WO1997019924A1 - Cyclohexylmethyl- et cyclohexylidene-methyl-pyridines, leurs procedes de fabrication, agents renfermant ces composes et leur utilisation comme pesticides et fongicides - Google Patents

Cyclohexylmethyl- et cyclohexylidene-methyl-pyridines, leurs procedes de fabrication, agents renfermant ces composes et leur utilisation comme pesticides et fongicides Download PDF

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WO1997019924A1
WO1997019924A1 PCT/EP1996/004985 EP9604985W WO9719924A1 WO 1997019924 A1 WO1997019924 A1 WO 1997019924A1 EP 9604985 W EP9604985 W EP 9604985W WO 9719924 A1 WO9719924 A1 WO 9719924A1
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halogen
compound
alkyl
formula
alkenyl
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PCT/EP1996/004985
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German (de)
English (en)
Inventor
Adolf Heinz Linkies
Dieter Bernd Reuschling
Werner Bonin
Ralf Braun
Harald Jakobi
Gerhard Krautstrunk
Martin Märkl
Wolfgang Schaper
Werner Knauf
Manfred Kern
Ulrich Sanft
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Hoechst Schering Agrevo Gmbh
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Priority to AU75711/96A priority Critical patent/AU7571196A/en
Publication of WO1997019924A1 publication Critical patent/WO1997019924A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom

Definitions

  • the invention relates to new substituted pyridines, processes for their preparation and their use as pesticides, in particular as insecticides, acaricides and fungicides.
  • the invention therefore relates to compounds of formula I and their N-oxides, in which
  • R represents identical or different radicals which are selected from the
  • n denotes 0, 1, 2, 3 or 4, preferably 0, 1 or 2, in particular 2,
  • R 1 and R 2 are identical or different and are selected from the series hydrogen, (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl, halogen (C 1 -C 4 ) alkyl, halogen (C 2 -C 4 ⁇ alkenyl, aryl and aralkenyl; and
  • R 3 represents hydrogen, or
  • R 1 and R 3 together represent a bond
  • R is as defined above;
  • R represents identical or different radicals which are selected from the
  • (C r C 4 ) alkyl (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, (C r C 4 ) alkoxy, (C 1 -C 4 ) alkanoyloxy, (C 2 -C 4 ) alkenyloxy, (C 2 -C 4 ) acyl, (C r C 4 ) alkoxycarbonyl, (C 2 -C 4 ) alkenyloxycarbonyl, Halogen (C r C 4 ) alkyl,
  • Radicals R 1 and R 2 bearing carbon atoms are cis-configured
  • n denotes 1, 2 or 3, preferably 1,
  • R 6 is defined as R 5 or is halo (C j -C ⁇ alkyl, halo (C 2 -C 10 ) alkenyl or aryl;
  • Aryl means phenyl or substituted phenyl;
  • Aralkyl means aryl (C r C 4 ) alkyl
  • halogen means a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine or bromine atom;
  • (C 1 -C 4 ) alkyl an unbranched or branched hydrocarbon radical having 1 to 4 carbon atoms, such as, for example, methyl, ethyl, propyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl - Or 1, 1-dimethylethyl radical
  • (C r C 10 ) alkyl the aforementioned alkyl radicals and, for example, the pentyl, 2-methylbutyl or
  • halogen (C 1 -C 4 ) alkyl or "halogen (C 1 -C 10 ) alkyl” one under the expression “(C r C 4 ) alkyl” or “(C r C 10 ) -Alkyl "called alkyl group in which one or more hydrogen atoms have been replaced by the above-mentioned halogen atoms, preferably chlorine or fluorine, such as, for example, the trifluoromethyl group, the 2,2,2-trifluoroethyl group, the chloromethyl, fluoromethyl group, the difluoromethyl group or the 1, 1, 2,2-tetrafluoroethyl group (the same applies to "haloalkenyl”);
  • Substituted phenyl means a phenyl radical which has one or more, preferably up to three identical or different substituents from the series (C r C 4 ) alkyl, halogen (C r C 4 ) alkyl, hydroxy (C r C 4 ) alkyl, (C r C 4 ) alkoxy, halogen (C 2 -C 4 ) - alkoxy, phenoxy, phenyl, nitro, hydroxy, cyano, (C r C 4 ) alkanoyl, benzoyl, (C 1 -C 4 ) alkanoyloxy and (C r C 4 ) alkoxycarbonyl;
  • substituted amino means an amino group which is substituted by one or two (C 1 -C 4 ) -alkyl groups or a (C, -C 4 ) -alkanoyl group;
  • (C 2 -C 4 ) acyl in particular a (C 2 -C 4 ) alkanoyl radical, such as acetyl, propionyl or butyryl.
  • radicals derived therefrom such as haloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl. They also apply to homologues.
  • R represents identical or different radicals which are selected from the
  • R and R are the same or different and are selected from the series
  • At least one of the radicals R 4 preferably has the cis configuration with respect to the carbon atom carrying the radicals R 1 and R 2 , unless R 1 and R 3 together represent a bond.
  • Compounds of the formula I, their N-oxides and salts, where n 1 and R 4 is in the 4-position of the cyclohexyl or cyclohexylidene radical.
  • the present invention relates to the compounds of the formula I in the form of the free base or a salt, in particular an acid addition salt.
  • Acids which can be used to bind salt are inorganic acids, such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid or organic acids, such as formic acid, acetic acid, propionic acid, malonic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, methanesulfonic acid or toluenesulfonic acid, toluenesulfonic acid .
  • Racemates and diastereomers can therefore occur.
  • the invention encompasses both the pure isomers and their mixtures.
  • the mixtures of diastereomers can be made by conventional methods, e.g. be separated into the components by selective crystallization from suitable solvents or by chromatography. Racemates can be separated into the enantiomers by the usual methods, e.g. by salt formation with an optically active acid, separation of the diastereomeric salts and release of the pure enantiomers using a base.
  • the invention also relates to a process for the preparation of compounds of the formula I or their N-oxides, which is characterized in that
  • R, R 2 and m are as defined above, R 7 is aryl or (C 1 -C 4 ) - alkoxy, R 8 is aryl, aryl is as defined above and X ⁇ is halide, or
  • R, R 1 , R 2 , R 4 , m and n are as defined in claim 1.
  • the olefination is usually carried out in a suitable solvent in the presence of a base.
  • a suitable solvent examples include ethers such as diethyl ether, tetrahydrofuran, dioxane and dimethoxyethane, aromatic solvents such as benzene, toluene and xylene; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide, preferred solvents are tetrahydrofuran and dimethyl sulfoxide.
  • Suitable bases are e.g.
  • organic lithium compounds such as butyllithium, phenylithium; Lithium diisopropylamide, alkali metal hydrides such as sodium hydride, alkali metal alcoholates such as sodium methylate and potassium tert. -butylate and alkali metal amides such as sodium amide and potassium amide.
  • the preferred base is sodium hydride.
  • the amount of base used per mole of phosphorus compound can be: 0.8 to 1.5 moles. Excesses of 5 to 10% base per mole of phosphorus compound are preferred.
  • the reaction temperature depends on the reactivity of the two components and is in the range between -50 ° C and -i- 200 o C.
  • the carbonyl compound is used in excess for complete conversion of the phosphorus compounds, the excess being up to 100%. Excesses of 10 to 20% are preferred.
  • the hydrogenation can be carried out in non-polar solvents such as aliphatic hydrocarbons or ethers or esters. Polar aprotic or protic solvents such as alcohols and carboxylic acids can also be used as solvents. Furthermore, the hydrogenation can be carried out in aqueous mineral acids or in mixtures of the solvents described. The hydrogenations can be carried out under normal pressure or under pressure. You can at temperatures between 0 ° C and 100 ° C. Hydrogenation at ambient temperature is preferred.
  • the usual hydrogenation catalysts can be used as catalysts, such as nickel catalysts or noble metal catalysts, in particular platinum and palladium catalysts.
  • the hydrogenation can provide different stereoisomers depending on the olefin used. The type and proportion of the possible isomers depends on the hydrogenation system and can be influenced by a suitable choice of the solvent and the catalyst.
  • the hydrogenation of 2-ethionyl-3-methoxy-4- (4-phenyl-cyclohexylidene methyD-pyridine in methanol with palladium on carbon largely yields the cis isomer.
  • the selection of the catalyst must also be made from the point of view of whether there are any more hydrogenable ones Groups are present in the molecule, for example halogen can be removed hydrolytically.
  • the isomers formed can be separated by chromatographic methods or by crystallization of salts with suitable acids. Another preferred synthetic route is via variant a 2 )
  • a cycloalkyl ketone is added to a 4-alkyl pyrid, at least one hydrogen having to be in the ⁇ position of the alkyl group. This type of reaction has been described (by O.F. Beumel, Jr., W.N. Smith v. B. Rybalka; Synthesis 1974, 43).
  • the reaction is carried out in ethers such as diethyl ether, tetrahydrofuran or dimethoxyethane.
  • solvents such as dimethyl sulfoxide or liquid ammonia can also be used.
  • the bases can be organic Lithium compounds such as lithium butyl, lithium phenyl or lithium diisopropylamide can be used. Alkali metal hydrides and alkali amides can also be used for this.
  • the reaction runs at temperatures between -100 ° C and + 30 ° C, the activity of the base used and the stability of the intermediate carbanion determine the temperature limits. Lithium diisopropylamide in THF at -70 ° C has proven to be the preferred system.
  • the carbonyl compound is used in an equimolar amount or preferably in excess.
  • Formed isomer mixtures can be separated by the usual methods, such as, for example, chromatographic methods or, for example, by the crystallization of suitable acid addition salts.
  • the alcohols are converted into the olefins by the customary methods (Houben-Weyl Alkene, Volume V / 1b pages 62-104, Georg Thiem Verlag Stuttgart 1972). It takes place in the liquid phase and can be alkaline or acid catalyzed.
  • Acidic catalysts which can be used are inorganic acids or organic acids, such as, for example, sulfonic acids, such as, for example, para-toluenesulfonic acid, or carboxylic acid, such as, for example, oxalic acid or trifluoroacetic acid.
  • Other catalysts are Lewis acids, such as BF 3 etherate or zinc chloride.
  • the reaction can be carried out at temperatures between 0 ° C and 200 ° C. To increase the reaction rate, the water can be distilled off azeotropically with a tug such as xylene or removed by a water-binding agent such as anhydrides such as acetic anhydride or trifluoroacetic anhydride.
  • Preferred reaction conditions are the elimination of the water with trifluoroacetic acid and trifluoroacetic anhydride and the azeotropic elimination with para-toluenesulfonic acid and xylene.
  • the hydroxyl group can also be converted into a leaving group by derivatization, which can then be used for one of the known elimination reactions.
  • Various isomers are possible for the elimination. In this way, compounds with an exocyclic or endocyclic double bond can form. They can be separated using the customary methods, such as, for example, chromatographic methods or crystallization of the acid addition salts suitable acids.
  • Bistriphenylphosphine palladium dichloride and copper iodide It is carried out at temperatures between 0 ° C and the boiling point of the solvent. In the present case, temperatures between 20 and 50 ° C were preferred.
  • substitution on the pyridine ring can also be made in another way, e.g. according to one of the methods that are reported by D. Spitzner (Houben-Weyl, Hetarene II, Volume E 7b, 1992, pages 568 to 659).
  • the T ⁇ methylsiiyl devis can be split off from the substituted 2-Tr ⁇ methyls ⁇ lyleth ⁇ nylpyr ⁇ d ⁇ n with acetic acid and Nat ⁇ umfluo ⁇ d at room temperature.
  • the other usual cleavage reagents for C-Si bonds can also be used for this purpose, such as tetraalkylammonium fluids, HF, etc.
  • the hydrogenation of the triple bond can be carried out using the systems customary for this. It can be carried out in protic solvents such as alcohols or carboxylic acids or in aprotic solvents such as ethers or esters and is catalyzed by the customary catalysts such as platinum, palladium, nickel. Of course, it can also be carried out in stages as a partial hydrogenation. Another important reaction is the subsequent filling of substituents on the pyridine, e.g. in the following way.
  • the type of reaction is described in F. Minisci (Synthesis 1973, 1).
  • the carboxylic acid on which the alkyl radical is based is used as the alkylating agent.
  • Other carboxylic acids such as propionic acid and pivalic acid can of course also be used, for example.
  • the reaction is silver catalyzed.
  • oxidizing agents such as ammonium peroxodisulfate, diacyl peroxides, carbonic acid peresters or perborates. It can be carried out in water, in carboxylic acids and in aromatic hydrocarbons and takes place at temperatures between 0 and 100 ° C.
  • Another important reaction sequence is:
  • N-oxides of pyridines are comprehensively described in A. Albani et al. S. Pietra (Heterocyclic N-oxides, CRC-Press, Inc. Boca Raton, USA, 1991). It is possible with peracids such as peracetic acid or 3-chloroperbenzoic acid, but can also be carried out with hydrogen peroxide in glacial acetic acid.
  • the reaction of the N-oxide to 2-cyanopyridine is described as a type of reaction (for Vorbrüggen (Synthesis 1 983, 316). Trimethylsilyl cyanide is used as the cyanide source, but the use of alkali metal cyanide and trimethylsilyl chloride is also possible.
  • the reaction of nitrile to the ketone represents an addition of an organometallic compound to a nitrile with subsequent hydrolysis of the.
  • organometallic compound e.g. Use lithium, magnesium, zinc, aluminum organyle to name just a few.
  • the type of reaction is described by G. Sumrell (J. Org. Chem. 19, 81 7 (1 954)).
  • the reduction of the formyl compound to the hydroxymethyl compound was carried out in the manner customary for this using sodium borohydride in tetrahydrofuran.
  • the conversion of the hydroxymethyl compounds into the chloromethyl compound was carried out in the usual way. It was done with thionyl chloride in methylene chloride. DMF was used as the catalyst.
  • the conversion of the chloroacetyl compound into the phosphonic acid ester was carried out by a Michaehs-Arbusov reaction as in G.M. Kosolapoff (Am. Soc. 67, 2259 (1 945))
  • the active compounds of the formula I are suitable, with good plant tolerance and favorable warm-blood toxicity, for combating animal pests, in particular insects, arachnids, nematodes, helminths and molluscs, very particularly preferably for combating insects and arachnids which are used in agriculture, in animal husbandry Forests, in the protection of stored goods and materials as well as in the hygiene sector. They are effective against normally sensitive and resistant species as well as all or individual stages of development.
  • the pests mentioned above include.
  • Thysanoptera e.g. Hercinoth ⁇ ps femorahs, Thrips tabaci.
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ⁇ bis, Doralis fabae, Doralis pomi, E ⁇ osoma lanigerum, Hyalopterus arundinis,
  • Oryzaephilus surinamensis Anthonumus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopohtes sordidus, Ceuthorrynchus assimihs, Hypera postica,
  • T ⁇ boiium spp. Teneb ⁇ o molitor, Agriotes spp. , Conoderus spp. , Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.
  • Hymenoptera e.g. Diprion s ⁇ p, Hoplocampa spp., Lasius spp. , Monomo ⁇ um pharaonis, Vespa spp ..
  • Helminths for example Haemonchus, Trichostrongulus, Ostertagia, Coope ⁇ a, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Asca ⁇ s and Heterakis as well as Fasciola.
  • Gastropoda e.g. Deroceras spp., A ⁇ on spp., Lymnaea spp., Galba spp., Succinea spp., Biomphala ⁇ a spp., Bulinus spp., Oncomelania spp ..
  • Bivalva e.g. Dreissena spp ..
  • Plant-parasitic nematodes that can be controlled according to the invention include, for example, the root-parasitic soil nematodes, such as those of the genera Meloidogyne (root-knot nematodes such as Meloidogyne incognita, Meloidogyne hapla and Meloidogyne javanica), Heterodera and Globodera (cyst-forming nematodes, such as Globodera rostochiensis, Globodera pallida, Heterodera trifoln) and of the genera Radopholus, such as simihs Radopholus, Pratylenchus such as Pratylenchus neglectus, Pratylenchus penetrans and Pratylenchus curvitatus;
  • the root-parasitic soil nematodes such as those of the genera Meloidogyne (root-knot nematodes such as Meloidogyne
  • Tylenchulus such as Tylenchulus semipenetrans, Tylenchorhynchus, such as Tylenchorhynchus dubius and Tylenchorhynchus elaytoni, Rotylenchus such as Rotylenchus robustus, Heliocotylenchus such as Haliöcotylenchus multicinetus, and Longonoimine such as Tongus longusudema 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 ⁇ tzemabosi) and Anguina (flower nematodes such as Anguina t ⁇ tici).
  • Ditylenchus stem parasites such as Ditylenchus dipsaci and Ditylenchus destructor
  • Aphelenchoides leaf nematodes such as Aphelenchoides ⁇ tzemabosi
  • Anguina flower nematodes such as Anguina t ⁇ tici.
  • 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
  • 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 the active ingredients of the formula I in an amount of 1 to 95% by weight.
  • WP Wettable powder
  • EC emulsifiable concentrates
  • SL aqueous solutions
  • SC oil or water-based dispersions
  • SE suspoemulsions
  • SE dusting agents
  • DP pickling agents
  • the necessary molding aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in:
  • Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain wetting agents, e.g. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, e.g. B. sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium.
  • wetting agents e.g. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, e.g. B. sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium.
  • Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyelohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers.
  • organic solvent e.g. Butanol, cyelohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons.
  • alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzene sulfonate or nonionic emulsifiers
  • fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan ethyl fatty acid sorboxate or sorboxethyl fatty acid sorboxate or sorbitan ethyl fatty acid sorboxate or sorbitan ethyl fatty acid sorboxate or sorbitan ethyl fatty acid sorboxate or sorbitan ethyl fatty acid sorboxate or sorbitan ethyl fatty acid sorboxate or sorbitan ethyl fatty acid sorboxate or sorbitan ethyl fatty acid sorboxate or sorbitan ethyl fatty
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, for example 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, for example polyvinyl alcohol, sodium polyacrylic acid or mineral oils, to the surface of carriers such as sand, kaolinite or granulated inert material.
  • Suitable active ingredients can also be used in the production of Fertilizer granules in the usual way - if desired in a mixture with fertilizers - are granulated.
  • the active substance concentration in wettable powders is e.g. about 10 to 90% by weight, the remainder to 100% by weight consists of conventional 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 wt .-% of active ingredient, sprayable solutions about 2 to 20 wt .-%. In the case of granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulation aids, 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. Dusty and granulated preparations and sprayable solutions are usually no longer diluted with other inert substances before use.
  • the required application rate varies. It can vary within wide limits, for example between 0.0005 and 1.0 kg / ha or more of active substance, but is preferably between 0.001 and 5 kg / ha.
  • the active compounds according to the invention can be used in their commercially available formulations and in the use forms prepared from these formulations in mixtures with other active compounds, such as insecticides, Attractants, Ste ⁇ lantien, Aka ⁇ ziden, nematicides, fungicides, growth regulating substances or herbicides are present.
  • the pesticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms, etc.
  • Preferred mixing partners are
  • 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 controlling endo- 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 powdering and by parenteral use in the form of, for example, injection.
  • novel 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.).
  • animal husbandry for example cattle, sheep, pigs and poultry such as chickens, geese, etc.
  • the animals are given the new compounds, if appropriate in suitable formulations (see above) and if necessary administered orally with the drinking water or feed. 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 new compounds can be used in cattle, for example, in doses of 0.01 to 1 mg / kg body weight.
  • the compounds of the formula I according to the invention are also notable for an excellent fungicidal action.
  • Fungal pathogens that have already penetrated into the plant tissue can be successfully combated curatively. This is particularly important and advantageous in the case of those fungal diseases which can no longer be effectively combated with the usual fungicides after infection has occurred.
  • the spectrum of action of the claimed compounds covers various economically important phytopathogenic fungi, such as e.g. Plasmopara viticola, Phytophthora infestans, Erysiphe graminis, Pyricularia oryzae, Pyrenophora teres, Leptosphaeria nodorum and Pellicularia sasakii and Puccinia recondita.
  • the compounds of the formula I according to the invention are therefore also suitable for treating seed (seed dressing).
  • the compounds according to the invention are also suitable for use in technical fields, for example as wood preservatives, as preservatives in paints, in cooling lubricants for metalworking or as preservatives in drilling and cutting oils.
  • the active compounds according to the invention can be used in their commercially available formulations either alone or in combination with other fungicides known from the literature.
  • fungicides known from the literature which can be combined according to the invention with the compounds of the formula I include the following products: aldimorph, andoprim, anilazines, BAS 480F, BAS 450F, benalaxyl, benodanil, benomyl, binapacryl, bitertanol, bromuconazole, buthiobate, captafol , Captan, Carbendazim, Carboxin, CGA 1 73506, Cyprofuram, Dichlofluanid, Dichlomezin, Diclobutrazol, Diethofencarb, Difenconazol (CGA 1 69374), Difluconazole, Dimethirimol, Dimethomorph, Diniconazole, Dinocap, Dithorphifonol, Dodimolidol, Dodimidolidol, Dodimidolol, Dodimidol, Dodimolidol, Dodim
  • Drug concentration of use forms can range from 0.0001 to
  • active ingredient 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • Example 8 4- (4-tert-butyl-cyclohexyl-1-methyl) -3-methoxy-2-tr-methyl-silylethynyl-pyridine
  • 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 quartz containing inert matter, 10 parts by weight of potassium sulphonate and 1 part by weight of sodium oleoylmethyltau ⁇ nsauresodium as a and dispersant mixes and grinds in a pin mill.
  • a dispersion concentrate which is easily 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 a fineness of less than 5 microns is ground.
  • An emulsifiable concentrate can be prepared from 1 5 parts by weight of active ingredient, 75 parts by weight of cyelohexane as a solvent and 10 parts by weight of oxyhydrogenated nonylphenol (1 0 EO) as an 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 wettable powder is approximately 5% and that of the inert carrier material approximately 95% of the finished granulate.
  • Rice seed was germinated on cotton wool in cultivated glasses and after growing to a stalk length of approx. 8 cm, the leaves were added to the test solution to be tested. After draining, the rice plants treated in this way were placed separately in the breeding container according to the test concentration and were each populated with 10 larvae (L3) of the species Nilaparvata lugens. After storing the closed breeding containers at 21 ° C, the mortality of the cicada larvae can be determined after 4 days.
  • the compounds according to Example 2 at a concentration of 250 ppm (based on the active ingredient) have a 100% effect on the test animals.
  • Tomato plants "first in the field" were sprayed to drip wet in the 3-4 leaf stage with 40% acetone / 60% water solutions of the claimed compounds. 24 hours later, the plants were inoculated with a spore suspension (20,000 spores / ml) from Phytophthora infestans and placed in a climatic chamber of approx. 15 ° C. and a relative humidity of approx. 99% for 2 days, followed by 3 to 4 days a relative humidity of 75 - 80%. The experiments are evaluated about 6 days after the treatment.
  • Wheat plants of the "Hörnet” variety were sprayed to runoff point in a 2-leaf stage with 40% acetone / 60% water solutions of the claimed compounds. 24 hours after the treatment, the plants were inoculated with an aqueous pycnospore suspension (0.5 million spores / ml) from the Leptosphaeria nodorum. The plants were grown in a climatic chamber at 1 8-20 ° C and a relative humidity of approx. 99% cultivated. The attempts were Evaluated 14 days after the inoculation.
  • the compounds from Example 6 gave a 2 when 50 mg of active substance / liter were used for spraying.
  • the active compounds were dissolved in 10% (w / v) in a mixture consisting of dimethylformamide (85 g), nonylphenyl polyglycol ether (3 g) and oxyethylated castor oil (7 g), and the emulsion concentrates thus obtained were dissolved in water diluted a test concentration of 500 ppm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)

Abstract

L'invention concerne des composés de formule (a), ainsi que leurs N-oxydes et leurs sels, formule dans laquelle Q désigne un 4-pyridyle éventuellement substitué; R1 et R2 désignent un H, alkyle, alkényle, halogénure d'alkyle, halogénure d'alkényle, aryle ou aralkyle, R3 est un H, ou bien R1 + R3 représentent, ensemble, une liaison, et R2 est tel que défini précédemment; R4 est un alkyle, alkényle, alkoxy, alkanoyloxy, alkényloxy, acyle, alkoxycarbonyle, alkényloxycarbonyle, halogénure d'alkyle, halogénure d'alkényle, halogénure d'alkoxy, halogénure d'alkényloxy, halogénure d'aryle, halogénure d'alkoxycarbonyle, un halogène ou un OH; et n=1, 2 ou 3. L'invention concerne en outre des procédés de fabrication de ces composés, des agents les renfermant, ainsi que leur utilisation comme pesticides et fongicides.
PCT/EP1996/004985 1995-11-27 1996-11-14 Cyclohexylmethyl- et cyclohexylidene-methyl-pyridines, leurs procedes de fabrication, agents renfermant ces composes et leur utilisation comme pesticides et fongicides WO1997019924A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU75711/96A AU7571196A (en) 1995-11-27 1996-11-14 Cyclohexylmethyl- and cyclohexylidenemethyl pyridines, processes for their production, agents containing them and their use as pesticides and fungicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19544100.1 1995-11-27
DE19544100A DE19544100A1 (de) 1995-11-27 1995-11-27 Cyclohexylmethyl- und Cyclohexylidenmethyl-Pyridine, Verfahren zu ihrer Herstellung, diese enthaltende Mittel und ihre Verwendung als Schädlingsbekämpfungsmittel und Fungizide

Publications (1)

Publication Number Publication Date
WO1997019924A1 true WO1997019924A1 (fr) 1997-06-05

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AU (1) AU7571196A (fr)
DE (1) DE19544100A1 (fr)
WO (1) WO1997019924A1 (fr)
ZA (1) ZA969864B (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080312281A1 (en) * 2004-12-24 2008-12-18 Matthew Colin Thor Fyfe G-Protein Coupled Receptor (Gpr116) Agonists and Use Thereof for Treating Obesity and Diabetes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2505461A (en) * 1947-08-04 1950-04-25 Reilly Tar & Chem Corp Alkylcyclohexylmethylpyridines
WO1993005050A1 (fr) * 1991-09-03 1993-03-18 Dowelanco Pesticides a base de 4-(aralcoxy ou aralkylamino)pyridine
WO1993004579A1 (fr) * 1991-09-03 1993-03-18 Dowelanco 4-aralkylpyridines en tant que nematicides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2505461A (en) * 1947-08-04 1950-04-25 Reilly Tar & Chem Corp Alkylcyclohexylmethylpyridines
WO1993005050A1 (fr) * 1991-09-03 1993-03-18 Dowelanco Pesticides a base de 4-(aralcoxy ou aralkylamino)pyridine
WO1993004579A1 (fr) * 1991-09-03 1993-03-18 Dowelanco 4-aralkylpyridines en tant que nematicides

Also Published As

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DE19544100A1 (de) 1997-05-28
ZA969864B (en) 1997-05-27
AU7571196A (en) 1997-06-19

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