EP1474389A2 - Delta1-pyrrolines - Google Patents

Delta1-pyrrolines

Info

Publication number
EP1474389A2
EP1474389A2 EP03734679A EP03734679A EP1474389A2 EP 1474389 A2 EP1474389 A2 EP 1474389A2 EP 03734679 A EP03734679 A EP 03734679A EP 03734679 A EP03734679 A EP 03734679A EP 1474389 A2 EP1474389 A2 EP 1474389A2
Authority
EP
European Patent Office
Prior art keywords
butyl
formula
spp
fluorine
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03734679A
Other languages
German (de)
English (en)
Inventor
Martin FÜSSLEIN
Thomas Seitz
Johannes Rudolf Jansen
Udo Kraatz
Christoph Erdelen
Andreas Turberg
Olaf Hansen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Bayer CropScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1474389A2 publication Critical patent/EP1474389A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • 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
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

  • the present invention relates to new ⁇ ⁇ pyrrolines, several ner drives for their preparation and their use as pesticides.
  • R 1 represents halogen or methyl
  • R 2 represents hydrogen or halogen
  • R 3 , R 4 , R 5 and R 6 independently of one another represent hydrogen, halogen, CrC 4 alkyl or C 1 -C 4 alkoxy,
  • X represents O (oxygen) or S (sulfur),
  • Y represents CR, 1 i 0 ⁇ or ⁇ (nitrogen),
  • R 7 , R 8 , R 9 and R 10 independently of one another for hydrogen, halogen, roitro, CC 4 - alkyl, CrC 4 -haloalkyl, -C-C 4 -haloalkoxy, C 1 -C 4 -haloalkylthio,
  • R 7 and R 8 or R 8 and R 9 or R 9 and R 10 together form a further saturated or unsaturated 5- or 6-membered ring, which in turn is one or two heteroatom groups from the series N, O, S or SO 2 may contain
  • n 0 or 1
  • R, ⁇ represents -CC alkyl or morpholino
  • R, 12 represents C 1 -C 4 alkyl or phenyl which is monosubstituted to tetrasubstituted, identically or differently, by halogen, CrC 4 alkyl or C 1 -C 4 alkoxy,
  • R 13 represents hydrogen or CC 4 alkyl.
  • the compounds of the formula (I) can optionally be present as geometric and / or optical isomers or regioisomers or their isomer mixtures in different compositions. Both the pure isomers and the isomer mixtures are claimed according to the invention.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, Y, R 7 , R 8 and R 9 have the meanings given above,
  • the compounds of the formula (I) according to the invention have very good insecticidal properties and can be used both in crop protection and in material protection to control unwanted pests, such as insects.
  • ⁇ ⁇ pyrrolines according to the invention are generally defined by the formula (I).
  • R 1 represents fluorine, chlorine, bromine or methyl
  • R 2 represents hydrogen, fluorine or chlorine
  • R 3 , R 4 , R 5 and R 6 independently of one another for hydrogen, fluorine, chlorine, bromine, Ci
  • X represents O (oxygen) or S (sulfur),
  • Y represents CR 10 or N (nitrogen)
  • R 7 , R, R and R 10 independently of one another are hydrogen, fluorine, chlorine, bromine, nitro, C 1 -C 4 -alkyl; C 1 -C -haloalkyl, CrC -haloalkoxy, -C-C 4 - haloalkylthio, each with 1 to 9 fluorine, chlorine and / or bromine atoms; C 1 -C 4 alkoxycarbonyl, phenyl, - (CH 2 ) m -SO 2 R ⁇ or -SO 2 NR 12 R 13 , or either R 7 and R 8 or R 8 and R 9 or R 9 and R 10 together form a further saturated or unsaturated 5- or 6-membered ring which again contain one or two heteroatom groups from the series N, O, S or SO 2 ,
  • n 0 or 1
  • R 11 represents C 1 -C 4 -all yl or morpholino
  • R 12 represents C 1 -C 4 -alkyl or phenyl which is optionally mono- to tetrasubstituted, identically or differently, by fluorine, chlorine, bromine, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,
  • R 13 represents hydrogen or -CC 4 alkyl.
  • R 1 represents fluorine, chlorine or methyl
  • R 2 represents hydrogen, fluorine or chlorine
  • R 3 and R 6 independently of one another for hydrogen, fluorine, chlorine, methyl, ethyl, n-
  • R 4 and R 5 each represent hydrogen
  • X represents O (oxygen) or S (sulfur),
  • Y represents CR 10 or N (nitrogen)
  • R 7 , R 8 , R 9 and R 10 independently of one another for hydrogen, fluorine, chlorine, bromine,
  • n 0 or 1
  • R 11 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl or
  • R 12 is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl or optionally one to three times, identical or different, by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-
  • R 13 represents hydrogen or methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl.
  • R 1 represents fluorine, chlorine or methyl
  • R 2 represents hydrogen, fluorine or chlorine
  • R 3 represents hydrogen, fluorine, chlorine, methyl, methoxy or ethoxy
  • R 4 , R 5 and R 6 each represent hydrogen
  • X stands for O (oxygen)
  • Y represents CR 10 or N (nitrogen)
  • R 7 , R 8 , R 9 and R 10 independently of one another for hydrogen, fluorine, chlorine, bromine,
  • ⁇ ⁇ pyrrolines of the formula (I) in which R 1 and R 2 are fluorine are also preferred.
  • ⁇ ⁇ pyrrolines of the formula (I) in which Y is CR 10 , particularly preferably in which Y is CH.
  • ⁇ ⁇ pyrrolines of the formula (I) in which R 3 represents hydrogen or fluorine. Also preferred are ⁇ ⁇ pyrrolines of the formula (I) in which X represents O (oxygen).
  • ⁇ ⁇ pyrroles of the formula (I) in which X represents S (sulfur).
  • ⁇ 1 -pyrrolines of the formula (I) in which R 4 and R 5 are hydrogen are also preferred.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, Y, R 7 , R 8 and R 9 have the meanings given above.
  • Saturated hydrocarbon residues such as alkyl can be straight-chain or branched as far as possible.
  • Formula (II) provides a general definition of the compounds required as starting materials when carrying out process (A) according to the invention.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, Y, R 7 , R 8 and R 9 are particularly preferred preferred or very particularly preferred for those meanings which have already been mentioned as preferred, particularly preferred etc. in connection with the description of the substances of the formula (I) according to the invention for these radicals.
  • the compounds of formula (IT) are new. They also have insecticides
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 have the meanings given above,
  • a diluent for example toluene and dimethylformamide
  • an acid binder for example 1,8-diazabicyclo [5.4.0] undec-7-ene, DBU
  • ⁇ 1 -pyrrolines required as starting materials when carrying out process (a) according to the invention are generally defined by the formula (m).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are preferred, particularly preferred or very particularly preferred for those meanings which are already associated with the Description of the substances of the formula (I) according to the invention for these radicals as being preferred, particularly preferred etc. have been mentioned.
  • ⁇ ⁇ pyrrolines of the formula (III) are known and / or can be prepared by known processes (cf. WO 98/22438 and DE10047109.9).
  • Formula (V) provides a general definition of the ⁇ 1 -pyrrolines required as starting materials when carrying out process (b) according to the invention.
  • R 1, R 2, R 3, R 4, R 5 and R 6 are preferred, particularly preferred and very particularly preferably has those meanings which have already in connection with
  • ⁇ 1 -pyrrolines of the formula (N) are known and / or can be prepared by known Ner processes (cf. WO 98/22438 and DE10047109.9).
  • ⁇ 1 -pyrrolines of the formula (N) can also be prepared by
  • R 14 has the meanings given above,
  • a diluent e.g. ethylene glycol dimethyl ether
  • Formula (TV) provides a general definition of the aniline derivatives required as starting materials when carrying out processes (a) and (b) according to the invention.
  • X, Y, R 7 , R 8 and R 9 are preferred, particularly preferred or very particularly preferred, for those meanings which are already known for these radicals in connection with the description of the substances of the formula (I) according to the invention preferred, particularly preferred, etc. were mentioned.
  • Aniline derivatives of the formula (IV) are known and / or can be prepared by known processes.
  • Aniline derivatives of the formula (IV) can be prepared, for example, from the analog nitroaryl compounds (cf. WO 99/32436).
  • the reduction of the nitro group to the amine is carried out either by using a metal catalyst (eg Ni, Pd, Pt) in the presence of hydrogen or a hydride donor (eg formate, cyclohexadiene, borohydride) (cf. Rylander: Hydrogenation Methods; Academic Press, London 1985).
  • Nitroaryls can also be obtained directly by using a strong hydride source (e.g.
  • LiAIH 4 see Seyden-Penne: Reductions by the Alumino- and Borohydrides in Organic Synthesis; VCH publishers, New York 1991) or by using a nuvalent metal (e.g. Fe, Sn, Ca) may be reduced in the presence of an acid.
  • a nuvalent metal e.g. Fe, Sn, Ca
  • the nitroaryl compounds are obtained by known processes (cf. March. Advanced Organic Chemistry, 3 .tau..sub.d Ed, John Wiley, New York 1985th).
  • Suitable diluents for carrying out process (A) according to the invention are all customary inert, organic solvents.
  • Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles, such as acetonitrile, propionitrile
  • Acetone, dimethoxyethane, dioxane, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethanol, toluene are particularly preferably used or optionally mixtures of these diluents with water.
  • Toluene or benzene are particularly preferably used.
  • reaction temperatures can be varied within a substantial range when carrying out process (A) according to the invention.
  • temperatures between 0 ° C and 140 ° C, preferably between 20 ° C and 120 ° C, particularly preferably between 80 ° C and 120 ° C.
  • the procedure is generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.
  • the processing takes place according to usual methods. In general, the procedure is such that the reaction mixture is diluted with an organic solvent and extracted. The organic phase is washed, dried, filtered and concentrated. The residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R ⁇ have the meanings given above,
  • Chloroform Chloroform; Alcohols such as methanol, ethanol, propanol; Nitriles such as acetonitrile; Esters such as methyl acetate or ethyl acetate. It is particularly preferred to use aliphatic hydrocarbons, such as hexane or heptane, and alcohols, such as methanol or propanol, very particularly preferably n-heptane and isopropanol or mixtures of these. In general, temperatures between 10 ° C and 60 ° C, preferably between 10 ° C and 40 ° C, particularly preferably at room temperature. The ⁇ -configured enantiomers obtained in this way are then used as starting materials for processes (a) or (c).
  • the active ingredients are suitable for protecting plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture , occur in forests, gardens and leisure facilities, in the protection of stored goods and materials, and in the hygiene sector. They can preferably be used as pesticides. You are against normally sensitive and resistant species and effective against all or individual stages of development.
  • the pests mentioned above include:
  • Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Thysanura e.g. Lepisma saccharina.
  • Collembola e.g. Onychiurus armatus.
  • Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
  • Leucophaea maderae, Blattella germanica From the order of the Dermaptera e.g. Forficula auricularia.
  • Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
  • Thysanoptera e.g. Hercmothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
  • Conoderus spp. Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Diptera e.g. Aedes spp., Anopheles spp., Culex spp.
  • Drosophila melanogaster Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tabanus spp.
  • Tannia spp. Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp.
  • Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.
  • Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.
  • Arachnida e.g. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallfnae, Eriophyes ribis, Phyllocoptrata oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., I. Chorioptes spp., Sarcoptes spp.,
  • Plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Tripusichppspp., Xiphinema spp.
  • the compounds of the formula (I) according to the invention are distinguished in particular by an excellent action against caterpillars, beetle larvae, spider mites, aphids and leaf miners.
  • the substances according to the invention also show a very good duration of action, e.g. against the caterpillars of the cotton capsule worm (Heliothis virescens) or the caterpillars of the army worm (Spodoptera frugiperda).
  • 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 are understood 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, cargo bodies, fruits and seeds and roots,
  • Bulbs and rhizomes are listed.
  • the plant parts also include harvest good as well as 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, spraying, vaporizing, atomizing, scattering, spreading, injecting and, in the case of propagation material, in particular in the case of seeds, furthermore by single- or multi-layer coating.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric 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 xylol 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 and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • alcohols such as butanol or glycol and their ethers and esters
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
  • strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • solid carriers e.g. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: 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. nonionic 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.
  • nonionic 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
  • 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
  • Active ingredient 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 activity spectrum or to prevent the development of resistance. In many cases you get it synergistic effects, ie the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • Calcium polysulphide carpropamid, capsimycin, captafol, captan, carbendazim, carbonyl xin, carvone, chinomethionat (Quinomethionat) Chlobenthiazon, chlorfenazole, chlorides roneb, chloropicrin, chlorothalonil, chlozolinate, Clozylacon, Cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,
  • Debacarb dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, dmiconazol, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dorphianzolone, epithidololone, epithodonolone, epithodonolone, epithodolone, epithodolone, epithodolone, epithodolone, epithidylolone, epithodolone, epidonylolodolone, epidonylolodolone, epidonylolodolone, epidonylolodolone, epidonylolodolone, epidonylolodolone, epi
  • Mancopper Mancozeb, Maneb, Meferimzone, Mepampyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin, Nickel-dimethylditbiocararbamat, Nitrot
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, dioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutichl, triazoxid, triazoxid, triazoxide, triazoxide
  • Tridemorph Trifloxystrobin, triflumizole, triforin, triticonazole, uiiiconazole,
  • Validamycin A, vinclozolin, viniconazole, zarilamide, zineb, ziram and Dagger G OK-8705, OK-8801, ⁇ - (l, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1H- 1, 2,4- triazole-1-ethanol, - (2,4-dichlorophenyl) -ß-fluoro- ⁇ -propyl-1H-1, 2,4-triazole-1-ethanol, ⁇ - (2,4-dichlorophenyl) -ß-methoxy - -methyl- 1 H- 1, 2,4-triazol-1-ethanol, ⁇ - (5-methyl-1, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] - methylene] -IH-1, 2,4-triazole-1-ethanol,
  • Methantetrathiol sodium salt Methyl 1 - (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) - 1Himidazole-5-carboxylate, methyl-N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl ) -DL-alaninate, methyl-N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate, N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo -3-furanyl) acetamide, N- (2,6-dimethylphenyl) -2-memoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
  • N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide N- (4-cyclohexylphenyl) -1, 4,5,6-tetrahydro-2-pyrimidinamine, N- (4-hexylphenyl ) - 1, 4,5,6-tetrahydro-2-pyrimidinamine, N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide, N- (6 methoxy) -3-pyridyl) cyclopropanecarboxamide,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Chlovaporthrin, Chromafenozide, Cis-Resmethrin,
  • Fenoxycarb fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenthion,
  • Fenvalerate fipronil, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,
  • Flufenoxuron Flumethrin, Flupyrazofos, Flutenzine, Fluvalinate, Fonophos,
  • Halofenozide HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
  • Metharhilic flavoviride methidathione, methiocarb, methoprene, methomyl,
  • Methoxyfenozide Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Milbe mycin, Monocrotophos,
  • Tefluthrin Temephos, Temivinphos, Terbufos, Tetrachlorvinphos, Tetradifon, Thetacypermetlirin, Thiacloprid, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate, Thiodicarb, Thiofanox, Thocythrine, Thuringythrin, Thuringythrin
  • Triarathenes triazamates, triazophos, triazuron, trichlophenidines, trichlorfon,
  • 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 compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in mixtures with inhibitors which break down the active compound after use in the environment of the plant on which
  • 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 xmd storage pests, the active ingredient is characterized by an excellent residual effect 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.
  • transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetic modified organisms) and their parts are treated.
  • 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 by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- and genotypes.
  • the treatment according to the invention can also cause superadditive (“synergistic”) effects.
  • superadditive for example, reduced application rates and / or extensions of the Spectrum of activity and / or an enhancement of the effect of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher crop yields , higher quality and / or higher
  • Nutritional value of the harvest products higher shelf life and / or workability of the harvested products possible, which go beyond the expected effects.
  • the preferred transgenic (genetically preserved) 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, acceleration of 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, bacteria and / or Viruses and an increased tolerance of the plants to certain herbicidal agents.
  • transgenic plants are the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes , Cotton, tobacco and rapeseed are highlighted.
  • the properties are particularly emphasized of the plants' increased defense against insects, arachnids, nematodes and snails due to toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (e.g. by the genes
  • Cry ⁇ A (a), CryIA (b), CrylA (c), CryLLA, CrylllA, Cryi ⁇ B2 3 Cry9c Cry2Ab, Cry3Bb and CryLF and their combinations) are produced in the plants (in following "Bt plants”).
  • SAR systemic acquired resistance
  • systemin phytoalexins
  • elicitors and resistance genes and correspondingly expressed proteins and toxins are also particularly emphasized as properties (“traits”)
  • the traits that are particularly emphasized are the increased ones
  • Tolerance of the plants to certain herbicidal active ingredients for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (e.g. "PAT" gene).
  • the genes which impart the desired properties can also occur in combinations with one another in the transgenic plants. Examples of “Bt plants” are maize, cotton, soybean and
  • Potato varieties named under the trade names YIELD GARD® e.g. corn, cotton, soy
  • KnockOut® e.g. corn
  • StarLink® e.g. corn
  • Bollgard® cotton
  • Nucotn® cotton
  • NewLeaf® potato
  • Examples of 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, soy), Liberty Link® (tolerance to phosphinotricin, e.g.
  • the herbicide-resistant plants include the varieties sold under the name Clearfield® (e.g. maize).
  • the active substances 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 shield ticks, leather ticks, space mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas.
  • animal parasites ectoparasites
  • parasitic fly larvae lice, hair lice, Featherlings and fleas.
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp. , Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
  • the active compounds of the formula (I) according to the invention are also suitable for combating 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 Hamsters, guinea pigs, rats and
  • Infest mice By combating these arthropods, deaths and reduced performance (in the case of meat, milk, wool, skins, eggs, honey, etc.) are to be reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry.
  • the active ingredients 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 (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, through nasal
  • 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:
  • Kalotermes flavicolhs 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.
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative,
  • Water repellants optionally desiccants and UV stabilizers and optionally dyes and pigments and 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 solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
  • Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
  • Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, turpentine oil xmd are advantageous Like. Used.
  • liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or locker oil and / or monochloronaphthalene, preferably ⁇ -monochloronaphthalene, are used.
  • the organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flame point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • Solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture 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 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, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as inden-coumarone resin, silicone resin, drying vegetable and / or drying oils and or physically drying binders based on a natural and / or synthetic resin used.
  • binders consisting of or containing an acrylate resin, a vinyl resin, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as inden-cou
  • 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 fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
  • the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycerol or glycerol ether - Kolether, glycerol ester and p-toluenesulfonic acid ester.
  • phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate
  • phosphoric acid esters such as tributyl phosphate
  • adipic acid esters such as di- (2-ethylhexyl) adipate
  • Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone. Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
  • polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
  • Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
  • a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
  • the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.
  • 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 chlorpyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin,
  • fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole,
  • the compounds according to the invention can be used to protect objects, in particular hulls, sieves, nets, structures,
  • Scalpellum species or by species from the group Balanomorpha (barnacles), such as Baianus or Pollicipes species, increases the frictional resistance of ships and, as a result, leads to a significant increase in operating costs due to increased energy consumption and, in addition, frequent dry dock stays.
  • heavy metals such as bis (trialkyltin) sulfides, tri - butyltin laurate, tri-n-butyltin chloride, copper (I) oxide, triethyltin chloride can be used , Tri-n-butyl (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, molybdenum disulfide, antimony oxide, polymeric butyl titanate, phenyl (bispyridine) bismuth chloride, tri- butyltin fluoride, manganese ethylene bisthiocarbamate, zinc dimethylamidithamate, zinc dimethylamidithiamate Zinc and copper salts of 2-pyridine-thiol-1-oxide, bisdimethyldithiocarbamoylzirikemylenbistbiocarbamate, zinc oxide, Copper (I) ethylene bisdithiocarbamate, copper
  • the ready-to-use antifouling paints can also be used if necessary
  • active ingredients preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients.
  • 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 further contain the usual ingredients such as e.g. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
  • Antifouling paints contain, in addition to the algicidal, fungicidal, moUuscicidal and insecticidal active compounds 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, especially in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile Rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumens, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and ninyl 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 that affect rheological 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 rooms, such as For example, apartments, factories, offices, vehicle cabins, etc. occur.
  • animal pests in particular insects, arachnids and mites, which live in closed rooms, such as For example, apartments, factories, offices, vehicle cabins, etc. occur.
  • insects in particular insects, arachnids and mites
  • closed rooms such as For example, apartments, factories, offices, vehicle cabins, etc. occur.
  • insects in particular insects, arachnids and mites, which live in closed rooms, such as For example, apartments, factories, offices, vehicle cabins, etc. occur.
  • active ingredients and auxiliaries in household insecticide products. They are effective against sensitive and resistant species as well as against all stages of development.
  • Dermanyssus gallinae Glyciphagus domesticus, Ornithodorus moubat, Rhipi- cephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissfmus, Dermatophagoides forinae.
  • Opiliones e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
  • the Isopoda e.g. Oniscus asellus, Porcellio scaber.
  • Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp.
  • Lepismodes inquilinus From the order of the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brannea, Periplaneta Füliginosa,
  • Saltatoria e.g. Acheta domesticus.
  • Dermaptera e.g. Forficula auricularia.
  • Aedes aegypti Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
  • Lepidoptera e.g. Acliroia grisella, Galleria mellonella, Plodia interpunctella, 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 xxmbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • sprayless spray agents e.g. Pump and atomizer sprays, fog machines, foggers, 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, moth bags and
  • Moth angels as granules or dusts, in lures or bait stations.
  • triphenylphosphine 995 mg are dissolved in 15 ml of toluene under argon. A solution of 156 mg of palladium acetate in 5 ml of toluene is added. After 10 minutes, the toluene solution of 0.89 g of 2- (4-bromophenyl) -5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrole, 0.35 g of 2-hydroxy-4 is added -fluoraniline xmd 0.5 g DBU, puts under carbon monoxide and warms to 95 ° C for about 20 h. Then aqueous citric acid and sodium chloride are added and the mixture is extracted with ethyl acetate. The organic phase is dried over sodium sulfate, filtered and concentrated. The
  • the crude product is purified by chromatography on silica gel (mobile phase: ethyl acetate / cyclohexane 1: 1).
  • the determination is carried out in the acidic range at pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile.
  • the values are marked in the tables with a).
  • the determination is carried out in the neutral range at pH 7.5 with 0.01 molar aqueous
  • the calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms), the logP values of which 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 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 are populated with Heliothis armigera 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.
  • 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 xmd 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 xmd 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 corresponds to that of the untreated control.
  • 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 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.
  • 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 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.
  • 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 ingredient 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.
  • 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 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.
  • 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.
  • 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.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Amount of emulsifier and dilute the concentrate with water to the desired concentration is required.
  • the active ingredient preparation is poured onto the floor.
  • the concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (mg / 1). You fill the bottom in 0.25 1 pots and let them stand at 20 ° C.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are treated by being dipped into the preparation of active compound of the desired concentration xmd filled with the tobacco bud caterpillar Heliothis virescens 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyrrole Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

La présente invention concerne de nouvelles DELTA 1-pyrrolines de formule (I), dans laquelle R1, R2, R3, R4, R5, R6, X, Y, R7, R8 et R9 ont les significations données dans la description. La présente invention concerne également plusieurs procédés pour produire ces composés et leur utilisation pour lutter contre des parasites, ainsi que de nouveaux produits intermédiaires et des procédés pour les produire.
EP03734679A 2002-02-01 2003-01-21 Delta1-pyrrolines Withdrawn EP1474389A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10204115 2002-02-01
DE10204115A DE10204115A1 (de) 2002-02-01 2002-02-01 DELTA·1·-Pyrroline
PCT/EP2003/000516 WO2003064385A2 (fr) 2002-02-01 2003-01-21 Delta1-pyrrolines

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EP1474389A2 true EP1474389A2 (fr) 2004-11-10

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US (1) US20050124497A1 (fr)
EP (1) EP1474389A2 (fr)
JP (1) JP2005521666A (fr)
KR (1) KR20040083482A (fr)
CN (1) CN1646489A (fr)
BR (1) BR0307341A (fr)
CA (1) CA2474594A1 (fr)
DE (1) DE10204115A1 (fr)
MX (1) MXPA04007359A (fr)
NZ (1) NZ534388A (fr)
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ZA (1) ZA200405969B (fr)

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TWI319387B (en) * 2002-04-05 2010-01-11 Astrazeneca Ab Benzamide derivatives
DE102004017435A1 (de) * 2004-04-08 2005-11-03 Bayer Cropscience Ag Annellierte Chinolinderivate
GB0521244D0 (en) * 2005-10-19 2005-11-30 Astrazeneca Ab Benzamide compounds
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US20050124497A1 (en) 2005-06-09
JP2005521666A (ja) 2005-07-21
DE10204115A1 (de) 2003-08-07
CA2474594A1 (fr) 2003-08-07
WO2003064385A2 (fr) 2003-08-07
MXPA04007359A (es) 2004-11-26
WO2003064385A3 (fr) 2003-10-02
ZA200405969B (en) 2006-02-22
NZ534388A (en) 2006-05-26
CN1646489A (zh) 2005-07-27
BR0307341A (pt) 2004-12-21

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