WO2003016293A1 - Oxadiazolyl benzoyl urees et thiadiazolyl benzoyl urees et leur utilisation en tant que pesticides - Google Patents

Oxadiazolyl benzoyl urees et thiadiazolyl benzoyl urees et leur utilisation en tant que pesticides Download PDF

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Publication number
WO2003016293A1
WO2003016293A1 PCT/EP2002/008572 EP0208572W WO03016293A1 WO 2003016293 A1 WO2003016293 A1 WO 2003016293A1 EP 0208572 W EP0208572 W EP 0208572W WO 03016293 A1 WO03016293 A1 WO 03016293A1
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Prior art keywords
spp
alkyl
compounds
formula
chlorine
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PCT/EP2002/008572
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German (de)
English (en)
Inventor
Fritz Maurer
Christoph Erdelen
Udo Reckmann
Andreas Turberg
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Bayer Cropscience Ag
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Publication of WO2003016293A1 publication Critical patent/WO2003016293A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5

Definitions

  • the present invention relates to new oxadiazolyl- and thiadiazolyl-benzoyl ureas, processes for their preparation and their use as pesticides.
  • R 1 represents hydrogen or halogen
  • R 2 represents halogen
  • R 3 represents halogen, alkyl or haloalkyl
  • n 0, 1 or 2 and Het for the groups
  • R 4 represents hydrogen, alkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylcarbonyloxyalkyl, optionally substituted aryl or optionally substituted arylalkyl and
  • X represents oxygen or sulfur.
  • R 1 and R 2 have the meaning given above
  • R 3 , n and Het have the meanings given above,
  • oxadiazolyl- and thiadiazolyl-benzoyl ureas according to the invention are generally defined by the formula (I).
  • R 1 preferably represents hydrogen, fluorine or chlorine.
  • R 2 preferably represents fluorine or chlorine.
  • R 3 preferably represents fluorine, chlorine, bromine, C, -C 4 -alkyl or C, -C 4 -haloalkyl.
  • n is preferably 0, 1 or 2. Het preferably stands for the groupings
  • R 4 preferably represents hydrogen, C, -C 4 -alkyl, C, -C 4 -alkoxy-C C 4 -alkyl, C, -C 4 -alkoxy-carbony 1-C, -C 4 -alkyl 1, C, -C 4 - alkyl 1-carbonyloxy-C, -C 4 - alkyl and for each optionally single to triple, the same or different by halogen, nitro, cyano, C, -C 4 - alkyl, C, -C 4 - alkoxy , C, -C 4 haloalkyl or -CC 4 haloalkoxy substituted phenyl or benzyl and
  • X represents oxygen or sulfur.
  • R 1 particularly preferably represents hydrogen, fluorine or chlorine.
  • R 2 particularly preferably represents fluorine or chlorine.
  • R 3 particularly preferably represents fluorine, chlorine, methyl or ethyl.
  • n particularly preferably represents 0, 1 or 2.
  • R 4 particularly preferably for hydrogen, C, -C 4 alkyl, C
  • X represents oxygen or sulfur.
  • R 1 very particularly preferably represents hydrogen, fluorine or chlorine.
  • R 2 very particularly preferably represents fluorine or chlorine.
  • R 3 very particularly preferably represents fluorine or chlorine
  • n very particularly preferably represents 0, 1 or 2.
  • R 4 very particularly preferably for hydrogen; Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl and for each optionally simple phenyl or benzyl which is substituted twice, identically or differently, by fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl or trifluoromethoxy.
  • radical definitions or explanations listed above or listed in preferred areas apply accordingly to the end products and to the starting and intermediate products. These residual definitions can be combined with one another, i.e. also between the respective preferred areas.
  • 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 benzoyl isocyanates to be used as starting materials for carrying out the process according to the invention.
  • the benzoyl isocyanates of the formula (II) are known and can be obtained by generally known methods.
  • Formula (III) provides a general definition of the substituted anilines to be used as starting materials in the process according to the invention.
  • the substituted anilines of the formula (III) are largely known (cf. e.g. DE-A-
  • R 3 and n have the meanings given above.
  • the aniline derivatives of the formula (purple) can be obtained by using 4-aminobenzamide oximes of the formula (IV)
  • R 3 and n have the meanings given above, heated under reflux in a conventional manner with trimethyl acetic acid derivatives, such as preferably alkyl esters or anhydride.
  • the 4-amino-benzamide oximes of the formula (IV) can be obtained in a general manner by reacting 4-amino-benzonitriles with hydroxylamine hydrochloride in the presence of a base such as potassium carbonate.
  • aniline derivatives of the formula (IIIb) can be obtained by using 4-aminobenzoic acid hydrazides of the formula (V)
  • R 3 and n have the meanings given above,
  • trimethyl acetic acid derivatives such as preferably alkyl esters, also in the form of the corresponding orthoesters.
  • the 4-aminobenzoic acid hydrazides of the formula (V) can be obtained in a generally known manner by reacting corresponding 4-amino-benzoic acid esters with hydrazine.
  • aniline derivatives of the formula (IIIc) can be obtained by reacting corresponding 4-amino-benzoic acid esters with pivalamidoxime in a generally known manner (cf. also the preparation examples).
  • the aniline derivatives of the formulas (IIla-c) can also be obtained in the customary manner from the corresponding 4-nitro derivatives (cf., for example, US Pat. No. 3,270,029).
  • the process according to the invention is preferably carried out using diluents. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene,
  • Methylene chloride ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene
  • ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl or methyl isobutyl ketone such as methyl acetate or ethyl ester
  • nitriles such as Acetonitrile or propionitrile
  • amides such as e.g.
  • reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between 0 ° C and 100 ° C, preferably at temperatures between 10 ° C and 80 ° C.
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in a larger excess. Working up is carried out using customary methods (cf. the production examples).
  • the active ingredients are suitable for combating animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests, in stock and
  • Isopoda e.g. 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 for example Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp ..
  • Thysanoptera for example Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
  • Homoptera e
  • Ceuthorrhynchus assimilis Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conodems spp., Melolontha melolontha, Costimallontronica oryzophilus.
  • Hymenoptera e.g. 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 substances according to the invention can be used with particularly good success for combating plant-damaging insects, for example against caterpillars of the cotton capsule worm (Heliothis virescens), the larvae of the horseradish beetle (Phaedon cochleariae), the caterpillars of the cockroach (Plutella xylostella) and caterpillars of the army worm (Spodoptera exigua and Spodoptera frugioerda).
  • caterpillars of the cotton capsule worm Heliothis virescens
  • the larvae of the horseradish beetle Phaedon cochleariae
  • the caterpillars of the cockroach Plutella xylostella
  • caterpillars of the army worm Spodoptera exigua and Spodoptera frugioerda
  • the compounds of the invention show a particularly good one
  • the compounds according to the invention can also be used in certain concentrations or application rates as herbicides and microbicides, for example as fungicides, antifungals 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 unwanted 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 those by
  • Plant variety rights of protectable or non-protectable plant varieties 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.
  • Storage room according to the usual treatment methods, e.g. by dipping, spraying, Evaporation, nebulization, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by means of 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, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers substances.
  • formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is to say liquid solvents and / or solid carriers
  • surface-active agents that is to say 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 silicic acid, aluminum oxide and silicates, as solid carriers for granules are possible: eg broken and fractionated natural pellets Rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic 2 granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifying and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulf
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • 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 compound 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 compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • active compounds 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.
  • Diethofencarb Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Diniconazol-M, Dinocap, Diphenylamin, Dipyrithione, Ditalimfos, Dithianon, Dodemorph, Dodine, Drazoxolon,
  • 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,
  • Metconazole methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,
  • Oxadixyl Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
  • Paclobutrazole pefurazoate, penconazole, pencycuron, Phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethililan
  • Tebuconazole Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, uniconazole
  • Bacillus popilliae Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos,
  • Chlo ⁇ yrifos Chlo ⁇ yrifos M, Chlovaporthrin, Cis-Resmethrin, Cispermethrin, Clocythrin, Cloethocarb, Clofentezine, Cyanophos, Cycloprene, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazine
  • Fenamiphos Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Flu
  • Halofenozide HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
  • the active compounds according to the invention can also be used in their commercially available formulations and in the formulations obtained from these formulations. use forms in 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 active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, 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.
  • plants and their parts can be treated according to the invention.
  • plant species and plant cultivars and their parts occurring wildly or obtained by conventional organic breeding methods, such as crossing or protoplast fusion are treated.
  • transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms) and their parts are treated.
  • the term "parts” or “parts of plants” or “plant parts” was explained above.
  • 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 bred by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, bio and genotypes. Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also cause superadditive (“synergistic”) effects.
  • transgenic plants or plant cultivars to be treated according to the invention include all plants which, through the genetic engineering modification, have received genetic material which contains them
  • traits are 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, accelerated ripening, higher harvest yields, higher quality and / or higher nutritional value of the crop products , higher shelf life and / or workability of the harvest products.
  • Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses, and an increased tolerance of the plants to certain herbicides
  • transgenic plants are the important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes and cotton and rapeseed are highlighted.
  • the traits are particularly emphasized, in particular the increased defense of the plants against insects by toxins arising in the plants those produced by the genetic material from Bacillus thuringiensis (e.g.
  • Bt plants by the genes Cry ⁇ A (a), Cry ⁇ A (b), Cry ⁇ A (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and their combinations.
  • SAR systemic acquired resistance
  • systemin phytoalexins
  • elicitors and resistance genes and correspondingly expressed proteins and toxins are also particularly emphasized as traits.
  • traits 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).
  • herbicidal active compounds for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example “PAT” gene).
  • genes imparting the desired properties can also occur in combinations with one another in the transgenic plants.
  • “Bt plants” are corn varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard®
  • herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soybeans), Liberty Link® (tolerance to phosphinotricin, e.g. rapeseed), IMI® (tolerance to Imidazolinone) and STS®
  • the herbicide-resistant plants include the varieties sold under the name Clearfield® (e.g. maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").
  • plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula I or the active compound mixtures according to the invention.
  • the preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants.
  • Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.
  • 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 linge, featherlings and fleas.
  • animal parasites ectoparasites
  • tick ticks leather ticks
  • mites running mites
  • flies stinging and licking
  • parasitic fly larvae lice, hair linge, featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtims 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., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota ., Philipomyia spp.,
  • Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..
  • Amblyomma spp. Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa 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, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice.
  • arthropods e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as e.g. Dogs, cats, house birds, aquarium fish and so-called experimental animals, such as Infest hamsters, guinea pigs, rats and mice.
  • 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, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by injections
  • implants through nasal Application, through dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, pumping in, and with the help of shaped articles containing active ingredients, such as collars, ear tags, tail tags , Limb straps, holsters, marking devices etc.
  • active ingredients such as collars, ear tags, tail tags , Limb straps, holsters, marking devices etc.
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.
  • formulations for example powders, emulsions, flowable agents
  • insects may be mentioned by way of example and preferably, but without limitation:
  • Termites like Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
  • Bristle tails such as Lepisma saccharina.
  • non-living materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.
  • the material to be protected against insect infestation is very particularly preferably wood and wood processing products.
  • 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 compounds can be used as such, in the form of concentrates or generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.
  • the amounts of formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally siccatives and UV stabilizers and, if appropriate Dyes and pigments as well as 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, test gasoline 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 are advantageous. Te ⁇ entinöl and the like. For use.
  • 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 has a flash point above 30 ° C., preferably above 45 ° C., and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced.
  • Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.
  • 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, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders on the Base of a natural and / or synthetic resin used.
  • binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumar
  • 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-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
  • 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 fixative (mixture) or a plasticizer (mixture).
  • fixative mixture
  • plasticizer mixture
  • 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 by industrial impregnation processes, e.g. vacuum, double vacuum or pressure processes.
  • the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.
  • 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 chloropyriphos, 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-n-one -octy-lisothiazolin-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.
  • heavy metals such as e.g. in bis (tri-alkyltin) sulfides, tri - "- butyltin laurate, tri-n-butyltin chloride, copper (I) oxide, triethyltin chloride, tri -" - butyl (2-phenyl-4-chlorohenoxy) tin, tributyltin oxide, Molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl (bispyridine) bismuth chloride, tri - «- butyltin fluoride, manganese ethylene bisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisthiocarbamate, zinc and copper salts of 2-pyridine thiocarbamide, zinc, bis-pyridynodi-ethoxydi-oxydi-oxydi-oxydi-oxydi-oxyd
  • 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: Algicides like
  • Fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb; or conventional antifouling agents such as
  • 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 constituents, such as, for example, in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Anti- fouling Marine Coatings, Noyes, Park Ridge, 1973.
  • 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, in particular 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, drying
  • 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 combating animal pests, in particular insects, arachnids and mites, which occur in closed rooms, such as, for example, apartments, factory halls, offices, vehicle cabins and others.
  • animal pests in particular insects, arachnids and mites, which occur in closed rooms, such as, for example, apartments, factory halls, offices, vehicle cabins and others.
  • insects in particular insects, arachnids and mites
  • closed rooms such as, for example, apartments, factory halls, offices, vehicle cabins and others.
  • active ingredients and auxiliaries in household insecticide products. They are effective against sensitive and resistant species and against all stages of development.
  • These pests include: From the order of the Sco ⁇ ionidea, for example Buthus occitanus.
  • Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Omithodoms moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis,
  • Opiliones e.g. Pseudosco ⁇ iones chelifer, Pseudosco ⁇ iones cheiridium, Opiliones phalangium.
  • Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp ..
  • 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. Campono tus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • Acetonitrile is added dropwise at room temperature to a solution of 0.97 g (5.3 mmol) of 2,6-difluorobenzoyl isocyanate in 20 ml of acetonitrile and the mixture is stirred for 18 hours Room temperature after. The precipitated product is then filtered off and washed with acetonitrile.
  • a mixture of 3 g (0.02 mol) of 4-aminobenzoic acid hydrazide and 15 ml of orthopropionic acid triethyl ester is heated under reflux for 18 hours. Then the reaction mixture is evaporated in vacuo and the residue in 20 ml 10 percent. Hydrochloric acid dissolved. The solution is adjusted to about pH 9-10 by adding dilute sodium hydroxide solution. The precipitated product is suctioned off and washed well with water.
  • a solution of 0.83 is added dropwise at room temperature to a solution of 1 g (4.6 mmol) of 4- (3-tert-butyl-l, 2,4-oxadiazol-5-yl) aniline in 30 ml of acetonitrile g (4.6 mmol) of 2-chlorobenzoyl isocyanate in 10 ml of acetonitrile and the mixture is stirred for 18 hours at room temperature. The precipitated product is then suctioned off and washed with acetonitrile.
  • Emulsifier 2 parts 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.
  • Soybean shoots (Glycine max) are treated by dipping into the active ingredient preparation of the desired concentration and populated with Heliothis virescens caterpillars 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.
  • Emulsifier 2 parts 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 leaf 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 2 parts 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 cockroach (Plutella xylostella) 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 compounds of preparation examples 3, 5, 6 and 15, for example show a kill of 100% after 7 days.
  • Emulsifier 2 parts 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 exigua) 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.
  • Solvent 7 parts by weight of dimethylformamide emulsifier: 2 parts 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 fmgiperda) 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 compounds of preparation examples 3, 4, 5, 6, 7, 8 and 15, for example show a kill of 100% and preparation examples 9 and 12 of 90% after 7 days.
  • Test animals Lucilia cuprina larvae
  • test tubes are removed for 2 days 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.

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

Abstract

La présente invention concerne des oxadiazolyl benzoyl urées et des thiadiazolyl benzoyl urées de formule (I), dans laquelle R<1>, R<2>, R<3>, n et Het ont les significations indiquées dans la description. L'invention concerne également un procédé de production de ces composés et leur utilisation en tant que pesticides.
PCT/EP2002/008572 2001-08-13 2002-08-01 Oxadiazolyl benzoyl urees et thiadiazolyl benzoyl urees et leur utilisation en tant que pesticides WO2003016293A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10139721.6 2001-08-13
DE2001139721 DE10139721A1 (de) 2001-08-13 2001-08-13 Oxadiazolyl- u. Thiadiazolyl-benzoylharnstoffe

Publications (1)

Publication Number Publication Date
WO2003016293A1 true WO2003016293A1 (fr) 2003-02-27

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DE (1) DE10139721A1 (fr)
WO (1) WO2003016293A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102690241A (zh) * 2011-03-24 2012-09-26 南开大学 含异噁唑啉和异噁唑结构的苯甲酰脲类化合物及制备和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986003941A1 (fr) * 1984-12-28 1986-07-17 Union Carbide Corporation Utilisation de composes d'acyl-uree pour l'elimination d'endoparasites et d'ectoparasites chez les animaux a sang chaud
WO2000046184A1 (fr) * 1999-02-06 2000-08-10 Aventis Cropscience Gmbh Derive n2-phenylamidine

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986003941A1 (fr) * 1984-12-28 1986-07-17 Union Carbide Corporation Utilisation de composes d'acyl-uree pour l'elimination d'endoparasites et d'ectoparasites chez les animaux a sang chaud
WO2000046184A1 (fr) * 1999-02-06 2000-08-10 Aventis Cropscience Gmbh Derive n2-phenylamidine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102690241A (zh) * 2011-03-24 2012-09-26 南开大学 含异噁唑啉和异噁唑结构的苯甲酰脲类化合物及制备和应用
CN102690241B (zh) * 2011-03-24 2014-07-09 南开大学 含异噁唑啉结构的苯甲酰脲类化合物及制备和应用

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