EP0719257A1 - Pyridines substituees, leurs procedes de preparation et leur utilisation comme pesticides et comme fongicides - Google Patents

Pyridines substituees, leurs procedes de preparation et leur utilisation comme pesticides et comme fongicides

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Publication number
EP0719257A1
EP0719257A1 EP94927551A EP94927551A EP0719257A1 EP 0719257 A1 EP0719257 A1 EP 0719257A1 EP 94927551 A EP94927551 A EP 94927551A EP 94927551 A EP94927551 A EP 94927551A EP 0719257 A1 EP0719257 A1 EP 0719257A1
Authority
EP
European Patent Office
Prior art keywords
halogen
alkyl
compounds
formula
spp
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94927551A
Other languages
German (de)
English (en)
Inventor
Dieter Bernd Reuschling
Adolf Heinz Linkies
Volkmar Wehner
Rainer Preuss
Wolfgang Schaper
Harald Jakobi
Peter Braun
Werner Knauf
Burkhard Sachse
Anna Waltersdorfer
Manfred Kern
Peter Lümmen
Werner Bonin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Hoechst Schering Agrevo GmbH
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Filing date
Publication date
Application filed by Hoechst Schering Agrevo GmbH filed Critical Hoechst Schering Agrevo GmbH
Publication of EP0719257A1 publication Critical patent/EP0719257A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon 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
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • 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
    • C07D213/60—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
    • C07D213/68—One oxygen atom attached in position 4
    • 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 4-amino and 4-hydroxypyridines, processes for their preparation and their use as pesticides, in particular as insecticides, acaricides and fungicides.
  • the invention therefore relates to compounds of formula 1 and their salts, in which
  • Aryl means phenyl or substituted phenyl
  • Aralkyl means aryl (C r C 4 ) alkyl; (2) XO, S, NH or NR, where R is as defined under (1) above;
  • Y is a bond or a divalent hydrocarbon radical with 1 to 6 C atoms, in which a methylene group can be replaced by an O atom, and which optionally with one or more, preferably up to three identical or different radicals from the line
  • Z denotes (C 3 -C 8 ) -cycloalkyl or (C 5 -C 8 ) -cycloalkenyl, both of which optionally have one or more, preferably up to three, identical or different radicals from the series
  • Hydroxy are substituted, where the substituents are ice or trans to Y and the cis position is preferred and, if only one substituent is present, this is preferably in the 4-position to Y in cyclohexyl.
  • halogen means a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine or bromine atom;
  • -C 4 ) alkyl an unbranched or branched hydrocarbon radical with 1 -4 hydrocarbon atoms, such as, for example, the methyl, ethyl, propyl, 1-methylethyl, 1-methylpropyl, 2- Methylpropyl or 1, 1-dimethylethyl radical
  • (C -, - C 10 ) alkyl the abovementioned alkyl radicals and, for example, the pentyl, 2-methylbutyl or the 1, 1-dimethylpropyl radical, the hexyl, heptyl , Octyl, 1, 1, 3,3-tetramethylbutyl, nonyl or decyl;
  • (C 3 -C 8 ) cycloalkyl preferably the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group;
  • (C 5 -C 8 ) cycloalkenyl preferably the cyclopentenyl, cyclohexenyl, cycloheptenyl or cyclooctenyl group;
  • (C r C 4 ) -haloalkyl an alkyl group called under the expression “(CC 4 ) -alkyl” in which one or more hydrogen atoms are replaced by the above-mentioned halogen atoms, preferably chlorine or fluorine, such as, for example 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 contains one or more, preferably up to three identical or different substituents from the series halogen, (C 1 -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 -, - C 4 ) alkanoyloxy, (C r C 4 ) alkoxycarbonyl;
  • substituted amino an amino group with one or two (C, - C 4) alkyl or an alkanoyl group is substituted (C 1 -C 4);
  • bivalent hydrocarbon radical with 1 to 6 carbon atoms one of an n-alkane or n-alkene by removing one hydrogen atom from each bivalent radical derived from the terminal carbon atoms of the chain, such as methylene, ethanediyl, trimethylene, tetramethylene;
  • (C 2 -C 4 ) acyl in particular a (C 2 -C 4 ) alkanoyl radical, such as acetyl, propionyl or butyryl.
  • R is as defined above; (2) XO, S or NH;
  • Z preferably denotes (C 3 -C 8 ) cycloalkyl or also (C 5 -C 8 ) cycloalkenyl, both of which are optionally substituted as defined above.
  • R is as defined above;
  • Y is a bond or a divalent hydrocarbon radical with 1 to 6 C atoms, in which a methylene group can be replaced by an O atom, and which optionally with one or more, preferably up to three identical or different radicals from the line
  • Z is (C 3 -C 6 ) cycloalkyl, which is optionally substituted as defined above.
  • the present invention relates to the compounds of formula 1 in the form of the free base or an acid addition salt.
  • Acids which can be used for salt formation 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, toluenesulfonic acid or .
  • the invention encompasses both the pure isomers and their mixtures.
  • the mixtures of diastereomers can be separated into the components by customary methods, for example by selective crystallization from suitable solvents or by chromatography. Racemates can be separated into the enantiomers by customary methods, for example by salt formation with an optically active acid, separation of the diastereomeric salts and release of the pure enantiomers using a base.
  • the invention further relates to a process for the preparation of compounds of formula 1, which is characterized in that compounds of formula 2
  • the substitution reaction described above is known in principle.
  • the leaving group L can be varied within wide limits and can mean, for example, a halogen atom such as fluorine, chlorine, bromine or iodine or alkylthio such as methyl or ethylthio, or alkanesulfonyloxy such as methane, trifluoromethane or ethanesulfonyloxy or arylsulfonyloxy such as benzenesulfonyloxy or toluenesulfonyloxy or alkylsulfonyl such as Methyl or ethyl sulfonyl or aryl sulfonyl such as phenyl or toluenesulfonyl.
  • a halogen atom such as fluorine, chlorine, bromine or iodine or alkylthio such as methyl or ethylthio
  • the compounds of formula 2 can be prepared by known methods [e.g. J. Med. Chem. 32, 1970 (1989), J. Org. Chem. 29 776 (1964), J. Prakt. Chem. 331, 369 (1,989)].
  • the reactions with alcohols and mercaptans are carried out in the presence of a strong base such as sodium hydride, potassium hydride or potassium tert. butylate in an inert aprotic solvent such as DMF, NMP, DMSO, THF, dioxane or sulfolane at a temperature between 0 ° C and 80 ° C; in the Reaction with alcoholates can also be beneficial to use the associated alcohol as a solvent.
  • a strong base such as sodium hydride, potassium hydride or potassium tert. butylate in an inert aprotic solvent such as DMF, NMP, DMSO, THF, dioxane or sulfolane
  • the conditions for the reaction of 2 with amines depend on the substituents R 1 -R 4 in 2 and on the structure of the amines used; if the radicals R 1 -R 4 in 2 are inert, 2 can be converted to 1 with an excess of amine with or without solvent at temperatures between 80 ° C. and 200 ° C. The excess of amine can be reduced and the temperature lowered if acidic catalysts such as phenol [J. Amer. Chem. Soc. 73, 2623 (1951)] or salts such as triethylammonium chloride or ammonium chloride.
  • acidic catalysts such as phenol [J. Amer. Chem. Soc. 73, 2623 (1951)] or salts such as triethylammonium chloride or ammonium chloride.
  • solvents examples include DMF, N, N-dimethylacetamide, DMSO, NMP, dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, sulfolane, toluene, chlorobenzene or xylene. Mixtures of the solvents mentioned can also be used.
  • R 1 -R 4 in 2 is an RO function, such as, for example, alkoxy or alkenyloxy
  • an RO function such as, for example, alkoxy or alkenyloxy
  • Exceptions are the reactions with anilines and O-alkyl- or O-aralkyl-hydroxylamines, which lead to products 3 and 4 (R 'is a substituent of the phenyl group).
  • Benzylamines initially deliver products in which the aforementioned RO function has been split. Subsequent alkylation enables these hydroxypyridines to be converted into the compounds analogous to 3.
  • the compounds of formula 3 can be catalytically hydrogenated to compounds of formula 1 by known methods [eg F. Zymalkowski, Catalytic Hydrogenations, p. 191, Enke Verlag, Stuttgart 1965] (Scheme 1).
  • the resulting cis / trans mixtures can be separated by crystallization or chromatography.
  • the compounds of the formula 5 are prepared by known methods [R. Huisgen et al. Chem. Ber. 101: 2559 (1968); CH Rayburn, WR Harlau, HR Haumer Am. Soc. 72, 1721 (1 950)] reductively converted into the compounds of formula 1.
  • the alcohols can be prepared, for example, by reducing a carbonyl group with a suitable reducing agent, for example a complex metal hydride or, in the case of an aldehyde or ketone, also with hydrogen and a hydrogenation catalyst.
  • a suitable reducing agent for example a complex metal hydride or, in the case of an aldehyde or ketone, also with hydrogen and a hydrogenation catalyst.
  • suitable substituted phenols can also be reacted with hydrogen in the presence of a hydrogenation catalyst.
  • the amines can be prepared, for example, by reducing an oxime or a nitrile with a suitable reducing agent, for example a complex metal hydride or hydrogen in the presence of a hydrogenation catalyst, reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction of an alkyl haiogenide or tosylate .
  • a suitable reducing agent for example a complex metal hydride or hydrogen in the presence of a hydrogenation catalyst
  • reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction of an alkyl haiogenide or tosylate reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction of an alkyl haiogenide or tosylate .
  • Suitable for the preparation of cyclohexylamine derivatives substituted anilines can be reacted with hydrogen in the presence of a hydrogenation
  • the compounds of the formula I according to the invention are 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 activity of the claimed compounds covers various agriculturally important phytopathogenic fungi, such as. B. Phytophthora infestans, Piasmopara viticola, but also Erysiphe graminis, Pyrenophora teres and Leptosphaeria nodorum.
  • the compounds according to the invention are also suitable for use in technical fields, for example as wood preservatives, as preservatives in sealing compounds, in paints, in cooling lubricants for metalworking or as preservatives in drilling and cutting oils.
  • the invention also relates to 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 formula 1.
  • WP wettable powder
  • EC emulsifiable concentrates
  • SC aqueous dispersions based on oil or water
  • SC suspoemulsions
  • DP dusts
  • mordants granules in the form of water-dispersible granules (WG)
  • ULV formulations microcapsules, waxes or baits.
  • fertilizers and / or growth regulators can also be prepared, e.g. B. 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, are also a wetting agent, in addition to a diluent or inert substance.
  • Emulsifiable concentrates are obtained by dissolving the active ingredient in an organic solvent, e.g. B. butanol, cyclohexanone, dimethylformamide, Xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers.
  • Alkylarylsulfonic acid calcium salts such as cadodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide-sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxethylene sorbitol esters.
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. B. talc, natural clays such as kaolin, bentonite, poryphillite 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. As 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 in a mixture with fertilizers.
  • the active ingredient concentration is e.g. B. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components.
  • the active substance concentration can be approximately 5 to 80% by weight.
  • Dust-like formulations usually contain 5 to 20% by weight.
  • the active ingredient content depends in part on whether the active compound is liquid or solid and which compound is liquid or solid 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 present in the commercial form are optionally diluted in the customary manner, for. B. with wettable powders, emulsifiable concentrates, dispersions and sometimes also with 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. B. between 0.005 and 10.0 kg / ha or more of active substance, but it is preferably between 0.01 and 5 kg / ha.
  • 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.
  • the active ingredient according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, nematicides or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, Carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms, etc.
  • Preferred mixture partners are:
  • BPMG Butylphenylmethylcarbamate
  • carbaryl carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, isoprocarb, methomyl, 5-methyl-m-cu-menyl-butyryl (methyl) carbamate, oxamyl, pirimicarb, propoxuryl, thiodanarboxarbox 4,6,9-triaza-4-benzyl-6,10-dimethyl-8-oxa-7-oxo-5, 1 1 -dithia-9-dodecenoate (OK 135), 1-methylthio- (ethylideneamino) -N -methyl-N- (morpholinothio) carbamate (UC 51717).
  • BPMG Butylphenylmethylcarbamate
  • carbaryl carbofuran, carbosulfan, cloethocarb, benfura
  • Drug concentration of use forms can range from 0.0001 to
  • active ingredient 95% by weight of active ingredient, preferably between 0.001 and 1% by weight.
  • the active substances are suitable for combating animal pests, in particular insects, arachnids, helminths and molluscs, very particularly preferably for combating insects and arachnids, which are used in agriculture, in animal husbandry, in forests, in stocks and material protection 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:
  • Rhipicephalus spp. Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa,
  • Thysanura for example Lepisma saccharina.
  • Collembola for example Onychiurus armatus.
  • Periplaneta americana Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis,
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
  • Feltia spp. Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni,
  • 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 cheopis, 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 and plant-damaging nematodes e.g. those of the genera Meloidogyne, Heterodera, Ditylenchus, Aphelenchoides, Radopholus, Globodera, Pratylenchus, Longidorus and Xiphinema.
  • Gastropoda e.g. Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphalaria spp., Bulinus spp., Oncomelania spp ..
  • Bivalva e.g. Dreissena spp ..
  • the invention also relates to insecticidal and acaricidal compositions which comprise the compounds of the formula 1 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.
  • WP wettable powder
  • EC emulsifiable concentrates
  • SC aqueous solutions
  • SC emulsions
  • sprayable solutions dispersions based on oil or water
  • SC suspoemulsions
  • DP dusts
  • WP wettable powder
  • SC emulsifiable concentrates
  • SC aqueous solutions
  • SC emulsions
  • DP dusts
  • WG water-dispersible granules
  • ULV ULV formulations, microcapsules, waxes or baits.
  • Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain, in addition to a diluent or an inert substance, wetting agents, for example polyoxethylated alkylphenol, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, for example sodium lignosulfonate, 2,2'-dinaphthylmethane-6, Contain 6'-disulfonic acid sodium, dibutylnaphthalenesulfonic acid sodium or oleylmethyl tauric acid sodium.
  • wetting agents for example polyoxethylated alkylphenol, 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 prepared by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers.
  • organic solvent for example butanol, cyclohexanone, dimethylformamide, xylene or even 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-Ethyle ⁇ oxid condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid ester or polyoxyethylene sorbitol esters.
  • calcium alkylarylsulfonates such as Ca dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-Ethyle ⁇ oxid condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan 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 granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
  • the active ingredient concentration in wettable powders is, for example, 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 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. 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 0.001 and 10.0 kg / ha or more of active substance, but it is preferably between 0.005 and 5 kg / ha.
  • 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, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • the pesticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms and others.
  • 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.
  • the novel compounds of formula 1 according to the invention can also be used particularly advantageously in livestock farming (for example cattle, sheep, pigs and poultry such as chickens, geese, etc.).
  • livestock farming for example cattle, sheep, pigs and poultry such as chickens, geese, etc.
  • the animals are given the new compounds, if appropriate in suitable formulations (cf. above) and if appropriate with the drinking water or feed orally. Since excretion in the feces is effective, the development of insects in the feces of the animals can be prevented very easily in this way.
  • the suitable dosages and formulations are in particular of the type and Developmental stage of the farm animals and also dependent on the infestation pressure and can be easily determined and determined according to the usual methods.
  • the new compounds can be used in cattle, for example, in doses of 0.01 to 1 mg / kg body weight.
  • Example 25 Was prepared analogously to Example 25 from 3-bromo-4-chloro-2-methylpyridine and 4-cis-tert-butylcyclohexylamine.
  • Example 25 Was prepared analogously to Example 25 from 3,4-dichloro-2-ethylpyridine and 4-cis tert. -butylcyclohexylamine.
  • Methylpyrrolidone heated to 120 ° C for 8 hours. After cooling, saturated aqueous sodium bicarbonate solution is added and with
  • the product prepurified by column chromatography is taken up in diisopropyl ether and mixed with ethereal hydrochloric acid.
  • Hydrochloride of the reaction product is filtered off and purified by crystallization from acetone; subsequent treatment with 2N sodium hydroxide solution and
  • Cis / trans ratio of the substituents on the cyclohexane ring 72/28
  • 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 the 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 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 ground to a fineness of less than 5 microns.
  • An emulsifiable concentrate can be prepared from 1 5 parts by weight of active ingredient, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol (10 AeO) 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 is sprayed onto the surface of an attapulgite granulate, dried and mixed intimately.
  • the weighting- is' tsanteil of the wettable powder about 5%
  • the inert carrier material is about 95% of the finished granules.
  • Tomato plants of the "Rheinlands Ruhm” variety were evenly dripping wet in the 3-4 leaf stage with aqueous suspensions of the claimed compounds. After drying, the plants were inoculated with a zoosporangia suspension of Phytophthora infestans and kept in a climatic chamber for 2 days under optimal infection conditions. The plants were then cultivated further in the greenhouse until the symptoms developed. The infection was assessed approximately 1 week after inoculation. The degree of infestation of the plants was expressed in% infected leaf area in comparison to the untreated, 100% infected control plants.
  • the plants were again placed in the climatic chamber overnight in order to stimulate the sporulation of the fungus. The infestation was then assessed. The degree of infestation was expressed in% affected leaf area compared to the untreated, 100% infected control plants.
  • Barley plants of the "Igri" variety were treated to runoff with an aqueous suspension of the claimed compounds at the 2-leaf stage. After the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of Pyrenophora teres and kept in a climatic chamber at 100% rel. Incubated humidity. The infected plants were then in a greenhouse at 25 ° C and 80% rel. Humidity continued to be cultivated.
  • Barley plants were heavily inoculated in the 3-leaf stage with conidia of barley mildew (Erysiphe graminis f. Sp. Hordei) and placed in a greenhouse at 20 ° C and a relative air humidity of 90-95%. 24 hours after inoculation, the plants were wetted uniformly with the compounds listed below in the stated active compound concentrations. After an incubation period of 10 days, the plants were examined for infestation with barley mildew. The degree of infestation was expressed in% infected leaf area compared to untreated, 100% infected control plants.
  • barley mildew Erysiphe graminis f. Sp. Hordei
  • Field beans (Vicia faba) heavily infested with black bean aphid (Aphis fabae) are sprayed with aqueous dilutions of wettable powder concentrates with an active substance content of 250 ppm until the stage of dripping begins. The aphid mortality is determined after 3 days. A 100% kill can be achieved with the compounds according to Examples 20, 10 and the hydrochloride of 10.

Landscapes

  • 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)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des composés de la formule (1) dans laquelle R?1, R2, R3 et R4¿ désignent H, halogène, un reste aliphatique ou un reste aromatique, X désigne O, S ou imino éventuellement substitué, Y désigne une liaison ou un reste hydrocarbure bivalent éventuellement substitué et Z désigne cycloalkyle éventuellement substitué ou cycloalkényle. L'invention concerne en outre leurs procédés de production et leur utilisation comme pesticides, notamment comme insecticides, acaricides et fongicides.
EP94927551A 1993-09-14 1994-09-02 Pyridines substituees, leurs procedes de preparation et leur utilisation comme pesticides et comme fongicides Withdrawn EP0719257A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4331180A DE4331180A1 (de) 1993-09-14 1993-09-14 Substituierte Pyridine, Verfahren zu ihrer Herstellung und ihre Verwendung als Schädlingsbekämpfungsmittel und Fungizide
DE4331180 1993-09-14
PCT/EP1994/002933 WO1995007892A1 (fr) 1993-09-14 1994-09-02 Pyridines substituees, leurs procedes de preparation et leur utilisation comme pesticides et comme fongicides

Publications (1)

Publication Number Publication Date
EP0719257A1 true EP0719257A1 (fr) 1996-07-03

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EP94927551A Withdrawn EP0719257A1 (fr) 1993-09-14 1994-09-02 Pyridines substituees, leurs procedes de preparation et leur utilisation comme pesticides et comme fongicides

Country Status (11)

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US (1) US5877322A (fr)
EP (1) EP0719257A1 (fr)
JP (1) JP3046355B2 (fr)
KR (1) KR960704847A (fr)
CN (1) CN1130900A (fr)
AU (1) AU7693694A (fr)
BR (1) BR9407491A (fr)
DE (1) DE4331180A1 (fr)
IL (1) IL110920A0 (fr)
WO (1) WO1995007892A1 (fr)
ZA (1) ZA947041B (fr)

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Publication number Priority date Publication date Assignee Title
DE19719590A1 (de) * 1997-05-09 1998-11-12 Hoechst Schering Agrevo Gmbh Substituierte Stickstoff-Heterocyclen, Verfahren zu ihrer Herstellung und ihre Verwendung als Schädlingsbekämpfungsmittel
AU2002953128A0 (en) * 2002-12-05 2002-12-19 Osmose (Australia) Pty Ltd Surface treatment for wood and wood products
US20110016770A1 (en) * 2008-02-18 2011-01-27 Sven Buchholz Method for combined application of two substances for simultaneous prevention and monitoring of differing types of pest
US8586505B2 (en) * 2009-07-16 2013-11-19 Sds Biotech K. K. 4-(3-butynyl)aminopyrimidine derivatives as pest control agents for agricultural and horticultural use
CN103664761A (zh) * 2013-12-06 2014-03-26 常熟市联创化学有限公司 一种4-吡啶酚的制备方法
US11445726B2 (en) * 2017-12-01 2022-09-20 Nippon Soda Co., Ltd. Pyridinium salt and pest control agent

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US3639413A (en) * 1969-09-26 1972-02-01 Dow Chemical Co (thio- sulfinyl- and sulfonyl) containing pyridine compounds
US3682936A (en) * 1970-10-02 1972-08-08 Dow Chemical Co Certain 6-(trifluoromethyl)-pyridinols
US3965109A (en) * 1971-03-19 1976-06-22 Imperial Chemical Industries Limited Certain aryl amino pyridines
US3911183A (en) * 1972-11-10 1975-10-07 Thomas M Hinkes Seed coating process and product
US4206215A (en) * 1976-02-25 1980-06-03 Sterling Drug Inc. Antimicrobial bis-[4-(substituted-amino)-1-pyridinium]alkanes
JPS6052146B2 (ja) * 1979-12-25 1985-11-18 石原産業株式会社 Ｎ−ピリジルアニリン系化合物、それらの製造方法及びそれらを含有する有害生物防除剤
US4698093A (en) * 1984-11-06 1987-10-06 Monsanto Company Herbicidal (2 or 6)-fluoroalkyl-4-amino pyridine derivatives
US4855308A (en) * 1987-12-04 1989-08-08 Warner-Lambert Company Method of treating senile cognitive decline with N'-substituted aminopyridine adrenergic agents
US5399564A (en) * 1991-09-03 1995-03-21 Dowelanco N-(4-pyridyl or 4-quinolinyl) arylacetamide and 4-(aralkoxy or aralkylamino) pyridine pesticides

Non-Patent Citations (1)

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Title
See references of WO9507892A1 *

Also Published As

Publication number Publication date
BR9407491A (pt) 1996-06-25
WO1995007892A1 (fr) 1995-03-23
ZA947041B (en) 1995-05-02
KR960704847A (ko) 1996-10-09
CN1130900A (zh) 1996-09-11
JP3046355B2 (ja) 2000-05-29
AU7693694A (en) 1995-04-03
US5877322A (en) 1999-03-02
DE4331180A1 (de) 1995-03-16
IL110920A0 (en) 1994-11-28
JPH09502447A (ja) 1997-03-11

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