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EP1305302A1 - Thioethers de fluoralcenyle heterocycliques et utilisation en tant que pesticides (i) - Google Patents

Thioethers de fluoralcenyle heterocycliques et utilisation en tant que pesticides (i)

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Publication number
EP1305302A1
EP1305302A1 EP01960418A EP01960418A EP1305302A1 EP 1305302 A1 EP1305302 A1 EP 1305302A1 EP 01960418 A EP01960418 A EP 01960418A EP 01960418 A EP01960418 A EP 01960418A EP 1305302 A1 EP1305302 A1 EP 1305302A1
Authority
EP
European Patent Office
Prior art keywords
spp
compounds
formula
methylene
methyl
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Withdrawn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
EP01960418A
Other languages
German (de)
English (en)
Inventor
Udo Kraatz
Bernd Gallenkamp
Heiko Rieck
Albrecht Marhold
Peter Wolfrum
Wolfram Andersch
Christoph Erdelen
Peter Lösel
Andreas Turberg
Olaf Hansen
Achim Harder
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 AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1305302A1 publication Critical patent/EP1305302A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • 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
    • 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
    • A01N43/88—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 three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/15—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/36—Seven-membered rings

Definitions

  • the present invention relates to novel heterocyclic fluoroalkenyl thioethers, processes for their preparation and their use as pesticides.
  • heterocyclic fluoroalkenyl thioethers have insecticidal, acaricidal and / or nematicidal properties (see, for example, US 3,914,251, US 5,952,359, WO 99/52874, WO 99/52882 or JP 11140063).
  • the effectiveness or range of action of these compounds is not always entirely satisfactory, particularly at low active substance concentrations and application rates.
  • X represents hydrogen, halogen or alkyl
  • n 2 to 10
  • n 0, 1 or 2
  • Y represents optionally substituted methylene
  • p 1, 2 or 3.
  • heterocyclic fluoroalkenyl thioethers of the formula (I) can be obtained if a) Mercapto derivatives of the formula (II)
  • the compounds of the formula (II) also being able to be used in the form of their salts, preferably the alkali metal salts, such as, in particular, the sodium or potassium salts; and if necessary
  • X, Y, m and p have the meaning given above, oxidized with an oxidizing agent, optionally in the presence of a diluent and optionally in the presence of a catalyst.
  • the new heterocyclic fluoroalkenyl thioethers of the formula (I) have highly pronounced biological properties and, above all, for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forestry, in the protection of stocks and materials, and occur in the hygiene sector, are suitable.
  • Formula (I) provides a general definition of the heterocyclic fluoroalkenyl thioethers according to the invention.
  • X preferably represents hydrogen, fluorine, chlorine or bromine
  • n preferably represents integers from 2 to 8.
  • n is preferably 0 or 2.
  • Y preferably represents methylene which is substituted once or twice, identically or differently, examples of which may be mentioned as substituents: in each case optionally by halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -
  • p is preferably 1 or 2.
  • X particularly preferably represents hydrogen or fluorine
  • n particularly preferably represents integers from 2 to 6.
  • n particularly preferably represents 0.
  • Y particularly preferably represents methylene which is monosubstituted or disubstituted, identically or differently substituted, examples of which may be mentioned as substituents: C 1 -C 4 -alkyl or phenyl which is monosubstituted or disubstituted, identically or differently, examples of which are mentioned: halogen , Cyano, nitro, C 1 -C 2 alkyl, -Ca alkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkyl, Ci-C 2 haloalkoxy or CrC 2 -
  • p particularly preferably represents 1.
  • X very particularly preferably represents fluorine.
  • n very particularly preferably represents 2 or 4.
  • Y very particularly preferably represents methylene which is monosubstituted or disubstituted by the same or different substituents, examples of which may be mentioned as substituents: methyl, ethyl or phenyl which is monosubstituted or disubstituted by the same or different substitution, examples of which are mentioned: fluorine, chlorine, Methyl, methoxy, trifluoromethyl, cyano or nitro. From the meanings given as preferred, particularly preferred or very particularly preferred, compounds of the formula (I) in which
  • X represents hydrogen or fluorine
  • n 2 or 4
  • n 0, 1 or 2
  • Y represents methylene optionally substituted once or twice, identically or differently by methyl or ethyl, or represents phenyl optionally substituted once or twice, identically or differently by fluorine, chlorine, methyl, methoxy, trifluoromethyl, cyano or nitro, and
  • p 1, 2 or 3.
  • hydrocarbon radicals such as alkyl - are also straight-chain or branched as far as possible, even in compounds with heteroatoms such as alkoxy.
  • Formula (II) provides a general definition of the mercapto derivatives to be used as starting materials for carrying out process (a) according to the invention.
  • the mercapto derivatives of the formula (Ha) are obtained in a generally known manner by, for example, halogen sulfonamides of the formula (IV) known in a first stage Hal , - (Y) 3 -SO 2 -NH 2 (IV)
  • R is C 1 -C - alkyl, preferably methyl and
  • Formula (III) provides a general definition of the fluoroalkenyl halogens to be used as starting materials in process (a) according to the invention.
  • Fluoroalkenyl halides of the formula (III) are known (see, for example, J. Chem. Soc. Perkin Trans. 2, 219 (1998); Tetrahedron Lett. 37, 5321 (1996); EP 0 334 796 or WO 95/4727) or commercially available.
  • Inert organic solvents are suitable as diluents for carrying out process (a) according to the invention.
  • These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, anisole, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, ether such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones such as acetone or butanone, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphorus-
  • Process (a) according to the invention can, if appropriate, be carried out in the presence of a basic reaction auxiliary.
  • All conventional inorganic or organic bases are suitable as such. These include, for example, alkali metal and alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide or calcium hydroxide, alkali metal carbonates or hydrogen carbonates, such as Sodium carbonate, potassium carbonate, cesium carbonate or sodium bicarbonate and tertiary amines, such as triethylamine, N, N-dimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
  • alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide or calcium hydroxide
  • alkali metal carbonates or hydrogen carbonates such as Sodium carbonate, potassium carbonate, ces
  • reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. In general, temperatures between 0 ° C and + 200 ° C, preferably at temperatures between + 20 ° C and + 140 ° C.
  • reaction products 0.3 to 3.0 mol, preferably a slight excess, of fluoroalkenyl halide of the formula (III) and, if appropriate, 0.5 to 2, are generally employed per mol of mercapto derivative of the formula (II) , 0 moles, preferably 0.5 to 1.0 mole of reaction auxiliary.
  • the reaction, working up and isolation of the reaction products is carried out according to generally customary methods.
  • Suitable oxidizing agents for carrying out process (b) according to the invention are all customary oxidizing agents which can be used for sulfur oxidation. Hydrogen peroxide, organic peracids such as peracetic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid or atmospheric oxygen are particularly suitable.
  • Inert organic solvents are also suitable as diluents for carrying out process (b) according to the invention. It is preferred to use hydrocarbons such as gasoline, benzene, toluene, hexane or petroleum ether, chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride or chlorobenzene, ethers such as diethyl ether, dioxane or tetrahydrofuran, carboxylic acids such as acetic acid or Propionic acid, or dipolar aprotic solvents such as acetonitrile, acetone, ethyl acetate or dimethylformamide. If appropriate, process (b) according to the invention can be carried out in the presence of a suitable catalyst. All metal salt catalysts customarily used for such sulfur oxidations are suitable as such. Examples include ammonium molybdate and sodium tungstate.
  • reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, temperatures between -20 ° C and + 70 ° C, preferably at temperatures between 0 ° C and + 50 ° C.
  • oxidizing agent For oxidation to the sulfone, 1.8 to 3.0 mol, preferably double molar amounts, of oxidizing agent are generally used per mol of compound of the formula (Ia).
  • the reaction, work-up and isolation of the end products is carried out by customary methods known to those skilled in the art.
  • the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector.
  • the active ingredients are particularly suitable for controlling nematodes. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include: From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Thysanura e.g. Lepisma saccharina.
  • Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
  • Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp ..
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.
  • Homoptera for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemph
  • Ceuthorrhynchus assimilis Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Agribiole spp., Tenebrio molitor. Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus. From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Hyalomma spp. Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp ..
  • Plant-parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaph.
  • the compounds of the invention can be particularly successful
  • Control of nematodes harmful to plants e.g. against Meloidogyne incognita larvae, but also for combating plant-damaging insects, e.g. against the peach aphid (Myzus persicae), the larvae of the horseradish beetle (Phaedon cochleariae) as well as against the caterpillars of the army worm (Spodoptera frugiperda) and for combating plant-damaging spider mites
  • the compounds according to the invention When applied in appropriate amounts, the compounds according to the invention also show fungicidal properties, in particular against Pyricularia.
  • the compounds according to the invention can also be used in certain concentrations or application rates as herbicides and microbicides, for example as fungicides, antifungal agents and bactericides. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.
  • plants and parts of plants can be treated.
  • Plants are understood here to mean all plants and plant populations, such as desired and undesirable wild plants or crop plants (including naturally occurring crop plants).
  • Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights.
  • Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
  • plants and their parts can be treated according to the invention.
  • transgenes are also preferred.
  • Plants and plant varieties if necessary by genetic engineering methods obtained in combination with conventional methods (Genetic Modified Organisms) and their parts treated.
  • Genetic Modified Organisms Genetic Modified Organisms
  • Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention.
  • Plant cultivars are understood to mean plants with new properties (“traits”) which have been grown both by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, bio and genotypes.
  • the treatment according to the invention can also cause superadditive (“synergistic") effects.
  • superadditive for example, reduced application rates and / or expansions of the activity spectrum and / or an increase in the action of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance , easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher storability and / or workability of the harvested products possible, which go beyond the effects to be expected.
  • the preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous valuable properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to water or soil salt content, increased flowering performance, easier harvesting,
  • the traits are particularly emphasized as the increased defense of the plants against insects by toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes CrylA (a), CryIA (b), Cry ⁇ A (c), CrylLA, Cry ⁇ iA, Cryi ⁇ B2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants”).
  • Bt plants As properties
  • Traits are also particularly emphasized the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • SAR systemic acquired resistance
  • the properties which are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene), the genes which confer the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants.
  • Bt plants are corn varieties, cotton varieties, soy varieties and potato varieties which are marketed under the trade names YTELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn) , StarLink® (e.g. maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • YTELD GARD® e.g. corn, cotton, soy
  • KnockOut® e.g. corn
  • StarLink® e.g. maize
  • Bollgard® cotton
  • Nucotn® cotton
  • NewLeaf® potato
  • herbicide-tolerant plants are maize, cotton and
  • Soybeans known as Roundup Ready® Tolerance to glyphosate e.g. corn, cotton, soy
  • Liberty Link® tolerance to phosphinotricin, e.g. rapeseed
  • IMI® tolerance to imidazolinones
  • STS® tolerance to sulfonylureas e.g. corn.
  • the herbicide-resistant plants include the varieties sold under the name Clearfield® (eg maize).
  • the treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space using the customary treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by single- or multi-layer coating.
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, impregnated with active ingredients
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents. thus emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as
  • Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g.
  • non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho- lipids such as cephalins and lecithins and synthetic phosphophides.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active substance 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 substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • Debacarb dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimiethirimol, dimethomorph, diniconazole,
  • Imazalil Imibenconazol, Iminoctadin, hninoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Jrumamycin, Isoprothiolan, Isovaledione,
  • Kasugamycin, Kresoxim-methyl copper preparations such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and Bordeaux mixture, Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
  • Oxadixyl Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
  • Paclobutrazole pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb,
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, dioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutichl, triazoxid, triazoxid, triazoxid, triazoxide
  • Tridemorph triflumizole, triforin, triticonazole
  • Methantetrathiol sodium salt Methyl l- (2,3-d dro-2,2-dime l-lH-mden-l-yl) -lH-imidazole-5-carboxylate,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron,
  • Fenamiphos Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate,
  • Fipronil Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxuron, Flucythrinate, Flufenoxuron, Flumethrin, Flutenzine, Fluvalinate, Fonophos, Fosmethilan, Fosthiazate, Fubfenprox, Furathiocarb,
  • Halofenozide HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
  • Imidacloprid indoxacarb, isazofos, isofenphos, isoxathion, ivermectin, IKI 220,
  • Metharhilicium flavoviride methidathione, methiocarb, methomyl, methoprene, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, monocrotophos,
  • the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds that increase the effectiveness of the active ingredients without the added synergist itself having to be active.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the drug concentration of the Application forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active ingredient When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
  • the active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas.
  • animal parasites ectoparasites
  • tick ticks leather ticks
  • mites running mites
  • flies stinging and licking
  • parasitic fly larvae lice, hair lice, Featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..
  • Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp ..
  • Nematocerina and Brachycerina e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp.
  • Actinedida Prostigmata
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypppectoles spp ., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, e.g. Cattle, sheep, goats,
  • the active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets,
  • formulations for example powders, emulsions, flowable agents
  • active compounds in an amount of 1 to 80% by weight, directly or after 100 to 10,000 times dilution, or use them as a chemical bath.
  • the agents according to the invention are suitable for combating pathogenic endoparasites which occur in humans and in animal husbandry and animal breeding in farm animals, breeding, zoo, laboratory, experimental and hobby animals. They are effective against all or individual stages of development of the pests and against resistant and normally sensitive species. By fighting the pathogenic endoparasites which occur in humans and in animal husbandry and animal breeding in farm animals, breeding, zoo, laboratory, experimental and hobby animals. They are effective against all or individual stages of development of the pests and against resistant and normally sensitive species. By fighting the pathogenic
  • Endoparasites are said to reduce illness, deaths and impaired performance (e.g. in the production of meat, milk, wool, hides, eggs, honey, etc.), so that the use of the active ingredients enables more economical and easier animal husbandry.
  • Pathogenic endoparasites include cestodes, trematodes, nematodes, acantocephals in particular: From the order of the Pseudophyllidea, for example: Diphyllobothrium spp., Spirometra spp., Schistocephalus spp., Ligula spp., Bothridium spp., Diphlogonoporus spp ..
  • Cyclophyllidea for example: Mesocestoides spp., Anoplocephala spp., Paranoplocephala spp., Moniezia spp., Thysanosomsa spp., Thysaniezia spp., Avitelellina spp., Stilesia spp., Cittotaenia spp., Andyella spp., Bertella spp spp., Taenia spp., Echinococcus spp., Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepis spp., Echinolepis spp., Echinocotyle spp., Diorchis spp., Dipylidium spp., Joyeuxiella spp., Diplop. ,
  • sppyl. sppyl. Catatropis spp.
  • Plagiorchis spp. Prosthogonimus spp., Dicrocoelium spp., Eurytrema spp., Troglotrema spp., Paragonimus spp., CoUyriclum spp., Nanophyetus spp., Opisthorchis spp., Clonorchis spp. Metorchis spp., Heterophyes spp., Metagonimus spp ..
  • Oesophagodontus spp. Trichonema spp., Gyalocephalus spp., Cylindropharynx spp., Poteriostomum spp., Cyclococercus spp., Cyhcostephanus spp., Oesophagostomum spp., Chabertia spp., Stephanurus spp., Ancylostoma spp., Uncinaria spp., Bunostomum spp., Globocephalus spp., Syngamususpppp., Cyastostong spp.
  • Dictyocaulus spp. Muellerius spp., Protostrongylus spp. Neostrongylus spp., Cystocaulus spp., Pneumostrongylus spp., Spicocaulus sp
  • Oxyuris spp. Enterobius spp., Passalurus spp., Syphacia spp., Aspiculuris spp., Heterakis spp ..
  • Ascaridia for example: Ascaris spp., Toxascaris spp., Toxocara spp.,
  • Livestock and breeding animals include mammals such as Cattle, horses, sheep, pigs, goats, camels, water buffalos, donkeys, rabbits, fallow deer, reindeer,
  • Fur animals such as mink, chinchilla, raccoon, birds such as chickens, geese, turkeys, Ducks, ostriches, fresh and saltwater fish such as trout, beef, eels, reptiles, insects such as honeybees and silkworms.
  • Laboratory and experimental animals include mice, rats, guinea pigs, golden hamsters, dogs and cats.
  • the pets include dogs and cats.
  • the application can be prophylactic as well as therapeutic.
  • the active ingredients are used directly or in the form of suitable preparations enterally, parenterally, dermally, nasally, by treating the environment or with the aid of shaped bodies containing the active ingredient, e.g. Strips, plates, ribbons, collars, ear tags, limb straps, marking devices.
  • the enteral application of the active ingredients takes place e.g. orally in the form of powder, tablets, capsules, pastes, drinkers, granules, orally applicable solutions, suspensions and emulsions, boluses, medicated feed or drinking water.
  • the dermal application happens e.g. in the form of diving (dipping), spraying (spraying) or pouring on (pour-on and spot-on).
  • Parenteral use happens e.g. in the form of injection (intramuscular, subcutaneous, intravenous, intraperitoneal) or by implants.
  • Suitable preparations are:
  • Solutions such as solutions for injection, oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, infusion formulations, gels;
  • Emulsions and suspensions for oral or dermal use and for injection are prepared by: semi-solid preparations; Formulations in which the active ingredient is processed in an ointment base or in an oil in water or water in oil emulsion base;
  • Solid preparations such as powders, premixes or concentrates, granules, pellets,
  • Solutions for injection are administered intravenously, intramuscularly and subcutaneously.
  • Injection solutions are made by adding the active ingredient in a suitable solvent
  • Solvent is dissolved and additives such as solubilizers, acids, bases, buffer salts, antioxidants, preservatives may be added.
  • additives such as solubilizers, acids, bases, buffer salts, antioxidants, preservatives may be added.
  • the solutions are sterile filtered and filled.
  • solvents such as
  • Alcohols such as ethanol, butanol, benzyl alcohol, glycerin, propylene glycol, polyethylene glycols, N-methyl-pyrrolidone, and mixtures thereof.
  • the active compounds can also be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
  • solubilizers solvents which promote the dissolution of the active ingredient in the main solvent or prevent its precipitation.
  • solvents which promote the dissolution of the active ingredient in the main solvent or prevent its precipitation.
  • examples are polyvinyl pyrrolidone, polyoxyethylated castor oil, polyoxyethylated sorbitan esters.
  • Preservatives are: benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid ester, n-butanol.
  • Oral solutions are applied directly. After prior dilution to the application concentration, concentrates are used orally. Oral solutions and Concentrates are produced as described above for the injection solutions, whereby sterile work can be dispensed with.
  • Solutions for use on the skin are dripped on, spread on, rubbed in, sprayed on or sprayed on. These solutions are prepared as described above for the injection solutions.
  • Thickeners are: inorganic thickeners such as bentonites, colloidal silica, aluminum monostearate, organic thickeners such as cellulose derivatives,
  • Gels are applied or spread on the skin or placed in body cavities. Gels are made by adding enough thickening agent to solutions that have been prepared as described for the injection solutions to form a clear mass with an ointment-like consistency.
  • the thickeners specified above are used as thickeners.
  • Pour-on formulations are poured or sprayed onto limited areas of the skin, the active ingredient penetrating the skin and acting systemically.
  • pour-on formulations are prepared by dissolving, suspending or emulsifying the active ingredient in suitable solvents or solvent mixtures that are compatible with the skin. If necessary, other auxiliaries such as dyes, absorption-promoting substances, antioxidants, light stabilizers and adhesives are added.
  • solvents water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerin, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol, mono-butyl glycol, mono Acetone, methyl ethyl ketone, aromatic and / or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, N-methylpyrrolidone, 2,2-dimethyl-4-oxy-methylene-1,3-dioxolane.
  • aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol
  • esters such as ethyl acetate, butyl acetate
  • benzyl benzoate ether
  • Dyes are all dyes approved for use on animals, which can be dissolved or suspended.
  • Substances that demand resorption are e.g. DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils, fatty acid esters, triglycerides, fatty alcohols.
  • spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils, fatty acid esters, triglycerides, fatty alcohols.
  • Antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid,
  • Light stabilizers are e.g. Novantisol acid.
  • Adhesives are e.g. Cellulose derivatives, starch derivatives, polyacrylates, natural polymers such as alginates, gelatin.
  • Emulsions can be used orally, dermally or as injections.
  • Emulsions are either water in oil or oil in water.
  • hydrophobic phase paraffin oils, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic / capric acid biglyceride, triglyceride mixture with vegetable fatty acids of chain length
  • Fatty acid esters such as ethyl stearate, di-n-butyryl adipate, lauric acid hexyl ester, dipropylene glycol pelargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length 6 -C 8 , isopropyl myristate, isopropyl palmitate, caprylic / capric alcohol ester of the saturated fatty length 12 - C 18 , isopropyl stearate, oleic acid oleyl ester, oleic acid decyl ester, ethyl oleate, lactic acid ethyl ester, waxy fatty acid esters such as artificial duckling gland fat, dibutyl phthalate, adipic acid diisopropyl ester, the latter related ester mixtures and others
  • Fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol.
  • Fatty acids such as Oleic acid and its mixtures.
  • hydrophilic phase The following can be mentioned as the hydrophilic phase:
  • Alcohols such as e.g. Propylene glycol, glycerin, sorbitol and their mixtures.
  • nonionic surfactants e.g. polyoxyethylated castor oil, polyoxyethylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether;
  • ampholytic surfactants such as di-Na-N-lauryl- ⁇ -iminodipropionate or lecithin;
  • anionic surfactants such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono / dialkyl polyglycol ether morphophosphate monoemanolamine salt;
  • cationic surfactants such as cetyltrimemylammonium chloride.
  • Other auxiliaries that may be mentioned are: viscosity-increasing and emulsion-stabilizing substances such as carboxymethyl cellulose, methyl cellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinyl pyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes , colloidal silica or mixtures of the listed substances.
  • Suspensions can be used orally, dermally or as an injection. They are produced by adding the active ingredient in a carrier liquid, if necessary with the addition of other auxiliaries such as wetting agents, dyes, substances requiring resorption,
  • the surfactants specified above may be mentioned as wetting agents (dispersants).
  • Semi-solid preparations can be administered orally or dermally. They differ from the suspensions and emulsions described above only in their higher viscosity.
  • the active ingredient is mixed with suitable carriers, if appropriate with the addition of auxiliaries, and brought into the desired shape.
  • Inorganic and organic substances serve as such.
  • Inorganic substances are e.g. Common salt, carbonates such as calcium carbonate, hydrogen carbonates, aluminum oxides,
  • Silicas, clays, precipitated or colloidal silicon dioxide, phosphates are, for example, sugar, cellulose, food and feed such as milk powder, animal meal, cereal flour and meal, starches.
  • Excipients are preservatives, antioxidants, dyes, which have already been listed above.
  • auxiliaries are lubricants and lubricants such as Magnesium stearate, stearic acid, talc, bentonite, decaying substances such as starch or cross-linked polyvinylpyrrolidone, binders such as e.g. Starch, gelatin or linear polyvinyl pyrrolidone as well as dry binders such as microcrystalline cellulose.
  • lubricants and lubricants such as Magnesium stearate, stearic acid, talc, bentonite, decaying substances such as starch or cross-linked polyvinylpyrrolidone, binders such as e.g. Starch, gelatin or linear polyvinyl pyrrolidone as well as dry binders such as microcrystalline cellulose.
  • the active substances can also be present in the preparations as a mixture with synergists or with other active substances which act against pathogenic endoparasites.
  • Active ingredients are e.g. L-2,3,5,6-tetrahydro-6-phenyl-imidazothiazole, benzimidazole carbamate, pyrantel.
  • Ready-to-use preparations contain the active ingredients in concentrations of 10 ppm to 20 percent by weight, preferably 0.1 to 10 percent by weight.
  • Preparations which are diluted before use contain the active compounds in concentrations of 0.5-90% by weight, preferably 5 to 50% by weight.
  • compositions generally maintain a weight ratio of praziquantel or epsiprantel to depsipeptide, such as 1 to 1 to 10, preferably 1 to 1 to 2, very particularly preferably 1 to 1.
  • insects may be mentioned by way of example and preferably, but without limitation:
  • Lyctus pubescens Trogoxylon aequale, Minthes rugicollis, Xyleboms spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.
  • Kalotermes flavicollis Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
  • Bristle tails such as Lepisma saccharina.
  • technical materials are to be understood as non-living materials, such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.
  • the one to be protected against insect attack is very particularly preferably
  • Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples:
  • the active substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellant, optionally siccatives and UV stabilizers and, where appropriate, dyes and pigments and other processing aids.
  • the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
  • the amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
  • organic-chemical solvent or solvent mixture and / or an oily or oily or low-volatility organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agents.
  • the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
  • Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
  • Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, Te ⁇ entinöl and Like. Used.
  • liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or locker oil and / or monochlomaphthalene, preferably ⁇ -monochlomaphthalene, are used.
  • the organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above
  • insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • part of the organic chemical solvent or solvent mixture is replaced by a polar organic chemical solvent or solvent mixture.
  • the organic-chemical binders which are known are water-dilutable and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, e.g. polyvinyl acetate,
  • Polyester resin polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as I den coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or Resin used.
  • the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellents, odor correctors and
  • At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
  • Alkyd resins having an oil content of more than 45% by weight, preferably 50 to, are preferred according to the invention
  • binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
  • the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycerol or glycerol ether - Kolether, glycerol ester and p-toluenesulfonic acid ester.
  • phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate
  • phosphoric acid esters such as tributyl phosphate
  • adipic acid esters such as di- (2-ethylhexyl) adipate
  • Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
  • Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
  • a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
  • the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.
  • the insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners.
  • the compounds mentioned in this document are an integral part of the present application.
  • Insecticides such as chlorophyros, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthron, trifluoropuron, methifluoropuron, methifluoropuron, methifluoropuron
  • fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluoride, tolylfluanid, 3-iodo-2-propynylbutylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro - octylisothiazolin-3-one.
  • the compounds according to the invention can be used to protect objects, in particular ship hulls, sieves, nets, structures, quay systems and signaling systems which come into contact with sea or brackish water.
  • Ledamo ⁇ ha barnacles
  • Balanomo ⁇ ha barnacles
  • Baianus or Pollicipes species increases the frictional resistance of Ships and subsequently leads to a significant increase in operating costs due to increased energy consumption and, moreover, frequent dry dock stays.
  • heavy metals such as e.g. in bis- (trialkyltin) sulfides, tri-ra- butyltin laurate, tri-fl-butyltin chloride, copper (I) oxide, triethyltin chloride, tri-butyl (2-phenyl-4-chl ⁇ henoxy) tin, tributyltin oxide, molybdenum disulfide , antimony oxide, polymeric butyl titanate, phenyl-fbispyridin) - bismuth chloride, tri - "- butylzinnfluorid, Manganethylenbisthiocarbamat, zinc dimethyldithiocarbamate, Zinkethylenbisthiocarbamat, zinc and copper salts of 2 Pyridinthiol- 1 oxide, Bisdimethyldithiocarbamoylzinkethylenbisthiocarba
  • the ready-to-use antifouling paints may also contain other active ingredients, preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients.
  • Suitable combination partners for the antifouling agents according to the invention are preferably:
  • Benzo [b] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlofluanide, fluorine folpet, 3-iodo-2-propynyl butyl carbamate, tolyl fluanide and azoles such as
  • anti-fouling agents such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethylthiocarbamoylthio) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridine thiol-l-oxide, pyridine triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5, 6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2 , 4,6-Trichlo ⁇ henylmaleinimid.
  • the antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular of 0.01 to 20% by weight.
  • the antifouling agents according to the invention furthermore contain the usual ones
  • antifouling paints contain in particular binders.
  • Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, especially in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile Rubbers, dry oils such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.
  • Paints may also contain inorganic pigments, organic
  • Paints may also contain materials such as rosin to enable controlled release of the active ingredients.
  • the paints may also contain plasticizers, modifiers that affect the rheological properties, and other conventional ingredients. Also in self-polishing antifouling
  • the active ingredients are also suitable for controlling animal pests, in particular insects, arachnids and mites, which live in closed spaces such as apartments, factory halls, offices, vehicle cabins and others. occurrence.
  • Sco ⁇ ionidea e.g. Buthus occitanus.
  • Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat,
  • Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp ..
  • Aedes aegypti Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
  • Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia inte ⁇ unctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
  • Ctenocephalides canis Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
  • Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • the mixture After stirring for 2.5 hours at room temperature, the mixture is poured onto ice water, extracted with ethyl acetate and the organic phase is washed with 10% sodium chloride solution. After drying over magnesium sulfate, the mixture is concentrated on a rotary evaporator and the oil which remains is crystallized in the acetone / dry ice bath with the addition of a little ethyl acetate.
  • 1,1-dioxide in 185 ml of dioxane and 185 ml of water are added 14.8 g (0.2 mol) of sodium hydrogen sulfide monohydrate and stirred overnight at 20 ° C.
  • the reaction mixture is acidified with dilute hydrochloric acid and the product extracted with dichloromethane.
  • the organic phase is washed twice with dilute hydrochloric acid, dried over magnesium sulfate and concentrated on a rotary evaporator.
  • Solvent 8 parts by weight of acetone emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • Vessels are filled with sand, active ingredient solution, Meloidogyne incognita egg larvae suspension and lettuce seeds.
  • the lettuce seeds germinate and the plantlets develop.
  • the galls develop at the roots.
  • the nematicidal effect is determined in% using the formation of bile. 100% means that no galls were found; 0% effect means that the number of galls on the treated plants corresponds to that of the untreated control.
  • Solvent 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Cabbage leaves (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are treated by being dipped into the preparation of active compound of the desired concentration.
  • the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the horseradish beetle (Phaedon cochleariae) while the leaves are still moist.
  • the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the army worm (Spodoptera frugiperda) while the leaves are still moist.
  • the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • the compound of preparation example 2 shows a kill of 100% after 7 days.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Bean plants Phaseolus vulgaris
  • Tetranychus urticae which are heavily infested with all stages of the common spider mite (Tetranychus urticae), are immersed in an active ingredient preparation of the desired concentration.
  • the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
  • the compound of preparation example 4 shows a kill of 100% after 7 days.
  • Test animals adult sucked females
  • the compound of preparation example 2 shows a kill of 90%
  • the compound of preparation example 4 shows a kill of 100%.
  • Test animals adult sucked females
  • the test is carried out in 5-fold determination. 1 ⁇ l of the solutions is injected into the abdomen, the animals are transferred to dishes and stored in an air-conditioned room.
  • the active ingredient control is carried out after 7 days on the storage of fertile eggs. Eggs, whose fertility is not visible from the outside, are kept in glass tubes until larvae hatch in the climatic chamber. An effect of 100% means that no tick has laid fertile eggs.
  • Test animals adults of Ctenocephalides felis
  • a suitable active ingredient solution is prepared from 20 mg of active ingredient with 1 ml of DMSO. 15 ⁇ l of this formulation are added to 3 ml of titrated bovine blood and stirred.
  • Fleas can be absorbed through the parafilm membrane. While the blood is being heated to 37 ° C, a temperature of 25 ° C is set in the area of the flob chambers. Controls are mixed with the same volume of DMSO without the addition of a compound. Triple determinations are carried out.
  • Test animals adult Musca domestica, trunk Reichswald (OP, SP,
  • the effectiveness of the active ingredient preparation is determined. 100% means that all flies have been killed; 0% means that no flies have been killed.
  • the compound of preparation example 2 shows a kill of 60%
  • the compound of preparation example 4 shows a kill of 40%.
  • Test animals Luc ⁇ lia cuprina larvae
  • test tube which contains approx. 1 cm 3 horse meat and 0.5 ml of the active ingredient preparation to be tested. The effectiveness of the active substance preparation is determined after 24 and 48 hours.
  • the test tubes are transferred to beakers with a sand-covered bottom. After a further 2 days, the test tubes are removed and the dolls are counted.
  • the effect of the active substance preparation is assessed according to the number of flies hatched after 1.5 times the development time of an untreated control. 100% means that no flies have hatched; 0% means that all flies hatched normally.
  • Nippostrongylus brasiliensis worms are isolated from the small intestine of female Wistar rats and collected in aqueous 0.9% NaCl containing 20 ⁇ g / ml sisomycin and 2 ⁇ g / ml canesten.
  • the incubation of both worm groups (male / female sex) is carried out in 1.0 ml medium, which is used for the determination of the acetylcholinesterase activity.
  • the incubation conditions and the determination of the enzyme activity were described in Martin et al., Pesticide Science (1996) 48, 343-349.
  • the compounds are dissolved in the specified solvent (10 mg to 0.5 ml) and brought to the desired concentration.
  • the controls contain only the solvent.
  • the vitality of the worms is characterized by the activity of acetylcholinesterase, which the worms actively secreted into the incubation medium.
  • the classification of acetylcholinesterase activity follows the work of
  • Test animals Trichinella spiralis larvae
  • Trichinella spiralis larvae are isolated from the skeletal muscles and muscles below the skin of SPF / CFW1 mice and collected in aqueous 0.9% NaCl containing 20 ⁇ g / ml sisomycin. 20 larvae in 2 ml of a
  • test compound 10 mg are dissolved in 0.5 ml of the specified solvent and enough of the solution obtained is added to the incubation medium such that the desired concentration is calibrated.
  • the controls contain only the solvent.
  • the experiment is ended after an incubation period of 5 days at a temperature of 19 ° C.
  • the anthelmintic activity of a substance is divided into 4 levels. 0 means no, 1 weak, 2 good and 3 full activity ( ⁇ 50%, 50 - 75%,> 75%, 100% of the larvae dead).

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)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Abstract

La présente invention concerne de nouveaux thioéthers de fluoralcényle hétérocycliques de la formule (I) dans laquelle X est hydrogène, halogène, ou alkyle ; m est un entier de 2 à 10 ; n est 0, 1 ou 2 ; Y est méthylène éventuellememt substitué ; et p est 1, 2, ou 3. L'invention concerne également des procédés de fabrication de ces composés ainsi que leur utilisation en tant que pesticides.
EP01960418A 2000-07-13 2001-06-29 Thioethers de fluoralcenyle heterocycliques et utilisation en tant que pesticides (i) Withdrawn EP1305302A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10034133A DE10034133A1 (de) 2000-07-13 2000-07-13 Heterocyclische Fluoralkenylthioether (l)
DE10034133 2000-07-13
PCT/EP2001/007432 WO2002006260A1 (fr) 2000-07-13 2001-06-29 Thioethers de fluoralcenyle heterocycliques et utilisation en tant que pesticides (i)

Publications (1)

Publication Number Publication Date
EP1305302A1 true EP1305302A1 (fr) 2003-05-02

Family

ID=7648846

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01960418A Withdrawn EP1305302A1 (fr) 2000-07-13 2001-06-29 Thioethers de fluoralcenyle heterocycliques et utilisation en tant que pesticides (i)

Country Status (7)

Country Link
US (2) US6927215B2 (fr)
EP (1) EP1305302A1 (fr)
JP (1) JP2004504312A (fr)
AU (1) AU2001281915A1 (fr)
DE (1) DE10034133A1 (fr)
WO (1) WO2002006260A1 (fr)
ZA (1) ZA200300273B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10201238A1 (de) * 2002-01-15 2003-07-24 Bayer Cropscience Ag Verfahren zur Herstellung von halogenierten 2-(3-Butenylsulfanyl)-1,3-thiazolen
DE10221119A1 (de) * 2002-05-13 2003-12-04 Bayer Cropscience Ag Verfahren zur Herstellung von substituierten Trifluorethylenen
DE10221120A1 (de) * 2002-05-13 2003-11-27 Bayer Cropscience Ag Verfahren zur Herstellung von substituierten Trifluorethylenen
DE10229776A1 (de) 2002-07-03 2004-01-22 Bayer Cropscience Ag Verfahren zum Herstellen von heterocyclischen Fluoralkenylsulfonen
EP1606174B1 (fr) * 2003-03-12 2006-07-19 Pallet Detection Systems Ltd Controle de l'infestation d'une charge palettisée
RU2379890C1 (ru) * 2008-11-12 2010-01-27 Общество с ограниченной ответственностью "Анвет" Бактерицидное средство

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US3345374A (en) * 1962-09-04 1967-10-03 Bayer Ag Certain oxathiazole and dithiazole derivatives
US3914251A (en) 1971-12-08 1975-10-21 Stauffer Chemical Co Certain trifluorobutenyl compounds and their utility as nematocides
EP0334796B1 (fr) 1988-03-19 1993-05-12 Hoechst Aktiengesellschaft Procédé de préparation d'hydrocarbures halogénés insaturés
WO1994029268A1 (fr) 1993-06-07 1994-12-22 Bayer Aktiengesellschaft Iodopropargylcarbamates et leur utilisation comme biocides pour la protection des vegetaux et des materiaux
WO1995004727A1 (fr) * 1993-08-05 1995-02-16 Zeneca Limited Procede de preparation de derives fluoroathenylthio heterocycliques
IL112721A0 (en) * 1994-03-10 1995-05-26 Zeneca Ltd Azole derivatives
DE19700062A1 (de) * 1997-01-03 1998-07-09 Bayer Ag S-Aryl-dithiazindioxide
DE19721627A1 (de) 1997-05-23 1998-11-26 Bayer Ag S-Pyridyl-dithiazoldioxide
JP3870515B2 (ja) 1997-11-07 2007-01-17 宇部興産株式会社 ５，６−ジヒドロ−（４ｈ）−１，３−チアジン誘導体、その製法及び農園芸用の有害生物防除剤
WO1999052874A1 (fr) * 1998-04-10 1999-10-21 Ube Industries, Ltd. Derives difluoroalcene, procede de production associe, et agent de lutte contre les ravageurs dans l'agriculture et l'horticulture
AU3169199A (en) 1998-04-13 1999-11-01 Nihon Nohyaku Co., Ltd. 1,2,3-thiadiazole derivative or salt thereof and pest control agent, and method of use thereof
DE19918294A1 (de) * 1999-04-22 2000-10-26 Bayer Ag O-Aryldithiazoldioxide

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Title
See references of WO0206260A1 *

Also Published As

Publication number Publication date
US6927215B2 (en) 2005-08-09
ZA200300273B (en) 2004-01-22
AU2001281915A1 (en) 2002-01-30
DE10034133A1 (de) 2002-01-24
WO2002006260A1 (fr) 2002-01-24
US20040127525A1 (en) 2004-07-01
JP2004504312A (ja) 2004-02-12
US20050256173A1 (en) 2005-11-17

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