be used to combat the nematode genera Ditylenchus (stem parasites such as Ditylenchus dipsaci and Ditylenchus destructor), Aphelenchoides (leaf nematodes such as Aphelenchoides ritzemabosi) and Anguina (flower nematodes such as Anguina tritici).
  • Ditylenchus stem parasites such as Ditylenchus dipsaci and Ditylenchus destructor
  • Aphelenchoides leaf nematodes such as Aphelenchoides ritzemabosi
  • Anguina flower nematodes such as Anguina tritici
  • the invention also relates to compositions, for example crop protection agents, preferably insecticidal, acaricidal, ixodicidal, nematicidal, molluscicidal or fungicidal, particularly preferably insecticidal and acaricidal compositions which contain one or more compounds of the formula (I) in addition to suitable formulation auxiliaries.
  • crop protection agents preferably insecticidal, acaricidal, ixodicidal, nematicidal, molluscicidal or fungicidal, particularly preferably insecticidal and acaricidal compositions which contain one or more compounds of the formula (I) in addition to suitable formulation auxiliaries.
  • the agents according to the invention generally contain 1 to 95% by weight of the active compounds of the formula (I).
  • the active ingredient and the other additives are combined and brought into a suitable form of use.
  • the invention also relates to compositions, in particular insecticidal and acaricidal compositions, which contain the compounds of the formula (I) in addition to suitable formulation auxiliaries.
  • the agents according to the invention generally contain 1 to 95% by weight of the active compounds of the formulas (I). They can be formulated in different ways, depending on how it is specified by the biological and / or chemical-physical parameters. Possible formulation options include:
  • WP Wettable powder
  • EC emulsifiable concentrates
  • SL aqueous solutions
  • SC oil or water-based dispersions
  • SE suspoemulsions
  • SE suspoemulsions
  • DP dusts
  • mordants granules in the form of , Spray, elevator and adsorption granules
  • WG water-dispersible granules
  • ULV formulations microcapsules, waxes or baits.
  • the necessary formulation aids i.e. Carrier and / or surface-active substances, such as inert materials, surfactants, solvents and other additives, are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Garriers", 2nd Ed., Darland Books, Caldwell N.J .; H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y .; Marsden, “Solvent Guide,” 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, “Detergents and Emulsifiers Annual", MC Publ.
  • Carrier and / or surface-active substances such as inert materials, surfactants, solvents and other additives
  • Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or inert substance, but also wetting agents, for example polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, for example sodium lignosulfonate, 2,2'-dinaphthylmethane-6, Contain 6'- disulfonic acid sodium.
  • wetting agents for example polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, for example sodium lignosulfonate, 2,2'-dinaphthylmethane-6, Contain 6'- disulfonic acid sodium.
  • Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers.
  • organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons.
  • emulsifiers may be used, for example: calcium alkylarylsulfonates such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid ester or Poiyoxethylensorbitester.
  • calcium alkylarylsulfonates such as Ca dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid ester or Po
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays, such as kaolin, bentonite, pyrophillite or diatomaceous earth.
  • Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material.
  • Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired as a mixture with fertilizers.
  • the active substance concentration in wettable powders is usually about 10 to 90% by weight, the remainder to 100% by weight consists of customary formulation components. In the case of emulsifiable concentrates, the active substance concentration can be approximately 5 to 80% by weight. Dust-like formulations usually contain 5 to 20% by weight % of active ingredient, sprayable solutions about 2 to 20 wt .-%. In the case of granules, the active substance content depends in part on whether the active compound is in liquid or solid form and which granulating agents, fillers, etc. are used.
  • the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers.
  • the concentrates which are commercially available, are diluted in the customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and sometimes also for microgranules using water. Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.
  • the required application rate varies. It can fluctuate within wide limits, e.g. between 0.0005 and 10.0 kg / ha or more of active substance, but it is preferably between 0.001 and 5 kg / ha of active substance.
  • the active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in mixtures with other active compounds, such as insecticides, attractants, standing antioxidants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • the pesticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds and substances produced by microorganisms.
  • Preferred mix partners are: 1. from the group of phosphorus compounds
  • Alanycarb (OK-135), Aldicarb, 2-sec-butylphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Benfuracarb, Ethiofencarb, Furathiocarb, HCN-801, Isoprocarb, Methomyl, 5-Methyl-m-cumenylbutyryl ( carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio (ethylideneamino) -N-methyl-N- (morpholinothio) carbamate (UC 51717), triazamate;
  • the active substance content of the use forms prepared from the commercially available formulations can be from 0.00000001 to 95% by weight of active substance, preferably between 0.00001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active compounds according to the invention are also suitable for combating endoparasites and ectoparasites in the veterinary field or in the field of animal husbandry.
  • the active compounds according to the invention are used here in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, dipping (dipping), spraying (spraying), pouring on (pour-on and spot) -on) and the pump and by parenteral use in the form of, for example, the injection.
  • the compounds of the formula (I) according to the invention can accordingly also be used particularly advantageously in animal husbandry (for example cattle, sheep, pigs and poultry such as chickens, geese, etc.).
  • the compounds are administered to the animals orally. Since excretion in the faeces is effective, the development of insects in the faeces of the animals can be prevented very easily in this way.
  • the appropriate dosages and formulations depend in particular on the type and stage of development of the livestock and also on the infestation pressure and can be easily determined and determined using the usual methods.
  • the compounds can be used in cattle, for example, in doses of 0.01 to 1 mg / kg of body weight.
  • the active compounds of the formula (I) according to the invention have an outstanding systemic action.
  • the active ingredients can therefore also be introduced into the plants via parts of plants, both underground and above ground (roots, stems, leaves), if the active ingredients are applied in liquid or solid form to the immediate vicinity of the plant (e.g. granules in the soil application, application in flooded rice fields).
  • the active compounds according to the invention can be used in a particular way to treat vegetative and generative propagation material, such as, for example, seeds from, for example, cereals, vegetables, cotton, rice, sugar beet and other crops and ornamental plants, onions, cuttings and tubers from other vegetatively propagated crops. and ornamental plants.
  • the treatment for this can take place before the sowing or planting process (e.g. by special techniques of seed coating, by dressing in liquid or solid form or seed box treatment), during the sowing process or planting or after the sowing or planting process by special application techniques (eg seed row treatment).
  • the amount of active ingredient used can be according to Application fluctuate in a larger range. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil.
  • the compounds of formula (I) can also be used to control harmful plants in crops of known or still to be developed genetically modified plants.
  • the transgenic plants are generally distinguished by particularly advantageous properties, for example resistance to certain crop protection agents, resistance to plant diseases or pathogens causing plant diseases, such as certain insects or microorganisms, such as fungi, bacteria or viruses.
  • Other special properties concern e.g. the crop in terms of quantity, quality, storability, composition and special ingredients.
  • Transgenic plants with an increased starch content or altered starch quality or with a different fatty acid composition of the crop are known.
  • cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn
  • crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables e.g. of cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or else crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables.
  • the invention therefore also relates to the use of compounds of the formula (I) for controlling harmful organisms in transgenic crop plants.
  • the use of the compounds according to the invention includes any other application in which compounds of the formula (I) act on the pests.
  • Such indirect applications can be, for example, the use of compounds which, for example in the soil, the plant or the pest, decompose or break down to give compounds of the formula (I).
  • amidoxime ester (4.0 g) was mixed with 80 ml of toluene and 60 ml of xylene and Amberlyst 15 (1.0 g). The reaction mixture was heated to 125 ° C for 6 h. The mixture was then filtered off with suction and the filtrate was concentrated in vacuo and purified by chromatography (silica gel, ethyl acetate / petroleum ether, 4: 1). Final stirring with n-heptane gave [5- (4'-trifluoromethylpyridin-3'yl) - [1, 2,4] oxdiazol-3-methyl] furfuryl sulfone as a light yellow solid (melting point 99 ° C.) .
  • the sodium sulfonate (0.95 g) described above was suspended in phosphorus oxychloride (30 ml) and heated to reflux for 5 hours. The excess phosphorus oxychloride was then distilled off and the remaining sulfonyl chloride was taken up in dichloromethane (10 ml). This suspension was mixed with ethyl methylamine (150 ml) and stirred for a further hour at room temperature.
  • reaction mixture was then concentrated, taken up in ethyl acetate, washed with water, dried (MgSO 4 ), filtered and concentrated.
  • a dusting agent is obtained by mixing 10 parts by weight of active ingredient and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill.
  • a wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of active compound, 65 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium as the wetting agent. and dispersant mixes and grinds in a pin mill.
  • a dispersion concentrate which is readily dispersible in water is prepared by mixing 40 parts by weight of active compound with 7 parts by weight of a sulfosuccinic acid half-ester, 2 parts by weight of a lignosulfonic acid sodium salt and 51 parts by weight of water and in a attritor ground to a fineness of less than 5 microns.
  • An emulsifiable concentrate can be prepared from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexane as solvent and 10 parts by weight of oxyethylated nonylphenol (10 EO) as emulsifier.
  • Granules can be produced from 2 to 15 parts by weight of active ingredient and an inert granule carrier material such as attapulgite, pumice granules and / or quartz sand.
  • a suspension of the wettable powder from example b) having a solids content of 30% is expediently used and sprayed onto the surface of an attapulgite granulate, dried and mixed intimately.
  • the proportion by weight of the spray powder is about 5% and that of the inert carrier material is about 95% of the finished granulate.
  • Germinated field bean seeds Vicia faba
  • germ roots were transferred to amber glass bottles filled with tap water and then coated with about 100 black bean aphids (Aphis fabae). Plants and aphids were then immersed in an aqueous solution of the preparation to be tested and formulated for 5 seconds. After draining, the plants and animals were stored in a climatic chamber (16 hours light / day, 25 ° C, 40-60% RH). After 3 and 6 days of storage, the effect of the preparation on the aphids was determined. At a concentration of 300 ppm (based on the content of active ingredient), the preparations according to Examples Nos. 2/29, 2/43, 2/67, 2/6, 3/6, 3/50, 3/75 and 3 caused / 49 90-100% aphid mortality.
  • the leaves of 12 rice plants with a stem length of 8 cm were immersed for 5 seconds in an aqueous solution of the preparation to be tested and formulated. After draining, the rice plants treated in this way were placed in a petri dish and populated with about 20 larvae (L3 stage) of the leafhopper species Nilaparvata lugens. After closing the petri dish, it was stored in a climatic chamber (16 hours light / day, 25 ° C, 40-60% RH). After 6 days of storage, the mortality of the leafhopper larvae was determined. At a concentration of 300 ppm (based on the content of active ingredient), the preparations according to Examples Nos. 2/97, 2/127, 2/153, 2/255, 3/50 and 3/75 brought about a 90-100% strength Mortality.
  • Germinated field bean seeds (Vicia faba) with germ roots were transferred to amber glass bottles filled with tap water.
  • Four milliliters of an aqueous solution of the preparation to be tested and formulated was pipetted into the amber glass vial.
  • the broad bean was heavily coated with about 100 black bean aphids (Aphis fabae).
  • the plant and animals were then stored in a climatic chamber (16 hours light / day, 25 ° C, 40-60% RH). After 3 and 6 days of storage, the root systemic effect of the preparation on the aphids was determined.
  • the preparations according to Examples No.

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Abstract

The invention relates to 4-trifluoromethyl-3-oxadiazolyl pyridines of general formula (I), to methods for the production thereof, to agents containing the inventive compounds, and to the use of these compounds for combating animal pests, especially insects, red spiders, ectoparasites and parasitic helminths. X and Y have the meanings cited in the description.

Description

Beschreibungdescription
4-Trifluormethyl-3-oxadiazolylpyridine, Verfahren zu ihrer Herstellung, sie enthaltende Mittel und ihre Verwendung als Schädlingsbekämpfungsmittel4-Trifluoromethyl-3-oxadiazolylpyridines, process for their preparation, compositions containing them and their use as pesticides
Die Erfindung betrifft 4-Trifluormethyl-3-oxadiazolylpyridine, Verfahren zu ihrer Herstellung, sie enthaltende Mittel sowie ihre Verwendung zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten, Spinnmilben, Ektoparasiten und Helminthen.The invention relates to 4-trifluoromethyl-3-oxadiazolylpyridines, processes for their preparation, compositions containing them and their use for controlling animal pests, in particular insects, spider mites, ectoparasites and helminths.
Es ist bereits bekannt, daß geeignet substituierte Pyridine akarizide und insektizide Wirkung zeigen. So sind in WO 95/07891 Pyridine beschrieben, die in 4-Position einen über ein Heteroatom verknüpften Cycloalkylrest und in 3-Position eine Gruppe unterschiedlicher Substituenten tragen. Jedoch ist die gewünschte Wirkung gegenüber den Schadorganismen nicht immer ausreichend. Darüber hinaus weisen diese Verbindungen oftmals unerwünschte toxikologische Eigenschaften gegenüber Säugetieren und aquatischen Lebewesen auf.It is already known that appropriately substituted pyridines show acaricidal and insecticidal activity. WO 95/07891 describes pyridines which bear a cycloalkyl radical linked via a hetero atom in the 4-position and a group of different substituents in the 3-position. However, the desired effect against the harmful organisms is not always sufficient. In addition, these compounds often have undesirable toxicological properties for mammals and aquatic organisms.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Verbindungen mit guten insektiziden und akariziden Eigenschaften bei gleichzeitig geringer Toxizität gegenüber Säugetieren und aquatischen Lebewesen.The object of the present invention is to provide compounds having good insecticidal and acaricidal properties and, at the same time, low toxicity to mammals and aquatic organisms.
In der nicht vorveröffentlichten WO-A-98/57969 sind 4-Haloalkylpyridine und -pyrimidine zur Verwendung als Schädlingsbekämpfungsmittel vorgeschlagen.In the unpublished WO-A-98/57969, 4-haloalkylpyridines and pyrimidines are proposed for use as pesticides.
Es wurde nun gefunden, daß Verbindungen der allgemeinen Formel (I), gegebenenfalls auch als Salze, im Vergleich zu den bereits bekannten Verbindungen ein gutes Wirkungsspektrum gegenüber tierischen Schädlingen bei gleichzeitig günstigeren toxikologischen Eigenschaften gegenüber Säugetieren und aquatischen Lebewesen aufweisen.It has now been found that compounds of the general formula (I), optionally also as salts, have a good spectrum of activity against animal pests in comparison with the already known compounds at the same time have more favorable toxicological properties compared to mammals and aquatic organisms.
Gegenstand der Erfindung sind daher 4-Trifluormethyl-3-oxadiazolylpyridinderivate der Formel (I),The invention therefore relates to 4-trifluoromethyl-3-oxadiazolylpyridine derivatives of the formula (I),
Figure imgf000004_0001
Figure imgf000004_0001
wobei die Symbole und Indizes folgende Bedeutungen haben:where the symbols and indices have the following meanings:
m ist 0 oder 1 ;m is 0 or 1;
X ist eine Einfachbindung, eine geradkettige Alkylengruppe mit 1 , 2 oder 3 C- Atomen oder eine verzweigten Alkylengruppe mit 3 bis 9 C-Atomen, wobei ein oder mehrere H-Atome durch F ersetzt sein können;X is a single bond, a straight-chain alkylene group with 1, 2 or 3 C atoms or a branched alkylene group with 3 to 9 C atoms, where one or more H atoms can be replaced by F;
Y ist -O-, -S-, -SO-, -SO2-, -O-CO-, -O-CO-O-, -SO2-O-, -O-SO2-, -NR1-, -NR2-CO-, -NR3-CO-O-, -NR4-CO-NR5-, -O-CO-CO-O-, -O-CO-NR6, -SO2-NR7, -NR8-SO2-;Y is -O-, -S-, -SO-, -SO 2 -, -O-CO-, -O-CO-O-, -SO 2 -O-, -O-SO 2 -, -NR 1 -, -NR 2 -CO-, -NR 3 -CO-O-, -NR 4 -CO-NR 5 -, -O-CO-CO-O-, -O-CO-NR 6 , -SO 2 - NR 7 , -NR 8 -SO 2 -;
R,R1,R2,R3,R4,R5,R6,R7,R8 sind gleich oder verschieden, unabhängig voneinander H, (CrC10)-Alkyl, (C2-C10)-Alkenyl, (C2-C10)-Alkinyl, (C3-C8)-Cycloalkyl, (C4-C8)-Cycloalkenyl, (C6-C8)-Cycloalkinyl, Heterocyclyl oder -(CH2)1^l- Heterocyclyl, wobei jede der acht letztgenannten Gruppen gegebenenfalls ein oder mehrfach substituiert ist, und wobei gegebenenfalls jeweils R und R1, R und R2, R und R5, R und R6, R und R7, R und R8 oder R und X zusammen auch ein Ringsystem bilden können; mit der Maßgabe, daß die Verbindungen, in denenR, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are the same or different, independently of one another H, (C r C 10 ) alkyl, (C 2 -C 10 ) Alkenyl, (C 2 -C 10 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 4 -C 8 ) cycloalkenyl, (C 6 -C 8 ) cycloalkynyl, heterocyclyl or - (CH 2 ) 1 ^ l - heterocyclyl, where each of the eight last-mentioned groups is optionally substituted one or more times, and where appropriate R and R 1 , R and R 2 , R and R 5 , R and R 6 , R and R 7 , R and R 8 or R and X together can also form a ring system; with the proviso that the compounds in which
X = -, Y = 0, R = H X = -, Y = O, R = Me X = -, Y = O, R = Et X = -, Y = O, R = CHF2 X = -, Y = O, R = CH2Ph X = CH2, Y = O, R = 2-Furanyl X = CH2, Y = O, R = Me X = CH2) Y = O, R = 5-lsoxazolyl X = CH2, Y = O, R = 5-Nitrolfuran-2-yl X = CH2CH2I Y = O, R = H X = CH2CH2; Y = O, R = MeX = -, Y = 0, R = H X = -, Y = O, R = Me X = -, Y = O, R = Et X = -, Y = O, R = CHF 2 X = -, Y = O, R = CH 2 Ph X = CH 2 , Y = O, R = 2-furanyl X = CH 2 , Y = O, R = Me X = CH 2) Y = O, R = 5-isoxazolyl X = CH 2 , Y = O, R = 5- Nitrolfuran-2-yl X = CH 2 CH 2 I Y = O, R = HX = CH 2 CH 2 ; Y = O, R = Me
X = CH2CH2, Y = O, R = CH2 <^jX = CH 2 CH 2 , Y = O, R = CH 2 <^ j
X = CH2CH2, Y = O, R = EtX = CH 2 CH 2 , Y = O, R = Et
X = CH2CH2, Y = O, R = HX = CH 2 CH 2 , Y = O, R = H
X = CH2CH2, Y =OC(0), R = 4-F-phenylX = CH 2 CH 2 , Y = OC (0), R = 4-F-phenyl
X = CH2CH2, Y = OC(O), R = 2,6-DifluorphenylX = CH 2 CH 2 , Y = OC (O), R = 2,6-difluorophenyl
X = CH2CH2, Y = OC(O), R = 4-NitrophenylX = CH 2 CH 2 , Y = OC (O), R = 4-nitrophenyl
X = CH2CH2, Y = OC(O), R = t-BuX = CH 2 CH 2 , Y = OC (O), R = t-Bu
X = CH2CH2, Y = 0C(0), R = CyclopropylX = CH 2 CH 2 , Y = 0C (0), R = cyclopropyl
X = CH2CH2, Y = OC(O), R = MeX = CH 2 CH 2 , Y = OC (O), R = Me
X = CH2CH2CH2, Y = O, R = HX = CH 2 CH 2 CH 2 , Y = O, R = H
X = -, Y = S(O), R = 4-BrombenzylX = -, Y = S (O), R = 4-bromobenzyl
X = CH2, Y = S, R = MeX = CH 2 , Y = S, R = Me
X = CH2, Y = S(O), R = MeX = CH 2 , Y = S (O), R = Me
X = CH2, Y = S(0)2, R = t-BuX = CH 2 , Y = S (0) 2 , R = t-Bu
X = CH2, Y = S, R = 2-ThienylX = CH 2 , Y = S, R = 2-thienyl
X = CH2CH2, Y = S, R = MeX = CH 2 CH 2 , Y = S, R = Me
X = CH2CH2, Y = S, R = n-PrX = CH 2 CH 2 , Y = S, R = n-Pr
X = CH2CH2, Y = S, R = BenzylX = CH 2 CH 2 , Y = S, R = benzyl
X = CH2CH2, Y = S, R = 2-Thienyl-methylX = CH 2 CH 2 , Y = S, R = 2-thienylmethyl
X = CH2CH2CH2, Y = S, R = MeX = CH 2 CH 2 CH 2 , Y = S, R = Me
X = CH2CH2CH2, Y = S(O), R = Me X = CH2CH2CH2CH2, Y = S, R = CH2CH2CH2CH2OMe ausgenommen sind.X = CH 2 CH 2 CH 2 , Y = S (O), R = Me X = CH 2 CH 2 CH 2 CH 2 , Y = S, R = CH 2 CH 2 CH 2 CH 2 OMe are excluded.
m ist vorzugsweise 0.m is preferably 0.
Ist m 1 und Y enthält eine S(O)n-Gruppe, so ist n vorzugweise 2.If m is 1 and Y contains an S (O) n group, then n is preferably 2.
X ist vorzugsweise eine Einfachbindung, CH2, CH2-CH2, CH2-CH(CH3) oderX is preferably a single bond, CH 2 , CH 2 -CH 2 , CH 2 -CH (CH 3 ) or
-CH2-C(CH3)2-. Y ist vorzugsweise -O-, -S-, -SO-, -SO2-, -O-CO-, -O-CO-O, -O-CO-NR6-,-CH 2 -C (CH 3 ) 2 -. Y is preferably -O-, -S-, -SO-, -SO 2 -, -O-CO-, -O-CO-O, -O-CO-NR 6 -,
-SO-NR7-, -O-SO2- oder -SO2-O-. R,R ,R2,R3,R4,R5,R6,R7,R8 sind vorzugsweise gleich oder verschieden, unabhängig voneinander H, (CrC6)-Alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C3-C8)- Cycloalkyl, (C4-C8)-Cycloalkenyl, (C6-C8)-Cycloalkinyl, Heterocyclyl, -(CH2)1^-Heterocyclyl, wobei die acht zuletzt genannten Reste gegebenenfalls mit einem oder mehreren Resten aus der Gruppe-SO-NR 7 -, -O-SO 2 - or -SO 2 -O-. R, R, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are preferably the same or different, independently of one another H, (C r C 6 ) alkyl, (C 2 -C 6 ) Alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 4 -C 8 ) cycloalkenyl, (C 6 -C 8 ) cycloalkynyl, heterocyclyl, - (CH 2 ) 1 ^ -Heterocyclyl, the eight last-mentioned radicals optionally with one or more radicals from the group
Halogen, Cyano, Nitro, Hydroxy, -C(=W)R9, (=W),Halogen, cyano, nitro, hydroxy, -C (= W) R 9 , (= W),
-C(=NOR9)R9, -C(=NNR9 2)R9, -C(=W)OR9, -C(=W)NR9 2, -OC(=W)R9,-C (= NOR 9 ) R 9 , -C (= NNR 9 2 ) R 9 , -C (= W) OR 9 , -C (= W) NR 9 2 , -OC (= W) R 9 ,
-OC(=W)OR9, -NR9C(=W)R9, -N[C(=W)R9]2, -NR9C(=W)OR9,-OC (= W) OR 9 , -NR 9 C (= W) R 9 , -N [C (= W) R 9 ] 2 , -NR 9 C (= W) OR 9 ,
-C(=W)NR9-NR9 2, -C(=W)NR9-NR9[C(=W)R9], -NR9-C(=W)NR9 2,-C (= W) NR 9 -NR 9 2 , -C (= W) NR 9 -NR 9 [C (= W) R 9 ], -NR 9 -C (= W) NR 9 2 ,
-NR9-NR9C(=W)R9, -NR9-N[C(=W)R9]21 -N[(C=W)R9]-NR9 2,-NR 9 -NR 9 C (= W) R 9 , -NR 9 -N [C (= W) R 9 ] 21 -N [(C = W) R 9 ] -NR 9 2 ,
-NR9-N[(C=W)R9]2, -NR9-NR9[(C=W)WR9],-NR 9 -N [(C = W) R 9 ] 2 , -NR 9 -NR 9 [(C = W) WR 9 ],
-NR9-[(C=W)NR9 2], -NR9(C=NR9)R9, -NR9(C=NR9)NR9 2,-NR 9 - [(C = W) NR 9 2 ], -NR 9 (C = NR 9 ) R 9 , -NR 9 (C = NR 9 ) NR 9 2 ,
-O-NR9 2, -O-NR9(C=W)R9, -SO2NR9 2, -NR9SO2R9, -SO2OR9, -OSO2R9,-O-NR 9 2 , -O-NR 9 (C = W) R 9 , -SO 2 NR 9 2 , -NR 9 SO 2 R 9 , -SO 2 OR 9 , -OSO 2 R 9 ,
-OR9, -NR9 2, -SR9, -SiR9 3, -SeR9, -PR9 2, -P(=W)R9 2,-OR 9 , -NR 9 2 , -SR 9 , -SiR 9 3 , -SeR 9 , -PR 9 2 , -P (= W) R 9 2 ,
-SOR9, -SO2R9, -PW2R9 2, -PW3R9 2, Aryl und Heterocyclyl, von denen die beiden letztgenannten Reste gegebenenfalls mit einem oder mehreren Resten aus der Gruppe-SOR 9 , -SO 2 R 9 , -PW 2 R 9 2 , -PW 3 R 9 2 , aryl and heterocyclyl, of which the latter two radicals optionally with one or more radicals from the group
(CrC6)-Alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C3-C8)-Cycloalkyl, (C4- C8)-Cycloalkenyl, (C6-C8)-Cycloalkinyl, (CrC6)-Haloalkyl, (C2-C6)-Haloalkenyl, (C2-C6)-Haloalkinyl, Halogen, -OR10, -NR10 2, -SR10, -SiR10 3, -C(=W)R10, -C(=W)OR10, -C(=W)NR10 2> -SOR10, -SO2R10, Nitro, Cyano und Hydroxy substituiert sind, substituiert sind, und wobei gegebenenfalls jeweils R und R1, R und R2, R und R5, R und(C r C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 4 - C 8 ) cycloalkenyl, ( C 6 -C 8 ) cycloalkynyl, (C r C 6 ) haloalkyl, (C 2 -C 6 ) haloalkenyl, (C 2 -C 6 ) haloalkynyl, halogen, -OR 10 , -NR 10 2 , -SR 10 , -SiR 10 3 , -C (= W) R 10 , - C (= W) OR 10 , -C (= W) NR 10 2> -SOR 10 , -SO 2 R 10 , nitro, cyano and hydroxy are substituted, and where appropriate R and R 1 , R and R 2 , R and R 5 , R and
R6, R und R7, R und R8 oder R und X zusammen auch ein Ringsystem bilden können.R 6 , R and R 7 , R and R 8 or R and X together can also form a ring system.
Bevorzugt zum Aufbau solcher Ringsysteme sind -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)2-O-(CH2)2-, -(CH2)2-NR3-(CH2)2-, -(thiophen-3,4-diyl)-C(O)-, CH(imidazolyl-)CF2C(O)-, -CH(Me)CH2C(O)-, -CMe2CH2C(O)-, -CH(Me)CH(Me)C(O)-, -CH2CH2CH2C(O)-, -CH(Me)CH2CH2C(O)-, -CH2CH(Me)CH2C(O)-, -CH2CMe2CH2C(O)-, -CH2C[-(CH2)4-]CH2C(O)-, -(1 ,2- Cyclohexylen)-C(O)-, -(Cyclohexen-4,5-diyl)-C(O)-, -CH2-C(H)Ph-CH2-C(O)-, -CMe=CMe-C(O)-, -CH2-CH2-C(O)-, besonders bevorzugt sind -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)2-O-(CH2)2-, -(CH2)2-NR3-(CH2)2-.Preferred for the construction of such ring systems are - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 2 -O- (CH 2 ) 2 -, - (CH 2 ) 2 -NR 3 - (CH 2 ) 2 -, - (thiophene-3,4-diyl) -C (O) -, CH (imidazolyl-) CF 2 C (O) -, -CH (Me) CH 2 C (O) -, -CMe 2 CH 2 C (O) -, -CH (Me) CH (Me) C (O) -, -CH 2 CH 2 CH 2 C (O) -, -CH (Me) CH 2 CH 2 C (O) -, -CH 2 CH (Me) CH 2 C (O) -, -CH 2 CMe 2 CH 2 C (O) -, -CH 2 C [- (CH 2 ) 4 - ] CH 2 C (O) -, - (1,2-cyclohexylene) -C (O) -, - (cyclohexene-4,5-diyl) -C (O) -, -CH 2 -C (H) Ph -CH 2 -C (O) -, -CMe = CMe-C (O) -, -CH 2 -CH 2 -C (O) -, particularly preferred are - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 2 -O- (CH 2 ) 2 -, - (CH 2 ) 2 -NR 3 - (CH 2 ) 2 -.
W ist O oder S.W is O or S.
R9 ist Wasserstoff,R 9 is hydrogen,
(C C6)-Alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C3-C8)-Cycloalkyl, (C4-C8)- Cycloalkenyl, (C3-C8)-Cycloalkyl-(C1-C4)-Alkyl, (C4-C8)-Cycloalkenyl- (C1-C4)-Alkyl, (C3-C8)-Cycloalkyl-(C2-C4)-Alkenyl, (C4-C8)-Cycloalkenyl-(C C4)-Alkenyl, (C1-C6)-Alkyl-(C3-C8)-Cycloalkyl, (C2-C6)-Alkenyl-(C3-C8)- Cycloalkyl, (C2-C6)-Alkinyl-(C3-C8)-Cycloalkyl, (C1-C6)-Alkyl-(C4-C8)- Cycloalkenyl, (C2-C6)-Alkenyl-(C4-C8)-Cycloalkenyl, wobei die vierzehn letztgenannten Reste gegebenenfalls mit einem oder mehreren Resten aus der Gruppe(CC 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 4 -C 8 ) cycloalkenyl, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -alkyl, (C 4 -C 8 ) -cycloalkenyl- (C 1 -C 4 ) -alkyl, (C 3 -C 8 ) -cycloalkyl- (C 2 -C 4 ) alkenyl, (C 4 -C 8 ) cycloalkenyl- (CC 4 ) alkenyl, (C 1 -C 6 ) alkyl- (C 3 -C 8 ) cycloalkyl, (C 2 -C 6 ) Alkenyl (C 3 -C 8 ) cycloalkyl, (C 2 -C 6 ) alkynyl (C 3 -C 8 ) cycloalkyl, (C 1 -C 6 ) alkyl (C 4 -C 8 ) - Cycloalkenyl, (C 2 -C 6 ) alkenyl- (C 4 -C 8 ) cycloalkenyl, the fourteen last-mentioned radicals optionally having one or more radicals from the group
Halogen, Cyano, Nitro, Hydroxy, Thio, Amino, Formyl, (CrC6)-Alkoxy, (C2-C6)-Alkenyloxy, (C2-C6)-Alkinyioxy, (C C6)-Haloalkyloxy, (C2-C6)- Haloalkenyloxy, (C2-C6)-Haloalkinyloxy, (C3-C8)-Cycloalkoxy, (C4-C8)- Cycloalkenyloxy, (C3-C8)-Halocycloalkoxy, (C4-C8)-Halocycloalkenyloxy, (C3-C8)-Cycloalkyl-(CrC4)-Alkoxy, (C4-C8)-Cycloalkenyl-(CrC4)-Alkoxy, (C3-C8)-Cycloalkyl-(C2-C4)-Alkenyloxy, (C4-C8)-Cycloalkenyl-(C1-C4)- Alkenyloxy, (CrC6)-Alkyl-(C3-C8)-Cycloalkoxy, (C2-C6)-Alkenyl-(C3-C8)- Cycloalkoxy, (C2-C6)-Alkinyl-(C3-C8)-Cycloalkoxy, (C C6)-Alkyl-(C4-C8)- Cycloalkenyloxy, (C2-C6)-Alkenyl-(C4-C8)-Cycloalkenyloxy, (CrC4)- Alkoxy-(C1-C6)-Alkoxy, (C1-C4)-Alkoxy-(C2-C6)-Alkenyloxy, Carbamoyl,
Figure imgf000008_0001
oder Dihaloalkylcarbamoyl, (C3-C8)-Mono- oder Dicycloalkylcarbamoyl, (C C6)-Alkoxycarbonyl, (C3-C8)-Cycloalkoxycarbonyl, (C C6)- Alkanoyloxy, (C3-C8)-Cycloalkanoyloxy, (C C6)-Haloalkoxycarbonyl, (C C6)-Haloalkanoyloxy, (C1-C6)-Alkanamido, (C^C -Haloalkanamido, (C2-C6)-Alkenamido, (C3-C8)-Cycloalkanamido, (C3-C8)-Cycloalkyl- (CrC4)-Alkanamido, (CrC6)-Alkylthio, (C2-C6)-Alkenylthio, (C2-C6)- Alkinylthio, (CrC6)-Haloalkylthio, (C2-C6)-Haloalkenylthio, (C2-C6)- Haloalkinylthio, (C3-C8)-Cycloalkylthio, (C4-C8)-Cycloalkenylthio, (C3-C8)-Halocycloalkthio, (C4-C8)-Halocycloalkenylthio, (C3-C8)- Cycloalkyl-(C1-C4)-Alkylthio, (C4-C8)-Cycloalkenyl-(C1-C4)-Alkylthio, (C3-C8)-Cycloalkyl-(C2-C4)-Alkenylthio, (C4-C8)-Cycloalkenyl-(CrC4)- Alkenylthio, (C C6)-Alkyl-(C3-C8)-Cycloalkylthio, (C2-C6)-Alkenyl- (C3-C8)-Cycloalkylthio, (C2-C6)-Alkinyl-(C3-C8)-Cycloalkylthio, (CrC6)- Alkyl-(C4-C8)-Cycloalkenylthio, (C2-C6)-Alkenyl-(C4-C8)-Cycloalkenylthio, (CrC6)-Alkylsulfinyl, (C2-C6)-Alkenylsulfιnyl, (C2-C6)-Alkinylsulfinyl, (Cr C6)-Haloalkylsulfinyl, (C2-C6)-Haloalkenylsulfιnyl, (C2-C6)- Haloalkinylsulfinyl, (C3-C8)-Cycloalkylsulfinyl, (C4-C8)- Cycloalkenylsulfinyl, (C3-C8)-Halocycloalksulfinyl, (C4-C8)- Halocycloalkenylsulfinyl, (C3-C8)-Cycloalkyl-(C1-C4)-Alkylsulfinyl, (C4- C8)-Cycloalkenyl-(C1-C4)-Alkylsulfιnyl, (C3-C8)-Cycloalkyl-(C2-C4)- Alkenylsulfinyl, (C4-C8)-Cycloalkenyl-(C1-C4)-Alkenylsulfinyl, (CrC6)- Alkyl-(C3-C8)-Cycloalkylsulfιnyl, (C2-C6)-Alkenyl-(C3-C8)- Cycloalkylsulfinyl, (C2-C6)-Alkinyl-(C3-C8)-Cycloalkylsuifinyl, (C C6)- Alkyl-(C4-C8)-Cycloalkenylsulfinyl, (C2-C6)-Alkenyl-(C4-C8)- Cycloalkenylsulfinyl, (C1-C6)-Alkylsulfonyl, (C2-C6)-Alkenylsulfonyl, (C2-C6)-Alkinylsulfonyl, (C C -Haloalkylsulfonyl, (C2-C6)- Haloalkenylsulfonyl, (C2-C6)-Haloalkinylsulfonyl, (C3-C8)- Cycloalkylsulfonyl, (C4-C8)-Cycloalkenylsulfonyl, (C3-C8)- Halocycloalksulfonyl, (C4-C8)-Halocycloalkenylsulfonyl, (C3-C8)- Cycloalkyl-(C1-C4)-Alkylsulfonyl, (C4-C8)-Cycloalkenyl-(CrC4)- Alkylsulfonyl, (C3-C8)-Cycloalkyl-(C2-C4)-Alkenylsulfonyl, (C4-C8)- Cycloalkenyl-(C1-C4)-Alkenylsulfonyl, (CrC6)-Alkyl-(C3-C8)- Cycloalkylsulfonyl, (C2-C6)-Alkenyl-(C3-C8)-Cycloalkylsulfonyl, (C2-C6)- Alkinyl-(C3-C8)-Cycloalkylsulfonyl, (CrC6)-Alkyl-(C4-C8)- Cycloalkenylsulfonyl, (C2-C6)-Alkenyl-(C4-C8)-Cycloalkenylsulfonyl, (C^C^-Alkylamino, (C2-C6)-Alkenylamino, (C2-C6)-Alkinylamino, (CT-CgJ-Haloalkylamino, (C2-C6)-Haloalkenylamino, (C2-C6)- Haloalkinylamino, (C3-C8)-Cycloalkylamino, (C4-C8)-Cycloalkenylamino, (C3-C8)-Halocycloalkamino, (C4-C8)-Halocycloalkenylamino, (C3-C8)- Cycloalkyl-(C C4)-Alkylamino, (C4-C8)-Cycloalkenyl-(C1-C4)-Alkylamino, (C3-C8)-Cycloalkyl-(C2-C4)-Alkenylamino, (C4-C8)-Cycloalkenyl-(CrC4)- Alkenylamino, (C1-C6)-Alkyl-(C3-C8)-Cycloalkylamino, (C2-C6)-Alkenyl- (C3-C8)-Cycloalkylamino, (C2-C6)-Alkinyl-(C3-C8)-Cycloalkylamino, (CrC6)-Alkyl-(C4-C8)-Cycloalkenylamino, (C2-C6)-Alkenyl-(C4-C8)- Cycloalkenylamino, (C C6)-Trialkylsilyl, Aryl, Aryloxy, Arylthio, Arylamino, Aryl-(C C4)-Alkoxy, Aryl-(C2-C4)-Alkenyloxy, Aryl-(C1-C4)- Alkylthio, Aryl-(C2-C4)-Alkenylthio, Aryl-(C1-C4)-Alkylamino, Aryl-(C2-C4)- Alkenylamino, Aryl-(CrC6)-Dialkylsilyl, Diaryl-(C1-C6)-Alkylsilyl, Triarylsilyl und 5- oder 6-gliedriges Heterocyclyl, wobei der cyclische Teil der vierzehn letztgenannten Reste gegebenenfalls durch einen oder mehrere Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Thio, (C1-C4)-Alkyl, (CrC4)- Haloalkyl, (C3-C8)-Cycloalkyl, (C C4)-Alkoxy, (CrC4)-Haloalkoxy, (C C4)-Alkylthio, (C C4)-Haloalkylthio, (d-CJ-Alkylamino, (C C4)- Haloalkylamino, Formyl und (d-C -Alkanoyl substituiert ist, substituiert sind,Halogen, cyano, nitro, hydroxyl, thio, amino, formyl, (C r C 6 ) alkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyl oxy, (CC 6 ) haloalkyloxy, (C 2 -C 6 ) - Haloalkenyloxy, (C 2 -C 6 ) haloalkynyloxy, (C 3 -C 8 ) cycloalkoxy, (C 4 -C 8 ) cycloalkenyloxy, (C 3 -C 8 ) halocycloalkoxy, (C 4 -C 8 ) - Halocycloalkenyloxy, (C 3 -C 8 ) -cycloalkyl- (C r C 4 ) -alkoxy, (C 4 -C 8 ) -cycloalkenyl- (C r C 4 ) -alkoxy, (C 3 -C 8 ) -cycloalkyl- (C 2 -C 4 ) alkenyloxy, (C 4 -C 8 ) cycloalkenyl- (C 1 -C 4 ) alkenyloxy, (C r C 6 ) alkyl- (C 3 -C 8 ) cycloalkoxy, ( C 2 -C 6 ) alkenyl (C 3 -C 8 ) cycloalkoxy, (C 2 -C 6 ) alkynyl (C 3 -C 8 ) cycloalkoxy, (CC 6 ) alkyl- (C 4 - C 8 ) - Cycloalkenyloxy, (C 2 -C 6 ) alkenyl- (C 4 -C 8 ) cycloalkenyloxy, (C r C 4 ) - alkoxy- (C 1 -C 6 ) alkoxy, (C 1 -C 4 ) alkoxy- (C 2 -C 6 ) alkenyloxy, carbamoyl,
Figure imgf000008_0001
or dihaloalkylcarbamoyl, (C 3 -C 8 ) mono- or dicycloalkylcarbamoyl, (CC 6 ) alkoxycarbonyl, (C 3 -C 8 ) cycloalkoxycarbonyl, (CC 6 ) alkanoyloxy, (C 3 -C 8 ) cycloalkanoyloxy, (CC 6 ) haloalkoxycarbonyl, (CC 6 ) haloalkanoyloxy, (C 1 -C 6 ) alkanamido, (C 1 -C 6 haloalkanamido, (C 2 -C 6 ) alkenamido, (C 3 -C 8 ) cycloalkanamido , (C 3 -C 8 ) cycloalkyl- (C r C 4 ) alkanamido, (C r C 6 ) alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, ( C r C 6 ) haloalkylthio, (C 2 -C 6 ) haloalkenylthio, (C 2 -C 6 ) haloalkynylthio, (C 3 -C 8 ) cycloalkylthio, (C 4 -C 8 ) cycloalkenylthio, (C 3 -C 8 ) halocycloalkylene, (C 4 -C 8 ) halocycloalkenylthio, (C 3 -C 8 ) cycloalkyl- (C 1 -C 4 ) alkylthio, (C 4 -C 8 ) cycloalkenyl- (C 1 -C 4 ) alkylthio, (C 3 -C 8 ) cycloalkyl- (C 2 -C 4 ) alkenylthio, (C 4 -C 8 ) cycloalkenyl- (C r C 4 ) - alkenylthio, (CC 6 ) -Alkyl- (C 3 -C 8 ) -cycloalkylthio, (C 2 -C 6 ) -alkenyl- (C 3 -C 8 ) -cycloalkylthio, (C 2 -C 6 ) -alkynyl- (C 3 -C 8 ) Cycloalkylthio, (C r C 6 ) - Alkyl- (C 4 -C 8 ) -cycloalkenylthio, (C 2 -C 6 ) -alkenyl- (C 4 -C 8 ) -cycloalkenylthio, (C r C 6 ) -alkylsulfinyl, (C 2 -C 6 ) Alkenylsulfonyl, (C 2 -C 6 ) alkynylsulfinyl, (C r C 6 ) haloalkylsulfinyl, (C 2 -C 6 ) haloalkenylsulfonyl, (C 2 -C 6 ) haloalkynylsulfinyl, (C 3 -C 8 ) -Cycloalkylsulfinyl, (C 4 -C 8 ) - cycloalkenylsulfinyl, (C 3 -C 8 ) -halocycloalksulfinyl, (C 4 -C 8 ) - halocycloalkenylsulfinyl, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 4 ) -Alkylsulfinyl, (C 4 - C 8 ) -cycloalkenyl- (C 1 -C 4 ) -Alkylsulfιnyl, (C 3 -C 8 ) -cycloalkyl- (C 2 -C 4 ) - alkenylsulfinyl, (C 4 -C 8 ) -Cycloalkenyl- (C 1 -C 4 ) alkenylsulfinyl, (C r C 6 ) - alkyl- (C 3 -C 8 ) -Cycloalkylsulfιnyl, (C 2 -C 6 ) alkenyl- (C 3 -C 8 ) - Cycloalkylsulfinyl, (C 2 -C 6 ) alkynyl (C 3 -C 8 ) cycloalkylsulfinyl, (CC 6 ) - alkyl- (C 4 -C 8 ) cycloalkenylsulfinyl, (C 2 -C 6 ) alkenyl- ( C 4 -C 8 ) cycloalkenylsulfinyl, (C 1 -C 6 ) alkylsulfonyl, (C 2 -C 6 ) alkenylsulfonyl, (C 2 -C 6 ) alkynylsulfonyl, (CC -haloalkylsulfonyl, (C 2 -C 6 ) - Haloalkenylsulfonyl, (C 2 -C 6 ) -haloalkynylsulfonyl, (C 3 -C 8 ) - cycloalkylsulfonyl, (C 4 -C 8 ) -cycloalkenylsulfonyl, (C 3 -C 8 ) - halocycloalksulfonyl, (C 4 -C 8 ) -Halocycloalkenylsulfonyl, (C 3 -C 8 ) - cycloalkyl- (C 1 -C 4 ) alkylsulfonyl, (C 4 -C 8 ) -cycloalkenyl- (C r C 4 ) - alkylsulfonyl, (C 3 -C 8 ) -Cycloalkyl- (C 2 -C 4 ) alkenylsulfonyl, (C 4 -C 8 ) - cycloalkenyl- (C 1 -C 4 ) alkenylsulfonyl, (C r C 6 ) alkyl- (C 3 -C 8 ) - Cycloalkylsulfonyl, (C 2 -C 6 ) alkenyl (C 3 -C 8 ) cycloalkylsulfonyl, (C 2 -C 6 ) alkynyl (C 3 -C 8 ) cycloalkylsulfonyl, (C r C 6 ) alkyl - (C 4 -C 8 ) - Cycloalkenylsulfonyl, (C 2 -C 6 ) alkenyl- (C 4 -C 8 ) -cycloalkenylsulfonyl, (C ^ C ^ alkylamino, (C 2 -C 6 ) alkenyl amino, (C 2 -C 6 ) alkynylamino, (C T -CgJ haloalkylamino, (C 2 -C 6 ) haloalkenylamino, (C 2 -C 6 ) haloalkynylamino, (C 3 -C 8 ) cycloalkylamino, (C 4 -C 8 ) cycloalkenylamino, (C 3 -C 8 ) halocycloalkamino, (C 4 -C 8 ) halocycloalkenylamino, (C 3 -C 8 ) cycloalkyl (CC 4 ) alkylamino, (C 4 -C 8 ) cycloalkenyl (C 1 -C 4 ) alkylamino, (C 3 -C 8 ) cycloalkyl (C 2 -C 4 ) alkenylamino, (C 4 -C 8 ) cycloalkenyl- (C r C 4 ) - alkenylamino, (C 1 -C 6 ) alkyl- (C 3 -C 8 ) cycloalkylamino, (C 2 -C 6 ) alkenyl- (C 3 -C 8 ) cycloalkylamino, (C 2 - C 6 ) alkynyl (C 3 -C 8 ) cycloalkylamino, (C r C 6 ) alkyl (C 4 -C 8 ) cycloalkenylamino, (C 2 -C 6 ) alkenyl (C 4 -C 8 ) - Cycloalkenylamino, (CC 6 ) -trialkylsilyl, aryl, aryloxy, arylthio, arylamino, aryl- (CC 4 ) -alkoxy, aryl- (C 2 -C 4 ) -alkenyloxy, aryl- (C 1 -C 4 ) Alkylthio, aryl- (C 2 -C 4 ) -alkenylthio, aryl- (C 1 -C 4 ) -alkylamino, aryl- (C 2 -C 4 ) -alkenylamino, aryl- (C r C 6 ) -dialkylsilyl, Diaryl- (C 1 -C 6 ) alkylsilyl, triarylsilyl and 5- or 6-membered heterocyclyl, the cyclic part of the fourteen last-mentioned radicals optionally being replaced by one or more radicals from the group halogen, cyano, nitro, amino, hydroxy, thio, (C 1 -C 4 ) -alkyl, (C r C 4 ) Haloalkyl, (C 3 -C 8 ) cycloalkyl, (CC 4 ) alkoxy, (C r C 4 ) haloalkoxy, (CC 4 ) -alkylthio, (CC 4 ) -haloalkylthio, (d-CJ-alkylamino, (CC 4 ) -haloalkylamino, formyl and (dC -alkanoyl) are substituted,
Aryl, 4-, 5- oder 6-gliedriges Heterocyclyl, wobei die beiden letztgenannten Reste gegebenenfalls durch einen oder mehrere Reste aus der GruppeAryl, 4-, 5- or 6-membered heterocyclyl, the latter two radicals optionally being substituted by one or more radicals from the group
Halogen, Cyano, Nitro, Hydroxy, Thio, Amino, Formyl, (C^C -Alkoxy, (C2-C6)-Alkenyloxy, (C2-C6)-Alkinyloxy, (C1-C6)-Haloalkyloxy, (C2-C6)- Haloalkenyloxy, (C2-C6)-Haloalkinyloxy, (C3-C8)-Cycloalkoxy, (C4-C8)- Cycloalkenyloxy, (C3-C8)-Halocycloalkoxy, (C4-C8)-Halocycloalkenyloxy, Carbamoyl, (CrC6)-Mono- oder Dialkylcarbamoyl, (CrC6)- Alkoxycarbonyl, (C1-C6)-Alkanoyloxy, (C C6)-Mono- oder Dihaloalkylcarbamoyl, (C C6)-Haloalkoxycarbonyl, (C C6)- Haloalkanoyloxy, (C C6)-Alkanamido, (C1-C6)-Haloalkanamido, (C2-C6)- Alkenamido, (CrC6)-Alkylthio, (C2-C6)-Alkenylthio, (C2-C6)-Alkinylthio, (C C6)-Haloalkylthio, (C2-C6)-Haloalkenylthio, (C2-C6)-Haloalkinylthio, (C3-C8)-Cycloalkylthio, (C4-C8)-Cycloalkenylthio, (C3-C8)-Halocycloalkthio, (C4-C8)-Halocycloalkenylthio, (CrC6)- Alkylsulfinyl, (C2-C6)-Alkenylsulfinyl, (C2-C6)-Alkinylsulfinyl, (CrC6)- Haloalkylsulfinyl, (C2-C6)-Haloalkenylsulfinyl, (C2-C6)-Haloalkinylsulfinyl, (C3-C8)-Cycloalkylsulfinyl, (C4-C8)-Cycloalkenylsulfinyl, (C3-C8)- Halocycloalksulfinyl, (C4-C8)-Halocycloalkenylsulfinyl, (C C6)- Alkylsulfonyl, (C2-C6)-Alkenylsulfonyl, (C2-C6)-Alkinylsulfonyl,
Figure imgf000010_0001
Haloalkylsulfonyl, (C2-C6)-Haloalkenylsulfonyl, (C2-C6)- Haloalkinylsulfonyl, (C3-C8)-Cycloalkylsulfonyl, (C4-C8)- Cycloalkenylsulfonyl, (C3-C8)-Halocycloalksulfonyl, (C4-C8)- Halocycloalkenylsulfonyl, (CrC6)-Alkylamino, (C2-C6)-Alkenylamino, (C2-C6)-Alkinylamino,
Figure imgf000010_0002
(C2-C6)- Haloalkenylamino, (C2-C6)-Haloalkinylamino, (C3-C8)-Cycloalkylamino, (C4-C8)-Cycloalkenylamino, (C3-C8)-Halocycloalkamino und (C4-C8)- Halocycloalkenylamino substituiert sind.Halogen, cyano, nitro, hydroxy, thio, amino, formyl, (C 1 -C 6 alkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 1 -C 6 ) haloalkyloxy , (C 2 -C 6 ) haloalkenyloxy, (C 2 -C 6 ) haloalkynyloxy, (C 3 -C 8 ) cycloalkoxy, (C 4 -C 8 ) cycloalkenyloxy, (C 3 -C 8 ) halocycloalkoxy , (C 4 -C 8 ) halocycloalkenyloxy, carbamoyl, (C r C 6 ) mono- or dialkylcarbamoyl, (C r C 6 ) alkoxycarbonyl, (C 1 -C 6 ) alkanoyloxy, (CC 6 ) mono - or dihaloalkylcarbamoyl, (CC 6 ) -haloalkoxycarbonyl, (CC 6 ) - haloalkanoyloxy, (CC 6 ) -alkanamido, (C 1 -C 6 ) -haloalkanamido, (C 2 -C 6 ) - alkenamido, (C r C 6 ) Alkylthio, (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, (CC 6 ) haloalkylthio, (C 2 -C 6 ) haloalkenylthio, (C 2 -C 6 ) haloalkynylthio , (C 3 -C 8 ) cycloalkylthio, (C 4 -C 8 ) cycloalkenylthio, (C 3 -C 8 ) halocycloalkthio, (C 4 -C 8 ) halocycloalkenylthio, (C r C 6 ) - alkylsulfinyl, (C 2 -C 6 ) alkenylsulfinyl, (C 2 -C 6 ) alkynylsulfinyl, (C r C 6 ) haloalkylsulfinyl, (C 2 -C 6 ) haloalkeny Isulfinyl, (C 2 -C 6 ) haloalkynylsulfinyl, (C 3 -C 8 ) cycloalkylsulfinyl, (C 4 -C 8 ) cycloalkenylsulfinyl, (C 3 -C 8 ) halocycloalksulfinyl, (C 4 -C 8 ) - Halocycloalkenylsulfinyl, (CC 6 ) alkylsulfonyl, (C 2 -C 6 ) alkenylsulfonyl, (C 2 -C 6 ) alkynylsulfonyl,
Figure imgf000010_0001
Haloalkylsulfonyl, (C 2 -C 6 ) haloalkenylsulfonyl, (C 2 -C 6 ) haloalkynylsulfonyl, (C 3 -C 8 ) cycloalkylsulfonyl, (C 4 -C 8 ) cycloalkenylsulfonyl, (C 3 -C 8 ) - Halocycloalksulfonyl, (C 4 -C 8 ) halocycloalkenylsulfonyl, (C r C 6 ) alkylamino, (C 2 -C 6 ) alkenylamino, (C 2 -C 6 ) alkynylamino,
Figure imgf000010_0002
(C 2 -C 6 ) haloalkenylamino, (C 2 -C 6 ) haloalkynylamino, (C 3 -C 8 ) cycloalkylamino, (C 4 -C 8 ) cycloalkenylamino, (C 3 -C 8 ) halocycloalkamino and (C 4 -C 8 ) halocycloalkenylamino are substituted.
Besonders bevorzugt sind R, R1-R8: H, (CrCβ)-Alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, Heterocyclyl, wobei die vier letztgenannten Reste gegebenenfalls mit einem oder mehreren, vorzugsweise einem bis vier, Resten aus der Gruppe Halogen, vorzugsweise F, CN, SiMe3, -O-(CrC6)-Alkyl, -S-(C,-C6)-Alkyl oder -0-CO-(C1-C6)-Alkyl substituiert sind.R, R 1 -R 8 : H, (C r C β ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, heterocyclyl are particularly preferred, the four last-mentioned radicals optionally with one or more, preferably one to four, radicals from the group halogen, preferably F, CN, SiMe 3 , -O- (C r C 6 ) -alkyl, -S- (C, -C 6 ) -alkyl or - 0-CO- (C 1 -C 6 ) alkyl are substituted.
Ganz besonders bevorzugt sind Verbindungen der Formel 1-1 bis I-32, auch in Form ihrer Pyridin-N-Oxide, wobei die Symbole und Indizes die oben angegebenen Bedeutungen haben:Compounds of the formulas 1-1 to I-32 are very particularly preferred, also in the form of their pyridine-N-oxides, the symbols and indices having the meanings given above:
Figure imgf000011_0001
Figure imgf000011_0001
1-1 I-2 I-31-1 I-2 I-3
Figure imgf000011_0002
Figure imgf000011_0002
I-5 I-6I-5 I-6
Figure imgf000011_0003
Figure imgf000011_0003
I-7 I-8
Figure imgf000012_0001
I-7 I-8
Figure imgf000012_0001
1-10 -1 11-10 -1 1
Figure imgf000012_0002
Figure imgf000012_0002
1-12 1-131-12 1-13
Figure imgf000012_0003
Figure imgf000012_0003
1-14 1-151-14 1-15
Figure imgf000012_0004
Figure imgf000012_0004
1-161-16
Figure imgf000012_0005
Figure imgf000012_0005
1-17 1-18 1-19
Figure imgf000013_0001
1-17 1-18 1-19
Figure imgf000013_0001
-20 1-21 I-22-20 1-21 I-22
Figure imgf000013_0002
Figure imgf000013_0002
-23 I-24 I-25-23 I-24 I-25
Figure imgf000013_0003
Figure imgf000013_0003
I-26 I-27I-26 I-27
Figure imgf000013_0004
Figure imgf000013_0004
-28 I-29-28 I-29
Figure imgf000013_0005
Figure imgf000013_0005
-30 1-31
Figure imgf000014_0001
-30 1-31
Figure imgf000014_0001
I-32I-32
In gleicher Weise bevorzugt sind die entsprechenden Formeln I-33 bis I-96 in denen Y -CH2CH2-, -CH2-CH(CH3)-, -CH2-CH2-CH2- und -CH2-C(CH3)2- bedeutet.Equally preferred are the corresponding formulas I-33 to I-96 in which Y is -CH 2 CH 2 -, -CH 2 -CH (CH 3 ) -, -CH 2 -CH 2 -CH 2 - and -CH 2 -C (CH 3 ) 2 - means.
Die Bezeichnung "Halogen" umfaßt Fluor, Chlor, Brom und Iod.The term "halogen" includes fluorine, chlorine, bromine and iodine.
Unter dem Ausdruck "(C1-C4)-Alkyl" ist ein unverzweigter oder verzweigterUnder the term "(C 1 -C 4 ) alkyl" is an unbranched or branched
Kohlenwasserstoffrest mit 1 , 2, 3 oder 4 Kohlenstoffatomen, wie z.B. der Methyl-, Ethyl-, Propyl-, Isopropyl-, 1 -Butyl-, 2-Butyl-, 2-Methylpropyl- oder tert.-Butylrest zu verstehen. Entsprechend ist unter Alkylresten mit einem größeren Bereich an Kohlenstoffatomen ein unverzweigter oder verzweigter gesättigter Kohlenwasserstoffrest zu verstehen, der eine Anzahl an Kohlenstoffatomen enthält, die dieser Bereichsangabe entspricht. Der Ausdruck "(C1-C6)-Alkyl" umfaßt demnach die vorgenannten Alkylreste, sowie z.B. den Pentyl-, 2-Methylbutyl-, 1 ,1-Dimethylpropyl- oder Hexyl-Rest. Unter dem Ausdruck "(C1-C10)-Alkyl" sind die vorgenannten Alkylreste, sowie z.B. der Nonyl-, 1-Decyl- oder 2-Decyl-Rest zu verstehen.To understand hydrocarbon radicals with 1, 2, 3 or 4 carbon atoms, such as the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical. Accordingly, alkyl radicals with a larger range of carbon atoms are to be understood as an unbranched or branched saturated hydrocarbon radical which contains a number of carbon atoms which corresponds to this range specification. The expression "(C 1 -C 6 ) alkyl" accordingly encompasses the abovementioned alkyl radicals and, for example, the pentyl, 2-methylbutyl, 1, 1-dimethylpropyl or hexyl radical. The expression "(C 1 -C 10 ) alkyl" means the aforementioned alkyl radicals and, for example, the nonyl, 1-decyl or 2-decyl radical.
Unter "(C1-C4)-Haloalkyl" ist eine unter dem Ausdruck "(C1-C4)-Alkyl" genannteUnder "(C 1 -C 4 ) haloalkyl" is one mentioned under the expression "(C 1 -C 4 ) alkyl"
Alkylgruppe zu verstehen, in der ein oder mehrere Wasserstoffatome durch die gleiche Anzahl gleicher oder verschiedener Halogenatome, bevorzugt Chlor oder Fluor, ersetzt sind, wie die Trifluormethyl-, die 1-Fluorethyl-, die 2,2,2-Trifluorethyl-, die Chlormethyl-, Fluormethyl-, die Difluormethyl- und die 1 ,1 ,2,2-Tetrafluorethylgruppe. Unter "(C-,-C4)-Alkoxy" ist eine Alkoxygruppe zu verstehen, derenTo understand alkyl group in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably chlorine or fluorine, such as the trifluoromethyl, the 1-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl -, Fluoromethyl, the difluoromethyl and the 1, 1, 2,2-tetrafluoroethyl group. "(C -, - C 4 ) alkoxy" means an alkoxy group, the
Kohlenwasserstoffrest die unter dem Ausdruck "(C1-C4)-Alkyl" angegebeneHydrocarbon radical that specified under the expression "(C 1 -C 4 ) alkyl"
Bedeutung hat. Sinngemäß sind Alkoxygruppen zu verstehen, die einen größeren Bereich an Kohlenstoffatomen umfassen.Has meaning. Alkoxy groups are to be understood analogously, which comprise a larger range of carbon atoms.
Die Bezeichnungen "Alkenyl" und "Alkinyl" mit einer vorangestellten Bereichsangabe von Kohlenstoffatomen bedeuten einen geradkettigen oder verzweigten Kohlenwasserstoffrest mit einer dieser Bereichsangabe entsprechenden Kohlenstoffatomzahl, der mindestens eine Mehrfachbindung beinhaltet, wobei sich diese an beliebiger Position des betreffenden ungesättigten Restes befinden kann. "(C2-C4)-Alkenyl" steht demnach z.B. für die Vinyl-, Allyl-, 2-Methyl-2-propen- oderThe terms "alkenyl" and "alkynyl" with a prefixed range of carbon atoms mean a straight-chain or branched hydrocarbon radical with a number of carbon atoms corresponding to this range, which contains at least one multiple bond, which can be located at any position of the unsaturated radical in question. "(C 2 -C 4 ) alkenyl" thus stands for example for the vinyl, allyl, 2-methyl-2-propene or
2-Butenyl-Gruppe; "(C2-C6)-Alkenyl" steht für die vorstehend genannten Reste sowie z.B. für die Pentenyl-, 2-Methylpentenyl- oder die Hexenyl-Gruppe. "(C2-C4)-2-butenyl group; "(C 2 -C 6 ) alkenyl" stands for the abovementioned radicals and, for example, for the pentenyl, 2-methylpentenyl or the hexenyl group. "(C 2 -C 4 ) -
Alkinyl" steht z.B. für die Ethinyl-, Propargyl-, 2-Methyl-2-propin- oder 2-Butinyl- Gruppe. Unter "(C2-C6)-Alkinyl" sind die vorstehend genannten Reste sowie z.B. dieAlkynyl "stands for example for the ethynyl, propargyl, 2-methyl-2-propyne or 2-butynyl group." (C 2 -C 6 ) -alkynyl "includes the radicals mentioned above and, for example, the
2-Pentinyl- oder die 2-Hexinyl-Gruppe und unter "(C2-C10)-Alkinyl" die vorstehend genannten Reste sowie z.B. die 2-Octinyl- oder die 2-Decinyl-Gruppe zu verstehen.2-pentynyl or the 2-hexynyl group and “(C 2 -C 10 ) -alkynyl” means the radicals mentioned above and, for example, the 2-octynyl or the 2-decynyl group.
"(C3-C8)-Cycloalkyl" steht für monocyclische Alkylreste, wie den Cyclopropyl-,"(C 3 -C 8 ) cycloalkyl" stands for monocyclic alkyl radicals, such as the cyclopropyl,
Cyclobutyl-, Cyclopentyl-, Cyclohexyl-, Cycloheptyl- oder Cyclooctylrest und für bicyclische Alkylreste, wie den Norbornylrest.Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl radical and for bicyclic alkyl radicals, such as the norbornyl radical.
Unter dem Ausdruck "(C3-C8)-Cycloalkyl-(CrC4)-alkyl " ist beispielsweise der Cyclopropylmethyl-, Cyclopentylmethyl-, Cyclohexylmethyl-, Cyclohexylethyl- und Cyclohexylbutyl-Rest und unter dem Ausdruck "(C1-C6)-Alkyl-(C3-C8)-cycloalkyl beispielsweise der 1-Methyl-cyclopropyl-, 1-Methyl-cyclopentyl-, 1-Methyl- cyclohexyl-, 3-Hexyl-cyclobutyl- und 4-tert.-Butyl-cyclohexyl-Rest zu verstehen. "(C1-C4)-Alkoxy-(C1-C6)-alkyloxy" bedeutet eine wie vorstehend definierte Alkoxy- Gruppe, die durch eine weitere Alkoxy-Gruppe substituiert ist, wie z.B. 1-Ethoxy- ethoxy.The expression "(C 3 -C 8 ) -cycloalkyl- (C r C 4 ) -alkyl" is, for example, the cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylbutyl radical and the expression "(C 1 - C 6 ) -alkyl- (C 3 -C 8 ) -cycloalkyl, for example 1-methyl-cyclopropyl-, 1-methyl-cyclopentyl-, 1-methyl-cyclohexyl-, 3-hexyl-cyclobutyl- and 4-tert.- To understand butyl-cyclohexyl radical. "(C 1 -C 4 ) alkoxy- (C 1 -C 6 ) alkyloxy" means an alkoxy group as defined above which is substituted by a further alkoxy group, such as 1-ethoxyethoxy.
Unter "(C3-C8)-Cycloalkoxy" oder "(C3-C8)-Cycloalkylthio" ist einer der oben angeführten (C3-C8)-Cycloalkyl-Reste, der über ein Sauerstoff- oder Schwefelatom verknüpft ist, zu verstehen.Under "(C 3 -C 8 ) cycloalkoxy" or "(C 3 -C 8 ) cycloalkylthio" is one of the (C 3 -C 8 ) cycloalkyl radicals mentioned above which is linked via an oxygen or sulfur atom , to understand.
"(C3-C8)-Cycloalkyl-(C1-C6)-alkoxy" bedeutet z.B. die Cyclopropylmethoxy,"(C 3 -C 8 ) cycloalkyl- (C 1 -C 6 ) alkoxy" means, for example, cyclopropylmethoxy,
Cyclobutylmethoxy-, Cyclopentylmethoxy-, Cyclohexylmethoxy-, Cyclohexylethoxy- oder die Cyclohexylbutoxy-Gruppe;Cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclohexylethoxy or the cyclohexylbutoxy group;
Der Ausdruck "(C1-C4)-Alkyl-(C3-C8)-cycloalkoxy" steht z.B. für die Methylcyclopropyloxy-, Methylcyclobutyloxy- oder die Butylcyciohexyloxy-Gruppe.The expression "(C 1 -C 4 ) alkyl (C 3 -C 8 ) cycloalkoxy" stands for example for the methylcyclopropyloxy, methylcyclobutyloxy or the butylcyciohexyloxy group.
"(C C6)-Alkylthio" steht für eine Alkylthiogruppe, deren Kohlenwasserstoffrest die unter dem Ausdruck "(C- CgJ-Alkyl" angegebene Bedeutung hat."(CC 6 ) -Alkylthio" stands for an alkylthio group whose hydrocarbon radical has the meaning given under the expression "(C-CgJ-alkyl".
Analog bedeuten "(C -C6)-Alkylsulfιnyl" z.B. die Methyl-, Ethyl-, Propyl-, isopropyl-,Analogously, "(C -C 6 ) alkylsulfionyl" means, for example, the methyl, ethyl, propyl, isopropyl,
Butyl-, Isobutyl-, sek.-Butyl- oder tert.-Butylsulfinyl-Gruppe und "(CrC6)-Alkylsulfonyl" z.B. die Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl-, Isobutyl-, sek.-Butyl- oder tert.-Butylsulfonyl-Gruppe.Butyl, isobutyl, sec-butyl or tert-butylsulfinyl group and "(C r C 6 ) -alkylsulfonyl", for example the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec .-Butyl or tert-butylsulfonyl group.
"(d-CgJ-Alkylamino" steht für ein Stickstoffatom, das durch ein oder zwei, gleiche oder verschiedene Alkylreste der obigen Definition substituiert ist."(d-CgJ-alkylamino" stands for a nitrogen atom which is substituted by one or two, identical or different alkyl radicals of the above definition.
Der Ausdruck "(C C6)-Mono- oder Dialkylcarbamoyl" bedeutet eine Carbamoylgruppe mit einem oder zwei Kohlenwasserstoffresten, die die unter dem Ausdruck "(C1-C6-Alkyl)" angegebene Bedeutung haben und die im Fall von zwei Kohlenwasserstoffresten gleich oder verschieden sein können. Analog bedeutet "(C1-C6)-Dihaloalkylcarbamoyl" eine Carbamoylgruppe, die zwei (C C6)-Haloalkylreste gemäß der obigen Definition oder einen
Figure imgf000017_0001
und einen (C C6)-Alkylrest gemäß der obigen Definition trägt.The term "(CC 6 ) mono- or dialkylcarbamoyl" means a carbamoyl group having one or two hydrocarbon radicals which have the meaning given under the expression "(C 1 -C 6 alkyl)" and which, in the case of two hydrocarbon radicals, is identical or can be different. Analogously, “(C 1 -C 6 ) -dihaloalkylcarbamoyl” means a carbamoyl group, the two (CC 6 ) -haloalkyl radicals as defined above or one
Figure imgf000017_0001
and carries a (CC 6 ) alkyl radical as defined above.
"(C C6)-Alkanoyl" steht z.B. für die Acetyl-, Propionyl-, Butyryl- oder 2-Methylbutyryl- Gruppe;"(CC 6 ) alkanoyl" stands for example for the acetyl, propionyl, butyryl or 2-methylbutyryl group;
Unter dem Ausdruck "Aryl" ist ein carbocyclischer, d.h. aus Kohlenstoffatomen aufgebauter, aromatischer Rest mit vorzugsweise 6 bis 14, insbesondere 6 bis 12 C-Atomen, wie beispielsweise Phenyl, Naphthyl oder Biphenylyl, vorzugsweise Phenyl zu verstehen. "Aroyl" bedeutet demnach einen wie vorstehend definierter Arylrest, der über eine Carbonyl-Gruppe gebunden ist, wie z.B. die Benzoyl-Gruppe.Under the term "aryl" is a carbocyclic, i.e. aromatic radical composed of carbon atoms and preferably having 6 to 14, in particular 6 to 12, carbon atoms, such as phenyl, naphthyl or biphenylyl, preferably phenyl. "Aroyl" therefore means an aryl radical as defined above which is bonded via a carbonyl group, such as e.g. the benzoyl group.
Der Ausdruck "Heterocyclyl" steht vorzugsweise für einen cyclischen Rest, der vollständig gesättigt, teilweise ungesättigt oder vollständig ungesättigt sein kann und der durch mindestens ein oder mehrere gleiche oder verschiedene Atome aus der Gruppe Stickstoff, Schwefel oder Sauerstoff unterbrochen sein kann, wobei jedoch nicht zwei Sauerstoffatome direkt benachbart sein dürfen und noch mindestens ein Kohlenstoffatom im Ring vorhanden sein muß, wie z.B. ein Rest von Thiophen, Furan, Pyrrol, Thiazol, Oxazol, Imidazol, Isothiazol, Isoxazol, Pyrazol, 1 ,3,4-Oxadiazol, 1 ,3,4-Thiadiazol, 1 ,3,4-Triazol, 1 ,2,4-Oxadiazol, 1 ,2,4-Thiadiazol, 1 ,2,4-Triazol, 1 ,2,3-Triazol, 1 ,2,3,4-Tetrazol, Benzo[b]thiophen, Benzo[b]furan, Indol, Benzo[c]thiophen, Benzo[c]furan, Isoindol, Benzoxazol, Benzothiazol, Benzimidazol, Benzisoxazol, Benzisothiazol, Benzopyrazol, Benzothiadiazol, Benzotriazol, Dibenzofuran, Dibenzothiophen, Carbazol, Pyridin, Pyrazin, Pyrimidin, Pyridazin, 1 ,3,5-Triazin, 1 ,2,4-Triazin, 1 ,2,4,5-Tetrazin, Chinolin, Isochinolin, Chinoxalin, Chinazolin, Cinnolin, 1 ,8-Naphthyridin, 1 ,5-Naphthyridin, 1 ,6-Naphthyridin, 1 ,7-Naphthyridin, Phthalazin, Pyridopyrimidin, Purin, Pteridin, 4H-Chinolizin, Piperidin, Pyrrolidin, Oxazolin, Tetrahydrofuran, Tetrahydropyran, Isoxzolidin oder Thiazolidin. Der Ausdruck "Heteroaromat" umfaßt demnach von den vorstehend unter "Heterocycly" genannten Bedeutungen jeweils die vollständig ungesättigten aromatischen heterocyclischen Verbindungen.The term "heterocyclyl" preferably stands for a cyclic radical which can be completely saturated, partially unsaturated or completely unsaturated and which can be interrupted by at least one or more identical or different atoms from the group consisting of nitrogen, sulfur or oxygen, but not two Oxygen atoms may be directly adjacent and at least one carbon atom must be present in the ring, such as a residue of thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1, 3,4-oxadiazole, 1, 3 , 4-thiadiazole, 1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3 , 4-tetrazole, benzo [b] thiophene, benzo [b] furan, indole, benzo [c] thiophene, benzo [c] furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benzotriazole, D , Dibenzothiophene, carbazole, pyridine, pyrazine, pyrimidine, pyridazine, 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,4,5-tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1, 8-naphthyridine, 1, 5-naphthyridine, 1, 6-naphthyridine, 1, 7-naphthyridine, Phthalazine, pyridopyrimidine, purine, pteridine, 4H-quinolizine, piperidine, pyrrolidine, oxazoline, tetrahydrofuran, tetrahydropyran, isoxzolidine or thiazolidine. The term "heteroaromatic" thus includes those above under "Heterocycly" meanings each the fully unsaturated aromatic heterocyclic compounds.
Heterocyclyl bedeutet besonders bevorzugt ein gesättigtes, teilgesättigtes oder aromatisches Ringsystem mit 3 bis 6 Ringgliedern und 1 bis 4 Heteroatomen aus der Gruppe O, S und N, wobei mindestens ein Kohlenstoffatom im Ring vorhanden sein muß.Heterocyclyl particularly preferably means a saturated, partially saturated or aromatic ring system with 3 to 6 ring members and 1 to 4 heteroatoms from the group O, S and N, where at least one carbon atom must be present in the ring.
Ganz besonders bevorzugt bedeutet Heterocyclyl ein Radikal des Pyridin, Pyrimidin, (1 ,2,4)-Oxadiazol, (1 ,3,4)-Oxadiazol, Pyrrol, Furan, Thiophen, Oxazol, Thiazol, Imidazol, Pyrazol, Isoxazol, 1 ,2,4-Triazol, Tetrazol, Pyrazin, Pyridazin, Oxazolin, Thiazolin, Tetrahydrofuran, Tetrahydropyran, Morpholin, Piperidin, Piperazin, Pyrrolin, Pyrrolidin, Oxazolidin, Thiazolidin, Oxiran und Oxetan.Heterocyclyl very particularly preferably denotes a radical of pyridine, pyrimidine, (1, 2,4) -oxadiazole, (1, 3,4) -oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1, 2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahydrofuran, tetrahydropyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine, oxirane and oxetane.
Figure imgf000018_0001
steht für einen über eine (C -C v-Alkoxygruppe verknüpften
Figure imgf000018_0001
stands for a linked via a (C -C v -alkoxy group
Arylrest, z.B. den Benzyloxy-, Phenylethoxy-, Phenylbutoxy- oder Naphthylmethoxy- Rest.Aryl radical, e.g. the benzyloxy, phenylethoxy, phenylbutoxy or naphthylmethoxy radical.
"Arylthio" bedeutet einen über ein Schwefelatom verknüpften Arylrest, z.B. den Phenylthio- oder den 1- oder 2-Naphthylthio-Rest. Analog bedeutet "Aryloxy" z.B. den Phenoxy- oder 1- oder 2-Naphthyloxy-Rest."Arylthio" means an aryl residue linked via a sulfur atom, e.g. the phenylthio or the 1- or 2-naphthylthio radical. Analogously "aryloxy" means e.g. the phenoxy or 1- or 2-naphthyloxy radical.
"Aryl-(C -C )-alkylthio" steht für einen Arylrest, der über einen Alkylthiorest verknüpft ist, z.B. der Benzylthio-, Naphthylmethylthio- oder die Phenylethylthio-Rest."Aryl- (C -C) alkylthio" represents an aryl radical linked via an alkylthio radical, e.g. the benzylthio, naphthylmethylthio or the phenylethylthio radical.
Der Ausdruck
Figure imgf000018_0002
bedeutet ein Siliciumatom, das drei gleiche oder verschiedene Alkylreste gemäß der obigen Definition trägt. Analog stehen
Figure imgf000018_0003
C6)-Dialkylsilyl" für ein Siliciumatom, das einen Arylrest und zwei gleiche oder verschiedene Alkylreste gemäß der obigen Definition trägt, "Diaryi-(C1-C6)-Alkylsilyl" für ein Siliciumatom, das einen Alkylrest und zwei gleiche oder verschiedene Arylreste gemäß der obigen Definition trägt, und "Triarylsilyl" für ein Siliciumatom, das drei gleiche oder verschiedene Arylreste gemäß der obigen Definition trägt.The expression
Figure imgf000018_0002
means a silicon atom bearing three identical or different alkyl radicals as defined above. Stand analog
Figure imgf000018_0003
C 6 ) dialkylsilyl "for a silicon atom which carries an aryl radical and two identical or different alkyl radicals as defined above," diaryi (C 1 -C 6 ) alkylsilyl "for a silicon atom which has one alkyl radical and two identical or different Carries aryl radicals as defined above, and "triarylsilyl" for a silicon atom bearing three identical or different aryl radicals as defined above.
In den Fällen, in denen zwei oder mehrere Reste R9 in einem Substituenten auftreten, wie z.B. bei -C(=W)NR9 2, können diese gleich oder verschieden sein.In the cases in which two or more R 9 radicals occur in a substituent, such as for example in the case of -C (= W) NR 9 2 , these can be the same or different.
Je nach Art der oben definierten Substituenten weisen die Verbindungen der allgemeinen Formel (I) saure oder basische Eigenschaften auf und können Salze bilden. Tragen die Verbindungen der allgemeinen Formel (I) beispielsweise Gruppen wie Hydroxy, Carboxy oder andere, saure Eigenschaften induzierende Gruppen, so können diese Verbindungen mit Basen zu Salzen umgesetzt werden. Geeignete Basen sind beispielsweise Hydroxide, Carbonate, Hydrogencarbonate der Alkali- und Erdalkalimetalle, insbesondere die von Natrium, Kalium, Magnesium und Calcium, weiterhin Ammoniak, primäre, sekundäre und tertiäre Amine mit (C C4)- Alkylresten sowie Mono-, Di- und Trialkanolamine von (C C4)-Alkanolen. Tragen die Verbindungen der allgemeinen Formel (I) beispielsweise Gruppen wie Amino, Alkylamino oder andere, basische Eigenschaften induzierende Gruppen, so können diese Verbindungen mit Säuren zu Salzen umgesetzt werden. Geeignete Säuren sind beispielsweise Mineralsäuren, wie Salz-, Schwefel- und Phosphorsäure, organische Säuren, wie Essigsäure oder Oxalsäure, und saure Salze, wie NaHSO4 und KHSO4. Die so erhältlichen Salze weisen ebenfalls insektizide, akarizide und nematizide Eigenschaften auf.Depending on the nature of the substituents defined above, the compounds of the general formula (I) have acidic or basic properties and can form salts. If the compounds of the general formula (I) carry, for example, groups such as hydroxyl, carboxy or other groups which induce acidic properties, these compounds can be reacted with bases to form salts. Suitable bases are, for example, hydroxides, carbonates, hydrogen carbonates of the alkali and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines with (CC 4 ) alkyl radicals and mono-, di- and trialkanolamines of (CC 4 ) alkanols. If the compounds of the general formula (I) carry, for example, groups such as amino, alkylamino or other groups which induce basic properties, these compounds can be reacted with acids to form salts. Suitable acids are, for example, mineral acids, such as hydrochloric, sulfuric and phosphoric acids, organic acids, such as acetic acid or oxalic acid, and acidic salts, such as NaHSO 4 and KHSO 4 . The salts obtainable in this way also have insecticidal, acaricidal and nematicidal properties.
Die Verbindungen der allgemeinen Formel (I) können ein oder mehrere asymmetrische Kohlenstoffatome oder Stereoisomere an Doppelbindungen aufweisen. Es können daher Enantiomere oder Diastereomere auftreten. Die Erfindung umfaßt sowohl die reinen Isomeren als auch deren Gemische. Die Gemische von Diastereomeren können nach gebräuchlichen Methoden, z.B. durch selektive Kristallisation aus geeigneten Lösungsmitteln oder durch Chromatographie in die Isomeren aufgetrennt werden. Racemate können nach üblichen Methoden in die Enantiomeren aufgetrennt werden. Die Herstellung der erfindungsgemäßen Verbindungen erfolgt nach an sich literaturbekannten Methoden, wie sie in Standardwerken zur Organischen Synthese, z.B. Houben-Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart, beschrieben werden.The compounds of the general formula (I) can have one or more asymmetric carbon atoms or stereoisomers on double bonds. Enantiomers or diastereomers can therefore occur. The invention encompasses both the pure isomers and their mixtures. The mixtures of diastereomers can be separated into the isomers by customary methods, for example by selective crystallization from suitable solvents or by chromatography. Racemates can be separated into the enantiomers by customary methods. The compounds according to the invention are prepared by methods known per se from the literature, as are described in standard works on organic synthesis, for example Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart.
Die Herstellung erfolgt dabei unter Reaktionsbedingungen, die für die genannten Umsetzungen bekannt und geeignet sind. Dabei kann man auch von an sich bekannten, hier nicht näher erwähnten Varianten Gebrauch machen.The preparation takes place under reaction conditions which are known and suitable for the reactions mentioned. Use can also be made of variants which are known per se and are not mentioned here in detail.
Die Ausgangsstoffe können gewünschtenfails auch in situ gebildet werden, und zwar derart, daß man sie aus dem Reaktionsgemisch nicht isoliert, sondern sofort weiter zu den Verbindungen der Formel (I) umsetzt.If desired, the starting materials can also be formed in situ, in such a way that they are not isolated from the reaction mixture, but instead are immediately reacted further to give the compounds of the formula (I).
Zur Herstellung von Verbindungen der allgemeinen Formel (I) setzt man z.B. aktivierte Derivate der Säure der allgemeinen Formel (II),For the preparation of compounds of general formula (I), e.g. activated acid derivatives of the general formula (II),
Figure imgf000020_0001
in Gegenwart einer Base mit einer Verbindung der Formel (III) um,
Figure imgf000020_0001
in the presence of a base with a compound of the formula (III),
HOHO
\\
NN
Figure imgf000020_0002
in welcher der Rest X-Y-R wie in Formel (I) definiert ist oder einer Vorstufe eines solchen Rests entspricht. Als aktiviertes Derivat kann beispielsweise ein Säurehalogenid, ein Ester oder ein Anhydrid eingesetzt werden. Als Basen eignen sich Amine, wie Triethylamin, Diisopropylethylamin, Pyridin oder Lutidin, Alkalimetallhydroxide, Alkaiimetallalkoholate, wie Natriumethanolat oder Kalium-tert- butanolat, oder Alkylmetallverbindungen, wie Butyllithium. Die beschriebene Reaktion kann je nach Wahl der Bedingungen als Einstufenprozeß oder als Zweistufenprozeß durchgeführt werden, wobei Verbindungen der Formel (IV) durchlaufen werden:
Figure imgf000020_0002
in which the radical XYR is as defined in formula (I) or corresponds to a precursor of such a radical. For example, an acid halide, an ester or an anhydride can be used as the activated derivative. Suitable bases are amines, such as triethylamine, diisopropylethylamine, pyridine or lutidine, alkali metal hydroxides, alkali metal alcoholates, such as sodium ethanolate or potassium tert-butoxide, or alkyl metal compounds, such as butyllithium. Depending on the conditions chosen, the reaction described can be carried out as a one-step process or as a two-step process, with compounds of the formula (IV) being run through:
Figure imgf000021_0001
Figure imgf000021_0001
Verbindungen der Formel (IV) können durch Erhitzen in einem inerten Lösungsmittel zu den 1 ,2,4-Oxadiazolen bei Temperaturen bis zu 180°C sowie durch Zusatz wasserentziehender Reagentien (z.B. Amberlyst) cyclisiert werden. Verbindungen der Formel (IV) sind auch direkt zugänglich aus der Säure der Formel (II) und Amidoximen der Formel (III) durch Verwendung eines wasserentziehenden Reagenzes wie Dicyclohexylcarbodiimid, 1-Ethyl-3-(3-dimethylamino- propyl)carbodiimid oder N,N'-Carbonyldiimidazol.Compounds of the formula (IV) can be cyclized by heating in an inert solvent to give the 1, 2,4-oxadiazoles at temperatures up to 180 ° C and by adding dehydrating reagents (e.g. Amberlyst). Compounds of the formula (IV) are also directly accessible from the acid of the formula (II) and amidoximes of the formula (III) by using a dehydrating reagent such as dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylamino-propyl) carbodiimide or N, N'-carbonyldiimidazole.
Sowohl 4-Trifluormethylnicotinsäure (II) wie auch Amidoxime der Formel (III) sind käuflich oder können nach literaturbekannten Verfahren hergestellt werden (siehe zum Beispiel: Houben-Weyl, Methoden der organischen Chemie, Band X/4, Seite 209-212; EP-A 0 580 374; G.F. Holland, J.N. Pereira, J. Med. Chem., 1967, 10, 149).Both 4-trifluoromethylnicotinic acid (II) and amidoximes of the formula (III) are commercially available or can be prepared by processes known from the literature (see, for example: Houben-Weyl, Methods of Organic Chemistry, Volume X / 4, pages 209-212; EP- A 0 580 374; GF Holland, JN Pereira, J. Med. Chem., 1967, 10, 149).
Nach beendetem Aufbau der Oxadiazolylgruppe, die in der nachfolgenden Grafik beispielhaft aufgezeigt wird, durch z.B. Kondensations-, Cyclisierungs- oder Cydoadditionsreaktionen kann der Rest R noch gewünschtenfalls weiter derivatisiert werden, wobei die breite Methodenpalette der organisch-chemischen Synthese eingesetzt werden kann.After the buildup of the oxadiazolyl group, which is shown in the graphic below as an example, by e.g. Condensation, cyclization or cydoaddition reactions can, if desired, be further derivatized using the broad range of methods of organic chemical synthesis.
Figure imgf000021_0002
Figure imgf000021_0002
NaOEt
Figure imgf000021_0003
Figure imgf000021_0004
Figure imgf000022_0001
NaOEt
Figure imgf000021_0003
Figure imgf000021_0004
Figure imgf000022_0001
Als zentrale Intermediate von Ethern, Thioethern und analogen Derivaten dienen haloalkyl-, hydroxyalkyl- sowie aminoalkylsubstituierte Oxadiazol-Derivate der Formel (V),Haloalkyl-, hydroxyalkyl- and aminoalkyl-substituted oxadiazole derivatives of the formula (V) serve as central intermediates of ethers, thioethers and analogous derivatives,
Figure imgf000022_0002
die dann nach Standardverfahren der organischen Synthese in die entsprechenden Zielverbindungen umgewandelt werden können.
Figure imgf000022_0002
which can then be converted into the corresponding target compounds using standard methods of organic synthesis.
Ether der Formel (I) sind durch Veretherung entsprechender Hydroxyverbindungen erhältlich, wobei die Hydroxyverbindung zweckmäßig zunächst in ein entsprechendes Metallderivat, z.B. durch Behandeln mit NaH, NaNH2, NaOH, KOH, Na2CO3 in das entsprechende Alkalimetallalkoholat übergeführt wird. Dieses kann dann mit dem entsprechenden Alkylhalogenid, Alkylsulfonat oder Dialkylsulfat umgesetzt werden, zweckmäßig in einem inertem Lösungsmittel, wie Aceton, 1 ,2- Dimethoxyethan, DMF oder Dimethylsulfoxid, oder auch mit einem Überschuß an wäßriger oder wäßrig-alkoholischer NaOH oder KOH bei Temperaturen zwischen etwa 20°C und 100°C. Derivate der Aminoverbindung (VI) können beispielsweise durch Reaktion der Chlorverbindung ((V), V = CI) mit AminenEthers of the formula (I) can be obtained by etherification of corresponding hydroxyl compounds, the hydroxyl compound advantageously first being converted into a corresponding metal derivative, for example by treatment with NaH, NaNH 2 , NaOH, KOH, Na 2 CO 3, into the corresponding alkali metal alcoholate. This can then be reacted with the corresponding alkyl halide, alkyl sulfonate or dialkyl sulfate, advantageously in an inert solvent such as acetone, 1, 2-dimethoxyethane, DMF or dimethyl sulfoxide, or with an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° C and 100 ° C. Derivatives of the amino compound (VI) can be obtained, for example, by reacting the chlorine compound ((V), V = CI) with amines
Figure imgf000023_0001
oder über das zentrale Intermediat ((V); V = NH2) hergestellt werden. Der Aufbau des zentralen Intermediats ((V); V = NH2) gelingt entweder durch Umsetzung des Chlorderivats ((V); V = CI) mit Ammoniak in Gegenwart einer geeigneten Base oder besser durch Reaktion desselben Chlorderivats ((V); V = CI) mit Kaliumphthalimid und anschließender Hydrazinolyse. Die weitere Derivatisierung dieses zentralen Intermediats ((V); V = NH2) erfolgt durch Umsetzung mit geeigneten Elektrophilen.
Figure imgf000023_0001
or via the central intermediate ((V); V = NH 2 ). The construction of the central intermediate ((V); V = NH 2 ) is achieved either by reacting the chlorine derivative ((V); V = CI) with ammonia in the presence of a suitable base or better by reacting the same chlorine derivative ((V); V = CI) with potassium phthalimide and subsequent hydrazinolysis. The further derivatization of this central intermediate ((V); V = NH 2 ) takes place by reaction with suitable electrophiles.
Figure imgf000023_0002
Zur Herstellung der Sulfoxide ((VII); n =1 ) und der Sulfone ((VII); n=2) verwendet man beispielsweise die entsprechenden Thioether der allgemeinen Formel (VII); n=0):
Figure imgf000023_0002
To prepare the sulfoxides ((VII); n = 1) and the sulfones ((VII); n = 2), for example, the corresponding thioethers of the general formula (VII) are used; n = 0):
Figure imgf000024_0001
Figure imgf000024_0001
Die Synthese gelingt durch Oxidation mit einem Oxidationsmittel, wie z.B. meta- Chlorperbenzoesäure, durch geeignete Wahl von Stöchiomethe und Temperatur.The synthesis is accomplished by oxidation with an oxidizing agent, e.g. meta-chloroperbenzoic acid, by suitable choice of stoichiomethe and temperature.
Figure imgf000024_0002
Figure imgf000024_0002
X = s OxidationX = s oxidation
TT
Figure imgf000024_0003
Figure imgf000024_0003
Oxidationoxidation
Figure imgf000024_0004
Die Synthese der Esteralkyl-substituierten Oxadiazol-Derivate (VIII) gelingt beispielsweise durch Substitution von Chlor in ((V); V = CI) mit Alkalicarboxylaten oder durch Veresterung des Hydroxyalkyloxadiazols ((V); V = OH) mit aktivierten Carbonsäurederivaten.
Figure imgf000024_0004
The synthesis of the esteralkyl-substituted oxadiazole derivatives (VIII) is possible, for example, by substituting chlorine in ((V); V = CI) with alkali metal carboxylates or by esterifying the hydroxyalkyloxadiazole ((V); V = OH) with activated carboxylic acid derivatives.
Figure imgf000025_0001
Figure imgf000025_0001
(VIII)(VIII)
Figure imgf000025_0002
Figure imgf000025_0002
Aus dem Hydroxyalkyloxadiazol ((V); V = OH) lassen sich auf analoge Weise auch die entsprechenden Sulfonate generieren.The corresponding sulfonates can also be generated in an analogous manner from the hydroxyalkyloxadiazole ((V); V = OH).
Figure imgf000025_0003
Zur Darstellung der Sulfonamide (X) wird die Chloralkylverbindung ((V); V = CI) mit Natriumsulfit in das entsprechende Natriumsulfonat (IX) überführt, das dann seinerseits zu dem angestrebten Sulfonamid (X) weiter derivatisiert werden kann.
Figure imgf000025_0003
To prepare the sulfonamides (X), the chloroalkyl compound ((V); V = CI) is converted into the corresponding sodium sulfonate (IX) with sodium sulfite, which in turn can then be further derivatized to the desired sulfonamide (X).
Figure imgf000026_0001
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000026_0002
Kollektionen aus Verbindungen der Formel (I), die nach oben genannten Schema synthetisiert werden können, können auch in parallelisierter Weise hergestellt werden, wobei dies in manueller, teilweise automatisierter oder vollständig automatisierter Weise geschehen kann. Dabei ist es beispielsweise möglich, die Reaktionsdurchführung, die Aufarbeitung oder die Reinigung der Produkte bzw. Zwischenstufen zu automatisieren. Insgesamt wird hierunter eine Vorgehensweise verstanden, wie sie beispielsweise durch S.H. DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis", Band 1 , Verlag Escom 1997, Seite 69 bis 77 beschrieben ist. Zur parallelisierten Reaktionsdurchführung und Aufarbeitung können eine Reihe von im Handel erhältlichen Geräten verwendet werden, wie sie beispielsweise von den Firmen Stern Corporation, Woodrolfe road, Tollesbury, Essex, CM9 8SE, England oder H+P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleißheim, Deutschland oder der Firma Radleys, Shirehill, Saffron Waiden, Essex, England, angeboten werden. Für die parallelisierte Aufreinigung von Verbindungen der allgemeinen Formel (I) beziehungsweise von bei der Herstellung anfallenden Zwischenprodukten stehen unter anderem Chromatographieapparaturen zur Verfügung, beispielsweise der Firma ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.Collections of compounds of formula (I) which can be synthesized according to the above-mentioned scheme can also be produced in a parallelized manner, this being possible in a manual, partially automated or fully automated manner. It is possible, for example, to automate the reaction, the work-up or the cleaning of the products or intermediate stages. Overall, this is understood to mean a procedure as described, for example, by SH DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis", Volume 1, Escom 1997, pages 69 to 77. A number of commercially available devices can be used for the parallel reaction and processing, for example from the companies Stern Corporation, Woodrolfe road, Tollesbury, Essex, CM9 8SE, England or H + P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleissheim, Germany or the company Radleys, Shirehill, Saffron Waiden, Essex, England. Chromatography apparatus, for example from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA, is available for the parallelized purification of compounds of the general formula (I) or of intermediate products obtained in the preparation.
Die aufgeführten Apparaturen führen zu einer moduiaren Vorgehensweise, bei der die einzelnen Arbeitsschritte automatisiert sind, zwischen den Arbeitsschritten jedoch manuelle Operationen durchgeführt werden müssen. Dies kann durch den Einsatz von teilweise oder vollständige integrierten Automationssystemen umgangen werden, bei denen die jeweiligen Automationsmodule beispielsweise durch Roboter bedient werden. Derartige Automationssysteme können zum Beispiel von der Firma Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA bezogen werden.The equipment listed leads to a modular procedure in which the individual work steps are automated, but manual operations must be carried out between the work steps. This can be avoided by using partially or completely integrated automation systems in which the respective automation modules are operated, for example, by robots. Automation systems of this type can be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA.
Neben den hier beschriebenen kann die Herstellung von Verbindungen der allgemeinen Formel (I) vollständig oder partiell durch Festphasen - unterstützte - Methoden erfolgen. Zu diesem Zweck werden einzelne Zwischenstufen oder alle Zwischenstufen der Synthese oder einer für die entsprechende Vorgehensweise angepaßten Synthese an ein Syntheseharz gebunden. Festphasen - unterstützte - Synthesemethoden sind in der Fachliteratur hinreichend beschrieben, z.B. Barry A. Bunin in "The Combinatorial Index", Verlag Academic Press, 1998. Die Verwendung von Festphasen unterstützten Synthesemethoden erlaubt eine Reihe von literaturbekannten Protokollen, die wiederum manuell oder automatisierten ausgeführt werden können. Zum Beispiel kann die "Teebeutelmethode" (Houghten, US 4,631 ,211 ; Houghten et al., Proc. Natl. Acad. Sei, 1985, 82, 5131-5135) mit Produkten der Firma IRORI, 11149 North Torrey Pines Road, La Jolla, CA 92037, USA teilweise automatisiert werden. Die Automatisierung von Festphasen unterstützten Parallelsynthesen gelingt beispielsweise durch Apparaturen der Firmen Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, CA 94070, USA oder MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Deutschland.In addition to those described here, compounds of the general formula (I) can be prepared completely or partially by methods supported by solid phases. For this purpose, individual intermediates or all intermediates in the synthesis or a synthesis adapted for the corresponding procedure are bound to a synthetic resin. Solid-phase-assisted synthesis methods are adequately described in the specialist literature, for example Barry A. Bunin in "The Combinatorial Index", published by Academic Press, 1998. The use of solid-phase-supported synthesis methods allows a number of literature-known protocols, which in turn are carried out manually or automatically can. For example, the "Tea bag method" (Houghten, US 4,631,211; Houghten et al., Proc. Natl. Acad. Sei, 1985, 82, 5131-5135) with products from IRORI, 11149 North Torrey Pines Road, La Jolla, CA 92037, USA to be partially automated. The automation of solid-phase-supported parallel syntheses is achieved, for example, by apparatus from Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, CA 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany.
Die Herstellung gemäß der hier beschriebenen Verfahren liefert Verbindungen der Formel (I) in Form von Substanzkollektionen, die Bibliotheken genannt werden. Gegenstand der vorliegenden Erfindung sind auch Bibliotheken, die mindestens zwei Verbindungen der Formel (I) enthalten.The preparation according to the processes described here provides compounds of the formula (I) in the form of substance collections which are called libraries. The present invention also relates to libraries which contain at least two compounds of the formula (I).
Die Verbindungen der Formel (I) eignen sich bei guter Pflanzenverträglichkeit und günstiger Warmblütertoxizität zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten, Spinnentieren, Helminthen und Mollusken, ganz besonders bevorzugt zur Bekämpfung von Insekten und Spinnentieren, die in derThe compounds of the formula (I) are suitable, with good plant tolerance and favorable warm-blood toxicity, for combating animal pests, in particular insects, arachnids, helminths and molluscs, very particularly preferably for combating insects and arachnids which are in the
Landwirtschaft, bei der Tierzucht, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie sind gegen normal sensible und resistenteAgriculture, animal husbandry, in forests, in the protection of stocks and materials and in the hygiene sector. They are normally sensitive and resistant
Arten sowie alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:Species as well as all or individual stages of development are effective. The pests mentioned above include:
Aus der Ordnung der Acarina z.B. Acarus siro, Argas spp., Ornithodoros spp.,From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp.,
Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.,
Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,
Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp., Eutetranychus spp..Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp., Eutetranychus spp ..
Aus der Ordnung der Isopoda z.B. Oniscus aselus, Armadium vulgäre, Porcellio scaber.From the order of the Isopoda e.g. Oniscus aselus, Armadium vulgäre, Porcellio scaber.
Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus.From the order of the Diplopoda e.g. Blaniulus guttulatus.
Aus der Ordnung der Chilopoda z.B. Geophilus carpophagus, Scutigera spp..From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spp ..
Aus der Ordnung der Symphyla z.B. Scutigerella immaculata. Aus der Ordnung der Thysanura z.B. Lepisma saccharina. Aus der Ordnung der Collembola z.B. Onychiurus armatus. Aus der Ordnung der Orthoptera z.B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria. Aus der Ordnung des Isoptera z.B. Reticulitermes spp..From the order of the Symphyla, for example, Scutigerella immaculata. From the order of the Thysanura, for example Lepisma saccharina. From the order of the Collembola, for example Onychiurus armatus. From the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria. From the order of the Isoptera, for example Reticulitermes spp ..
Aus der Ordnung der Anoplura z.B. Phylloera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.. Aus der Ordnung der Mallophaga z.B. Trichodectes pp., Damalinea spp.. Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci. Aus der Ordnung der Heteroptera z.B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius proiixus, Triatoma spp.. Aus der Ordnung der Homoptera z.B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelus bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp..From the order of the anoplura e.g. Phylloera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp .. From the order of the Mallophaga e.g. Trichodectes pp., Damalinea spp .. From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci. From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius proiixus, Triatoma spp .. From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phoralonosiphum, spp. Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp ..
Aus der Ordnung der Lepidoptera z.B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantha spp., Bucculatrix thurbe ella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantha spp., Bucculatrix thurbe ella, Phyllocnotis spp., Agrella Epp. Spp. Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Cauleria Capellaellaella, Galleria mellononeella, Galleria mellononeella fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
Aus der Ordnung der Coleoptera z.B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylloides chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrynchus assimilis, Hypera postica, Dermestes spp., Trogoderma, Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.From the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylloides chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatordorrisusimimususimimusimimususimimususimimususimimususimimusimimususimimususimimususimimususimimususimimususimimususimidusimimususimica sop., Syst spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon zolitica, Costely
Aus der Ordnung der Hymenoptera z.B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp..From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp ..
Aus der Ordnung der Diptera z.B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxys spp. Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
Aus der Ordnung der Siphonaptera z.B. Xenopsylla cheopsis, Ceratophyllus spp.. Aus der Ordnung der Arachnida z.B. Scorpio maurus, Latrodectus mactans. Aus der Klasse der Helminthen z.B. Haemonchus, Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris und Heterakis sowie Fasciola.From the order of the Siphonaptera e.g. Xenopsylla cheopsis, Ceratophyllus spp .. From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans. From the class of the helminths e.g. Haemonchus, Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis as well as Fasciola.
Aus der Klasse der Gastropoda z.B. Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphala a spp., Bulinus spp., Oncomelania spp..From the class of the Gastropoda e.g. Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphala a spp., Bulinus spp., Oncomelania spp ..
A ΔIuIsC d rlce-rr k Kllaacscsee- d rl«e-rr R Biivvaallvvaa z 7. RB. r D-rr.e-ιiis:s-:ee-nna--- c snpnp.A ΔIuIsC d rlce-rr k Kllaacscsee- d rl «e-rr R Biivvaallvvaa z 7. RB. r D-rr.e-ιiis: s-: ee-nna --- c snpnp.
Zu den pflanzenparasitären Nematoden, die erfindungsgemäß bekämpft werden können, gehören beispielsweise die wurzelparasitären Bodennematoden wie z.B. solche der Gattungen Meloidogyne (Wurzelgallennematoden, wie Meloidogyne incognita, Meloidogyne hapla und Meloidogyne javanica), Heterodera und Globodera (zystenbildende Nematoden, wie Globodera rostochiensis, Globodera pallida, Heterodera trifolii) sowie der Gattungen Radopholus wie Radopholus similis, Pratylenchus wie Pratyglenchus neglectus, Pratylenchus penetrans und Pratylenchus curvitatus;The plant-parasitic nematodes which can be controlled according to the invention include, for example, the root-parasitic soil nematodes such as, for example, those of the genera Meloidogyne (root-bile nematodes, such as Meloidogyne incognita, Meloidogyne hapla and Meloidogyne javanica), heterodera and Globodera (cyst-forming nematodes such as Globodera rostochiensis, Globodera pallida, Heterodera trifolii) and the genera Radopholus such as Radopholus similis, Pratylenchus such as Pratyglenchus neglectus, Pratylenchus penetrans and Pratylenchus curvitatus;
Tylenchulus wie Tylenchulus semipenetrans, Tylenchorhynchus, wie Tylenchorhynchus dubius und Tylenchorhynchus claytoni, Rotylenchus wie Rotylenchus robustus, Heliocotylenchus wie Haiiocotylenchus multicinctus, Belonoaimus wie Belonoaimus longicaudatus, Longidorus wie Longidorus elongatus, Trichodorus wie Trichodorus primitivus und Xiphinema wie Xiphinema index.Tylenchulus such as Tylenchulus semipenetrans, Tylenchorhynchus, such as Tylenchorhynchus dubius and Tylenchorhynchus claytoni, Rotylenchus such as Rotylenchus robustus, Heliocotylenchus such as Haiiocotylenchus multicinctus, Belonoaimus such as Belonoaimus Trachususus longusus x longus.
Ferner lassen sich mit den erfindungsgemäßen Verbindungen die Nematodengattungen Ditylenchus (Stengelparasiten, wie Ditylenchus dipsaci und Ditylenchus destructor), Aphelenchoides (Blattnematoden, wie Aphelenchoides ritzemabosi) und Anguina (Blütennematoden, wie Anguina tritici) bekämpfen.The compounds of the invention can also be used to combat the nematode genera Ditylenchus (stem parasites such as Ditylenchus dipsaci and Ditylenchus destructor), Aphelenchoides (leaf nematodes such as Aphelenchoides ritzemabosi) and Anguina (flower nematodes such as Anguina tritici).
Die Erfindung betrifft auch Mittel, beispielsweise Pflanzenschutzmittel, vorzugsweise insektizide, akarizide, ixodizide, nematizide, molluskizide oder fungizide, besonders bevorzugt insektizide und akarizide Mittel, die eine oder mehrere Verbindungen der Formel (I) neben geeigneten Formulierungshilfsmitteln enthalten.The invention also relates to compositions, for example crop protection agents, preferably insecticidal, acaricidal, ixodicidal, nematicidal, molluscicidal or fungicidal, particularly preferably insecticidal and acaricidal compositions which contain one or more compounds of the formula (I) in addition to suitable formulation auxiliaries.
Die erfindungsgemäßen Mittel enthalten die Wirkstoffe der Formel (I) im allgemeinen zu 1 bis 95 Gew.-%.The agents according to the invention generally contain 1 to 95% by weight of the active compounds of the formula (I).
Zur Herstellung der erfindungsgemäßen Mittel gibt man den Wirkstoff und die weiteren Zusätze zusammen und bringt sie in eine geeignete Anwendungsform.To prepare the agents according to the invention, the active ingredient and the other additives are combined and brought into a suitable form of use.
Die Erfindung betrifft auch Mittel, insbesondere insektizide und akarizide Mittel, die die Verbindungen der Formel (I) neben geeigneten Formulierungshilfsmitteln enthalten. Die erfindungsgemäßen Mittel enthalten die Wirkstoffe der Formeln (I) im allgemeinen zu 1 bis 95 Gew.-%. Sie können auf verschiedene Art formuliert werden, je nachdem wie es durch die biologischen und/oder chemischphysikalischen Parameter vorgegeben ist. Als Formulierungsmöglichkeiten kommen daher beispielsweise in Frage:The invention also relates to compositions, in particular insecticidal and acaricidal compositions, which contain the compounds of the formula (I) in addition to suitable formulation auxiliaries. The agents according to the invention generally contain 1 to 95% by weight of the active compounds of the formulas (I). They can be formulated in different ways, depending on how it is specified by the biological and / or chemical-physical parameters. Possible formulation options include:
Spritzpulver (WP), emulgierbare Konzentrate (EC), wäßrige Lösungen (SL), Emulsionen, versprühbare Lösungen, Dispersionen auf Öl- oder Wasserbasis (SC), Suspoemulsionen (SE), Stäubemittel (DP), Beizmittel, Granulate in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, wasserdispergierbare Granulate (WG), ULV-Formulierungen, Mikrokapseln, Wachse oder Köder.Wettable powder (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions, sprayable solutions, oil or water-based dispersions (SC), suspoemulsions (SE), dusts (DP), mordants, granules in the form of , Spray, elevator and adsorption granules, water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits.
Diese einzelnen Formulierungstypen sind im Prinzip bekannt und beispielsweise beschrieben in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.These individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel, d.h. Träger- und/oder oberflächenaktive Stoffe, wie Inertmaterialien, Tenside, Lösungsmittel und weitere Zusatzstoffe sind ebenfalls bekannt und beispielsweise beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Garriers", 2nd Ed., Darland Books, Caldwell N.J.; H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y.; Marsden, "Solvente Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Athylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1967; Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986.The necessary formulation aids, i.e. Carrier and / or surface-active substances, such as inert materials, surfactants, solvents and other additives, are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Garriers", 2nd Ed., Darland Books, Caldwell N.J .; H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y .; Marsden, "Solvent Guide," 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1967; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen Stoffen, Düngemitteln und/oder Wachstumsregulatoren herstellen, z.B. in Form einer Fertigformulierung oder als Tankmix. Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdünnungs- oder Inertstoff noch Netzmittel, z.B. polyoxethylierte Alkylphenole, polyoxethylierte Fettalkohole, Alkyl- oder Alkylphenol-sulfonate und Dispergiermittel, z.B. ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6,6'- disulfonsaures Natrium enthalten.Based on these formulations, combinations with other pesticidally active substances, fertilizers and / or growth regulators can also be made produce, for example in the form of a finished formulation or as a tank mix. Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or inert substance, but also wetting agents, for example polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, for example sodium lignosulfonate, 2,2'-dinaphthylmethane-6, Contain 6'- disulfonic acid sodium.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen Lösungsmittel, z.B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen unter Zusatz von einem oder mehreren Emulgatoren hergestellt. Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calcium-Salze wie Ca- dodecylbenzol-sulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid-Kondensationsprodukte, Alkylpolyether, Sorbitanfettsäureester, Polyoxyethylensorbitan-Fettsäureester oder Poiyoxethylensorbitester.Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. As emulsifiers may be used, for example: calcium alkylarylsulfonates such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid ester or Poiyoxethylensorbitester.
Stäubemittel erhält man durch Vermählen des Wirkstoffes mit fein verteilten festen Stoffen, z.B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit, Pyrophillit oder Diatomeenerde. Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z.B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays, such as kaolin, bentonite, pyrophillite or diatomaceous earth. Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired as a mixture with fertilizers.
In Spritzpulvern beträgt die Wirkstoffkonzentration üblicherweise etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 5 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten meistens 5 bis 20 Gew.- % an Wirkstoff, versprühbare Lösungen etwa 2 bis 20 Gew.-%. Bei Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhiifsmittel, Füllstoffe usw. verwendet werden.The active substance concentration in wettable powders is usually about 10 to 90% by weight, the remainder to 100% by weight consists of customary formulation components. In the case of emulsifiable concentrates, the active substance concentration can be approximately 5 to 80% by weight. Dust-like formulations usually contain 5 to 20% by weight % of active ingredient, sprayable solutions about 2 to 20 wt .-%. In the case of granules, the active substance content depends in part on whether the active compound is in liquid or solid form and which granulating agents, fillers, etc. are used.
Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Lösungsmittel, Füll- oder Trägerstoffe.In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers.
Zur Anwendung werden die in handelsüblicher Form vorliegenden Konzentrate gegebenenfalls in üblicher Weise verdünnt, z.B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und teilweise auch bei Mikrogranulaten mittels Wasser. Staubförmige und granulierte Zubereitungen sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt.For use, the concentrates, which are commercially available, are diluted in the customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and sometimes also for microgranules using water. Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.
Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit u.a. variiert die erforderliche Aufwandmenge. Sie kann innerhalb weiter Grenzen schwanken, z.B. zwischen 0,0005 und 10,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,001 und 5 kg/ha Wirkstoff.With the external conditions such as temperature, humidity, etc. the required application rate varies. It can fluctuate within wide limits, e.g. between 0.0005 and 10.0 kg / ha or more of active substance, but it is preferably between 0.001 and 5 kg / ha of active substance.
Die erfindungsgemäßen Wirkstoffe können in ihren handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischungen mit anderen Wirkstoffen, wie Insektiziden, Lockstoffen, Stehlantien, Akariziden, Nematiziden, Fungiziden, wachstumsregulierenden Stoffen oder Herbiziden vorliegen.The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in mixtures with other active compounds, such as insecticides, attractants, standing antioxidants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
Zu den Schädlingsbekämpfungsmitteln zählen beispielsweise Phosphorsäureester, Carbamate, Carbonsäureester, Formamidine, Zinnverbindungen und durch Mikroorganismen hergestellte Stoffe.The pesticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds and substances produced by microorganisms.
Bevorzugte Mischungspartner sind: 1. aus der Gruppe der PhosphorverbindungenPreferred mix partners are: 1. from the group of phosphorus compounds
Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Bromophos, Bromophos-ethyl, Cadusafos (F-67825), Chlorethoxyphos, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Demeton, Demeton-S-methyl, Demeton-S-methyl sulfon, Dialifos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitriothion, Fensulfothion, Fenthion, Fonofos, Formothion, Fosthiazate (ASC- 66824) Heptenophos, Isazophos, Isothioate, Isoxathion, Malathion, Methacrifos, Methamidophos, Methidathion, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosphocarb (BAS-301 ), Phosmet, Phosphamidon, Phoxim, Pirimiphos, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinalphos, Sulprofos, Temephos, Terbufos, Tebupirimfos.Tetrachlorvinphos, Thiometon, Triazophos, Trichlorphon, Vamidothion;Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Bromophos, Bromophos-ethyl, Cadusafos (F-67825), Chlorethoxyphos, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Demeton, Demeton-S-methyl, Demeton-S-methyl sulfon, Dialifos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitriothion, Fensulfothion, Fenthion, Fonofos, Formothion, Fosthiazate (ASC- 66824io) Hep Malathion, Methacrifos, Methamidophos, Methidathion, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosphocarb (BAS-301), Phosmet, Phosphamidoniphoxim , Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinalphos, Sulprofos, Temephos, Terbufos, Tebupirimfos.Tetrachlorvinphos, Thiometon, Triazophos, Vichothothi on;
2. aus der Gruppe der Carbamate2. from the group of carbamates
Alanycarb (OK-135), Aldicarb, 2-sec-Butylphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Benfuracarb, Ethiofencarb, Furathiocarb, HCN-801 , Isoprocarb, Methomyl, 5-Methyl-m- cumenylbutyryl(methyl)carbamate, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, 1-Methylthio(ethylideneamino)-N-methyl-N-(morpholinothio)carbamate (UC 51717), Triazamate;Alanycarb (OK-135), Aldicarb, 2-sec-butylphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Benfuracarb, Ethiofencarb, Furathiocarb, HCN-801, Isoprocarb, Methomyl, 5-Methyl-m-cumenylbutyryl ( carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio (ethylideneamino) -N-methyl-N- (morpholinothio) carbamate (UC 51717), triazamate;
3. aus der Gruppe der Carbonsäureester3. from the group of carboxylic acid esters
Acrinathrin, Allethrin, Alphametrin, 5-Benzyl-3-furylmethyl-(E)-(1 R)-cis-2,2-di- methyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, Beta-Cyfluthrin, Beta-Cypermethrin, Bioallethrin, Bioallethrin((S)-cyclopentylisomer), Bioresmethrin, Bifenthrin, (RS)-1-Cyano-1-(6-phenoxy-2-pyridyl)methyl-(1 RS)-trans-3-(4- tert.butylphenyl)-2,2-dimethylcyclopropanecarboxylate (NCI 85193), Cycloprothrin, Cyfluthrin, Cyhalothrin, Cythithrin, Cypermethrin, Cyphenothrin, Deltamethrin, Empenthrin, Esfenvalerate, Fenfluthrin, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate (D-Isomer), Imiprothrin (S-41311 ), Lambda-Cyhaloth n, Permethrin, Phenothrin ((R)-Isomer), Prallethrin, Pyrethrine (natürliche Produkte), Resmethrin, Tefluthrin, Tetramethrin, Theta-Cypermethrin (TD-2344), Tralomethrin, Transfluthrin, Zeta-Cypermethrin (F-56701 );Acrinathrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl- (E) - (1 R) -cis-2,2-dimethyl-3- (2-oxothiolan-3-ylidenemethyl) cyclopropanecarboxylate, beta-cyfluthrin, Beta-cypermethrin, bioallethrin, bioallethrin ((S) -cyclopentyl isomer), bioresmethrin, bifenthrin, (RS) -1-cyano-1- (6-phenoxy-2-pyridyl) methyl- (1 RS) -trans-3- ( 4- tert.butylphenyl) -2,2-dimethylcyclopropane decarboxylate (NCI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cythithrin, cypermethrin, cyphenothrin, deltamethrin, Empenthrin, Esfenvalerate, Fenfluthrin, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate (D-isomer), Imiprothrin (S-41311), Lambda-Cyhaloth n, Permethrin, Phenothrin ((R) -Isomer), Pralletine (natural products) ), Resmethrin, tefluthrin, tetramethrin, theta-cypermethrin (TD-2344), tralomethrin, transfluthrin, zeta-cypermethrin (F-56701);
4. aus der Gruppe der Amidine Amitraz, Chlordimeform;4. from the group of the amidines amitraz, chlorodime form;
5. aus der Gruppe der Zinnverbindungen Cyhexatin, Fenbutatinoxide;5. from the group of tin compounds cyhexatin, fenbutatin oxide;
6. Sonstige6. Other
Abamectin, ABG-9008, Acetamiprid, Anagrapha falcitera, AKD-1022, AKD-3059, ANS-118, Bacillus thuringiensis, Beauveria bassianea, Bensultap, Bifenazate (D- 2341 ), Binapacryl, BJL-932, Bromopropylate, BTG-504, BTG-505, Buprofezin, Camphechlor, Cartap, Chlorobenzilate, Chlorfenapyr, Chlorfluazuron, 2-(4- Chlorphenyl)-4,5-diphenylthiophen (UBI-T 930), Chlorfentezine, Chromafenozide (ANS-118), CG-216, CG-217, CG-234, A-184699, Cyclopropancarbonsäure-(2- naphthylmethyl)ester (Ro12-0470), Cyromazin, Diacloden (Thiamethoxam), Diafenthiuron, N-(3,5-Dichlor-4-(1 ,1 ,2,3,3,3-hexafiuor-1-propyloxy) phenyl)carbamoyl)-2-chlorbenzcarboximidsäureethylester, DDT, Dicofol, Diflubenzuron, N-(2,3-Dihydro-3-methyl-1 ,3-thiazol-2-ylidene)-2,4-xylidine, Dinobuton, Dinocap, Diofenolan, DPX-062, Emamectin-Benzoate (MK-244), Endosulfan, Ethiprole (Sulfethiprole), Ethofenprox, Etoxazole (YI-5301 ), Fenazaquin, Fenoxycarb, Fipronil, Fluazuron, Flumite (Flufenzine, SZI-121 ), 2-Fluoro-5-(4-(4- ethoxyphenyl)-4-methyl-1-pentyl)diphenylether (MTI 800), Granulöse- und Kernpolyederviren, Fenpyroximate, Fenthiocarb, Flubenzimine, Flucycloxuron, Flufenoxuron, Flufenprox (ICI-A5683), Fluproxyfen, Gamma-HCH, Halofenozide (RH-0345), Halofenprox (MTI-732), Hexaflumuron (DE_473), Hexythiazox, HOI- 9004, Hydramethylnon (AC 217300), Lufenuron, Imidacloprid, Indoxacarb (DPX- MP062), Kanemite (AKD-2023), M-020, MTI-446, Ivermectin, M-020, Methoxyfenozide (Intrepid, RH-2485), Milbemectin, NC-196, Neemgard, Nitenpyram (TI-304), 2-Nitromethyl-4,5-dihydro-6H-thiazin (DS 52618), 2-Nitromethyl-3,4- dihydrothiazol (SD 35651 ), 2-Nitromethylene-1 ,2-thiazinan-3-ylcarbamaldehyde (WL 108477), Pyriproxyfen (S-71639), NC-196, NC-1111 , NNI-9768, Novaluron (MCW- 275), OK-9701 , OK-9601 , OK-9602, Propargite, Pymethrozine, Pyridaben, Pyrimidifen (SU-8801 ), RH-0345, RH-2485, RYI-210, S-1283, S-1833, SB7242, Sl- 8601 , Silafluofen, Silomadine (CG-177), Spinosad, SU-9118, Tebufenozide, Tebufenpyrad (MK-239), Teflubenzuron, Tetradifon, Tetrasul, Thiacloprid, Thiocyclam, TI-435, Tolfenpyrad (OMI-88), Triazamate (RH-7988), Triflumuron, Verbutin, Vertalec (Mykotal), YI-5301 ,Abamectin, ABG-9008, Acetamiprid, Anagrapha falcitera, AKD-1022, AKD-3059, ANS-118, Bacillus thuringiensis, Beauveria bassianea, Bensultap, Bifenazate (D-2341), Binapacryl, BJL-932, Bromopropylate, BTG-504, BTG-505, buprofezin, camphechlor, cartap, chlorobenzilate, chlorfenapyr, chlorfluazuron, 2- (4-chlorophenyl) -4,5-diphenylthiophene (UBI-T 930), chlororfentezine, chromafenozide (ANS-118), CG-216, CG -217, CG-234, A-184699, cyclopropanecarboxylic acid (2-naphthylmethyl) ester (Ro12-0470), cyromazine, diacloden (thiamethoxam), diafenthiuron, N- (3,5-dichloro-4- (1, 1, 2,3,3,3-hexafiuor-1-propyloxy) phenyl) carbamoyl) -2-chlorobenzcarboximidic acid ethyl ester, DDT, dicofol, diflubenzuron, N- (2,3-dihydro-3-methyl-1, 3-thiazole-2- ylidene) -2,4-xylidine, dinobutone, dinocap, diofenolan, DPX-062, emamectin benzoate (MK-244), endosulfan, ethiprole (sulfethiprole), ethofenprox, etoxazole (YI-5301), fenazaquin, fenoxycarb, fipronil Fluazuron, flumite (Flufenzine, SZI-121), 2-fluoro-5- (4- (4-ethoxyphenyl) -4-m ethyl-1-pentyl) diphenyl ether (MTI 800), granular and nuclear polyhedron viruses, fenpyroximate, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, flufenprox (ICI-A5683), fluproxyfen, gamma-HCH, halofenozide (RH-0345), Halofenozide (RHproxx45), -732), Hexaflumuron (DE_473), Hexythiazox, HOI- 9004, Hydramethylnon (AC 217300), Lufenuron, Imidacloprid, Indoxacarb (DPX- MP062), Kanemite (AKD-2023), M-020, MTI-446, Ivermectin, M-020, Methoxyfenozide (Intrepid, RH-2485), Milbemectin, NC-196, Neemgard, Nitenpyram (TI-304), 2- Nitromethyl-4,5-dihydro-6H-thiazine (DS 52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1, 2-thiazinan-3-ylcarbamaldehydes (WL 108477), pyriproxyfen ( S-71639), NC-196, NC-1111, NNI-9768, Novaluron (MCW-275), OK-9701, OK-9601, OK-9602, Propargite, Pymethrozine, Pyridaben, Pyrimidifen (SU-8801), RH -0345, RH-2485, RYI-210, S-1283, S-1833, SB7242, Sl-8601, Silafluofen, Silomadine (CG-177), Spinosad, SU-9118, Tebufenozide, Tebufenpyrad (MK-239), Teflubenzuron , Tetradifon, Tetrasul, Thiacloprid, Thiocyclam, TI-435, Tolfenpyrad (OMI-88), Triazamate (RH-7988), Triflumuron, Verbutin, Vertalec (Mycotal), YI-5301,
Die oben genannten Kombinationspartner stellen bekannte Wirkstoffe dar, die zum großen Teil in Ch.R Worthing, S.B. Walker, The Pesticide Manual, 11. Auflage, British Crop Protection Council Farnham, 1997 beschrieben sind.The above-mentioned combination partners are known active ingredients, which are largely in Ch.R Worthing, S.B. Walker, The Pesticide Manual, 11th edition, British Crop Protection Council Farnham, 1997.
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann von 0,00000001 bis zu 95 Gew.-% Wirkstoff, vorzugsweise zwischen 0,00001 und 1 Gew.-% liegen.The active substance content of the use forms prepared from the commercially available formulations can be from 0.00000001 to 95% by weight of active substance, preferably between 0.00001 and 1% by weight.
Die Anwendung geschieht in einer den Anwendungsformen angepaßten üblichen Weise.The application takes place in a customary manner adapted to the application forms.
Die erfindungsgemäßen Wirkstoffe eignen sich auch zur Bekämpfung von Endo- und Ektoparasiten auf dem veterinärmedizinischen Gebiet bzw. auf dem Gebiet der Tierhaltung. Die Anwendung der erfindungsgemäßen Wirkstoffe geschieht hier in bekannter Weise wie durch orale Anwendung in Form von beispielsweise Tabletten, Kapseln, Tränken, Granulaten, durch dermale Anwendung in Form beispielsweise des Tauchens (Dippen), Sprühens (Sprayen), Aufgießen (pour-on and spot-on) und des Einpudems sowie durch parenterale Anwendung in Form beispielsweise der Injektion. Die erfindungsgemäßen Verbindungen der Formel (I) können demgemäß auch besonders vorteilhaft in der Viehhaltung (z.B. Rinder, Schafe, Schweine und Geflügel wie Hühner, Gänse usw.) eingesetzt werden. In einer bevorzugten Ausführungsform der Erfindung werden den Tieren die Verbindungen, gegebenenfalls in geeigneten Formulierungen und gegebenenfalls mit dem Trinkwasser oder Futter oral verabreicht. Da eine Ausscheidung im Kot in wirksamer Weise erfolgt, läßt sich auf diese Weise sehr einfach die Entwicklung von Insekten im Kot der Tiere verhindern. Die jeweils geeigneten Dosierungen und Formulierungen sind insbesondere von der Art und dem Entwicklungsstadium der Nutztiere und auch vom Befallsdruck abhängig und lassen sich nach den üblichen Methoden leicht ermitteln und festlegen. Die Verbindungen können bei Rindern z.B. in Dosierungen von 0,01 bis 1 mg/kg Körpergewicht eingesetzt werden.The active compounds according to the invention are also suitable for combating endoparasites and ectoparasites in the veterinary field or in the field of animal husbandry. The active compounds according to the invention are used here in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, dipping (dipping), spraying (spraying), pouring on (pour-on and spot) -on) and the pump and by parenteral use in the form of, for example, the injection. The compounds of the formula (I) according to the invention can accordingly also be used particularly advantageously in animal husbandry (for example cattle, sheep, pigs and poultry such as chickens, geese, etc.). In a preferred embodiment of the invention, the compounds, if appropriate in suitable formulations and if appropriate with the drinking water or feed, are administered to the animals orally. Since excretion in the faeces is effective, the development of insects in the faeces of the animals can be prevented very easily in this way. The appropriate dosages and formulations depend in particular on the type and stage of development of the livestock and also on the infestation pressure and can be easily determined and determined using the usual methods. The compounds can be used in cattle, for example, in doses of 0.01 to 1 mg / kg of body weight.
Neben den bisher genannten Applikationsverfahren zeigen die erfindungsgemässen Wirkstoffe der Formel (I) eine hervorragende systemische Wirkung. Die Wirkstoffe können daher auch über Pflanzenteile, unterirdische wie oberirdische (Wurzel, Stengel, Blatt), in die Pflanzen eingebracht werden, wenn die Wirkstoffe in flüssiger oder fester Form in die direkte Umgebung der Pflanze appliziert werden (z.B. Granulate in der Erdapplikation, Applikation in gefluteten Reisfeldern).In addition to the application processes mentioned hitherto, the active compounds of the formula (I) according to the invention have an outstanding systemic action. The active ingredients can therefore also be introduced into the plants via parts of plants, both underground and above ground (roots, stems, leaves), if the active ingredients are applied in liquid or solid form to the immediate vicinity of the plant (e.g. granules in the soil application, application in flooded rice fields).
Daneben sind die erfindungsgemäßen Wirkstoffe in besonderer Weise zu Behandlung von vegetativen und generativen Vermehrungsmaterial einsetzbar, wie z.B. von Saatgut von beispielsweise Getreide, Gemüse, Baumwolle, Reis, Zuckerrübe und anderen Kultur- und Zierpflanzen, von Zwiebeln, Stecklingen und Knollen weiterer vegetativ vermehrter Kultur- und Zierpflanzen. Die Behandlung hierfür kann vor der Saat bzw. dem Pflanzvorgang erfolgen (z.B. durch spezielle Techniken des Seedcoatings, durch Beizung in flüssiger oder fester Form oder Seedboxtreatment), während des Saatvorgangs bzw. des Pflanzens oder nach dem Saat- bzw. Pflanzvorgang durch spezielle Applikationstechniken (z.B. Saatreihenbehandlung). Die angewandte Wirkstoffmenge kann entsprechend der Anwendung in einem größerem Bereich schwanken. Im allgemeinen liegen die Aufwandmengen zwischen 1 g und 10 kg Wirkstoff pro Hektar Bodenfläche.In addition, the active compounds according to the invention can be used in a particular way to treat vegetative and generative propagation material, such as, for example, seeds from, for example, cereals, vegetables, cotton, rice, sugar beet and other crops and ornamental plants, onions, cuttings and tubers from other vegetatively propagated crops. and ornamental plants. The treatment for this can take place before the sowing or planting process (e.g. by special techniques of seed coating, by dressing in liquid or solid form or seed box treatment), during the sowing process or planting or after the sowing or planting process by special application techniques ( eg seed row treatment). The amount of active ingredient used can be according to Application fluctuate in a larger range. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil.
Die Verbindungen der Formel (I) können auch zur Bekämpfung von Schadpflanzen in Kulturen von bekannten oder noch zu entwickelnden gentechnisch veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten Pflanzenschutzmitteln, Resistenzen gegenüber Pflanzenkrankheiten oder Erregern von Pflanzenkrankheiten, wie bestimmten Insekten oder Mikroorganismen, wie Pilzen, Bakterien oder Viren. Andere besondere Eigenschaften betreffen z.B. das Erntegut hinsichtlich Menge, Qualität, Lagerfähigkeit, Zusammensetzung und spezieller Inhaltsstoffe. So sind transgene Pflanzen mit erhöhtem Stärkegehalt oder veränderter Qualität der Stärke oder solche mit anderer Fettsäurezusammensetzung des Ernteguts bekannt.The compounds of formula (I) can also be used to control harmful plants in crops of known or still to be developed genetically modified plants. The transgenic plants are generally distinguished by particularly advantageous properties, for example resistance to certain crop protection agents, resistance to plant diseases or pathogens causing plant diseases, such as certain insects or microorganisms, such as fungi, bacteria or viruses. Other special properties concern e.g. the crop in terms of quantity, quality, storability, composition and special ingredients. Transgenic plants with an increased starch content or altered starch quality or with a different fatty acid composition of the crop are known.
Bevorzugt ist die Anwendung in wirtschaftlich bedeutenden transgenen Kulturen von Nutz- und Zierpflanzen, z.B. von Getreide, wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis, Maniok und Mais, oder auch Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten.Preferred is the use in economically important transgenic crops of useful and ornamental plants, e.g. of cereals, such as wheat, barley, rye, oats, millet, rice, cassava and corn, or else crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables.
Bei der Anwendung in transgenen Kulturen, insbesondere mit Insektenresistenzen treten neben den in anderen Kulturen zu beobachtenden Wirkungen gegenüber Schadorganismen oftmals Wirkungen auf, die für die Applikation in der jeweiligen transgenen Kultur spezifisch sind, beispielsweise ein verändertes oder speziell erweitertes Schädlingsspektrum, das bekämpft werden kann oder veränderte Aufwandmengen, die für die Applikation eingesetzt werden können.When used in transgenic cultures, in particular with insect resistance, in addition to the effects on harmful organisms which can be observed in other cultures, there are often effects which are specific to the application in the respective transgenic culture, for example an altered or specially expanded pest spectrum which can be controlled or changed application rates that can be used for the application.
Gegenstand der Erfindung ist deshalb auch die Verwendung von Verbindungen der Formel (I) zur Bekämpfung von Schadorganismen in transgenen Kulturpflanzen. Die Anwendung der erfindungsgemäßen Verbindungen beinhaltet neben direkter Applikation auf die Schädlinge jede andere Applikation, bei der Verbindungen der Formel (I) auf die Schädlinge wirken. Solche indirekten Applikationen können beispielsweise in der Anwendung von Verbindungen liegen, die, beispielsweise im Boden, der Pflanze oder dem Schädling, zu Verbindungen der Formel (I) zerfallen oder abgebaut werden.The invention therefore also relates to the use of compounds of the formula (I) for controlling harmful organisms in transgenic crop plants. In addition to direct application to the pests, the use of the compounds according to the invention includes any other application in which compounds of the formula (I) act on the pests. Such indirect applications can be, for example, the use of compounds which, for example in the soil, the plant or the pest, decompose or break down to give compounds of the formula (I).
Auf den Inhalt der deutschen Patentanmeldung 198 581 93.9, deren Priorität die vorliegende Anmeldung beansprucht, sowie auf den Inhalt der beiliegenden Zusammenfassung wird hiermit ausdrücklich Bezug genommen; sie gelten durch Zitat als Bestandteil dieser Beschreibung.The content of the German patent application 198 581 93.9, the priority of which is claimed by the present application, and the content of the enclosed abstract are hereby expressly referred to; by quotation they are part of this description.
Nachfolgende Beispiele dienen zur Erläuterung der Erfindung.The following examples serve to explain the invention.
A. Chemische BeispieleA. Chemical examples
Beispiel 1example 1
Eine Lösung von 4-Trifluormethylnicotinsäure (2,2 g) in 40 ml THF wurde bei Raumtemperatur mit 1 ,1-Carbonyldiimidazol (1 ,9 g) versetzt und 30 min auf 40°C erhitzt. Anschließend gab man Furfurylsulfonylacetamidoxim (2,5 g) zu und ließ bei 40°C weitere 5 h rühren. Dann wurde das Reaktionsgemisch im Vakuum eingeengt und auf Eiswasser gegossen. Der entstandene Niederschlag wurde abgesaugt und abschließend im Trockenschrank getrocknet. Man erhielt 4- Trifluormethylnicotinsäure-(furfurylsulfonylacetamidoxim)-ester in Form eines farblosen Feststoffs (Schmelzpunkt 171°C).A solution of 4-trifluoromethylnicotinic acid (2.2 g) in 40 ml THF was mixed with 1,1-carbonyldiimidazole (1,9 g) at room temperature and heated to 40 ° C. for 30 min. Furfurylsulfonylacetamidoxim (2.5 g) was then added and the mixture was stirred at 40 ° C. for a further 5 h. Then the reaction mixture was concentrated in vacuo and poured onto ice water. The resulting precipitate was filtered off and finally dried in a drying cabinet. 4-Trifluoromethylnicotinic acid (furfurylsulfonylacetamidoxim) ester was obtained in the form of a colorless solid (melting point 171 ° C.).
1H-NMR (DMSO-d6, 300 MHz): 4.09 (s, 2H), 4.86 (s, 2H), 6.55 (m, 1 H), 6.63 (m, 1H), 7.08 (s, 2H), 7.75 (m, 1 H), 7.94 (d, J=5Hz, 1 H), 9.07 (d, J=5Hz, 1 H), 9.30 (s, 1 H). Beispiel 2 1 H-NMR (DMSO-d 6 , 300 MHz): 4.09 (s, 2H), 4.86 (s, 2H), 6.55 (m, 1H), 6.63 (m, 1H), 7.08 (s, 2H), 7.75 (m, 1H), 7.94 (d, J = 5Hz, 1H), 9.07 (d, J = 5Hz, 1H), 9.30 (s, 1H). Example 2
Den zuvor beschriebenen Amidoximester (4,0 g) versetzte man mit 80 ml Toluol und 60 ml Xylol sowie Amberlyst 15 (1 ,0 g). Das Reaktionsgemisch wurde 6 h auf 125°C erhitzt. Anschließend wurde abgesaugt und das Filtrat im Vakuum eingeengt und durch Chromatographie (Kieselgel, Ethylacetat/Petrolether, 4:1) gereinigt. Durch abschließendes Ausrühren mit n-Heptan erhielt man [5-(4'-Trifluormethylpyridin-3'yl)- [1 ,2,4]-oxdiazol-3-methyl]-furfuryl-sulfon als hellgelben Feststoff (Schmelzpunkt 99°C).The previously described amidoxime ester (4.0 g) was mixed with 80 ml of toluene and 60 ml of xylene and Amberlyst 15 (1.0 g). The reaction mixture was heated to 125 ° C for 6 h. The mixture was then filtered off with suction and the filtrate was concentrated in vacuo and purified by chromatography (silica gel, ethyl acetate / petroleum ether, 4: 1). Final stirring with n-heptane gave [5- (4'-trifluoromethylpyridin-3'yl) - [1, 2,4] oxdiazol-3-methyl] furfuryl sulfone as a light yellow solid (melting point 99 ° C.) .
1H-NMR (CDC-3, 300 MHz): 4.53 (s, 2H), 4.62 (s, 2H), 6.44 (m, 1 H), 6.69 (m 1H), 7.54 (m, 1 H), 7.82 (d, J=5Hz, 1 H), 9.08 (d, J=5Hz, 1 H), 9.40 (s, 1 H). 1 H NMR (CDC- 3 , 300 MHz): 4.53 (s, 2H), 4.62 (s, 2H), 6.44 (m, 1 H), 6.69 (m 1H), 7.54 (m, 1 H), 7.82 (d, J = 5Hz, 1H), 9.08 (d, J = 5Hz, 1H), 9.40 (s, 1H).
Beispiel 3Example 3
Figure imgf000041_0001
Figure imgf000041_0001
Ein Gemisch von 3-Chlormethyl-5-(4-trifluormethyl-3-pyridyl)-1 ,2,4-oxadiazol (1 ,0 g), Natriumsulfit (0,9 g), Wasser (18 ml) und Methanol (18 ml) wurde 6 Stunden lang bei 50° gerührt. Anschließend wurde das Reaktionsgemisch eingeengt der Rückstand in Methanol aufgenommen und filtriert. Danach wurde die Methanol-Lösung eingeengt und den Rückstand mit Dieethylether ausgerührt. Auf diese Weise wurdeA mixture of 3-chloromethyl-5- (4-trifluoromethyl-3-pyridyl) -1, 2,4-oxadiazole (1, 0 g), sodium sulfite (0.9 g), water (18 ml) and methanol (18 ml) was stirred at 50 ° for 6 hours. The reaction mixture was then concentrated, the residue was taken up in methanol and filtered. The methanol solution was then concentrated and the residue was triturated with dieethyl ether. That way
Figure imgf000041_0002
Figure imgf000041_0002
als schwach gelblicher Feststoff erhalten (Fp = 214°C). 1H-NMR (DMSO-d6, 300 MHz): 4.02 (s, 2H), 8.09 (d, J=5H, 1 H), 9.15 (d, J=5Hz, 1 H), 9.33 (s, 1 H).obtained as a pale yellowish solid (mp = 214 ° C.). 1 H NMR (DMSO-d 6 , 300 MHz): 4.02 (s, 2H), 8.09 (d, J = 5H, 1 H), 9.15 (d, J = 5Hz, 1 H), 9.33 (s, 1 H).
Das oben beschriebene Natriumsulfonat (0,95 g) wurde in Phosphoroxychlohd 30 ml) suspendiert und 5 Stunden lang auf Rückflußtemperatur erhitzt. Anschließend wurde das überschüssige Phosphoroxychlohd abdestilliert und das zurückbleibende Sulfonylchlorid in Dichlormethan (10 ml) aufgenommen. Diese Suspension wurde mit Ethylmethylamin (150 ml) versetzt und noch eine Stunde bei Raumtemperatur nachgerührt.The sodium sulfonate (0.95 g) described above was suspended in phosphorus oxychloride (30 ml) and heated to reflux for 5 hours. The excess phosphorus oxychloride was then distilled off and the remaining sulfonyl chloride was taken up in dichloromethane (10 ml). This suspension was mixed with ethyl methylamine (150 ml) and stirred for a further hour at room temperature.
Anschließend wurde mit Wasser, 5 %iger wäßriger Kaliumhydrogensulfatlösung und mit gesättigter Natriumhydrogencarbonatlösung gewaschen. Das nach Trocknen (MgSO4) und Einengen der Dichlormethanphase erhaltene Rohprodukt wurde chromatographisch gereinigt. Auf diese Weise wurde das gewünschte Sulfonamid als farbloses öl erhalten.It was then washed with water, 5% strength aqueous potassium hydrogen sulfate solution and with saturated sodium hydrogen carbonate solution. The crude product obtained after drying (MgSO 4 ) and concentration of the dichloromethane phase was purified by chromatography. In this way, the desired sulfonamide was obtained as a colorless oil.
1H-NMR (CDCI3, 300 MHz): 1.23 (6, J=7Hz, 3H), 2.92 (s, 3H), 3.25 (Q, J=7Hz), 2H), 4.54 (s, 2H), 7.90 (d, J=5Hz, 1 H), 9.06 (d, J=5Hz, 1 H), 9.35 (s, 1 H). 1 H-NMR (CDCI 3 , 300 MHz): 1.23 (6, J = 7Hz, 3H), 2.92 (s, 3H), 3.25 (Q, J = 7Hz), 2H), 4.54 (s, 2H), 7.90 (d, J = 5Hz, 1H), 9.06 (d, J = 5Hz, 1H), 9.35 (s, 1H).
In analoger Weise werden die in Tabelle 1 aufgeführten Sulfonamide hergestellt.The sulfonamides listed in Table 1 are prepared in an analogous manner.
Beispiel 4Example 4
3-[(2-Hydroxyethyl)thiomethyl]-5-(4-trifluormethyl-3-pyridyl)-1 ,2,4-oxadiazol3 - [(2-Hydroxyethyl) thiomethyl] -5- (4-trifluoromethyl-3-pyridyl) -1, 2,4-oxadiazole
Zu einer Lösung von 3-Chlormethyl-5-(4-trifluormethyl-3-pyridyl)-1 ,2,4-oxadiazol (0,5 g), 2-Mercaptoethanol (0,13 g) in Methanol (5 ml) wurde Natriummethanolatlösung (0,31 ml, 30 % in Methanol) gegeben und 5 Stunden bei Raumtemperatur gerührt. Anschließend wurde Wasser zugesetzt und mit Essigsäureethylester extrahiert. Die organische Phase wurde mit Wasser gewaschen, getrocknet (MgSO4), filtriert und eingeengt. Die chromatographische Reinigung erfolgte an Kieselgel mit Heptan/Essigsäureethylester. Das Rohprodukt ergab die gewünschte Verbindung als schwach braunes Öl.To a solution of 3-chloromethyl-5- (4-trifluoromethyl-3-pyridyl) -1, 2,4-oxadiazole (0.5 g), 2-mercaptoethanol (0.13 g) in methanol (5 ml) Added sodium methoxide solution (0.31 ml, 30% in methanol) and stirred for 5 hours at room temperature. Then water was added and extracted with ethyl acetate. The organic phase was washed with water, dried (MgSO 4 ), filtered and concentrated. The chromatographic purification was carried out on silica gel with heptane / ethyl acetate. The crude product gave the desired compound as a light brown oil.
1H-NMR (CDCI3, 300 MHz): 2.88 (t, J=7Hz, 2H), 3.04 (b, s, 1H), 3.82 (t, J=7Hz, 2H), 3.94 (s, 2H), 7.80 (d, J=5Hz, 1 H), 9.04 (d, J=5Hz, 1 H), 9.35 (s, 1 H). 1 H-NMR (CDCI 3 , 300 MHz): 2.88 (t, J = 7Hz, 2H), 3.04 (b, s, 1H), 3.82 (t, J = 7Hz, 2H), 3.94 (s, 2H), 7.80 (d, J = 5Hz, 1H), 9.04 (d, J = 5Hz, 1H), 9.35 (s, 1H).
Beispiel 5Example 5
3-Ethoxymethy!-5-(4-thfluormethyl-3-pyridyl)-1 ,2,4-oxadiazol3-ethoxymethy! -5- (4-thfluoromethyl-3-pyridyl) -1, 2,4-oxadiazole
3-lodmethyl-5-(4-trifluormethyl-3-pyridyl)-1 ,2,4-oxadiazol (0,5 g) wurde in einer frisch hergestellten Natriumethanolatlösung (30 mg Natrium in 7 ml Ethanol) gelöst und 6 Stunden lang bei Raumtemperatur gerührt.3-Iodomethyl-5- (4-trifluoromethyl-3-pyridyl) -1, 2,4-oxadiazole (0.5 g) was dissolved in a freshly prepared sodium ethanolate solution (30 mg sodium in 7 ml ethanol) and added for 6 hours Room temperature stirred.
Anschließend wurde das Reaktionsgemisch eingeengt, in Essigsäureethylester aufgenommen, mit Wasser gewaschen, getrocknet (MgSO4), filtriert und eingeengt.The reaction mixture was then concentrated, taken up in ethyl acetate, washed with water, dried (MgSO 4 ), filtered and concentrated.
Die chromatographische Reinigung des Rohprodukts ergab den gewünschten Ether als gelbliches Öl.Chromatographic purification of the crude product gave the desired ether as a yellowish oil.
Η-NMR (CDCI3, 300 MHz): 1.31 (t, J=7Hz, 3H), 3.72 (t, J=7Hz, 2H), 4.76 (s, 2H), 7.70 (d, J=5Hz, 1 H), 9.03 (d, J=5Hz, 1 H), 9.33 (s, 1H).Η NMR (CDCI 3 , 300 MHz): 1.31 (t, J = 7Hz, 3H), 3.72 (t, J = 7Hz, 2H), 4.76 (s, 2H), 7.70 (d, J = 5Hz, 1H ), 9.03 (d, J = 5Hz, 1H), 9.33 (s, 1H).
In analoger Weise werden die in Tabelle 1 aufgeführten Ether hergestellt. Beispiel 6The ethers listed in Table 1 are prepared in an analogous manner. Example 6
Ethyl-[(4'-(trifluormethyl)pyridin-3'-yl)-5-[1 ,2,4]-oxadiazol-3-methyl]-carbonatEthyl - [(4 '- (trifluoromethyl) pyridin-3'-yl) -5- [1, 2,4] oxadiazol-3-methyl] carbonate
3-Hydroxymethyl-5-(4'-(trifluormethyl)-pyridin-3'-yl)-[1 ,2,4]-oxadiazol (1 ,0 g) wurde in Acetonitril (10 ml) vorgelegt und mit Triethylamin (0,5 g) versetzt. Nach Zugabe von Chlorameisensäureethylester (0,5 g) wurde 6 h bei Raumtemperatur gerührt. Das Reaktionsgemisch wurde sodann mit Ethylacetat (5 ml) versetzt, mit 2N Natriumcarbonatlösung gewaschen und über MgSO4 getrocknet. Das nach Abfiltrieren des Trockenmittels und Einengen im Vakuum erhaltene Rohprodukt wurde säulenchromatographisch (Kieselgel, n-Heptan/Ethylacetat, 1 :1 ) gereinigt. Man erhielt das angestrebte Produkt als Öl.3-Hydroxymethyl-5- (4 '- (trifluoromethyl) pyridin-3'-yl) - [1, 2,4] oxadiazole (1, 0 g) was placed in acetonitrile (10 ml) and triethylamine (0 , 5 g). After addition of ethyl chloroformate (0.5 g), the mixture was stirred at room temperature for 6 h. The reaction mixture was then treated with ethyl acetate (5 ml), washed with 2N sodium carbonate solution and dried over MgSO 4 . The crude product obtained after filtering off the drying agent and concentrating in vacuo was purified by column chromatography (silica gel, n-heptane / ethyl acetate, 1: 1). The desired product was obtained as an oil.
1H-NMR (CDCI3, 300 MHz): 1.38 (t, J=7Hz, 3H), 4.31 (q, J=7Hz, 2H), 5.43 (s, 2H), 7.80 (d, J=5Hz, 1 H), 9.04 (d, J=5Hz, 1 H), 9.37 (s, 1 H). 1 H-NMR (CDCI 3 , 300 MHz): 1.38 (t, J = 7Hz, 3H), 4.31 (q, J = 7Hz, 2H), 5.43 (s, 2H), 7.80 (d, J = 5Hz, 1 H), 9.04 (d, J = 5Hz, 1H), 9.37 (s, 1H).
Tabelle 1 :Table 1 :
Figure imgf000044_0001
Figure imgf000044_0001
Figure imgf000044_0002
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000044_0002
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Tabelle 2:Table 2:
Figure imgf000052_0001
Figure imgf000052_0001
Figure imgf000052_0002
Figure imgf000052_0002
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000056_0002
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000056_0002
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000061_0001
Tabelle 3:Table 3:
Figure imgf000062_0001
Figure imgf000062_0001
Figure imgf000062_0002
Figure imgf000062_0002
Figure imgf000063_0002
Figure imgf000063_0002
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Bsp. Nr. Y R R' m.p. [°C]
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Example No.YRR 'mp [° C]
181 OC(O )NR' i-Pr Me 182 OC(O )NR' n-Bu Me 183 OC(O )NR i-Bu Me 184 OC(O )NR' Allyl Me 185 OC(O )NR' CH2C≡CH Me 186 OC(O )NR' CH=CH2 Me 187 OC(O )NR' CH2CH2 Me 188 OC(O )NR' CF3 Me 189 OC(O )NR CH2C 3 Me 190 OC(O )NR' CH2CN Me 191 OC(O )NR' Cyclopropyl Me 192 OC(O )NR Cyciopropylmethyl Me 193 OC(O )NR' CH2C02Me Me 194 OC(O )NR CH2CH2NMe2 Me 195 OC(O )NR' CH2-(N-morpholinyl) Me 196 OC(O )NR 2-Chlor-pyhdin-5-yl-methyl Me 197 OC(O )NR' n-Hex Me 198 OC(O )NR' 2-Furanyl Me 199 OC(O )NR' 2-Pyrimidinyl Me 200 OC(O )NR 2-Oxazolyl Me 201 OC(O )NR' 5-[1 ,2,4]-oxdiazolyl Me 202 OC(O )NR' Tetrazolyl Me181 OC (O) NR 'i-Pr Me 182 OC (O) NR' n-Bu Me 183 OC (O) NR i-Bu Me 184 OC (O) NR 'Allyl Me 185 OC (O) NR' CH 2 C≡CH Me 186 OC (O) NR 'CH = CH 2 Me 187 OC (O) NR' CH 2 CH 2 Me 188 OC (O) NR 'CF 3 Me 189 OC (O) NR CH 2 C 3 Me 190 OC (O) NR 'CH 2 CN Me 191 OC (O) NR' Cyclopropyl Me 192 OC (O) NR Cyciopropylmethyl Me 193 OC (O) NR 'CH 2 C0 2 Me Me 194 OC (O) NR CH 2 CH 2 NMe 2 Me 195 OC (O) NR 'CH 2 - (N-morpholinyl) Me 196 OC (O) NR 2-chloro-pyhdin-5-yl-methyl Me 197 OC (O) NR' n-Hex Me 198 OC (O) NR '2-furanyl Me 199 OC (O) NR' 2-pyrimidinyl Me 200 OC (O) NR 2-oxazolyl Me 201 OC (O) NR '5- [1, 2,4] -oxdiazolyl Me 202 OC (O) NR 'tetrazolyl Me
203 OC(O)NR' H Et203 OC (O) NR 'H Et
204 OC(O)NR Me Et204 OC (O) NR Me Et
205 OC(O)NR' Et Et205 OC (O) NR 'Et Et
206 OC(O)NR' n-Pr Et206 OC (O) NR 'n-Pr Et
207 OC(O)NR i-Pr Et207 OC (O) NR i-Pr Et
208 OC(O)NR n-Bu Et208 OC (O) NR n-Bu Et
209 OC(O)NR" i-Bu Et209 OC (O) NR "i-Bu Et
210 OC(O)NR Allyl Et210 OC (O) NR Allyl Et
211 OC(O)NR' CH2C≡CH Et211 OC (O) NR 'CH 2 C≡CH Et
212 OC(O)NR CH=CH2 Et212 OC (O) NR CH = CH 2 Et
213 OC(O)NR CH2CH F Et213 OC (O) NR CH 2 CH F Et
214 OC(O)NR CF3 Et214 OC (O) NR CF 3 Et
215 OC(O)NR CH2CF3 Et215 OC (O) NR CH 2 CF 3 Et
216 OC(O)NR CH2CN Et216 OC (O) NR CH 2 CN Et
217 OC(O)NR Cyclopropyl Et217 OC (O) NR cyclopropyl Et
218 OC(O)NR' Cyciopropylmethyl Et218 OC (O) NR 'cyciopropylmethyl Et
219 OC(O)NR CH2C02Me Et219 OC (O) NR CH 2 C0 2 Me Et
220 OC(O)NR' CH2CH2NMe2 Et220 OC (O) NR 'CH 2 CH 2 NMe 2 Et
221 OC(O)NR CH2-(N-morpholinyl) Et221 OC (O) NR CH 2 - (N-morpholinyl) Et
222 OC(O)NR 2-Chlor-pyridin-5-yl-methyl Et222 OC (O) NR 2-chloro-pyridin-5-yl-methyl Et
223 OC(O)NR n-Hex Et223 OC (O) NR n-Hex Et
224 OC(O)NR 2-Furanyl Et224 OC (O) NR 2-furanyl Et
225 OC(O)NR' 2-Pyrimidinyl Et225 OC (O) NR '2-pyrimidinyl Et
226 OC(O)NR 2-Oxazolyl Et226 OC (O) NR 2-oxazolyl Et
227 OC(O)NR 5-[1 ,2,4]-oxdiazolyl Et227 OC (O) NR 5- [1, 2,4] oxdiazolyl Et
228 OC(O)NR' Tetrazolyl Et228 OC (O) NR 'tetrazolyl Et
229 OC(O)C(O)Q H Bsp. Nr. Y R' m.p. [°C]229 OC (O) C (O) QH Example No. YR 'mp [° C]
230 OC(O)C(0)0 Me 231 OC(O)C(0)0 Et 232 OC(0)C(0)0 n-Pr 233 OC(0)C(O)0 i-Pr 234 OC(O)C(O)0 n-Bu 235 OC(O)C(O)0 i-Bu 236 OC(O)C(0)0 Allyl 237 OC(O)C(0)0 CH2C≡CH 238 OC(O)C(O)0 CH=CH2 239 OC(O)C(0)0 CH2Cπ F 240 OC(O)C(O)0 CF3 241 OC(O)C(O)0 CH CF3 242 OC(O)C(O)O CH2CN 243 OC(O)C(O)0 Cyclopropyl 244 OC(O)C(O)O Cyciopropylmethyl 245 OC(O)C(0)0 CH2C02Me 246 OC(O)C(O)0 CH2CH2NMe2 247 OC(O)C(0)0 CH2-(N-morpholinyl) 248 OC(O)C(0)0 2-Chlor-pyridin-5-yl-methyl 249 OC(O)C(O)0 n-Hex 250 OC(O)C(O)0 Furanyl 251 OC(O)C(O)O 2-Pyrimidinyl 252 OC(O)C(0)O 2-Oxazolyl 253 OC(O)C(0)0 5-[1 ,2,4]-oxdiazolyl 254 OC(O)C(O)0 Tetrazolyl230 OC (O) C (0) 0 Me 231 OC (O) C (0) 0 Et 232 OC (0) C (0) 0 n-Pr 233 OC (0) C (O) 0 i-Pr 234 OC (O) C (O) 0 n-Bu 235 OC (O) C (O) 0 i-Bu 236 OC (O) C (0) 0 allyl 237 OC (O) C (0) 0 CH 2 C≡CH 238 OC (O) C (O) 0 CH = CH 2 239 OC (O) C (0) 0 CH 2 Cπ F 240 OC (O) C (O) 0 CF 3 241 OC (O) C (O) 0 CH CF 3 242 OC (O) C (O) O CH 2 CN 243 OC (O) C (O) 0 cyclopropyl 244 OC (O) C (O) O cyciopropylmethyl 245 OC (O) C (0) 0 CH 2 C0 2 Me 246 OC (O) C (O) 0 CH 2 CH 2 NMe 2 247 OC (O) C (0) 0 CH 2 - (N-morpholinyl) 248 OC (O) C (0) 0 2-chlorine -pyridin-5-yl-methyl 249 OC (O) C (O) 0 n-hex 250 OC (O) C (O) 0 furanyl 251 OC (O) C (O) O 2-pyrimidinyl 252 OC (O) C (0) O 2-oxazolyl 253 OC (O) C (0) 0 5- [1, 2,4] -oxdiazolyl 254 OC (O) C (O) 0 tetrazolyl
255 S(O)2NR' H H255 S (O) 2 NR 'HH
256 S(0)2NR' Me H256 S (0) 2 NR 'Me H
257 S(O)2NR Et H257 S (O) 2 NR Et H
258 S(0)2NR' n-Pr H258 S (0) 2 NR 'n-Pr H
259 S(O)2NR" i-Pr H259 S (O) 2 NR "i-Pr H
260 S(O)2NR n-Bu H260 S (O) 2 NR n-Bu H
261 S(O)2NR' i-Bu H261 S (O) 2 NR 'i-Bu H
262 S(O)2NR' Allyl H262 S (O) 2 NR 'Allyl H
263 S(O)2NR CH2C≡CH H263 S (O) 2 NR CH 2 C≡CH H
264 S(O)2NR' CH=CH2 H264 S (O) 2 NR 'CH = CH 2 H
265 S(O)2NR' CH2CH2F H265 S (O) 2 NR 'CH 2 CH 2 FH
266 S(O)2NR CF3 H266 S (O) 2 NR CF 3 H
267 S(0)2NR' CH CF3 H267 S (0) 2 NR 'CH CF 3 H
268 S(O)2NR CH2CN H268 S (O) 2 NR CH 2 CN H
269 S(0)2NR Cyclopropyl H269 S (0) 2 NR cyclopropyl H
270 S(O)2NR' Cyciopropylmethyl H270 S (O) 2 NR 'cyciopropylmethyl H
271 S(O)2NR" CH2CO2Me H271 S (O) 2 NR "CH 2 CO 2 Me H
272 S(O)2NR CH2CH2NMe2 H272 S (O) 2 NR CH 2 CH 2 NMe 2 H
273 S(0)2NR' CH2-(N-morpholinyl) H273 S (0) 2 NR 'CH 2 - (N-morpholinyl) H
274 S(O)2NR' 2-Chlor-pyridin-5-yl-methyl H274 S (O) 2 NR '2-chloro-pyridin-5-yl-methyl H
275 S(0)2NR n-Hex H275 S (0) 2 NR n-Hex H
276 S(0)2NR' Furanyl H276 S (0) 2 NR 'Furanyl H
277 S(O)2NR' 2-Pyrimidinyl H277 S (O) 2 NR '2-pyrimidinyl H
278 S(0)2NR 2-Oxazolyl H Bsp. Nr. Y R m.p. [°C]278 S (0) 2 NR 2-oxazolyl H Example No.YR mp [° C]
279 S(0)2NR 5-[1 ,2,4]-oxdiazolyl 280 S(O)2NR' Tetrazolyl279 S (0) 2 NR 5- [1, 2,4] oxdiazolyl 280 S (O) 2 NR 'tetrazolyl
281 S(O)2NR' H Me 282 S(O)2NR Me Me 283 S(O)2NR' Et Me 284 S(O)2NR' n-Pr Me 285 S(O)2NR' i-Pr Me 286 S(O)2NR n-Bu Me 287 S(O)2NR i-Bu Me 288 S(O)2NR" Allyl Me 289 S(O)2NR' CH2C≡CH Me 290 S(O)2NR' CH=CH2 Me 291 S(O)2NR' CH2CH2F Me 292 S(O)2NR CF3 Me 293 S(O)2NR' CH2CF3 Me 294 S(O)2NR' CH2CN Me 295 S(O)2NR' Cyclopropyl Me 296 S(O)2NR' Cyciopropylmethyl Me 297 S(O)2NR CH2CO2Me Me 298 S(O)2NR' CH2CH2NMe2 Me 299 S(O)2NR CH2-(N-morpholinyl) Me 300 S(O)2NR' 2-Chlor-pyridin-5-yl-methyl Me 301 S(O)2NR' n-Hex Me 302 S(O)2NR' Furanyl Me 303 S(O)2NR' 2-Pyrimidinyl Me 304 S(O)2NR' 2-Oxazolyl Me 305 S(O)2NR' 5-[1 ,2,4]-oxdiazolyl Me 306 S(O)2NR Tetrazolyl Me281 S (O) 2 NR 'H Me 282 S (O) 2 NR Me Me 283 S (O) 2 NR' Et Me 284 S (O) 2 NR 'n-Pr Me 285 S (O) 2 NR' i -Pr Me 286 S (O) 2 NR n-Bu Me 287 S (O) 2 NR i-Bu Me 288 S (O) 2 NR "Allyl Me 289 S (O) 2 NR 'CH 2 C≡CH Me 290 S (O) 2 NR 'CH = CH 2 Me 291 S (O) 2 NR' CH 2 CH 2 F Me 292 S (O) 2 NR CF 3 Me 293 S (O) 2 NR 'CH 2 CF 3 Me 294 S (O) 2 NR 'CH 2 CN Me 295 S (O) 2 NR' cyclopropyl Me 296 S (O) 2 NR 'cyciopropylmethyl Me 297 S (O) 2 NR CH 2 CO 2 Me Me 298 S (O) 2 NR 'CH 2 CH 2 NMe 2 Me 299 S (O) 2 NR CH 2 - (N-morpholinyl) Me 300 S (O) 2 NR' 2-chloropyridin-5-yl-methyl Me 301 S (O) 2 NR 'n-Hex Me 302 S (O) 2 NR' Furanyl Me 303 S (O) 2 NR '2-Pyrimidinyl Me 304 S (O) 2 NR' 2-Oxazolyl Me 305 S (O) 2 NR '5 - [1, 2,4] -oxdiazolyl Me 306 S (O) 2 NR Tetrazolyl Me
307 S(O)2NR' H Et307 S (O) 2 NR 'H Et
308 S(0)2NR Me Et308 S (0) 2 NR Me Et
309 S(O)2NR" Et Et309 S (O) 2 NR "Et Et
310 S(O)2NR n-Pr Et310 S (O) 2 NR n-Pr Et
311 S(O)2NR' i-Pr Et311 S (O) 2 NR 'i-Pr Et
312 S(0)2NR n-Bu Et312 S (0) 2 NR n-Bu Et
313 S(0)2NR' i-Bu Et313 S (0) 2 NR 'i-Bu Et
314 S(O)2NR' Allyl Et314 S (O) 2 NR 'Allyl Et
315 S(O)2NR' CH2C--CH Et315 S (O) 2 NR 'CH 2 C - CH Et
316 S(O)2NR' CH=CH2 Et316 S (O) 2 NR 'CH = CH 2 Et
317 S(O)2NR' CH2CH2F Et317 S (O) 2 NR 'CH 2 CH 2 F Et
318 S(O)2NR' CF3 Et318 S (O) 2 NR 'CF 3 Et
319 S(O)2NR' CH2CF3 Et319 S (O) 2 NR 'CH 2 CF 3 Et
320 S(O)2NR' CH2CN Et320 S (O) 2 NR 'CH 2 CN Et
321 S(O)2NR Cyclopropyl Et321 S (O) 2 NR cyclopropyl Et
322 S(O)2NR Cyciopropylmethyl Et322 S (O) 2 NR cyciopropylmethyl Et
323 S(0)2NR' CH2CO2Me Et323 S (0) 2 NR 'CH 2 CO 2 Me Et
324 S(O)2NR CH2CH2NMe2 Et324 S (O) 2 NR CH 2 CH 2 NMe 2 Et
325 S(O)2NR' CH2-(N-morpholinyl) Et325 S (O) 2 NR 'CH 2 - (N-morpholinyl) Et
326 S(0)2NR' 2-Chlor-pyridin-5-yl-methyl Et326 S (0) 2 NR '2-chloro-pyridin-5-yl-methyl Et
327 S(O)2NR' n-Hex Et
Figure imgf000069_0001
327 S (O) 2 NR 'n-Hex Et
Figure imgf000069_0001
Tabelle 4:Table 4:
Figure imgf000070_0001
Figure imgf000070_0001
Figure imgf000070_0002
Figure imgf000071_0001
Figure imgf000072_0001
Bsp. Nr. Y R' m.p. [°C]
Figure imgf000070_0002
Figure imgf000071_0001
Figure imgf000072_0001
Example No. YR 'mp [° C]
137 OC(O)0 i-Bu 138 OC(O)O Allyl 139 OC(0)0 CH2C≡CH 140 OC(0)0 CH=CH2 141 OC(0)0 CH2CH2F 142 OC(0)0 CF3 143 OC(0)0 CH2CF3 144 OC(0)0 CH2CN 145 OC(0)0 Cyclopropyl 146 OC(O)O Cyciopropylmethyl 147 OC(O)0 CH2CO2Me 148 OC(0)0 CH2CH2NMe2 149 OC(O)0 CH2-(N-morpholinyl) 150 OC(O)0 2-Chlor-pyridin-5-yl-methyl 151 OC(0)0 n-Hex 152 OC(0)0 2-Furanyl 153 OC(0)0 2-Pyrimidinyl 154 OC(O)0 2-Oxazolyl 155 OC(0)O 5-[1 ,2,4]-oxdiazolyl 156 OC(0)O Tetrazolyl137 OC (O) 0 i-Bu 138 OC (O) O Allyl 139 OC (0) 0 CH 2 C≡CH 140 OC (0) 0 CH = CH 2 141 OC (0) 0 CH 2 CH 2 F 142 OC (0) 0 CF 3 143 OC (0) 0 CH 2 CF 3 144 OC (0) 0 CH 2 CN 145 OC (0) 0 cyclopropyl 146 OC (O) O cyciopropylmethyl 147 OC (O) 0 CH 2 CO 2 Me 148 OC (0) 0 CH 2 CH 2 NMe 2 149 OC (O) 0 CH 2 - (N-morpholinyl) 150 OC (O) 0 2-chloro-pyridin-5-yl-methyl 151 OC (0) 0 n -Hex 152 OC (0) 0 2-furanyl 153 OC (0) 0 2-pyrimidinyl 154 OC (O) 0 2-oxazolyl 155 OC (0) O 5- [1, 2,4] -oxdiazolyl 156 OC (0 ) O tetrazolyl
157 OC(O)NR H H157 OC (O) NR H H
158 OC(O)NR' Me H158 OC (O) NR 'Me H
159 OC(O)NR" Et H159 OC (O) NR "Et H
160 OC(O)NR' n-Pr H160 OC (O) NR 'n-Pr H
161 OC(O)NR' i-Pr H161 OC (O) NR 'i-Pr H
162 OC(0)NR' n-Bu H162 OC (0) NR 'n-Bu H
163 OC(0)NR' i-Bu H163 OC (0) NR 'i-Bu H
164 OC(0)NR' Allyl H164 OC (0) NR 'Allyl H
165 OC(0)NR' CH2C≡CH H165 OC (0) NR 'CH 2 C≡CH H
166 OC(O)NR' CH=CH2 H166 OC (O) NR 'CH = CH 2 H
167 OC(0)NR' CH2CH2F H167 OC (0) NR 'CH 2 CH 2 FH
168 OC(0)NR' CF3 H168 OC (0) NR 'CF 3 H
169 OC(O)NR CH2CF3 H169 OC (O) NR CH 2 CF 3 H
170 OC(0)NR' CH2CN H170 OC (0) NR 'CH 2 CN H
171 OC(O)NR' Cyclopropyl H171 OC (O) NR 'cyclopropyl H
172 OC(O)NR Cyciopropylmethyl H172 OC (O) NR Cyciopropylmethyl H
173 OC(0)NR' CH2C02Me H173 OC (0) NR 'CH 2 C0 2 Me H
174 OC(0)NR CH2CH2NMe2 H174 OC (0) NR CH 2 CH 2 NMe 2 H
175 OC(0)NR' CH2-(N-morpholinyl) H175 OC (0) NR 'CH 2 - (N-morpholinyl) H
176 OC(O)NR' 2-Chlor-pyhdin-5-yl-methyl H176 OC (O) NR '2-chloro-pyhdin-5-yl-methyl H
177 OC(0)NR' n-Hex H177 OC (0) NR 'n-Hex H
178 OC(O)NR' 2-Furanyl H178 OC (O) NR '2-furanyl H
179 OC(O)NR' 2-Pyrimidinyl H179 OC (O) NR '2-pyrimidinyl H
180 OC(0)NR' 2-Oxazolyl H180 OC (0) NR '2-oxazolyl H
181 OC(O)NR' 5-[1 ,2,4]-oxdiazolyl H181 OC (O) NR '5- [1,2,4] oxdiazolyl H
182 OC(0)NR' Tetrazolyl H182 OC (0) NR 'tetrazolyl H
183 OC(0)NR' H Me 184 OC(0)NR' Me Me 185 OC(0)NR' Et Me
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
183 OC (0) NR 'H Me 184 OC (0) NR' Me Me 185 OC (0) NR 'Et Me
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Bsp. Nr. Y R R' m.p. [°C].
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Ex. No. YRR 'mp [° C].
243 OC(0)C(0)0 cyclobutyl 244 OC(0)C(0)0 Me 245 OC(O)C(0)0 Et 246 OC(O)C(O)0 n-Pr 247 OC(O)C(O)0 i-Pr 248 OC(O)C(O)O n-Bu 249 OC(O)C(O)O i-Bu 250 OC(O)C(O)O Allyl 251 OC(O)C(O)0 CH2C≡CH 252 OC(O)C(0)0 CH=CH2 253 OC(O)C(O)O CH2CH2F 254 OC(O)C(O)0 CF3 255 OC(O)C(O)O CH2CF3 256 OC(O)C(O)0 CH2CN 257 OC(O)C(O)0 Cyclopropyl 258 OC(O)C(O)0 Cyciopropylmethyl 259 OC(O)C(O)0 CH2CO2Me 260 OC(0)C(0)0 CH2CH2NMe2 261 OC(O)C(0)0 CH2-(N-morpholinyl) 262 OC(O)C(O)O 2-Chlor-pyridin-5-yl-methyl 263 OC(O)C(O)0 n-Hex 264 OC(O)C(O)0 2-Furanyl 265 OC(O)C(O)0 2-Pyrimidinyl 266 OC(O)C(O)0 2-Oxazolyl 267 OC(O)C(O)0 5-[1 ,2,4]-oxdiazolyl 268 OC(O)C(O)0 Tetrazolyl243 OC (0) C (0) 0 cyclobutyl 244 OC (0) C (0) 0 Me 245 OC (O) C (0) 0 Et 246 OC (O) C (O) 0 n-Pr 247 OC (O ) C (O) 0 i-Pr 248 OC (O) C (O) O n-Bu 249 OC (O) C (O) O i-Bu 250 OC (O) C (O) O Allyl 251 OC (O ) C (O) 0 CH 2 C≡CH 252 OC (O) C (0) 0 CH = CH 2 253 OC (O) C (O) O CH 2 CH 2 F 254 OC (O) C (O) 0 CF 3 255 OC (O) C (O) O CH 2 CF 3 256 OC (O) C (O) 0 CH 2 CN 257 OC (O) C (O) 0 cyclopropyl 258 OC (O) C (O) 0 Cyciopropylmethyl 259 OC (O) C (O) 0 CH 2 CO 2 Me 260 OC (0) C (0) 0 CH 2 CH 2 NMe 2 261 OC (O) C (0) 0 CH 2 - (N-morpholinyl) 262 OC (O) C (O) O 2-chloropyridin-5-yl-methyl 263 OC (O) C (O) 0 n-hex 264 OC (O) C (O) 0 2-furanyl 265 OC ( O) C (O) 0 2-pyrimidinyl 266 OC (O) C (O) 0 2-oxazolyl 267 OC (O) C (O) 0 5- [1, 2,4] oxdiazolyl 268 OC (O) C (O) 0 tetrazolyl
269 S(0)2NR' H Me269 S (0) 2 NR 'H Me
270 S(O)2NR' Me Me270 S (O) 2 NR 'Me Me
271 S(O)2NR Et Me271 S (O) 2 NR Et Me
272 S(0)2NR n-Pr Me272 S (0) 2 NR n-Pr Me
273 S(O)2NR i-Pr Me273 S (O) 2 NR i-Pr Me
274 S(0)2NR n-Bu Me274 S (0) 2 NR n-Bu Me
275 S(O)2NR i-Bu Me275 S (O) 2 NR i-Bu Me
276 S(0)2NR' Allyl Me276 S (0) 2 NR 'Allyl Me
277 S(0)2NR' CH2C≡CH Me277 S (0) 2 NR 'CH 2 C≡CH Me
278 S(O)2NR CH=CH2 Me278 S (O) 2 NR CH = CH 2 Me
279 S(0)2NR' CH CH2F Me279 S (0) 2 NR 'CH CH 2 F Me
280 S(O)2NR CF3 Me280 S (O) 2 NR CF 3 Me
281 S(O)2NR' CH2CF3 Me281 S (O) 2 NR 'CH 2 CF 3 Me
282 S(0)2NR' CH2CN Me282 S (0) 2 NR 'CH 2 CN Me
283 S(0)2NR' Cyclopropyl Me283 S (0) 2 NR 'cyclopropyl me
284 S(0)2NR Cyciopropylmethyl Me284 S (0) 2 NR cyciopropylmethyl Me
285 S(0)2NR' CH2CO2Me Me285 S (0) 2 NR 'CH 2 CO 2 Me Me
286 S(0)2NR' CH2CH2NMe2 Me286 S (0) 2 NR 'CH 2 CH 2 NMe 2 Me
287 S(0)2NR CH2-(N-morpholinyl) Me287 S (0) 2 NR CH 2 - (N-morpholinyl) Me
288 S(O)2NR' 2-Chlor-pyridin-5-yl-methyl Me288 S (O) 2 NR '2-chloro-pyridin-5-yl-methyl Me
289 S(0)2NR' n-Hex Me289 S (0) 2 NR 'n-Hex Me
290 S(0)2NR 2-Furanyl Me290 S (0) 2 NR 2-furanyl Me
291 S(0)2NR 2-Pyrimidinyl Me
Figure imgf000084_0001
291 S (0) 2 NR 2-pyrimidinyl Me
Figure imgf000084_0001
Tabelle 6:Table 6:
Figure imgf000085_0001
Figure imgf000085_0001
Figure imgf000085_0002
Figure imgf000086_0001
Figure imgf000087_0001
Bsp. Nr. Y R' m.p. [°C]
Figure imgf000085_0002
Figure imgf000086_0001
Figure imgf000087_0001
Example No. YR 'mp [° C]
138 OC(0)0 CH CF3 139 OC(0)0 CH2CN 140 OC(0)0 Cyclopropyl 141 OC(0)0 Cyciopropylmethyl 142 OC(0)0 CH2CO2Me 143 OC(O)O CH2CH2NMe2 144 OC(O)0 CH2-(N-morpholinyl) 145 OC(O)O 2-Chlor-pyhdin-5-yl-methyl 146 OC(0)0 2-Furanyl 147 OC(0)0 2-Pyrimidinyl 148 OC(O)0 2-Oxazolyl 149 OC(0)O 5-[1 ,2,4]-oxdiazolyl 150 OC(O)O Tetrazolyl138 OC (0) 0 CH CF 3 139 OC (0) 0 CH 2 CN 140 OC (0) 0 cyclopropyl 141 OC (0) 0 cyciopropylmethyl 142 OC (0) 0 CH 2 CO 2 Me 143 OC (O) O CH 2 CH 2 NMe 2 144 OC (O) 0 CH 2 - (N-morpholinyl) 145 OC (O) O 2-chloro-pyhdin-5-yl-methyl 146 OC (0) 0 2-furanyl 147 OC (0) 0 2-pyrimidinyl 148 OC (O) 0 2-oxazolyl 149 OC (0) O 5- [1, 2,4] oxdiazolyl 150 OC (O) O tetrazolyl
151 OC(0)NR' H H151 OC (0) NR 'H H
152 OC(O)NR' Me H152 OC (O) NR 'Me H
153 OC(0)NR' Et H153 OC (0) NR 'Et H
154 OC(0)NR' n-Pr H154 OC (0) NR 'n-Pr H
155 OC(0)NR' i-Pr H155 OC (0) NR 'i-Pr H
156 OC(0)NR' n-Bu H156 OC (0) NR 'n-Bu H
157 OC(0)NR' i-Bu H157 OC (0) NR 'i-Bu H
158 OC(0)NR' Allyl H158 OC (0) NR 'Allyl H
159 OC(O)NR' CH2C≡-CH H159 OC (O) NR 'CH 2 C≡-CH H
160 OC(O)NR CH=CH2 H160 OC (O) NR CH = CH 2 H
161 OC(O)NR CH2CH2F H161 OC (O) NR CH 2 CH 2 FH
162 OC(O)NR' CF3 H162 OC (O) NR 'CF 3 H
163 OC(O)NR' CH2Cr3 H163 OC (O) NR 'CH 2 Cr 3 H
164 OC(0)NR CH2CN H164 OC (0) NR CH 2 CN H
165 OC(O)NR Cyclopropyl H165 OC (O) NR cyclopropyl H
166 OC(O)NR Cyciopropylmethyl H166 OC (O) NR cyciopropylmethyl H
167 OC(O)NR CH2CO2Me H167 OC (O) NR CH 2 CO 2 Me H
168 OC(0)NR CH2CH2NMe2 H168 OC (0) NR CH 2 CH 2 NMe 2 H
169 OC(0)NR CH2-(N-morpholinyl) H169 OC (0) NR CH 2 - (N-morpholinyl) H
170 OC(O)NR 2-Chlor-pyridin-5-yl-methyl H170 OC (O) NR 2-chloro-pyridin-5-yl-methyl H
171 OC(0)NR' 2-Furanyl H171 OC (0) NR '2-furanyl H
172 OC(0)NR 2-Pyrimidinyl H172 OC (0) NR 2-pyrimidinyl H
173 OC(O)NR' 2-Oxazolyl H173 OC (O) NR '2-oxazolyl H
174 OC(0)NR' 5-[1 ,2,4]-oxdiazolyl H174 OC (0) NR '5- [1,2,4] oxdiazolyl H
175 OC(0)NR' Tetrazolyl H175 OC (0) NR 'tetrazolyl H
176 OC(0)NR' H Me 177 OC(0)NR' Me Me 178 OC(0)NR' Et Me 179 OC(0)NR' n-Pr Me 180 OC(0)NR' i-Pr Me 181 OC(0)NR' n-Bu Me 182 OC(O)NR' i-Bu Me 183 OC(0)NR' Allyl Me 184 OC(O)NR' CH2C≡CH Me 185 OC(0)NR' CH=CH2 Me 186 OC(O)NR' CH2CH2F Me Bsp. Nr. Y R R' m.p. [°C]176 OC (0) NR 'H Me 177 OC (0) NR' Me Me 178 OC (0) NR 'Et Me 179 OC (0) NR' n-Pr Me 180 OC (0) NR 'i-Pr Me 181 OC (0) NR 'n-Bu Me 182 OC (O) NR' i-Bu Me 183 OC (0) NR 'Allyl Me 184 OC (O) NR' CH 2 C≡CH Me 185 OC (0) NR ' CH = CH 2 Me 186 OC (O) NR 'CH 2 CH 2 F Me Example No.YRR 'mp [° C]
187 OC(0)NR' CF3 Me 188 OC(0)NR CH2CF3 Me 189 OC(0)NR' CH2CN Me 190 OC(0)NR' Cyclopropyl Me 191 OC(O)NR' Cyciopropylmethyl Me 192 OC(0)NR' CH2C02Me Me 193 OC(0)NR' CH2CH2NMe2 Me 194 OC(O)NR' CH2-(N-morpholinyl) Me 195 OC(O)NR' 2-Chlor-pyridin-5-yl-methyl Me 196 OC(O)NR' Furanyl Me 197 OC(O)NR' 2-Pyrimidinyl Me 198 OC(0)NR' 2-Oxazolyl Me 199 OC(O)NR' 5-[1 ,2,4]-oxdiazolyl Me 200 OC(0)NR Tetrazolyl Me187 OC (0) NR 'CF 3 Me 188 OC (0) NR CH 2 CF 3 Me 189 OC (0) NR' CH 2 CN Me 190 OC (0) NR 'Cyclopropyl Me 191 OC (O) NR' Cyciopropylmethyl Me 192 OC (0) NR 'CH 2 C0 2 Me Me 193 OC (0) NR' CH 2 CH 2 NMe 2 Me 194 OC (O) NR 'CH 2 - (N-morpholinyl) Me 195 OC (O) NR' 2-chloro-pyridin-5-yl-methyl Me 196 OC (O) NR 'Furanyl Me 197 OC (O) NR' 2-Pyrimidinyl Me 198 OC (0) NR '2-Oxazolyl Me 199 OC (O) NR' 5- [1, 2,4] oxdiazolyl Me 200 OC (0) NR tetrazolyl Me
201 OC(O)NR' H Et201 OC (O) NR 'H Et
202 OC(O)NR' Me Et202 OC (O) NR 'Me Et
203 OC(O)NR Et Et203 OC (O) NR Et Et
204 OC(O)NR' n-Pr Et204 OC (O) NR 'n-Pr Et
205 OC(O)NR' i-Pr Et205 OC (O) NR 'i-Pr Et
206 OC(0)NR' n-Bu Et206 OC (0) NR 'n-Bu Et
207 OC(O)NR i-Bu Et207 OC (O) NR i-Bu Et
208 OC(O)NR' Allyl Et208 OC (O) NR 'Allyl Et
209 OC(O)NR' CH2C=CH Et209 OC (O) NR 'CH 2 C = CH Et
210 OC(O)NR' CH=CH2 Et210 OC (O) NR 'CH = CH 2 Et
211 OC(0)NR' CH2CH2F Et211 OC (0) NR 'CH 2 CH 2 F Et
212 OC(0)NR' CF3 Et212 OC (0) NR 'CF 3 Et
213 OC(0)NR' CH CFs Et213 OC (0) NR 'CH CFs Et
214 OC(0)NR CH2CN Et214 OC (0) NR CH 2 CN Et
215 OC(O)NR Cyclopropyl Et215 OC (O) NR cyclopropyl Et
216 OC(O)NR' Cyciopropylmethyl Et216 OC (O) NR 'cyciopropylmethyl Et
217 OC(O)NR' CH2CO2Me Et217 OC (O) NR 'CH 2 CO 2 Me Et
218 OC(O)NR' CH2CH2NMe2 Et218 OC (O) NR 'CH 2 CH 2 NMe 2 Et
219 OC(O)NR' CH2-(N-morpholinyl) Et219 OC (O) NR 'CH 2 - (N-morpholinyl) Et
220 OC(O)NR' 2-Chlor-pyridin-5-yl-methyl Et220 OC (O) NR '2-chloro-pyridin-5-yl-methyl Et
221 OC(0)NR' 2-Furanyl Et221 OC (0) NR '2-furanyl Et
222 OC(O)NR" 2-Pyrimidinyl Et222 OC (O) NR "2-pyrimidinyl Et
223 OC(0)NR' 2-Oxazolyl Et223 OC (0) NR '2-oxazolyl Et
224 OC(0)NR' 5-[1 ,2,4]-oxdiazolyl Et224 OC (0) NR '5- [1,2,4] oxdiazolyl Et
225 OC(0)NR' Tetrazolyl Et225 OC (0) NR 'tetrazolyl Et
226 OC(O)C(O)O n-Hex 227 OC(O)C(O)O Me 228 OC(0)C(O)O Et 229 OC(O)C(O)O n-Pr 230 OC(0)C(O)0 i-Pr 231 OC(O)C(O)0 n-Bu 232 OC(0)C(O)0 i-Bu 233 OC(O)C(0)0 Allyl 234 OC(0)C(O)0 CH2C=CH 235 OC(0)C(0)0 CH=CH2
Figure imgf000090_0001
Figure imgf000091_0001
B. Formulierungsbeispiele226 OC (O) C (O) O n-Hex 227 OC (O) C (O) O Me 228 OC (0) C (O) O Et 229 OC (O) C (O) O n-Pr 230 OC (0) C (O) 0 i-Pr 231 OC (O) C (O) 0 n-Bu 232 OC (0) C (O) 0 i-Bu 233 OC (O) C (0) 0 allyl 234 OC (0) C (O) 0 CH 2 C = CH 235 OC (0) C (0) 0 CH = CH 2
Figure imgf000090_0001
Figure imgf000091_0001
B. Formulation examples
a) Ein Stäubemittel wird erhalten, indem man 10 Gew.-Teile Wirkstoff und 90 Gew.-Teile Talkum als Inertstoff mischt und in einer Schlagmühle zerkleinert.a) A dusting agent is obtained by mixing 10 parts by weight of active ingredient and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill.
b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25 Gew.-Teile Wirkstoff, 65 Gew.-Teile kaolinhaltigen Quarz als Inertstoff, 10 Gew.-Teile ligninsulfonsaures Kalium und 1 Gew.-Teil oleoylmethyltaurinsaures Natrium als Netz- und Dispergiermittel mischt und in einer Stiftmühle mahlt.b) A wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of active compound, 65 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium as the wetting agent. and dispersant mixes and grinds in a pin mill.
c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat stellt man her, indem man 40 Gew.-teile Wirkstoff mit 7 Gew.-Teilen eines Sulfobemsteinsäurehalbesters, 2 Gew.-Teilen eines Ligninsulfonsäure- Natriumsalzes und 51 Gew.-Teilen Wasser mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron vermahlt.c) A dispersion concentrate which is readily dispersible in water is prepared by mixing 40 parts by weight of active compound with 7 parts by weight of a sulfosuccinic acid half-ester, 2 parts by weight of a lignosulfonic acid sodium salt and 51 parts by weight of water and in a attritor ground to a fineness of less than 5 microns.
d) Ein emulgierbares Konzentrat läßt sich herstellen aus 15 Gew.-Teilen Wirkstoff, 75 Gew.-Teilen Cyclohexan als Lösungsmittel und 10 Gew.-Teilen oxethyliertem Nonylphenol (10 EO) als Emulgator.d) An emulsifiable concentrate can be prepared from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexane as solvent and 10 parts by weight of oxyethylated nonylphenol (10 EO) as emulsifier.
e) Ein Granulat läßt sich herstellen aus 2 bis 15 Gew.-Teilen Wirkstoff und einem inerten Granulatträgermaterial wie Attapulgit, Bimsgranulat und/oder Quarzsand. Zweckmäßigerweise verwendet man eine Suspension des Spritzpulvers aus Beispiel b) mit einem Feststoffanteil von 30 % und spritzt diese auf die Oberfläche eines Attapulgitgranulats, trocknet und vermischt innig. Dabei beträgt der Gewichtsanteil des Spritzpuivers ca. 5 % und der des inerten Trägermaterials ca. 95 % des fertigen Granulats. C. Biologische Beispielee) Granules can be produced from 2 to 15 parts by weight of active ingredient and an inert granule carrier material such as attapulgite, pumice granules and / or quartz sand. A suspension of the wettable powder from example b) having a solids content of 30% is expediently used and sprayed onto the surface of an attapulgite granulate, dried and mixed intimately. The proportion by weight of the spray powder is about 5% and that of the inert carrier material is about 95% of the finished granulate. C. Biological examples
Beispiel 1example 1
Angekeimte Ackerbohnen-Samen (Vicia faba) mit Keimwurzeln wurden in mit Leitungswasser gefüllte Braunglasfiäschchen übertragen und anschließend mit ca. 100 schwarzen Bohnenblattläusen (Aphis fabae) belegt. Pflanzen und Blattläuse wurden dann für 5 Sekunden in eine wäßrige Lösung des zu prüfenden und formulierten Präparates getaucht. Nach dem Abtropfen wurden Pflanze und Tiere in einer Klimakammer gelagert (16 Stunden Licht/Tag, 25 °C, 40-60 % RF). Nach 3 und 6 Tagen Lagerung wurde die Wirkung des Präparates auf die Blattläuse festgestellt. Bei einer Konzentration von 300 ppm (bezogen auf den Gehalt an Wirkstoff) bewirkten die Präparate gemäß Beispiele Nr. 2/29, 2/43, 2/67, 2/6, 3/6, 3/50, 3/75 und 3/49 eine 90-100 %ige Mortalität der Blattläuse.Germinated field bean seeds (Vicia faba) with germ roots were transferred to amber glass bottles filled with tap water and then coated with about 100 black bean aphids (Aphis fabae). Plants and aphids were then immersed in an aqueous solution of the preparation to be tested and formulated for 5 seconds. After draining, the plants and animals were stored in a climatic chamber (16 hours light / day, 25 ° C, 40-60% RH). After 3 and 6 days of storage, the effect of the preparation on the aphids was determined. At a concentration of 300 ppm (based on the content of active ingredient), the preparations according to Examples Nos. 2/29, 2/43, 2/67, 2/6, 3/6, 3/50, 3/75 and 3 caused / 49 90-100% aphid mortality.
Die Numerierung der Verbindungen ist mit Tabelle/Nr. in der Tabelle angegeben.The numbering of the connections is with table / no. given in the table.
Beispiel 2Example 2
Die Blätter von 12 Reispflanzen mit einer Halmlänge von 8 cm wurden für 5 Sekunden in eine wäßrige Lösung des zu prüfenden und formulierten Präparates getaucht. Nach dem Abtropfen wurden die so behandelten Reispflanzen in eine Petrischale gelegt und mit ca. 20 Larven (L3-Stadium) der Reiszikadenart Nilaparvata lugens besetzt. Nach dem Verschließen der Petrischale wurde diese in einer Klimakammer gelagert (16 Stunden Licht/Tag, 25 °C, 40-60 % RF). Nach 6 Tagen Lagerung wurde die Mortalität der Zikadenlarven bestimmt. Bei einer Konzentration von 300 ppm (bezogen auf den Gehalt an Wirkstoff) bewirkten die Präparate gemäß Beispiele Nr. 2/97, 2/127, 2/153, 2/255, 3/50 und 3/75 eine 90-100 %ige Mortalität. Beispiel 3The leaves of 12 rice plants with a stem length of 8 cm were immersed for 5 seconds in an aqueous solution of the preparation to be tested and formulated. After draining, the rice plants treated in this way were placed in a petri dish and populated with about 20 larvae (L3 stage) of the leafhopper species Nilaparvata lugens. After closing the petri dish, it was stored in a climatic chamber (16 hours light / day, 25 ° C, 40-60% RH). After 6 days of storage, the mortality of the leafhopper larvae was determined. At a concentration of 300 ppm (based on the content of active ingredient), the preparations according to Examples Nos. 2/97, 2/127, 2/153, 2/255, 3/50 and 3/75 brought about a 90-100% strength Mortality. Example 3
Angekeimte Ackerbohnen-Samen (Vicia faba) mit Keimwurzeln wurden in mit Leitungswasser gefüllte Braunglasfiäschchen übertragen. Vier Mililiter einer wäßrigen Lösung des zu prüfenden und formulierten Präparates wurde in das Braunglasfiäschchen hineinpipettiert. Anschließend wurde die Ackerbohne mit ca. 100 schwarzen Bohnenblattläusen (Aphis fabae) stark belegt. Pflanze und Tiere wurden dann in einer Klimakammer gelagert (16 Stunden Licht/Tag, 25 °C, 40-60 % RF). Nach 3 und 6 Tagen Lagerung wurde die wurzelsystemische Wirkung des Präparates auf die Blattläuse festgestellt. Bei einer Konzentration von 30 ppm (bezogen auf den Gehalt an Wirkstoff) bewirkten die Präparate gemäß Beispiele Nr. 2/29, 2/43, 2/55, 2/67, 2/97, 2/6, 2/167, 2/153, 3/6, 3/50, 3/75 und 3/49 eine 90- 100 %ige Mortalität der Blattläuse durch wurzelsystemische Wirksamkeit. Germinated field bean seeds (Vicia faba) with germ roots were transferred to amber glass bottles filled with tap water. Four milliliters of an aqueous solution of the preparation to be tested and formulated was pipetted into the amber glass vial. Then the broad bean was heavily coated with about 100 black bean aphids (Aphis fabae). The plant and animals were then stored in a climatic chamber (16 hours light / day, 25 ° C, 40-60% RH). After 3 and 6 days of storage, the root systemic effect of the preparation on the aphids was determined. At a concentration of 30 ppm (based on the content of active ingredient), the preparations according to Examples No. 2/29, 2/43, 2/55, 2/67, 2/97, 2/6, 2/167, 2 / 153, 3/6, 3/50, 3/75 and 3/49 a 90-100% mortality of aphids due to root systemic effectiveness.

Claims

Patentansprüche claims
1. 4-Trifluormethyl-3-oxadiazolylpyridine der allgemeinen Formel (I), gegebenenfalls auch in Form der Salze,1. 4-trifluoromethyl-3-oxadiazolylpyridines of the general formula (I), optionally also in the form of the salts,
Figure imgf000095_0001
m ist O oder l ;
Figure imgf000095_0001
m is O or l;
X ist eine Einfachbindung, eine geradkettige Alkylengruppe mit 1 , 2 oder 3 C- Atomen oder einer verzweigten Alkylengruppe mit 3 bis 9 C-Atomen, wobei ein oder mehrere H-Atome durch F ersetzt sein können;X is a single bond, a straight-chain alkylene group with 1, 2 or 3 C atoms or a branched alkylene group with 3 to 9 C atoms, where one or more H atoms can be replaced by F;
Y ist -O-, -S-, -SO-, -SO2-, -O-CO-, -O-CO-O-, -SO2-O-, -O-SO2-, -NR1-, -NR2-CO-, -NR3-CO-O-, -NR4-CO-NR5-, -O-CO-CO-O-, -O-CO-NR6, -SO2-NR7 oder -NR8-SO2-;Y is -O-, -S-, -SO-, -SO 2 -, -O-CO-, -O-CO-O-, -SO 2 -O-, -O-SO 2 -, -NR 1 -, -NR 2 -CO-, -NR 3 -CO-O-, -NR 4 -CO-NR 5 -, -O-CO-CO-O-, -O-CO-NR 6 , -SO 2 - NR 7 or -NR 8 -SO 2 -;
R,R1,R2,R3,R4,R5,R6,R7,R8 sind gleich oder verschieden, unabhängig voneinander H, (CrC10)-Alkyl, (C2-C10)-Alkenyl, (C2-C10)-Alkinyl, (C3-C8)-Cycloalkyl, (C4- C8)-Cycloalkenyl, (C6-C8)-Cycloalkinyl, Heterocyclyl oder -(CH2)1^- Heterocyclyl, wobei jede der acht letztgenannten Gruppen gegebenenfalls ein oder mehrfach substituiert ist, und wobei gegebenenfalls jeweils R und R\ R und R2, R und R5, R und R6, R und R7, R und R8 oder R und X jeweils zusammen auch ein Ringsystem bilden können; mit der Maßgabe, daß die Verbindungen, in denenR, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are the same or different, independently of one another H, (C r C 10 ) alkyl, (C 2 -C 10 ) Alkenyl, (C 2 -C 10 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 4 - C 8 ) cycloalkenyl, (C 6 -C 8 ) cycloalkynyl, heterocyclyl or - (CH 2 ) 1 ^ - Heterocyclyl, where each of the eight latter groups is optionally substituted one or more times, and where appropriate R and R \ R and R 2 , R and R 5 , R and R 6 , R and R 7 , R and R 8 or R and X together can also form a ring system; with the proviso that the compounds in which
X = -, Y = O, R = HX = -, Y = O, R = H
X = -, Y = O, R = MeX = -, Y = O, R = Me
X = -, Y = O, R = EtX = -, Y = O, R = Et
X = -, Y = O, R = CHF2 X = -, Y = O, R = CHF 2
X = -, Y = O, R = CH2PhX = -, Y = O, R = CH 2 Ph
X = CH2, Y = O, R = 2-Furanyl X = CH2, Y = O, R = MeX = CH 2 , Y = O, R = 2-furanyl X = CH 2 , Y = O, R = Me
X = CH2, Y = O, R = 5-isoxazolylX = CH 2 , Y = O, R = 5-isoxazolyl
X = CH2, Y = O, R = 5-nitrol-furan-2-ylX = CH 2 , Y = O, R = 5-nitrol-furan-2-yl
X = CH2CH2, Y = O, R = HX = CH 2 CH 2 , Y = O, R = H
X = CH2CH2; Y = O, R = MeX = CH 2 CH 2 ; Y = O, R = Me
.o X = CH2CH2, Y = O, R = CH2 —.o X = CH 2 CH 2 , Y = O, R = CH 2 -
X = CH2CH2, Y = O, R = EtX = CH 2 CH 2 , Y = O, R = Et
X = CH2CH2, Y = O,X = CH 2 CH 2 , Y = O,
X = CH2CH2; Y =OC(O), R = 4-F-phenylX = CH 2 CH 2 ; Y = OC (O), R = 4-F-phenyl
X = CH2CH2, Y = OC(O), R = 2,6-DifluorphenylX = CH 2 CH 2 , Y = OC (O), R = 2,6-difluorophenyl
X = CH2CH2, Y = OC(O), R = 4-NitrophenylX = CH 2 CH 2 , Y = OC (O), R = 4-nitrophenyl
X = CH2CH2, Y = OC(O), R = t-BuX = CH 2 CH 2 , Y = OC (O), R = t-Bu
X = CH2CH2, Y = OC(O), R = CyclopropylX = CH 2 CH 2 , Y = OC (O), R = cyclopropyl
X = CH2CH2, Y = OC(O), R = MeX = CH 2 CH 2 , Y = OC (O), R = Me
X = CH2CH2CH2, Y = O, R = HX = CH 2 CH 2 CH 2 , Y = O, R = H
X = -, Y = S(O), R = 4-BrombenzylX = -, Y = S (O), R = 4-bromobenzyl
X = CH2, Y = S, R = MeX = CH 2 , Y = S, R = Me
X = CH2, Y = S(O), R = MeX = CH 2 , Y = S (O), R = Me
X = CH2, Y = S(O)2, R = t-BuX = CH 2 , Y = S (O) 2 , R = t-Bu
X = CH2, Y = S, R = 2-ThienylX = CH 2 , Y = S, R = 2-thienyl
X = CH2CH2, Y = S, R = MeX = CH 2 CH 2 , Y = S, R = Me
X = CH2CH2, Y = S, R = n-PrX = CH 2 CH 2 , Y = S, R = n-Pr
X = CH2CH2, Y = S, R = BenzylX = CH 2 CH 2 , Y = S, R = benzyl
X = CH2CH2, Y = S, R = 2-Thienyl-methylX = CH 2 CH 2 , Y = S, R = 2-thienylmethyl
X = CH2CH2CH2, Y = S, R = MeX = CH 2 CH 2 CH 2 , Y = S, R = Me
X = CH2CH2CH2, Y = SO, R = Me X = CH2CH2CH2CH2, Y = S, R = CH2CH2CH2CH2OMe ausgenommen sind.X = CH 2 CH 2 CH 2 , Y = SO, R = Me X = CH 2 CH 2 CH 2 CH 2 , Y = S, R = CH 2 CH 2 CH 2 CH 2 OMe are excluded.
2. 4-Trifluormethyl-3-oxadiazolylpyridine nach Anspruch 1 , dadurch gekennzeichnet, daß m in der Formel (I) 0 bedeutet.2. 4-trifluoromethyl-3-oxadiazolylpyridine according to claim 1, characterized in that m in the formula (I) is 0.
3. 4-Trifluormethyl-3-oxadiazolylpyridine nach Anspruch 1 und/oder 2, dadurch gekennzeichnet, daß X in der Formel (I) eine Einfachbindung, -CH2-, -CH2-CH2-, -CH2-CH(CH3)- oder -CH2-C(CH3)2- bedeutet.3. 4-trifluoromethyl-3-oxadiazolylpyridine according to claim 1 and / or 2, characterized in that X in the formula (I) is a single bond, -CH 2 -, -CH 2 -CH 2 -, -CH 2 -CH ( CH 3 ) - or -CH 2 -C (CH 3 ) 2 - means.
4. 4-Trifluormethyl-3-oxadiazolylpyridine nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß Y in der Formel (I) -O-, -S-, -SO-, -SO2-, -O-CO-, -O-CO-O-, -O-CO-NR6-, -SO2-NR7-, -O-SO2- oder -SO2-O- bedeutet.4. 4-trifluoromethyl-3-oxadiazolylpyridines according to one or more of claims 1 to 3, characterized in that Y in the formula (I) -O-, -S-, -SO-, -SO 2 -, -O- CO-, -O-CO-O-, -O-CO-NR 6 -, -SO 2 -NR 7 -, -O-SO 2 - or -SO 2 -O- means.
5. Verfahren zur Herstellung von Verbindungen der allgemeinen Formel (I) nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß aktivierte Derivate der Säure der allgemeinen Formel (II),5. A process for the preparation of compounds of the general formula (I) according to one or more of claims 1 to 4, characterized in that activated derivatives of the acid of the general formula (II),
Figure imgf000097_0001
Figure imgf000097_0001
in Gegenwart einer Base mit einer Verbindung der Formel (III),in the presence of a base with a compound of the formula (III),
Figure imgf000097_0002
Figure imgf000097_0002
in welcher der Rest X-Y-R wie in Formel (I) definiert ist, oder eine Vorstufe eines dort definierten Restes darstellt, umgesetzt werden. in which the radical XYR is as defined in formula (I) or represents a precursor of a radical defined there.
6. Mittel mit insektizider, akarizider und/oder nematizider Wirkung, gekennzeichnet durch einen Gehalt an mindestens einer Verbindung nach einem der Ansprüche 1 bis 4.6. Agents with insecticidal, acaricidal and / or nematicidal activity, characterized by a content of at least one compound according to one of claims 1 to 4.
7. Mittel mit insektizider, akarizider und nematizider Wirkung nach Anspruch 6 in Mischung mit Träger- und/oder oberflächenaktiven Stoffen.7. agents with insecticidal, acaricidal and nematicidal activity according to claim 6 in a mixture with carrier and / or surface-active substances.
8. Mittel nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß es einen weiteren Wirkstoff aus der Gruppe Akarizide, Fungizide, Herbizide, Insektizide, Nematizide oder wachstumsregulierende Stoffe enthält.8. Composition according to claim 6 or 7, characterized in that it contains a further active ingredient from the group acaricides, fungicides, herbicides, insecticides, nematicides or growth-regulating substances.
9. Verwendung einer Verbindungen nach einem der Ansprüche 1 bis 4 oder eines Mittels nach Anspruch 6 oder 7, zur Herstellung eines Tierarzneimittels.9. Use of a compound according to any one of claims 1 to 4 or an agent according to claim 6 or 7 for the manufacture of a veterinary medicinal product.
10. Verfahren zur Bekämpfung von Schadinsekten, Acarina und Nematoden, dadurch gekennzeichnet, daß man eine wirksame Menge einer Verbindung nach einem der Ansprüche 1 bis 4 oder eines Mittels nach einem der Ansprüche 6 bis 8 auf den Ort der gewünschten Wirkung appliziert.10. A method for controlling insect pests, acarina and nematodes, characterized in that an effective amount of a compound according to one of claims 1 to 4 or an agent according to one of claims 6 to 8 is applied to the location of the desired action.
11. Verfahren zum Schutz von Nutzpflanzen vor der unerwünschten Einwirkung durch Schadinsekten, Acarina und Nematoden, dadurch gekennzeichnet, daß mindestens eine der Verbindungen nach einem der Ansprüche 1 bis 4 oder ein Mittel nach einem oder mehreren der Ansprüche 6 bis 8 zur Behandlung des Nutzpflanzen-Saatgutes verwendet wird.11. A method for protecting useful plants from the undesired action by insect pests, acarina and nematodes, characterized in that at least one of the compounds according to one of claims 1 to 4 or an agent according to one or more of claims 6 to 8 for the treatment of useful plants. Seed is used.
12. Verwendung von Verbindungen nach einem der Ansprüche 1 bis 4 oder eines Mittels nach einem der Ansprüche 6 bis 8 zur Bekämpfung von Schadinsekten, Acarina und Nematoden. 12. Use of compounds according to one of claims 1 to 4 or an agent according to one of claims 6 to 8 for controlling insect pests, acarina and nematodes.
PCT/EP1999/009684 1998-12-17 1999-12-09 4-trifluoromethyl-3-oxadiazolyl pyridines, methods for the production thereof, agents containing these compounds, and their use as pesticides WO2000035913A1 (en)

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