EP1417178A2 - Derives d'amide heterocycliques et leur utilisation comme pesticides - Google Patents

Derives d'amide heterocycliques et leur utilisation comme pesticides

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Publication number
EP1417178A2
EP1417178A2 EP02740745A EP02740745A EP1417178A2 EP 1417178 A2 EP1417178 A2 EP 1417178A2 EP 02740745 A EP02740745 A EP 02740745A EP 02740745 A EP02740745 A EP 02740745A EP 1417178 A2 EP1417178 A2 EP 1417178A2
Authority
EP
European Patent Office
Prior art keywords
optionally
spp
compounds
formula
alkyl
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Withdrawn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
EP02740745A
Other languages
German (de)
English (en)
Inventor
Graham Holmwood
Klaus-Günther TIETJEN
Michael Schindler
Christoph Erdelen
Ulrike Wachendorff-Neumann
Andreas Turberg
Olaf Hansen
Angelika Lubos-Erdelen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
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Bayer CropScience AG
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Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1417178A2 publication Critical patent/EP1417178A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
    • C07D207/50—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to new heterocyclic amide derivatives, processes for their preparation and their use as pesticides.
  • R 1 and R 2 independently of one another for hydrogen, alkyl, alkoxyalkyl, alkylthioalkyl, for optionally substituted cycloalkyl, for optionally substituted heterocyclyl or together with the carbon atoms to which they are attached, for an optionally substituted mono- or bicyclic, carbo - or heterocyclic grouping.
  • R 3 and R 4 independently of one another each represent optionally substituted aryl or hetaryl. Furthermore, it was found that the new compounds of the formula (I) are obtained if compounds of the formula (II)
  • R 1 , R 2 and R 3 have the meaning given above,
  • R 4 has the meaning given above and
  • R 5 represents halogen (in particular chlorine) or hydroxy
  • R 1 and R 2 independently of one another preferably represent hydrogen, Ci-Cg-alkyl, C 1 -C 6 -alkoxy-C 1 -C 3 -alkyl, C j -C ß- alkylthio-C C ß -alkyl, each for optionally substituted by C ⁇ -C 3 alkyl, substituted C 3 -C 7 -cycloalkyl which may be substituted by one or two oxygen and / or sulfur atoms interrupted, if appropriate, or, together with the C atoms to which they are attached, optionally by C ⁇ -C3 alkyl substituted C 3 -C 4 ⁇ alkanediyl in which two not directly adjacent carbon atoms optionally form a further cycle which may optionally be interrupted by an oxygen and / or sulfur atoms.
  • R 3 preferably represents in each case optionally, single or double, identical or different by Ci-C ⁇ alkyl, CC ⁇ alkoxy, halogen, C j -C ⁇ haloalkyl, Cj-C -haloalkoxy, cyano, nitro, C j -C ⁇ alkylsulfonyl, C 1 -C 4 -
  • Haloalkylsulfonyl, thioamide or tetrazole substituted phenyl or hetaryl e.g. pyridyl, thienyl, furyl, pyrimidinyl.
  • R 4 preferably represents in each case optionally mono- to tetrasubstituted by identical or different substituents from Cj-C 4 alkyl, C j -C ⁇ alkoxy, Ci-C ⁇ alkoxy-Ci-C ⁇ alkoxy, halogen, C ⁇ -C 4 -haloalkyl , C j -C 4 haloalkoxy or cyano substituted phenyl, where two adjacent C atoms optionally form a five- or six-membered carbocycle which can optionally be interrupted by one or two oxygen atoms or hetaryl (for example pyridyl, thienyl, furyl, pyrimidinyl ).
  • R 1 and R 2 independently of one another particularly preferably represent hydrogen, C j -
  • R 3 particularly preferably represents phenyl, pyridyl, in each case optionally, mono- or disubstituted, identically or differently, by methyl, fluorine, chlorine, bromine, iodine, cyano, nitro, methoxy, trifluoromethyl, trifluoromethoxy, sulfonylmethyl, sulfonyltrifluoromethyl, thioamide or tetrazole .
  • R 4 particularly preferably represents in each case optionally, once to four times, identically or differently by methyl, ethyl, fluorine, chlorine, bromine,
  • R 1 very particularly preferably represents hydrogen or methyl
  • R 2 very particularly preferably represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, cyclopentyl, cyclohexyl or
  • R 1 and R 2 together with the carbon atoms to which they are attached very particularly preferably represent C 3 -C 4 -alkanediyl which is substituted, once or twice, by methyl or C4-alkanediyl in which two are not directly adjacent C atoms optionally form a further cycle which can optionally be interrupted by an oxygen atom
  • R 3 very particularly preferably represents phenyl which is substituted once or twice, identically or differently, by methyl, fluorine, chlorine, bromine, iodine, nitro, cyano, methoxy or trifluoromethyl.
  • R 4 very particularly preferably represents phenyl which is optionally substituted once, once to four times, identically or differently by methyl, ethyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy, trifluoromethoxy, 2-methoxyethoxy or cyano, two adjacent C atoms optionally form a five- or six-membered carbocycle which can optionally be interrupted by one or two oxygen atoms.
  • hydrocarbon radicals such as alkyl - are also straight-chain or branched as far as possible, even in compounds with heteroatoms such as alkoxy. If, for example, 1-amino-4,5-dimethyl-2- (3,5-dimethylphenyl) imidazole and 4-ethylbenzoyl chloride are used as starting materials, the reaction sequence of the process according to the invention can be represented by the following formula:
  • the compounds to be used as starting materials for carrying out the process according to the invention are generally defined by the formulas (II) and (III).
  • the compounds of formula (II) are new except for 1-amino-2-phenylimidazole, 1-amino-2- (4-chlorophenyl) imidazole, 1-amino-2- (4-methoxyphenyl) imidazole and 1-amino -2- (3,4-dimethoxyphenyl) imidazole. They can be obtained by using compounds of the formula (IV)
  • R 1 , R 2 and R 3 have the meanings given above and R 6 denotes alkyl or optionally substituted phenyl,
  • hydrolytically cleaves an acid optionally in the presence of a diluent.
  • the compounds of formula (III) can be prepared according to the preparation examples (III-1, III-2 and III-3).
  • the method according to the invention is preferably carried out using diluents.
  • 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
  • Acid acceptors which can be used in the process according to the invention are all acid binders which can customarily be used for such reactions.
  • Alkali metal and alkaline earth metal hydrides such as lithium, sodium, potassium or calcium hydride, alkali metal or alkaline earth metal hydroxides, such as lithium, sodium, potassium or calcium hydroxide, alkali metal or alkaline earth metal carbonates or hydrogen carbonates, such as sodium or potassium carbonates or hydrogen carbonate or calcium carbonate, alkali metal acetate, such as sodium or potassium acetate, alkali metal alcoholate, such as sodium or potassium tert-butoxide, and also basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine,
  • DBN 1,5-diazabicyclo [4,3,0] non-5-ene
  • DBU 1,8-diazabicyclo - [5,4,0] -undec-7-ene
  • DBU 1,4-diazabicyclo- [2,2,2]
  • the carboxylic acid-activating reagent (coupling reagent) in the process according to the invention is found to be all those which are suitable for producing an amide bond (cf. for example: Houben-Weyl, Methods of Organic Chemistry, Volume 15/2; Bodanszky et al., Peptide Synthesis 2nd ed . (Wiley & Sons, New York 1976) or Gross,
  • acid binders such as amines, in particular tertiary amines, and alkali and alkaline earth compounds can be used as basic reaction auxiliaries for carrying out the process according to the invention.
  • Examples include the hydroxides, oxides and carbonates of lithium, sodium, potassium, magnesium, calcium and barium, as well as further basic compounds such as amidine bases or guanidine bases such as 7-methyl-l, 5,7-triazabicyclo- (4.4.0) dec -5-ene (MTBD); Diazabicyclo (4.3.0) nonen (DBN), diazabicyclo (2.2.2) octane (DABCO), 1,8-diaza-bicyclo (5.4.0) undecene (DBU) cyclohexyl-tetrabutylguanidine (CyTBG), cyclohexyltetramethylguanidine (CyTMG) , N, N, N, N-tetramethyl-1,8-naphthalenediamine, pentamethylpiperidine, tertiary amines such as triethylamine, trimethylamine, tribenzylamine, triisopropylamine, tributylamine, tribenzy
  • reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between -20 ° C and 80 ° C, preferably at temperatures between 0 ° C and 50 ° 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 required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. It can also be advantageous to have 2 or more
  • R 1 and R 2 have the meaning given above
  • R 3 have the meaning given above and
  • R 4 have the meaning given above
  • the active substances are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in forests, in
  • 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 accidentalis.
  • 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, Pemphi
  • 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 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.
  • all 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 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, and roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
  • 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 according to the customary treatment methods, e.g. by dipping, spraying, evaporating, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by means of one or more layers
  • 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
  • Possible solid carriers are: e.g. Ammonium salts and natural rock flours, such as kaolins, clays,
  • Talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, 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 and 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 phospholipids.
  • 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 compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance.
  • fungicides bactericides
  • acaricides nematicides or insecticides
  • synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • Imazalil Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Immoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Iprovalicarb, Irumamycin, Isoprothiolan, Isovaledione,
  • Kasugamycin, Kresoxim-methyl, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-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, picoxystrobin, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone,
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, dioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutichl, triazoxid, triazoxid, triazoxide, triazoxide
  • Tridemo ⁇ h Trifloxystrobin, triflumizole, triforin, triticonazole,
  • Fenamiphos Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate,
  • Fipronil Fluazuron, Flubrocythrinate, Flucycloxuron, Flucythrinate, Flufenoxuron, Flumethrin, Flutenzine, Fluvalinate, Fonophos, Fosmethilan, Fosthiazate, Fubfenprox, Furathiocarb,
  • Halofenozide HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
  • Metharhilicium flavoviride methidathione, methiocarb, methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, mübemycin, monocrotophos,
  • Paecilomyces fumosoroseus Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A,
  • Pirimiphos M Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothoat, Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridathion, Pyrimidifen, Pyriproxyfen,
  • Tefluthrin Tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, tetradifon, thetacypermethrin, thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, triodicarb, thiofanox, thuringienshrin, tri Triflumuron, trimethacarb,
  • the active compounds according to the invention can also 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.
  • 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.
  • 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 crossbreeding or protoplast fusion are treated.
  • transgenes are
  • Plants and plant varieties that have been obtained by genetic engineering methods, possibly in combination with conventional methods (Genetic Modified Organisms) and their parts treated.
  • Genetic Modified Organisms Geneous Modified Organisms
  • 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 grown both 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.
  • 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 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 harvested products , higher shelf life and / or workability of the harvested 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,
  • transgenic plants Bacteria and / or viruses and an increased tolerance of the plants to certain herbicidal active ingredients.
  • 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.
  • Bt plants As traits, special features are raised 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 Cry ⁇ A (a), Cry ⁇ A (b), Cry ⁇ A (c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and their combinations) are produced in the plants (hereinafter "Bt plants”).
  • Bt plants As properties
  • Traits are also emphasized in particular the increased defense of plants against fungi, bacteria and viruses through 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 herbicides
  • Active substances for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (e.g. "PAT” gene).
  • the genes imparting the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants. Examples of “Bt plants” include corn, cotton, soy and potato, which are among the
  • YIELD GARD® e.g. corn, cotton, soy
  • KnockOut® e.g. corn
  • StarLink® e.g. corn
  • Bollgard® cotton
  • Nucotn® cotton
  • NewLeaf® potato
  • herbicide-tolerant plants are maize varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready® (tolerance to glyphosate e.g. maize,
  • the herbicide-resistant plants include the varieties sold under the name Clearfield® (e.g. maize). Of course, these apply
  • 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, space mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas.
  • animal parasites ectoparasites
  • tick ticks leather ticks
  • space mites space mites
  • running 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.
  • Siphonaptrida for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
  • Pulex spp. From the order of the Siphonaptrida, for example Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
  • Heteropterida for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectolich spp., Pod ., 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, 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. By fighting these arthropods, death traps and
  • 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, watering, drenching, granules, pastes, boluses, the feed-through method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal Application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), des
  • 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.
  • insects may be mentioned by way of example and preferably, but without limitation:
  • Lyctus pubescens Trogoxylon aequale, Minthes rugicollis, Xyleborus 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.
  • 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:
  • Lumber wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles,
  • 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.
  • formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solution or
  • Diluents Diluents, emulsifiers, dispersants and / or binders or fixatives, Water repellants, optionally desiccants and UV stabilizers and optionally dyes and pigments as well as other processing aids.
  • insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active ingredient according to the invention in a concentration of
  • 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.
  • the organic chemical solvents used are preferably oily or oily ones
  • Solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, are used.
  • 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.
  • 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 above 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 is replaced by an aliphatic polar organic chemical solvent or solvent mixture.
  • 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 known organic-chemical binders are water-thinnable and / or soluble or dispersible or emulsifiable in the organic-chemical solvents used
  • Synthetic resins 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 based on a natural and / or synthetic resin are 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-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin are 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-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 with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used 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 originate from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyrphthalate, 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 or higher glycerol glycerol ether - Kolether, glycerol ester and p-toluenesulfonic acid ester.
  • phthalic acid esters such as dibutyl, dioctyl or benzyl butyrphthalate
  • phosphoric acid esters such as tributyl phosphate
  • adipic acid esters such as di- (2-ethylhexyl) adipate
  • stearates such as butyl ste
  • Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and 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.
  • 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, transfluthrin, methoxyphenoprid, methoxuronoprid, thiaclurophen
  • fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole,
  • 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.
  • barnacles such as various Lepas and Scalpellum species
  • Balanomo ⁇ ha (barnacles) such as Baianus or pollicipes species
  • heavy metals such as e.g. in bis (trialkyltin) sulfides, tri-w-butyltin laurate, tri-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 (bispyridine) - bismuth chloride, tri - «- butyltin fluoride, manganese ethylene bisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisthiocarbamate, zinc and copper salts of 2-pyridinethiol-1-oxide, bisdimethyldihyldihamidoxydiaminodiaminodiaminodiimide, bisdimethyldihoxy
  • 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 preferably:
  • Molluscicides such as 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, e.g. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
  • Antifouling paints contain algicides, fungicides, and mousicides and insecticidal active substances according to the invention, 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 pigments or dyes, which are preferably insoluble in sea water. Paints may also contain materials such as rosin to enable controlled release of the active ingredients. The paints may also contain plasticizers, modifiers affecting theological properties, and other conventional ingredients. The compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.
  • 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, etc. occurrence. To control these pests, they can be used alone or in combination with other active ingredients and auxiliaries in household insecticide products.
  • Sco ⁇ ionidea for example Buthus occitanus.
  • Acarina for example Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimides for Dinaematophago, Dermatophago.
  • Opiliones e.g. Pseudosco ⁇ iones chelifer, Pseudosco ⁇ iones cheiridium, Opiliones phalangium.
  • Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp.
  • Psocoptera for example Lepinatus spp., Liposcelis spp.
  • Coleptera for example Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
  • 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.
  • Rhodinus prolixus Triatoma infestans.
  • Classes of insecticides are used in aerosols, non-pressurized sprays, e.g. pump and atomizer sprays, automatic fog machines, foggels, foams, gels, vaporizer products with vaporizer plates made of cellulose or plastic, liquid vaporizers, gel and membrane vaporizers, propeller-driven vaporizers, energy-free or passive evaporation systems, moth papers Bags, moth bags and moth gels, as granules or dusts, in lures or bait stations ..
  • the reaction solution is poured onto pH7 buffer and extracted 3 times with ethyl acetate.
  • the organic phase is dried and concentrated.
  • the residue is dissolved in 20 ml of methanol, mixed with 6 ml of concentrated sodium hydroxide solution and stirred at room temperature for 1 hour. It is poured onto water and the pH is adjusted to pH7 with concentrated hydrochloric acid. It is extracted 3 times with ethyl acetate.
  • the organic phase is dried and concentrated.
  • Benzyltrimethylammonium hydroxide 50% solution in methanol, 10 g; 0.06M is slowly added dropwise to a mixture of 2,5-dimethylphenol (60 g; 0.491M) and acrylonitrile (156.9 g; 2.957M) at -10 ° C ) too.
  • the mixture is slowly brought to room temperature, then refluxed for 3 days and concentrated. The residue is washed with dilute saline and extracted with chloroform.
  • the crude product B1 (50 g, 0.2026M) is added dropwise to the rapidly stirred polyphosphoric acid (84%, 1028 g) at 180-185 ° C. and kept at this temperature for 2.5 h.
  • the hot reaction mixture is poured onto ice water and extracted with chloroform.
  • the compound Dl (16.0 g, 0.084M), dissolved in 150 ml of anhydrous chloroform, is mixed with a spatula tip of aluminum chloride at 0 ° C., then bromine (4.32 ml; 0.0839M); the temperature is kept below 4 ° C during the addition. The mixture is then stirred at room temperature for 1 h, water is added and the mixture is extracted with chloroform.
  • the compound El (18.0 g, 0.07 IM) is dissolved in 200 ml of anhydrous THF, cooled to -70 ° C. under argon, with n-butyllithium (15% in hexane, 46.22 ml; 0.075M) added dropwise, stirred at - 70 ° C for 1 h and then poured onto dry ice. After 8 h, water is added, the mixture is acidified with dilute hydrochloric acid and the solid is filtered off with suction.
  • Morpholine (86 g; 0.987M) and formaldehyde (35% solution in water, 86 g; IM) in 250 ml isopropanol are boiled under reflux for 10 min, cooled to 0 ° C and with a solution of 3-methyl pyrocatechol (124 g ; IM) added dropwise in 400 ml of isopropanol within 15 min.
  • the reaction mixture is boiled under reflux for 15 min, cooled, concentrated under vacuum and the residue is recrystallized from isopropanol.
  • the compound B2 (117.44 g; 0.526M) is dissolved in 2 l of ethanol, 48 g of 10 gusty palladium on carbon are added and the mixture is hydrogenated at 80 ° C. overnight under 60 bar of hydrogen.
  • the hydrogenation mixture is freed from the catalyst by means of filtration over kieselguhr, the filtrate is concentrated in vacuo, the residue is dissolved in chloroform and washed successively with dilute hydrochloric acid and saturated sodium chloride solution, dried and concentrated in vacuo. 34.02 g of compound C2 (purity 85% according to LC / MS) are obtained.
  • Phosphate buffer solution acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.
  • the calibration was carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the
  • the lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
  • 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% means that the number of galls on the treated plants of the untreated
  • Example B the compound of preparation example No. 1-52 shows an exemplary active ingredient concentration of 20 ppm and a kill of 100% after 14 days.
  • Example B the compound of preparation example No. 1-52 shows an exemplary active ingredient concentration of 20 ppm and a kill of 100% after 14 days.
  • 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 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.
  • the compound of preparation example No. 1-82 shows a kill of 100% after 7 days at an exemplary active ingredient concentration of 1000 ppm.
  • 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 compounds of Preparation Examples Nos. 1-48, 1-54, 1-60, 1-61, 1-63, 1-65, 1-66, 1-69, 1-82 show an exemplary active ingredient concentration of 1,000 ppm a 100% kill after 7 days.
  • 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.
  • 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 effect 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 No. 1-4 at an exemplary active ingredient concentration of 100 ppm shows a kill of 100% after 7 days.
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted to the desired concentrations with a 0.01% lecithin solution.
  • Mosquito larvae (Aedes aegypti) are placed in the active ingredient preparation of the desired concentration.
  • the effect on the larvae is determined. 100% means that all animals showed severe symptoms or were killed; 0% means that no animals have been harmed.
  • the compound of preparation example No. 1-19 shows a kill of 100% at an exemplary active ingredient concentration of 17 ppm
  • Test animals Lucilia cuprina larvae
  • test tube containing 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 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)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

L'invention concerne de nouveaux dérivés d'amide hétérocycliques de formule (I), dans laquelle R<1>, R<2>, R<3> et R<4> ont la signification susmentionnée. La présente invention porte également sur un procédé de préparation associé et sur leur utilisation comme produit phytosanitaire.
EP02740745A 2001-07-06 2002-06-24 Derives d'amide heterocycliques et leur utilisation comme pesticides Withdrawn EP1417178A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10132896 2001-07-06
DE10132896A DE10132896A1 (de) 2001-07-06 2001-07-06 Heterocyclische Amidderivate
PCT/EP2002/006940 WO2003004464A2 (fr) 2001-07-06 2002-06-24 Derives d'amide heterocycliques

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EP1417178A2 true EP1417178A2 (fr) 2004-05-12

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US (1) US20040248958A1 (fr)
EP (1) EP1417178A2 (fr)
JP (1) JP2004533484A (fr)
KR (1) KR20040012962A (fr)
CN (1) CN100374424C (fr)
AU (1) AU2002314190B2 (fr)
BR (1) BR0210841A (fr)
DE (1) DE10132896A1 (fr)
MX (1) MXPA03012073A (fr)
WO (1) WO2003004464A2 (fr)

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UA82875C2 (en) * 2003-04-30 2008-05-26 Insecticidal (dihalopropenyl) phenylalkyl substituted dihydrobenzofuran and dihydrobenzopyran derivatives and method for controlling insects
DE102007002410A1 (de) * 2007-01-17 2008-07-24 Merck Patent Gmbh Synthese von Chromanderivaten
RU2571076C2 (ru) * 2010-11-03 2015-12-20 ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи Пестицидная композиция
CA2852776A1 (fr) * 2011-10-26 2013-05-02 Dow Agrosciences Llc Compositions pesticides et procedes associes
WO2013174843A1 (fr) * 2012-05-24 2013-11-28 Bayer Cropscience Ag Thioamides d'acide n-(tétrazol-5-yl)- et n-(triazol-5-yl)aryle carboxylique et leur utilisation comme herbicides

Citations (1)

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Publication number Priority date Publication date Assignee Title
EP0253084A2 (fr) * 1986-05-13 1988-01-20 F. Hoffmann-La Roche Ag Sels d'imidazolium 1,3-disubstitués

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Publication number Priority date Publication date Assignee Title
US3686110A (en) * 1970-02-27 1972-08-22 Meuch & Co Inc 1-oxybenzimidazoles
GB1401284A (en) * 1971-11-13 1975-07-16 Beecham Group Ltd Imidazole insecticides
BE793718A (fr) * 1972-01-07 1973-07-05 Merck & Co Inc Aminobenzimidazoles
IL85556A (en) * 1987-03-05 1994-06-24 May & Baker Ltd Method for exterminating pests using a history of 2-phenylimidazole, certain compounds of this type and a process for their preparation
DK59888A (da) * 1987-03-20 1988-09-21 Hoffmann La Roche Imidazolderivater
HU207051B (en) * 1987-12-30 1993-03-01 Chinoin Gyogyszer Es Vegyeszet Process for producing 4-chloro-3-sulfamoylbenzoic acid hydrazides and pharmaceutical compositions comprising such compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0253084A2 (fr) * 1986-05-13 1988-01-20 F. Hoffmann-La Roche Ag Sels d'imidazolium 1,3-disubstitués

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO03004464A3 *

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CN100374424C (zh) 2008-03-12
MXPA03012073A (es) 2004-03-26
AU2002314190B2 (en) 2007-06-28
JP2004533484A (ja) 2004-11-04
WO2003004464A2 (fr) 2003-01-16
US20040248958A1 (en) 2004-12-09
KR20040012962A (ko) 2004-02-11
WO2003004464A3 (fr) 2003-06-05
WO2003004464A8 (fr) 2004-03-04
BR0210841A (pt) 2004-07-13
DE10132896A1 (de) 2003-01-16
CN1551870A (zh) 2004-12-01

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