EP2493881A1 - Novel solid form of 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5h)-one - Google Patents

Novel solid form of 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5h)-one

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Publication number
EP2493881A1
EP2493881A1 EP10766065A EP10766065A EP2493881A1 EP 2493881 A1 EP2493881 A1 EP 2493881A1 EP 10766065 A EP10766065 A EP 10766065A EP 10766065 A EP10766065 A EP 10766065A EP 2493881 A1 EP2493881 A1 EP 2493881A1
Authority
EP
European Patent Office
Prior art keywords
spp
methyl
amino
furan
solid form
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Withdrawn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
EP10766065A
Other languages
German (de)
French (fr)
Inventor
Britta Olenik
Robert Velten
Peter Jeschke
Norbert Lui
Christian Funke
Wolfgang Wirth
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 Intellectual Property GmbH
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
Priority to EP10766065A priority Critical patent/EP2493881A1/en
Publication of EP2493881A1 publication Critical patent/EP2493881A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents

Definitions

  • the present invention relates to a novel solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one, a process for the preparation of this novel solid form and their advantageous use for the preparation of stable applications.
  • the compound in the amorphous state is highly viscous and therefore can not be converted into formulations in which the active ingredient is in solid (dry) form.
  • Such economically relevant formulations are, for example, granules, encapsulated granules, tablets, water-dispersible granules, water-dispersible tablets, water-dispersible powders or water-dispersible powders for seed treatment, dust formulations, formulations in which the active ingredient is in dispersed form, for example: suspension concentrates, oil-based suspension concentrates, Suspoemulsions, or suspension concentrates for seed treatment.
  • Formulations are, for example, economically relevant if the active ingredients to be used are particularly suitable for the preparation of formulations which require the use of grinding processes and / or if such formulations have good storage stability.
  • the invention therefore relates to the novel solid form of compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one which is characterized that she has one Melting point in the range of 65 ° C to 75 ° C, in particular a melting range of 72 ° C to 74 ° C and / or the X-ray powder diffractogram of this compound at 25 ° C and using Cu-Ka radiation (1 .540598 ⁇ ) has at least 3 characteristic signals, in particular at least 4 or 6 characteristic signals and preferably all of the following characteristic 2 ⁇ (2Theta) values:
  • characteristic signals refers to those signals (2 ⁇ (2Theta) values, Ir or Raman bands) which clearly stand out from background noise and which are characteristic of the measured compound.
  • the new solid form further has the characteristic 2 theta values of the lattice plane spacings "d" listed in Table 1.
  • the compound has a melting point in the range of 72 ° C to 74 ° C and the X-ray powder diffractogram of the new solid form has the signals shown in Figure la.
  • the new solid form of 4 - [[(6-chloro-pyridin-3-yl) -methyl] (2,2-difluoroethyl) -amino] -furan-2 (5H) -one also has the di-T e ll e 2 reproduced major Raman bands and the main IR bands listed in Table 3.
  • the major bands of the amorphous form are indicated in Tables 2 and 3, respectively.
  • Table 3 Location of the principal bands of the infrared spectrum of the known amorphous form and the new solid form
  • suspension concentrates oil-based suspension concentrates and e.g. water-dispersible granules and similar formulations for the treatment of seeds is thereby possible.
  • the compound 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form is outstandingly suitable for the preparation of Agents for combating animal pests, in particular pests found in agriculture and forestry.
  • the invention therefore also means for controlling such pests, which contain the new solid form alone or in admixture with excipients and carriers, as well as in admixture with other active ingredients.
  • the invention also includes compositions containing the compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the novel solid form.
  • compositions containing less than 20% by weight of the novel solid form, more preferably less than 15% by weight, most preferably less than 10% by weight, most preferably less than 5% by weight, most preferred less than 4, 3, 2 or 1 wt .-% of the new solid form included.
  • composition also includes formulations and uses.
  • the invention also provides processes for the preparation of agents for combating pathogens which comprise the compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -on in the new solid form.
  • the compound 4 - [[(6-chloro-pyridin-3-yl) -methyl] (2,2-difluoro-ethyl) -amino] -furan-2 (5H) -one in the new solid form can be converted in known manner into the usual formulations, such as suspension concentrates , Oil-based suspension concentrates, colloidal concentrates, dispersible concentrates, emulsifiable concentrates (emulsion concentrates), emulsion mordants, suspension mordants, granules, microgranules, suspoemulsions, water-soluble granules, water-soluble concentrates and water-dispersible granules, as well as corresponding ready-to-use formulations (so-called ready-to-use formulations).
  • suspension concentrates Oil-based suspension concentrates, colloidal concentrates, dispersible concentrates, emulsifiable concentrates (emulsion concentrates), emulsion mordants, suspension mordants, granule
  • the active compound should be present in a concentration of about 0.0001 to 90% by weight of the total mixture, i. in amounts sufficient to achieve the necessary dosage level.
  • the formulations are prepared by stretching the compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form with water, solvents and / or carriers, optionally with the use of emulsifiers and / or dispersants, and / or other excipients, such as Penetration aids.
  • suspension concentrates including those used for seed treatment
  • further adjuvants are generally added in addition to the active ingredient and an extender (water, solvent or oil).
  • an extender water, solvent or oil
  • a wetting agent is used, to stabilize the suspension in the liquid phase
  • dispersing agents are used for emulsifying the non-aqueous phase emulsifiers are used in solvent or oil-containing suspension concentrates.
  • anti-freeze agents, biocides, thickeners, dyes, spreading agents and / or receiving conveyors are incorporated.
  • the new solid compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is obtained by the method described below.
  • the compound 4 [(6-chk-yridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is described, for example, in WO 2007/115644 (Page 51, Example 1) described.
  • the resulting 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is in an amorphous state.
  • amorphous 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is dissolved in a solvent or a solvent mixture at temperatures of at least 30 ° C, preferably of at least 50 ° C, dissolved and slowly cooled until the desired crystals precipitate.
  • the amount of solvent used is chosen so that the mixture remains easy to stir during the crystallization.
  • the slow cooling takes place linearly or stepwise.
  • the cooling takes place in stages, wherein the crystallization solution is stirred at a certain temperature, preferably at about 40 ° C for several hours, preferably 2 to 20 hours, more preferably 4 to 20 hours, most preferably 4 to 16 hours before continuing be cooled until the desired crystals precipitate.
  • seed crystals are optionally added to the solution to accelerate crystallization.
  • the addition of the seed crystals can in principle be done while stirring, but then the solution must be saturated so that the seed crystals do not dissolve.
  • the seed crystals are added after stirring.
  • Suitable solvents are all solvents in which 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one dissolves.
  • Particularly suitable are halogenated hydrocarbons (eg chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene), ethers (eg ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, anisole, phenetole, cyclohexylmethyl ether, dimethyl ether, diethyl ether, dimethyl glycol diphenyl ether, dipropl ether, diisopropyl ether, di -n-butyl ether, diisobutyl ether, diisoamyl ether, ethylene glycol dimethyl ether, isopropyl eth
  • Preferred solvents are ethers, aromatic Hydrocarbons such as benzene, toluene, xylene, chlorobenzene, esters and aliphatic alcohols and mixtures thereof.
  • Particularly preferred solvents or solvent mixtures are isopropanol, toluene, methyl THF diethyl carbonate, chlorobenzene, n-butyl acetate and i-butyl acetate, n-butanol, ethanol, ethyl malonate, methyl t.butylether, and mixtures of toluene and butanol, toluene and n Butyl acetate and methyl t-butyl ether. Solvent blends with more than 2 components are also possible.
  • the compound 4 - [[(6-chloro-pyridin-3-yl) -methyl] (2,2-difluoroethyl) -amino] furan-2 (5H) -one in the new solid form is suitable with good plant tolerability, favorable toxicity to warm-blood and good environmental performance for protecting plants and plant organs, increasing crop yields, improving the quality of the crop and controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs used in agriculture, horticulture, livestock breeding, in forests, gardens and recreational facilities, in supplies and materials, and in the hygiene sector. They can preferably be used as crop protection agents. It is effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the above mentioned pests include:
  • Anoplura e.g. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
  • Arachnids e.g. Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri , Eutetranychus spp., Eriophyes spp., Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Nuphersa spp., Oligonychus spp., Ornithodoros
  • Phyllotreta spp. Popillia japonica, Premnotrypes spp., Psylliodes spp., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Starchus spp., Symphyletes spp., Tanymecus spp., Ten ebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
  • Hyppobosca spp. Hypoderma spp., Liriomyza spp. Lucilla spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia spp., Phorbia spp., Prodiplosis spp., Psila rosae, Rhagoletis spp , Stomoxys spp., Tabanus spp., Tannia spp., Tetanops spp., Tipula spp.
  • Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.
  • helminths e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum , Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Ne
  • protozoa such as Eimeria
  • Hymenoptera e.g. Athalia spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Lepidoptera From the order of Lepidoptera, for example, Acronicta major, Adoxophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyelois transitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius , Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp., Cnephasia spp., Conopomorph
  • Orthoptera e.g. Acheta domesticus, Blatta orientalis, Blattella germanica, Dichroplus spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
  • siphonaptera e.g. Ceratophyllus spp., Xenopsylla cheopis.
  • Thysanoptera e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Anaphothrips obscurus e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Thysanura e.g. Lepisma saccharina.
  • the plant parasitic nematodes include, for example, Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Trichodorus spp., Tylenchulus semipenetrans, Xiphinema spp ..
  • the compound according to the invention may optionally also be used in certain concentrations or application rates as a herbicide, safener, growth regulator or plant properties improver, or as a microbicide, for example as a fungicide, antimycotics, bactericide, viricide (including anti-viral agents) or as an anti-MLO agent ( Mycoplasma-like organism) and RLO (Rickettsia-like-organism).
  • the compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form can be converted into further formulations.
  • Such formulations are, for example, solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural substances, active substance-impregnated synthetic substances, fertilizers and ultrafine encapsulations in polymeric materials.
  • Solid formulations are preferred according to the invention.
  • the formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally with the use of surface-active agents, ie wetting agents, emulsifiers, dispersants and / or foam-destroying agents.
  • extenders ie liquid solvents and / or solid carriers
  • surface-active agents ie wetting agents, emulsifiers, dispersants and / or foam-destroying agents.
  • Excipients which can be used are those which are suitable for imparting special properties to the composition itself and / or preparations derived therefrom (for example spray liquor, seed dressing), such as certain technical properties and / or specific biological properties.
  • Typical auxiliaries are: extenders, solvents and carriers.
  • polar and non-polar organic chemical liquids e.g. from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified), ketones (such as cyclohexanone), esters (also fats and oils) and (poly) ethers, the simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulfones and sulfoxides (such as dimethyl sulfoxide).
  • aromatic and non-aromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • alcohols and polyols which may also be substituted, etherified and / or esterified
  • ketones such as
  • organic solvents can also be used as auxiliary solvents.
  • Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, aliphatic hydrocarbons or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols and their ethers and Esters, ketones such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, and water.
  • the carrier means a natural or synthetic, organic or inorganic substance which may be solid or liquid, with which the active ingredients are mixed or combined for better applicability, in particular for application to plants or plant parts or seeds.
  • the solid or liquid carrier is generally inert and should be useful in agriculture.
  • Suitable solid or liquid carriers are: e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules are suitable: e.g.
  • emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.
  • Alkylaryl polyglycol ethers alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are non-ionic and / or ionic substances, e.g.
  • fatty alcohol POE and / or POP ethers from the classes of fatty alcohol POE and / or POP ethers, acid and / or POP-POE esters, alkyl-aryl and / or POP-POE ethers, fatty and / or POP-POE adducts, POE and / or POP polyol derivatives, POE and / or POP sorbitan or sugar adducts, alkyl or aryl sulfates, sulfonates and phosphates or the corresponding PO ether adducts.
  • lignin and its sulfonic acid derivatives simple and modified celluloses, aromatic and / or aliphatic sulfonic acids and their adducts with formaldehyde.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids may be used in the formulations.
  • Dyes such as inorganic pigments such as 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.
  • Other additives may be fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Stabilizers such as cold stabilizers, preservatives, antioxidants, light stabilizers or other chemical and / or physical stability-improving agents may also be present.
  • the active ingredient content of the forms of application prepared from the formulations can vary widely.
  • the active ingredient concentration of the use forms is in the range of 0.00000001 to 97 wt .-% of active ingredient, preferably in the range of 0.0000001 to 97 wt .-%, particularly preferably in the range of 0.000001 to 83 wt .-% or 0, 000001 to 5 wt .-% and most preferably in the range of 0.0001 to 1 wt .-%.
  • the compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form may be used in mixtures with other active ingredients such as insecticides, attractants, Sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners (eg cloquintocet-mexyl, fenchlorazole-ethylester, isoxadifen-ethyl, mefenpyr-diethyl, fenclorim and cumyluron), fertilizers or semiochemicals or also with agents for improvement the plant properties are present.
  • active ingredients such as insecticides, attractants, Sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners (eg cloquinto
  • Suitable mixing partners are in particular the following insecticides, acaricides and nematicides:
  • acetylcholinesterase (AChE) inhibitors such as carbamates, eg alanycarb, aldicarb, bendocarb, benfuracarb, butocarboxime, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, Pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or organophosphates, eg acephates, azamethiphos, azinophos (-methyl, -ethyl), cadusafos, chloroethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl),
  • GABA-controlled chloride channel antagonists such as organochlorines, e.g. Chlordane and endosulfan (alpha); or fiproles (phenylpyrazoles), e.g. Ethiprole, fipronil, pyrafluprole and pyriprole;
  • sodium channel modulators / voltage dependent sodium channel blockers such as pyrethroids, e.g. Acrinathrin, allethrin (d-cis-trans, d-trans), bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin (beta), cyhalothrin (gamma, lambda), cypermethrin (alpha, beta , theta, zeta), cyphenothrin [(lR) trans isomers], deltamethrin, dimefluthrin, empenthrin [(EZ) (lR) isomers], esfenvalerates, etofenprox, fenpropathrin, fenvalerates, flucythrinates, flumethrin, fluvalinates (tau-), Halfenprox, Im
  • nicotinergic acetylcholine receptor agonists such as neonicotinoids, e.g. Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; or nicotine;
  • Allosteric acetylcholine receptor modulators such as spinosyns, e.g. Spinetoram and spinosad;
  • chloride channel activators such as avermectins / milbemycins, e.g. Abamectin, Emamectin benzoate, Lepimectin and Milbemectin;
  • Juvenile hormone analogs e.g. Hydroprene, kinoprene, methoprene; or fenoxycarb; Pyrimidines;
  • agents with unknown or nonspecific modes of action such as fumigants, e.g. Methyl bromide and other alkyl halides; or chloropicrin; sulfuryl fluoride; Borax; Tartar emetic;
  • mite growth inhibitors eg clofentezine, diflovidazine, hexythiazox, etoxazole
  • Microbial disruptors of insect intestinal membrane such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and BT plant proteins, eg, CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A , Cry3Ab, Cry3Bb, Cry34 / 35Abl; (12) inhibitors of oxidative phosphorylation, ATP disruptors such as diafenthiuron; or organotin compounds, eg azocyclotine, cyhexatin, fenbutatin oxide; or prop
  • inhibitors of chitin biosynthesis type 0, such as benzoylureas, e.g. Bistrifluron, chlorofluorazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron;
  • inhibitors of chitin biosynthesis type 1, such as Bupro fezin;
  • Moulting agents such as Cyromazine
  • ecdysone agonists such as diacylhydrazines, e.g. Chromafenozide, Halofenozide, Methoxyfenozide and Tebufenozide;
  • octopaminergic agonists such as amitraz
  • complex III electron transport inhibitors such as hydramethylnone; acequinocyl; fluacrypyrim;
  • inhibitors of acetyl-CoA carboxylase such as tetronic acid derivatives, eg, spirodiclofen and spiromesifen; or tetramic acid derivatives, eg spirotetramat;
  • complex IV electron transport inhibitors such as phosphines, eg
  • ryanodine receptor effectors such as diamides, e.g. chlorantraniliprole
  • drugs with unknown mechanism of action such as amidoflumet, benzoximes, bifenazates, quinomethionate, cryolites, cyflumetofen, dicofol, flufenerim, pyridalyl and pyrifluquinazone; or the following known effective compounds 4 - ⁇ [(6-bromopyrid-3-yl) methyl] (2-fluoroethyl) amino ⁇ furan-2 (5H) -one (b known from WO 2007/1 1 5644), 4- ⁇ [(6-fluoropyrid-3-yl) methyl] (2,2-difluoroethyl) amino ⁇ furan-2 (5H) -one (known from WO 2007/1 15644), 4 - ⁇ [(2-chloro-1, 3-thiazol-5-yl) methyl] (2-fluoroethyl) amino ⁇ furan-2 (5H) -one (known from WO 2007/1 15644), 4- ⁇ [(6-
  • inhibitors of nucleic acid synthesis such as benalaxyl, benalaxyl-M, bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazole, metalaxyl, metalaxyl-M, ofurace, oxadixyl and oxolic acid;
  • inhibitors of respiration such as diflumetorim as an inhibitor at the complex I of the respiratory chain; Bixafen, boscalid, carboxin, fenfuram, flutolanil, fluopyram, furametpyr, furmecyclox, isopyrazam (mixture of the syn-epimeric racemate 1RS, 4SR, 9RS and the anti-epimeric racemate 1RS, 4SR, 9SR), isopyrazam (syn epimeric racemate 1RS, 4SR, 9RS), isopyrazam (syn-epimeric enantiomer 1R, 4S, 9R), isopyrazam (syn-epimeric enantiomer 1S, 4R, 9S), isopyrazam (anti-epimeric racemate 1RS, 4SR, 9SR), isopyrazam (anti-epimeric Enantiomer 1R, 4S, 9S), isopyrazam (anti-epimeric Enantiomer 1
  • (D) decouplers such as binapacryl, dinocap, fluazinam and meptyldinocap;
  • (E) inhibitors of ATP production such as, for example, fentin acetate, fentin chloride, fentin hydroxide and silthiofam;
  • (F) inhibitors of amino acid and protein biosynthesis such as andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim and pyrimethanil;
  • (G) signal transduction inhibitors such as fenpiclonil, fludioxonil and quinoxyfen;
  • (H) inhibitors of lipid and membrane synthesis such as biphenyl, chlozolinate, edifenphos, etridiazole, iodocarb, Iprobenfos, iprodione, isoprothiolane, procymidone, propamocarb,
  • inhibitors of ergosterol biosynthesis such as aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamide, fenpropidin, fenpropimorph, Fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclo
  • (K) inhibitors of melanin biosynthesis such as carpropamide, diclocymet, fenoxanil, fthalide, pyroquilone and tricyclazole; (L) resistance inducers such as acibenzolar-S-methyl, probenazole and tiadinil.
  • (M) Compounds with multisite activity such as, for example, Bordeaux mixture, captafol, captan, chlorothalonil, copper naphthenate, copper oxide, copper oxychloride, copper preparations, such as copper hydroxide, copper sulfate, dichlofluanid, dithianone, dodine and its free base, Ferbam, Fluorofolpet, Folpet, Guazatine, Guazatine acetate, iminoctadine, iminoctadinal besylate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, zinc metiram, copper oxine, propamidine, propineb, sulfur and sulfur preparations such as calcium polysulfide, thiram, tolylfluanid, zineb and ziram;
  • Also suitable as mixing partners are the following herbicides or plant growth regulators: acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, aminopyralid, amitrole , Ammonium Sulfamate, Ancymidol, Anilofos, Asulam, Atrazine, Azafenidine, Azimsulfuron, Aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H, BAS-800H, Beflubutamide, Benazoline, Benazoline -ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfuron
  • Chlorfenprop Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl, Chlormequat-chloride, Chloronitrofen, Chlorophthalim, Chlorthal-dimethyl, Chlorotoluron,
  • Metobenzuron Metobenzuron, Metobenzuron, Metobromuron, Metolachlor, S-Metolachlor, Metosulam,
  • CDEC compact disc sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate-trimesium), sulfosulfuron, SYN-523, SYP-249, SYP-298, SYP-300, tebutam, tebuthiuron, tecnazene, tefuryltrione, tembotrione, tepraloxydim, terbacil , Terbucarb, terbuchlor, terbumetone, terbuthylazine, terbutryn, TH-547, thenylchloro, thiafluamides, thiazafluron, thiazopyr, thidiazimine, thidiazuron, thiencarbazones, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, t
  • the active substances mentioned are denoted either by the "common name” according to the International Organization for Standardization (ISO) or by their chemical name or code number and always include all forms of use, such as acids, salts, esters or modifications, such as isomers, stereoisomers and optical isomers. By way of example, one or more application forms or modifications are mentioned.
  • the invention also relates to compositions for combating animal pests, in particular pests which are found in agriculture and in forests, containing the new solid form of 4- [[(6-chloropyridin-3-yl) methyl] (2,2-) difluoroethyl) amino] furan-2 (5H) -one and at least one of the aforementioned active ingredients.
  • the compound 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the novel solid form may also be used as an insecticide in its commercial formulations and in the formulations prepared from these formulations in admixture with synergists available.
  • Synergists are compounds that increase the effect of the active ingredients without the added synergist itself having to be active.
  • the compound 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form may also be used as insecticides in their commercial formulations and in the forms of use prepared from these formulations in mixtures with inhibitors which reduce degradation of the active ingredient after application in the environment of the plant, on the surface of plant parts or in plant tissues.
  • the active ingredient content of the application forms prepared from the commercial formulations can vary widely.
  • the active ingredient concentration of the use forms may be from 0.00000001 up to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.
  • plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop 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 varieties which can or can not be protected by plant breeders' rights.
  • Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, as well as roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
  • the treatment according to the invention of the plants and plant parts with the new solid active substance or the active substance combinations containing the new solid active ingredient takes place directly or by acting on their environment, habitat or storage space according to the usual treatment methods, for example by dipping, spraying, evaporating, atomizing, spreading, painting , Injecting and propagating material, in particular seed, continue by single or multi-layer wrapping.
  • plants which can be treated according to the invention mention may be made of the following: cotton, flax, grapevine, fruits, vegetables, such as Rosaceae sp.
  • Ribesioidae sp. for example, pomes such as apple and pear, but also drupes such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries
  • Ribesioidae sp. Juglandaceae sp.
  • Betulaceae sp. Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example, banana trees and plantations), Rubiaceae sp.
  • Asteraceae sp. for example sunflower
  • Brassicaceae sp. for example, white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes and rapeseed, mustard, horseradish and cress
  • Fabacae sp. for example, bean, peanuts
  • Papilionaceae sp. for example, soybean
  • Solanaceae sp. for example potatoes
  • the treatment according to the invention of the plants and plant parts with the new solid active ingredient or the active compound combinations according to the invention is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, eg by dipping, spraying, evaporating, atomizing, spreading, spreading and in the case of propagation material, especially in seeds, further by single or multi-layer wrapping.
  • Much of the damage to crops caused by pests occurs as early as the infestation of the seed during storage and after the seed has been introduced into the soil and during and immediately after the germination of the plants. This phase is particularly critical, as the roots and shoots of the growing plant are particularly sensitive and even minor damage can lead to the death of the entire plant. There is therefore a particular interest in protecting the seed and the germinating plant by the use of suitable agents.
  • the present invention therefore more particularly relates to a method of protecting seed and germinating plants from infestation by pests by treating the seed with an agent according to the invention.
  • the invention also relates to the use of the agents according to the invention for the treatment of seeds for the protection of the seed and the resulting plant from pests.
  • the invention relates to seed which has been treated with an agent according to the invention for protection against pests.
  • Seed is understood to be conventional seed or transgenic seed. In transgenic seeds, the plants resulting from this seed are capable of expressing a pest-targeted protein. These are the seeds of plants, which usually contain at least one heterologous gene which controls the expression of a polypeptide, in particular insecticidal properties.
  • the heterologous genes in transgenic seed can come from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • the present invention is particularly useful for the treatment of transgenic seed containing at least one heterologous gene derived from Bacillus sp. and whose gene product shows efficacy against European corn borer and / or corn rootworm. Most preferably, this is a heterologous gene derived from Bacillus thuringiensis.
  • Insecticidal protein By treating such seeds with the agents of the invention, certain pests may already be affected by the expression of e.g. Insecticidal protein can be controlled, and also be protected by the means of the invention from damage.
  • compositions of the invention are suitable for the protection of seed of any plant variety as mentioned above, which is used in agriculture, in the greenhouse, in forests or in horticulture.
  • these are seeds of corn, peanut, canola, rapeseed, poppy seeds, soybean, cotton, turnip (eg sugar beet and fodder beet), rice, millet, wheat, barley, oats, rye, sunflower, tobacco, potatoes or vegetables (eg tomatoes, cabbages).
  • the compositions according to the invention are likewise suitable for the treatment of the seed of fruit plants and vegetables as already mentioned above. Of particular importance is the treatment of the seeds of maize, soya, cotton, wheat and canola or rapeseed.
  • the agent according to the invention is applied to the seed alone or in a suitable formulation.
  • the seed is treated in a condition that is so stable that no damage occurs during the treatment.
  • the treatment of the seed can be done at any time between harvesting and sowing.
  • seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp.
  • the amount of the agent and / or other additives applied to the seed is chosen so that germination of the seed is not impaired or the resulting plant is not damaged. This is especially important for active ingredients, which can show phytotoxic effects in certain application rates.
  • the agents according to the invention can be applied directly, ie without containing further components and without being diluted. In general, it is preferable to apply the agents to the seed in the form of a suitable formulation.
  • Suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 Al, WO 2002/080675 Al, WO 2002 / 028186 A2.
  • the new solid form of 4 - [[(6-chloro-pyridin-3-yl) -methyl] (2,2-difluoroethyl) -amino] -furan-2 (5H) -one can be converted into the usual seed-dressing formulations, such as solutions, Emulsions, suspensions, powders, foams, slurries or other coating materials for seeds, as well as ULV formulations.
  • seed-dressing formulations such as solutions, Emulsions, suspensions, powders, foams, slurries or other coating materials for seeds, as well as ULV formulations.
  • These formulations are prepared in a known manner by mixing the active ingredients with conventional additives, such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and water.
  • Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1 known dyes.
  • Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds. Preference is given to using alkylnaphthalene sulfonates, such as diisopropyl or diisobutylnaphthalene sulfonates.
  • Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds.
  • Preferably usable are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide, block polymers, alkylphenol polyglycol ethers and tri-stryrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
  • Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
  • Defoamers which may be present in the seed dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds.
  • Preferably usable are silicone defoamers and magnesium stearate.
  • Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal.
  • Suitable secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and highly dispersed silicic acid.
  • Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents.
  • Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
  • the gibberellins are known (see R. Wegler "Chemie der convinced- und Swdlingsbekungsstoff", Vol. 2, Springer Verlag, 1970, pp. 401-412).
  • the seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds, including seed of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression.
  • the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water
  • all mixing devices customarily usable for the dressing can be considered.
  • the seed is placed in a mixer which adds either desired amount of seed dressing formulations either as such or after prior dilution with water and mixes until evenly distributed the formulation on the seed.
  • a drying process follows.
  • plants and their parts can be treated.
  • wild or conventional biological breeding methods such as crossing or protoplast fusion obtained plant species and plant varieties and their parts treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above.
  • Plant varieties are understood as meaning plants having new traits which have been bred by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.
  • the treatment according to the invention may also give rise to superadditive ("synergistic") effects.
  • superadditive for example, reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents usable in 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 power facilitated harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products, which exceed the actual expected effects.
  • the preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits").
  • traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value Harvested products, higher shelf life and / or workability of the harvested products.
  • Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants against certain herbicidal active substances.
  • transgenic plants are the important crops, such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, oilseed rape, as well as fruit plants (with the fruits apples, pears, citrus fruits and grapes) Soya, potato, cotton, tobacco and oilseed rape are particularly emphasized.
  • Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins produced in the plants, in particular those produced by the genetic material from Bacillus thuringiensis (eg by the genes CrylA (a) , CrylA (b), CrylA (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) in the plants (hereinafter "Bt plants”). Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • SAR systemic acquired resistance
  • Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene).
  • the genes which confer the desired properties (“traits") can also occur in combinations with one another in the transgenic plants.
  • Examples of “Bt plants” are maize varieties, cotton varieties, soybean varieties and potato varieties which are sold under the trade names YIELD GARD® (eg corn, cotton, soya), KnockOut® (eg maize), StarLink® (eg maize), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties, which are sold under the trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), IMI® (tolerance against imidazolinone) and STS® (tolerance to sulfonylureas eg corn).
  • Roundup Ready® tolerance to glyphosate eg corn, cotton, soy
  • Liberty Link® tolerance to phosphinotricin, eg rapeseed
  • IMI® tolerance against imidazolinone
  • STS® tolerance to sulfonylureas eg corn
  • Clearfield® varieties eg corn
  • the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one can also be used in the veterinary sector against animal parasites (ecto- and Endoparasites) such as ticks, leather ticks, mange mites, running mites, flies (stinging and licking), parasitizing fly larvae, lice, hair pieces, featherlings and fleas.
  • animal parasites ecto- and Endoparasites
  • These parasites include: From the order of the Anoplurida eg Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
  • Nematocenna and Brachycenna e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp , Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilla spp., Chrysomyia
  • siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
  • Heteropterida e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
  • Actinedida Prostigmata
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp , Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
  • the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is also useful in the control of arthropods such as livestock eg cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, Geese, bees, other pets such as dogs, cats, caged birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice infested.
  • arthropods such as livestock eg cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, Geese, bees, other pets such as dogs, cats, caged birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice infested.
  • the active ingredients or compositions may be used as suitable formulations, for example, powders, emulsions, flowables.
  • suitable formulations contain the active ingredients in a concentration in the range of 0.1 to 80 wt .-%, preferably in the range of 1- 60 wt .-%, particularly preferably in the range of 5 to 30 wt .-%.
  • the formulations may be applied directly or diluted, preferably after 100 to 10,000 fold dilution.
  • the active compounds or the compositions can also be used as a chemical bath.
  • insects By way of example and preferably without limiting however, the following insects are mentioned:
  • Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus; Bristle tails like Lepisma saccharina.
  • Non-living materials such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood, wood processing products and paints.
  • the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is also useful for controlling domestic pests in household hygiene and stored product protection, in particular of insects, arachnids and mites, in enclosed spaces, such as apartments, factory buildings, offices, vehicle cabins, etc. occurrence. They can be used to control these pests, alone or in combination with other active ingredients and adjuvants in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
  • Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
  • Opiliones eg Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium. From the order of the Isopoda eg Oniscus asellus, Porcellio scaber.
  • Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
  • Saltatoria e.g. Acheta domesticus.
  • Dermaptera e.g. Forficula auricularia.
  • Diptera e.g. 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. From the order of Lepidoptera e.g. Achroia 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 umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • Anoplura eg Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis.
  • Heteroptera eg Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
  • Application is in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, misting machines, foggers, foams, gels, evaporator products with evaporator plates of cellulosic or plastic, liquid evaporators, gel and membrane evaporators, propeller driven evaporators, energyless or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in Litter or bait stations.
  • Pump and atomizer sprays misting machines, foggers, foams, gels, evaporator products with evaporator plates of cellulosic or plastic, liquid evaporators, gel and membrane evaporators, propeller driven evaporators, energyless or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in Litter or bait stations.
  • Figure lb X-ray powder diffractogram of amorphous 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one prepared according to WO 2009/036899.
  • Figure 2a Infrared (IR) spectra of the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one.
  • Figure 2b Infrared (IR) spectra of the amorphous form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one.
  • Figure 3a Raman spectra of the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one.
  • Figure 3b Raman spectra of the amorphous form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one.
  • X-ray powder diffractometry spectra were taken with an XPERT-PRO diffractometer using Cu-Ka radiation (1.54060 A wavelength) at 25 ° C, the 2 ⁇ value can be in the range of 2 - 38 °.
  • the recording was carried out at a step size of 0, 0130 ° 2 ⁇ .
  • IR Infrared
  • Raman spectra were recorded on a Bruker RFS / 100 FT Raman spectrometer whose laser has a wave wave number (Laser Wave Number) of 15798.7 cm -1 and the resolution of the device is 1 cm -1 . 128 scans were performed per spectrum.
  • ⁇ -NMR (CDC1 3 , 298K) corresponds to that of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in an amorphous state as you can read above.
  • ⁇ -NMR (CDC1 3 , 298K) corresponds to that of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in amorphous state as above specified.
  • the moistened Solid mixture is transferred under the lowest possible pressure and energy input through a suitable extruder in product strands, which disintegrate on exit from the die and during drying in the rod-shaped water-dispersible granules.
  • care is taken that the product temperature does not exceed 40 ° C in the individual formulation steps.
  • the water-dispersible granules are stored for eight weeks at 40 ° C.
  • the subsequent verification of the chemical and physical properties revealed only minor tolerable deviations of the values compared to the initial values.
  • the product is fully applicable and effective even after storage.

Abstract

The invention relates to a novel solid form of 4-[[(6-Chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, to a method for the production of same, and to the use of same in agrochemical preparations.

Description

Neue feste Form von 4-[[(6-Chlorpyridin-3-vUmethyll(2.,2-difluorethvnaininolfuran-2(5HVon  New solid form of 4 - [[(6-chloropyridine-3-vymethyl] (2, 2-difluoroethvnaininolfuran-2 (5HVon
Die vorliegende Erfindung betrifft eine neue feste Form von 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on, ein Verfahren zur Herstellung dieser neuen festen Form und deren vorteilhafte Verwendung zur Zubereitung von stabilen Anwendungsformen. The present invention relates to a novel solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one, a process for the preparation of this novel solid form and their advantageous use for the preparation of stable applications.
Die Verbindung 4-[[(6-Chlo yridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on sowie Methoden zur Herstellung dieser Verbindung sind bekannt. Auch ist bekannt, dass diese Verbindung Insektizide bzw. akarizide Wirkung besitzt. So beschreibt beispielsweise die WO 2007/1 15644 erstmals die Herstellung dieser Verbindung sowie seine Verwendung zur Bekämpfung von Arthropoden, insbesondere Insekten. Die Herstellung der Verbindung wurde weiterhin in WO2009/036899 beschrieben. Es wurde nun festgestellt, dass die mit den bekannten Verfahren hergestellte Verbindung sich nicht in einer wirtschaftlich relevanten Form anwenden läßt, das die mit diesen Verfahren hergestellte Verbindung in amorphen Zustand vorliegt. Was schon daran zu erkennen ist, dass kein Schmelzpunkt zu ermitteln ist. Schmelzpunkte sind immer dann vorhanden, wenn eine Fernordnung, vor allem wenn eine Kristallstruktur vorhanden ist. Gleichfalls erhält man kein aufgelöstes Röntgen-Pulverdiffraktogramm wie aus Abbildung la ersichtlich ist. The compound 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one and methods for the preparation of this compound are known. It is also known that this compound has insecticidal or acaricidal activity. For example, WO 2007/1 15644 describes for the first time the preparation of this compound and its use for controlling arthropods, in particular insects. The preparation of the compound was further described in WO2009 / 036899. It has now been found that the compound prepared by the known processes can not be applied in an economically relevant form which the compound produced by these processes is in an amorphous state. What can already be recognized by the fact that no melting point is to be determined. Melting points are always present when a distant order, especially if a crystal structure is present. Likewise, no resolved X-ray powder diffractogram is obtained, as can be seen from Figure la.
Insbesondere ist es nachteilig, dass die Verbindung im amorphen Zustand hochviskos ist und sich deshalb nicht in Formulierungen, in denen der Wirkstoff in fester (trockener) Form vorliegt, überführen lässt. Solche wirtschaftlich relevanten Formulierungen sind beispielsweise Granulate, verkapselte Granulate, Tabletten, wasserdispergierbare Granulate, wasserdispergierbare Tabletten, wasserdispergierbare Pulver oder wasserdispergierbare Pulver für Saatgutbehandlung, Staub- Formulierungen, Formulierungen, in denen der Wirkstoff in dispergierter Form vorliegt wie z.B.: Suspensionskonzentrate, Öl basierte Suspensionskonzentrate, Suspoemulsionen, oder Suspensionskonzentrate für die Saatgutbehandlung. Formulierungen sind beispielsweise dann wirtschaftlich relevant, wenn sich die zu verwendenden Wirkstoffe zur Herstellung von Formulierungen, die eine Verwendung von Mahlprozessen erfordern, besonders gut eignen und/oder solche Formulierungen eine gute Lagerstabilität aufweisen. In particular, it is disadvantageous that the compound in the amorphous state is highly viscous and therefore can not be converted into formulations in which the active ingredient is in solid (dry) form. Such economically relevant formulations are, for example, granules, encapsulated granules, tablets, water-dispersible granules, water-dispersible tablets, water-dispersible powders or water-dispersible powders for seed treatment, dust formulations, formulations in which the active ingredient is in dispersed form, for example: suspension concentrates, oil-based suspension concentrates, Suspoemulsions, or suspension concentrates for seed treatment. Formulations are, for example, economically relevant if the active ingredients to be used are particularly suitable for the preparation of formulations which require the use of grinding processes and / or if such formulations have good storage stability.
Überraschenderweise wurde nun eine neue feste Form von 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on gefunden, die die oben genannten Nachteile vermeidet. Die Erfindung bezieht sich deshalb auf die neue feste Form der Verbindung 4-[[(6-Chlorpyridin-3- yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on, die dadurch gekennzeichnet ist, dass sie einen Schmelzpunkt im Bereich von 65 °C bis 75 °C, insbesondere einen Schmelzbereich von 72°C bis 74 °C aufweist und/oder das Röntgen-Pulverdiffraktogramm dieser Verbindung bei 25 °C und Verwendung von Cu-Ka-Strahlung ( 1 .540598 Ä) mindestens 3 charakteristische Signale, insbesondere mindestens 4 oder 6 charakteristische Signale und vorzugsweise alle der folgenden charakteristische 2Θ (2Theta)-Werte aufweist: Surprisingly, a new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one has now been found, which avoids the abovementioned disadvantages. The invention therefore relates to the novel solid form of compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one which is characterized that she has one Melting point in the range of 65 ° C to 75 ° C, in particular a melting range of 72 ° C to 74 ° C and / or the X-ray powder diffractogram of this compound at 25 ° C and using Cu-Ka radiation (1 .540598 Ä ) has at least 3 characteristic signals, in particular at least 4 or 6 characteristic signals and preferably all of the following characteristic 2Θ (2Theta) values:
2Θ = 16,8° ±0,2  2Θ = 16.8 ° ± 0.2
2Θ = 17,8° ±0,2  2Θ = 17.8 ° ± 0.2
2Θ = 20,2° ±0,2  2Θ = 20.2 ° ± 0.2
2Θ = 21 ,7° ±0,2  2Θ = 21, 7 ° ± 0.2
2Θ = 23,6° ±0,2  2Θ = 23.6 ° ± 0.2
2Θ = 23,9° ±0,2  2Θ = 23.9 ° ± 0.2
2Θ = 24,7° ±0,2  2Θ = 24.7 ° ± 0.2
2Θ = 25,3° ±0,2  2Θ = 25.3 ° ± 0.2
Gemäß der Erfindung bezeichnet der Ausdruck "charakteristische Signale" solche Signale (2Θ (2Theta)-Werte, Ir- oder Raman-Banden), die sich klar vom Hintergrundrauschen abheben und die für die gemessene Verbindung charakteristisch sind. According to the invention, the term "characteristic signals" refers to those signals (2Θ (2Theta) values, Ir or Raman bands) which clearly stand out from background noise and which are characteristic of the measured compound.
Die neue feste Form weist ferner zu den charakteristischen 2 Theta- Werten die in Tabelle 1 aufgeführten Netzebenenabstände "d" auf. The new solid form further has the characteristic 2 theta values of the lattice plane spacings "d" listed in Table 1.
Tabelle 1 : Charakteristische 2 Theta- Werte und Netzebenenabstände "d" der neuen festen Form der Verbindung 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on, ermittelt durch Röntgen-Pulverspektroskopie Table 1: Characteristic 2 theta values and lattice spacings "d" of the new solid form of compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) - on, determined by X-ray powder spectroscopy
Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung besitzt die Verbindung einen Schmelzpunkt im Bereich von 72 °C bis 74 °C und das Röntgen-Pulverdiffraktogramm der neuen festen Form weist die in Abbildung la wiedergegebenen Signale auf. According to a preferred embodiment of the present invention, the compound has a melting point in the range of 72 ° C to 74 ° C and the X-ray powder diffractogram of the new solid form has the signals shown in Figure la.
Neben Schmelzpunkt und Röntgen-Pulverdiffraktogramm weist die neue feste Form von 4-[[(6- Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on außerdem di e in T ab e ll e 2 wiedergegebenen Ramanhauptbanden und die in Tabelle 3 aufgeführten IR-Hauptbanden auf. In Tabelle 2 und 3 sind zusätzlich jeweils die Hauptbanden der amorphen Form angegeben. In addition to melting point and X-ray powder diffractogram, the new solid form of 4 - [[(6-chloro-pyridin-3-yl) -methyl] (2,2-difluoroethyl) -amino] -furan-2 (5H) -one also has the di-T e ll e 2 reproduced major Raman bands and the main IR bands listed in Table 3. In addition, the major bands of the amorphous form are indicated in Tables 2 and 3, respectively.
Tabelle 2: Lage der Hauptbanden im Ramanspektrum der bekannten amorphen und der neuen festen Form Table 2: Position of the main bands in the Raman spectrum of the known amorphous and the new solid form
Tabelle 3: Lage der Hauptbanden des Infrarotspektrums der bekannten amorphen Form und der neuen festen Form Table 3: Location of the principal bands of the infrared spectrum of the known amorphous form and the new solid form
Es wurd e üb e rr as ch en d g e fun de n , d as s 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on in der neuen festen Form für die wirtschaftlich relevante Anwendung ausreichend thermodynamisch stabil ist und auch bei längerer Lagerung sich nicht in eine andere Form umwandelt. It has been reported that the s - 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -onine the new solid form for the economically relevant application is sufficiently thermodynamically stable and does not convert to a different form even with prolonged storage.
Die Herstellung von Suspensionskonzentraten, Öl basierten Suspensionskonzentraten und z.B. wasserdispergierbaren Granulaten sowie ähnlicher Formulierungen zur Behandlung von Saatgut wird dadurch möglich. The preparation of suspension concentrates, oil-based suspension concentrates and e.g. water-dispersible granules and similar formulations for the treatment of seeds is thereby possible.
Die Verbindung 4-[[(6-Chlo yridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on in der neuen festen Form eignet sich aufgrund ihrer Stabilität hervorragend für die Zubereitung von Mitteln zur Bekämpfung von tierischen Schädlingen, insbesondere von Schädlingen, die in Landwirtschaft und Forsten vorkommen. Gegenstand der Erfindung sind daher auch Mittel zur Bekämpfung solcher Schädlinge, welche die neue feste Form alleine oder in Mischung mit Hilfs- und Trägerstoffen, sowie in Mischung mit anderen Wirkstoffen enthalten. Die Erfindung schließt auch Zusammensetzungen ein, die die Verbindung 4-[[(6-Chlorpyridin-3- yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on in der neuen festen Form enthalten. Bevorzugt sind Zusammensetzungen, die weniger als 20 Gew.-% der neuen feste Form, besonders bevorzugt weniger als 15 Gew.-%, ganz besonders bevorzugt weniger als 10 Gew.-%, insbesondere bevorzugt weniger als 5 Gew. %, am meisten bevorzugt weniger als 4, 3, 2 oder 1 Gew.-% der neuen festen Form enthalten. Die Bezeichnung "Zusammensetzung" umfasst auch Formulierungen und Anwendungsformen. Gegenstand der Erfindung sind ferner auch Verfahren zur Herstellung von Mitteln zur Bekämpfung von S chädlingen, welche die Verbindung 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on in der neuen festen Form verwenden. Durch den Einsatz der Verbindung 4-[[(6-Chlo yridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on in der neuen festen Form wird die Sicherheit für Zubereitungen die die Verbindung 4-[[(6-Chlorpyridin-3- yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on enthalten erhöht und somit das Risiko falscher Dosierungen verringert. The compound 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form is outstandingly suitable for the preparation of Agents for combating animal pests, in particular pests found in agriculture and forestry. The invention therefore also means for controlling such pests, which contain the new solid form alone or in admixture with excipients and carriers, as well as in admixture with other active ingredients. The invention also includes compositions containing the compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the novel solid form. Preferred are compositions containing less than 20% by weight of the novel solid form, more preferably less than 15% by weight, most preferably less than 10% by weight, most preferably less than 5% by weight, most preferred less than 4, 3, 2 or 1 wt .-% of the new solid form included. The term "composition" also includes formulations and uses. The invention also provides processes for the preparation of agents for combating pathogens which comprise the compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -on in the new solid form. The use of the compound 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form, the safety for preparations that the Compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one contained increased, thus reducing the risk of incorrect dosages.
Die Verbindung 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on in der neuen festen Form kann in bekannter Weise in die üblichen Formulierungen, wie Suspensionskonzentrate, Öl basierte Suspensionskonzentrate, kolloidale Konzentrate, dispergierbare Konzentrate, emulgierbare Konzentrate (Emulsionskonzentrate), Emulsionsbeizen, Suspensionsbeizen, Granulate, Mikrogranulate, Suspoemulsionen, wasserlösliche Granulate, wasserlösliche Konzentrate und wasserdispergierbare Granulate, wie auch entsprechender anwendungsfertiger Formulierungen (sogenannter ready-to-use Formulierungen) unter Verwendung geeigneter Hilfs- und Trägerstoffe oder Lösemittel überführt werden. Hierbei soll die wirksame Verbindung in einer Konzentration von etwa 0,0001 bis 90 Gew.-% der Gesamtmischung vorhanden sein, d.h. in Mengen, die ausreichend sind, um den notwendigen Dosierungsspiegel zu erreichen. Die Formulierungen werden beispielsweise hergestellt durch Verstrecken der Verbindung 4-[[(6- Chlorpyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on in der neuen festen Form mit Wasser, Lösemitteln und/oder Trägerstoffen, gegebenenfalls unter Verwendung von Emulgier- und/oder Dispergiermitteln, und/oder anderen Hilfsstoffen, wie z.B. Penetrationshilfsmitteln. The compound 4 - [[(6-chloro-pyridin-3-yl) -methyl] (2,2-difluoro-ethyl) -amino] -furan-2 (5H) -one in the new solid form can be converted in known manner into the usual formulations, such as suspension concentrates , Oil-based suspension concentrates, colloidal concentrates, dispersible concentrates, emulsifiable concentrates (emulsion concentrates), emulsion mordants, suspension mordants, granules, microgranules, suspoemulsions, water-soluble granules, water-soluble concentrates and water-dispersible granules, as well as corresponding ready-to-use formulations (so-called ready-to-use formulations). be converted using suitable excipients and carriers or solvents. Here, the active compound should be present in a concentration of about 0.0001 to 90% by weight of the total mixture, i. in amounts sufficient to achieve the necessary dosage level. For example, the formulations are prepared by stretching the compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form with water, solvents and / or carriers, optionally with the use of emulsifiers and / or dispersants, and / or other excipients, such as Penetration aids.
Bei der Herstellung von Suspensionskonzentraten, auch von solchen, die zur Saatgutbehandlung verwendet werden, werden im Allgemeinen neben dem Wirkstoff und einem Streckmittel (Wasser, Lösungsmittel oder Öl) weitere Hilfsmittel zugegeben. Zur Befeuchtung des Wirkstoffs in der kontinuierlichen Phase wird ein Netzmittel eingesetzt, zur Stabilisierung der Suspension in der flüssigen Phase werden Dispergierhilfsmittel verwendet, zum Emulgieren der nicht wässerige Phase werden bei Lösungsmittel oder Öl enthaltenden Suspensionskonzentraten Emulgiermittel eingesetzt. Sofern notwendig werden Frostschutzmittel, Biozide, Verdickungsmittel, Farbstoffe, Spreizmittel oder / und Aufnahmeförderer eingearbeitet. Die neue feste Verbindung 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on wird durch das nachfolgend beschriebene Verfahren erhalten. Die Verbindung 4 [(6-Chk^yridin-3- yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on wird wie beispielsweise in WO 2007/115644 (Seite 51, Beispiel 1) beschrieben hergestellt. Das so erhaltene 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on liegt in amorphen Zustand vor. In the preparation of suspension concentrates, including those used for seed treatment, further adjuvants are generally added in addition to the active ingredient and an extender (water, solvent or oil). For wetting the active ingredient in the continuous phase, a wetting agent is used, to stabilize the suspension in the liquid phase dispersing agents are used for emulsifying the non-aqueous phase emulsifiers are used in solvent or oil-containing suspension concentrates. If necessary, anti-freeze agents, biocides, thickeners, dyes, spreading agents and / or receiving conveyors are incorporated. The new solid compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is obtained by the method described below. The compound 4 [(6-chk-yridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is described, for example, in WO 2007/115644 (Page 51, Example 1) described. The resulting 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is in an amorphous state.
Zur Herstellung der erfindungsgemäßen Verbindung wird amorphes 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on in einem Lösungsmittel oder einem Lösungsmittelgemisch bei Temperaturen von mindestens 30°C, vorzugsweise von mindestens 50 °C, aufgelöst und langsam abgekühlt bis die gewünschten Kristalle ausfallen. Die Menge des verwendeten Lösungsmittels wird so gewählt, dass die Mischung während der Kristallisation gut rührbar bleibt. For the preparation of the compound according to the invention, amorphous 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is dissolved in a solvent or a solvent mixture at temperatures of at least 30 ° C, preferably of at least 50 ° C, dissolved and slowly cooled until the desired crystals precipitate. The amount of solvent used is chosen so that the mixture remains easy to stir during the crystallization.
Das langsame Abkühlen findet linear oder stufenweise statt. Bevorzugt findet das Abkühlen stufenweise statt, wobei die Kristallisationslösung bei einer bestimmten Temperatur, vorzugsweise bei etwa 40 °C für einige Stunden, vorzugsweise 2 bis 20 Stunden, besonders bevorzugt 4 bis 20 Stunden ganz besonders bevorzugt 4 bis 16 Stunden gerührt wird, bevor sie weiter abgekühlt werden bis dass die gewünschten Kristalle ausfallen. The slow cooling takes place linearly or stepwise. Preferably, the cooling takes place in stages, wherein the crystallization solution is stirred at a certain temperature, preferably at about 40 ° C for several hours, preferably 2 to 20 hours, more preferably 4 to 20 hours, most preferably 4 to 16 hours before continuing be cooled until the desired crystals precipitate.
Sofern vorhanden, werden der Lösung gegebenenfalls Impfkristalle zugesetzt, um die Kristallisation zu beschleunigen. Das Zusetzen der Impfkristalle kann grundsätzlich während des Rührens geschehen, wobei dann aber die Lösung derart gesättigt sein muss, dass sich die Impfkristalle nicht lösen. Bevorzugt werden die Impfkristalle nach dem Rühren zugesetzt. If present, seed crystals are optionally added to the solution to accelerate crystallization. The addition of the seed crystals can in principle be done while stirring, but then the solution must be saturated so that the seed crystals do not dissolve. Preferably, the seed crystals are added after stirring.
Geeignete Lösungsmittel sind alle Lösungsmittel in denen sich 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on löst. Insbesondere geeignet sind Halogenkohlenwasserstoffe (z.B. Chlorbenzol, Brombenzol, Dichlorbenzol, Chlortoluol, Trichlorbenzol), Ether (z.B. Ethylpropylether, Methyl-tert-butylether, n-Butylether, Anisol, Phenetol, Cyclohexylmethylether, Dimethylether, Diethylether, Dimethylglycol Diphenylether, Diproplether, Diisopropylether, Di-n- butylether, Diisobutylether, Diisoamylether, Ethylenglycoldimethylether, Isopropylethylether, Methyl-tert-butylether, Tetrahydrofuran, Methyl-Tetrahydrofuran, Dioxan, Dichlordiethylether, Methyl-THF und Polyether des Ethylenoxids und/oder Propylenoxids), Nitrokohlenwasserstoffe (z.B. Nitromethan, Nitroethan, Nitropropan, Nitrobenzol, Chlornitrobenzol, o-Nitrotoluol), aliphatische, cycloaliphatische oder aromatische Kohlenwasserstoffe (z.B. Pentan, n-Hexan, n- Heptan, n-Oktan, Nonan beispielsweise sogenannte White Spirits mit Komponenten mit Siedepunkten im Bereich beispielsweise von 40°C bis 250°C, Cymol, Benzinfraktionen innerhalb eines Siedeintervalles von 70°C bis 190°C, Cyclohexan, Methylcyclohexan, Petrolether, Ligroin, Octan, Benzol, Toluol, Xylol), Ester (z.B. Malonester, Essigsäure-n-butylester (n-Butylacetat), Methylacetat, Ethylacetat, Isobutylacetat, Dimethylcarbonat, Diethylcarbonat, Dibutylcarbonat, Ethylencarbonat); und aliphatische Alkohole (z.B. Methanol, Ethanol, n-Propanol und Isopropanol un d n-Butanol, tert- Amylalkohol). Bevorzugte Lösungsmittel sind Ether, aromatische Kohlenwasserstoffe wie Benzol, Toluol, Xylol, Chlorbenzol, Ester und aliphatische Alkohole und Gemische davon. Besonders bevorzugte Lösungsmittel bzw. Lösungsmittelgemische sind Isopropanol, Toluol, Methyl-THF Diethylcarbonat, Chlorbenzol, n-Butylacetat und i-Butylacetat, n- Butanol, Ethanol, Malonsäureethylester, Methyl-t.butylether, sowie Mischungen aus Toluol und Butanol, Toluol und n-Butylacetat, Malonsäureethylester und Methyl-t.-butylether, und Butylacetat und Methyl-t.-butylether. Lösungsmittelmischungen mit mehr als 2 Komponenten sind auch möglich. Suitable solvents are all solvents in which 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one dissolves. Particularly suitable are halogenated hydrocarbons (eg chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene), ethers (eg ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, anisole, phenetole, cyclohexylmethyl ether, dimethyl ether, diethyl ether, dimethyl glycol diphenyl ether, dipropl ether, diisopropyl ether, di -n-butyl ether, diisobutyl ether, diisoamyl ether, ethylene glycol dimethyl ether, isopropyl ethyl ether, methyl tert-butyl ether, tetrahydrofuran, methyl-tetrahydrofuran, dioxane, dichlorodiethyl ether, methyl THF and polyethers of ethylene oxide and / or propylene oxide), nitrohydrocarbons (eg nitromethane, nitroethane, nitropropane , Nitrobenzene, chloronitrobenzene, o-nitrotoluene), aliphatic, cycloaliphatic or aromatic hydrocarbons (eg pentane, n-hexane, n-heptane, n-octane, nonane for example, so-called white spirits with components having boiling points in the range, for example, from 40 ° C to 250 ° C, cymene, gasoline fractions within a boiling interval of 70 ° C to 190 ° C, cyclohexane, methylcyclohexane, petroleum ether, ligroin, octane, benzene, toluene, xylene), esters (eg malonic ester, n-butyl acetate (n-butyl acetate), methyl acetate, ethyl acetate, isobutyl acetate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate , Ethylene carbonate); and aliphatic alcohols (eg, methanol, ethanol, n-propanol and isopropanol and n-butanol, tert-amyl alcohol). Preferred solvents are ethers, aromatic Hydrocarbons such as benzene, toluene, xylene, chlorobenzene, esters and aliphatic alcohols and mixtures thereof. Particularly preferred solvents or solvent mixtures are isopropanol, toluene, methyl THF diethyl carbonate, chlorobenzene, n-butyl acetate and i-butyl acetate, n-butanol, ethanol, ethyl malonate, methyl t.butylether, and mixtures of toluene and butanol, toluene and n Butyl acetate and methyl t-butyl ether. Solvent blends with more than 2 components are also possible.
Die erfindungsgemäße Verbindung 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan- 2(5H)-on in der neuen festen Form eignet sich bei guter Pflanzenverträglichkeit, günstiger Warm- blütertoxizität und guter Umweltverträglichkeit zum Schutz von Pflanzen und Pflanzenorganen, zur Steigerung der Ernteerträge, Verbesserung der Qualität des Erntegutes und zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten, Spinnentieren, Helminthen, Nematoden und Mollusken, die in der Landwirtschaft, im Gartenbau, bei der Tierzucht, in Forsten, in Gärten und Freizeiteinrichtungen, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie können vorzugsweise als Pflanzenschutzmittel eingesetzt werden. Sie ist gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören: The compound 4 - [[(6-chloro-pyridin-3-yl) -methyl] (2,2-difluoroethyl) -amino] furan-2 (5H) -one in the new solid form is suitable with good plant tolerability, favorable toxicity to warm-blood and good environmental performance for protecting plants and plant organs, increasing crop yields, improving the quality of the crop and controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs used in agriculture, horticulture, livestock breeding, in forests, gardens and recreational facilities, in supplies and materials, and in the hygiene sector. They can preferably be used as crop protection agents. It is effective against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include:
Aus der Ordnung der Anoplura (Phthiraptera) z.B. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.. From the order of the Anoplura (Phthiraptera) e.g. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
Aus der Klasse der Arachnida z.B. Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Nuphersa spp., Oligonychus spp., Ornitho- doros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici. From the class of arachnids, e.g. Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri , Eutetranychus spp., Eriophyes spp., Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Nuphersa spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
Aus der Klasse der Bivalva z.B. Dreissena spp.. From the class of bivalva, e.g. Dreissena spp ..
Aus der Ordnung der Chilopoda z.B. Geophilus spp., Scutigera spp.. From the order of Chilopoda e.g. Geophilus spp., Scutigera spp.
Aus der Ordnung der Coleoptera z.B. Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apion spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Ctenicera spp., Curculio spp., Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Hellula undalis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnostema consanguinea, Lema spp., Leptinotarsa decemlineata, Leucoptera spp., Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp., Megascelis spp., Melanoms spp., Meligethes aeneus, Melolontha spp., Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus spp., Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Phyllotreta spp., Popillia japonica, Premnotrypes spp., Psylliodes spp., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.. From the order of the Coleoptera eg Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apion spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Ctenicera spp., Curculio spp., Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Hellula and alis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnostema consanguinea, Lema spp., Leptinotarsa decemlineata, Leucoptera spp., Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp., Megascelis spp Melanoms spp., Meligethes aeneus, Melolontha spp., Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus spp., Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp. Phyllotreta spp., Popillia japonica, Premnotrypes spp., Psylliodes spp., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Starchus spp., Symphyletes spp., Tanymecus spp., Ten ebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
Aus der Ordnung der Collembola z.B. Onychiurus armatus. From the order of Collembola e.g. Onychiurus armatus.
Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus. From the order of diplopoda e.g. Blaniulus guttulatus.
Aus der Ordnung der Diptera z.B. Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chironomus spp., Chrysomyia spp., Cochliomyia spp., Contarinia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dasyneura spp., Delia spp., Dermatobia hominis, Droso- phila spp., Echinocnemus spp., Fannia spp., Gastrophilus spp., Hydrellia spp., Hylemyia spp., Hyp- pobosca spp., Hypoderma spp., Liriomyza spp.. Lucilla spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia spp., Phorbia spp., Prodiplosis spp., Psila rosae, Rhagoletis spp., Stomoxys spp., Tabanus spp., Tannia spp., Tetanops spp., Tipula spp.. From the order of Diptera e.g. Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chironomus spp., Chrysomyia spp., Cochliomyia spp., Contarinia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dasyneura spp., Delia spp., Dermatobia hominis, Drosophila spp., Echinocnemus spp., Fannia spp., Gastrophilus spp., Hydrellia spp., Hylemyia spp. Hyppobosca spp., Hypoderma spp., Liriomyza spp. Lucilla spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia spp., Phorbia spp., Prodiplosis spp., Psila rosae, Rhagoletis spp , Stomoxys spp., Tabanus spp., Tannia spp., Tetanops spp., Tipula spp.
Aus der Klasse der Gastropoda z.B. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp..  From the class Gastropoda, e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.
Aus der Klasse der Helminthen z.B. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymeno- lepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti. From the class of helminths e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum , Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca Volvulus, Ostertagia spp., Paragonimus spp., Schistosome spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria , Wuchereria bancrofti.
Weiterhin lassen sich Protozoen, wie Eimeria, bekämpfen. Aus der Ordnung der Heteroptera z.B. Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Monaionion atratum, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. Aus der Ordnung der Homoptera z.B. Acyrthosipon spp., Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Ferrisia spp., Geococcus coffeae, Hieroglyphus spp., Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Lao- delphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes spp., Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.. Furthermore, protozoa, such as Eimeria, can be combated. From the order of the Heteroptera eg Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp , Eusystus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Monaionion atratum, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus Spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. From the order of Homoptera eg Acyrthosipon spp., Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp. , Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii , Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Drosicha spp., Dysaphis spp. Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Ferrisia spp., Geococcus coffeae, Hieroglyphus spp., Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodefax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri , Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum , Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes spp., Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.
Aus der Ordnung der Hymenoptera z.B. Athalia spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp..  From the order of Hymenoptera e.g. Athalia spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
Aus der Ordnung der Isopoda z.B. Armadillidium vulgare, Oniscus asellus, Porcellio scaber.  From the order of isopods e.g. Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
Aus der Ordnung der Isoptera z.B. Acromyrmex spp., Atta spp., Cornitermes cumulans, Microtermes obesi, Odontotermes spp., Reticulitermes spp, Aus der Ordnung der Lepidoptera z.B. Acronicta major, Adoxophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyelois transitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalo- cerus spp., Cnephasia spp., Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eidana saccharina, Ephestia kuehniella, Epinotia spp., Epiphyas postvittana, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., Hedylepta spp., Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homoeosoma spp., Homona spp., Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp., Lifhocolletis spp., Lifhophane antennata, Lobesia spp., Loxagrotis albicosta, Lymantria spp., Lyonetia spp., Malacosoma neustria, Maruca testulalis, Mamestra brassicae, Mocis spp., Mythimna separata, Nymphula spp., Oiketicus spp., Oria spp., Orthaga spp., Ostrinia spp., Oulema oryzae, Panolis flammea, Parnara spp., Pectinophora spp., Perileucoptera spp., Phthorimaea spp., Phyllocnistis citrella, Phyllonorycter spp., Pieris spp., Platynota stultana, Plusia spp., Plutella xylo- stella, Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Scotia segetum, Sesamia spp., Sparganothis spp., Spodoptera spp., Stathmopoda spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix spp., Trichoplusia spp., Tuta absoluta, Virachola spp.. From the order of the Isoptera eg Acromyrmex spp., Atta spp., Cornitermes cumulans, Microtermes obesi, Odontotermes spp., Reticulitermes spp. From the order of Lepidoptera, for example, Acronicta major, Adoxophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyelois transitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius , Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp., Cnephasia spp., Conopomorpha spp., Conotrachelus Spp., Copitarsia spp., Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eidana saccharina, Ephestia kuehniella, Epinotia spp., Epiphyas postvittana, Etiella spp., Eulia spp , Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., Hedylepta spp., Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homoeosoma spp., Hom ona spp., Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp., Lifhocolletis spp., Lifhophane antennata, Lobesia spp., Loxagrotis albicosta, Lymantria spp., Lyonetia spp., Malacosoma neustria, Maruca testulalis, Mamestra brassicae, Mocis spp., Mythimna separata, Nymphula spp., Oiketicus spp., Oria spp., Orthaga spp., Ostrinia spp., Oulema oryzae, Panolis flammea, Parnara spp., Pectinophora spp., Perileucoptera spp. Phthorimaea spp., Phyllocnis citrella, Phyllonorycter spp., Pieris spp., Platynota stultana, Plusia spp., Plutella xylostella, Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Scotia segetum, Sesamia spp., Sparganothis spp., Spodoptera spp., Stathmopoda spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix spp ., Trichoplusia spp., Tuta absoluta, Virachola spp.
Aus der Ordnung der Orthoptera z.B. Acheta domesticus, Blatta orientalis, Blattella germanica, Dichroplus spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.  From the order of Orthoptera e.g. Acheta domesticus, Blatta orientalis, Blattella germanica, Dichroplus spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
Aus der Ordnung der Siphonaptera z.B. Ceratophyllus spp., Xenopsylla cheopis.  From the order of siphonaptera e.g. Ceratophyllus spp., Xenopsylla cheopis.
Aus der Ordnung der Symphyla z.B. Scutigerella spp.. From the order of Symphyla e.g. Scutigerella spp ..
Aus der Ordnung der Thysanoptera z.B. Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp..  From the order of Thysanoptera e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
Aus der Ordnung der Thysanura z.B. Lepisma saccharina. From the order of Thysanura e.g. Lepisma saccharina.
Zu den pflanzenparasitären Nematoden gehören z.B. Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Trichodorus spp., Tylenchulus semipenetrans, Xiphinema spp.. Die erfindungsgemäße Verbindung kann gegebenenfalls in bestimmten Konzentrationen bzw. Aufwandmengen auch als Herbizid, Safener, Wachstumsregulator oder Mittel zur Verbesserung der Pflanzeneigenschaften, oder als Mikrobizid, beispielsweise als Fungizid, Antimykotika, Bakterizid, Virizid (einschließlich Mittel gegen Viroide) oder als Mittel gegen MLO (Mycoplasma-like- organism) und RLO (Rickettsia-like-organism) verwendet werden. The plant parasitic nematodes include, for example, Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Trichodorus spp., Tylenchulus semipenetrans, Xiphinema spp .. The compound according to the invention may optionally also be used in certain concentrations or application rates as a herbicide, safener, growth regulator or plant properties improver, or as a microbicide, for example as a fungicide, antimycotics, bactericide, viricide (including anti-viral agents) or as an anti-MLO agent ( Mycoplasma-like organism) and RLO (Rickettsia-like-organism).
Neben den vorgenannten Formulierungen kann die Verbindung 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on in der neuen festen Form in weitere Formulierungen überführt werden. Solche Formulierungen sind beispielsweise Lösungen, Emulsionen, Spritzpulver, wasser- und ölbasierte Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, lösliche Granulate, Streugranulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-imprägnierte Naturstoffe, Wirkstoff- imprägnierte synthetische Stoffe, Düngemittel sowie Feinstverkapselungen in polymeren Stoffen. Erfindungsgemäß bevorzugt sind Feststoffformulierungen. In addition to the above-mentioned formulations, the compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form can be converted into further formulations. Such formulations are, for example, solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural substances, active substance-impregnated synthetic substances, fertilizers and ultrafine encapsulations in polymeric materials. Solid formulations are preferred according to the invention.
Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Netzmitteln, Emulgiermitteln, Dispergiermitteln und/oder schaumzerstörenden Mitteln. Die Herstellung der Formulierungen erfolgt entweder in geeigneten Anlagen oder auch vor oder während der Anwendung. The formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally with the use of surface-active agents, ie wetting agents, emulsifiers, dispersants and / or foam-destroying agents. The preparation of the formulations is carried out either in suitable systems or before or during use.
Als Hilfsstoffe können solche Stoffe Verwendung finden, die geeignet sind, dem Mittel selbst oder und/oder davon abgeleitete Zubereitungen (z.B. Spritzbrühen, Saatgutbeizen) besondere Eigenschaften zu verleihen, wie bestimmte technische Eigenschaften und/oder auch besondere biologische Eigenschaften. Als typische Hilfsmittel kommen in Frage: Streckmittel, Lösemittel und Trägerstoffe. Excipients which can be used are those which are suitable for imparting special properties to the composition itself and / or preparations derived therefrom (for example spray liquor, seed dressing), such as certain technical properties and / or specific biological properties. Typical auxiliaries are: extenders, solvents and carriers.
Als Streckmittel eignen sich z.B. Wasser, polare und unpolare organische chemische Flüssigkeiten z.B. aus den Klassen der aromatischen und nicht-aromatischen Kohlenwasserstoffe (wie Paraffine, Alkylbenzole, Alkylnaphthaline, Chlorbenzole), der Alkohole und Polyole (die ggf. auch substituiert, verethert und/oder verestert sein können), der Ketone (wie Cyclohexanon), Ester (auch Fette und Öle) und (poly-)Ether, der einfachen und substituierten Amine, Amide, Lactame (wie N- Alkylpyrrolidone) und Lactone, der Sulfone und Sulfoxide (wie Dimethylsulfoxid). As extender, e.g. Water, polar and non-polar organic chemical liquids e.g. from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified), ketones (such as cyclohexanone), esters ( also fats and oils) and (poly) ethers, the simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulfones and sulfoxides (such as dimethyl sulfoxide).
Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösemittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösemittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, aliphatische Kohlenwasserstoffe oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole sowie deren Ether und Ester, Ketone wie Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie N-Methylpyrrolidon, Dimethylsulfoxid, sowie Wasser. In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, aliphatic hydrocarbons or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols and their ethers and Esters, ketones such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, and water.
Erfindungsgemäß bedeutet Trägerstoff eine natürliche oder synthetische, organische oder anorganische Substanz, welcher fest oder flüssig sein kann, mit welchen die Wirkstoffe zur besseren Anwendbarkeit, insbesondere zum Aufbringen auf Pflanzen oder Pflanzenteile oder Saatgut, gemischt oder verbunden sind. Der feste oder flüssige Trägerstoff ist im Allgemeinen inert und sollte in der Landwirtschaft verwendbar sein. According to the invention, the carrier means a natural or synthetic, organic or inorganic substance which may be solid or liquid, with which the active ingredients are mixed or combined for better applicability, in particular for application to plants or plant parts or seeds. The solid or liquid carrier is generally inert and should be useful in agriculture.
Als feste oder flüssige Trägerstoffe kommen in Frage: z.B. Ammoniumsalze und natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Sand, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Papier, Sägemehl, Kokosnussschalen, Maiskolben und Tabak- stängeln; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B . Alkylaryl-polyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweiß- hydrolysate; als Dispergiermittel kommen in Frage nicht-ionische und/oder ionische Stoffe, z.B. aus den Klassen der Fettalkohol-POE- und/oder POP-Ether, Säure- und/oder POP- POE-Ester, Alkyl- Aryl- und/oder POP- POE-Ether, Fett- und/oder POP- POE-Addukte, POE- und/oder POP-Polyol Derivate, POE- und/oder POP-Sorbitan- oder Zucker- Addukte, Alky- oder Aryl-Sulfate, Sulfonate und Phosphate oder die entsprechenden PO-Ether-Addukte. Ferner können Einsatz finden Lignin und seine Sulfonsäure-Derivate, einfache und modifizierte Cellulosen, aromatische und/oder aliphatische Sulfonsäuren sowie deren Addukte mit Formaldehyd. Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholipide. Suitable solid or liquid carriers are: e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules are suitable: e.g. crushed and fractionated natural rocks such as calcite, marble, sand, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are non-ionic and / or ionic substances, e.g. from the classes of fatty alcohol POE and / or POP ethers, acid and / or POP-POE esters, alkyl-aryl and / or POP-POE ethers, fatty and / or POP-POE adducts, POE and / or POP polyol derivatives, POE and / or POP sorbitan or sugar adducts, alkyl or aryl sulfates, sulfonates and phosphates or the corresponding PO ether adducts. Furthermore, find use lignin and its sulfonic acid derivatives, simple and modified celluloses, aromatic and / or aliphatic sulfonic acids and their adducts with formaldehyde. Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids may be used in the formulations.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden. Weitere Additive können Duftstoffe, mineralische oder vegetabile gegebenenfalls modifizierte Öle, Wachse und Nährstoffe (auch Spurennährstoffe), wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink sein. Dyes such as inorganic pigments such as 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. Other additives may be fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Weiterhin enthalten sein können Stabilisatoren wie Kältestabilisatoren, Konservierungsmittel, Oxidationsschutzmittel, Lichtschutzmittel oder andere die chemische und/oder physikalische Stabilität verbessernde Mittel. Stabilizers such as cold stabilizers, preservatives, antioxidants, light stabilizers or other chemical and / or physical stability-improving agents may also be present.
Der Wirkstoffgehalt der aus den Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen liegt im Bereich von 0,00000001 bis 97 Gew.-% Wirkstoff, vorzugsweise im Bereich von 0,0000001 bis 97 Gew.-%, besonders bevorzugt im Bereich von 0,000001 bis 83 Gew.-% oder 0,000001 bis 5 Gew.-% und ganz besonders bevorzugt im Bereich von 0,0001 bis 1 Gew.-%. The active ingredient content of the forms of application prepared from the formulations can vary widely. The active ingredient concentration of the use forms is in the range of 0.00000001 to 97 wt .-% of active ingredient, preferably in the range of 0.0000001 to 97 wt .-%, particularly preferably in the range of 0.000001 to 83 wt .-% or 0, 000001 to 5 wt .-% and most preferably in the range of 0.0001 to 1 wt .-%.
Die Verbindung 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on in der neuen festen Form kann in Mischungen mit anderen Wirkstoffen wie Insektiziden, Lockstoffen, Sterilantien, Bakteriziden, Akariziden, Nematoziden, Fungiziden, wachstumsregulierenden Stoffen, Herbi- ziden, Safenern (z.B. Cloquintocet-mexyl, Fenchlorazol-ethylester, Isoxadifen-ethyl, Mefenpyr-diethyl, Fenclorim und Cumyluron), Düngemitteln oder Semiochemicals oder auch mit Mitteln zur Verbesserung der Pflanzeneigenschaften vorliegen. Das gilt insbesondere für ihre handelsüblichen Formulierungen sowie für die aus diesen Formulierungen bereiteten Anwendungsformen. D as gilt s owohl für Wirkstoffkombinationen als auch für Tank-Mix Mischungen. Als Mischpartner eignen sich insbesondere die folgenden Insektizide, Akarizide und Nematizide: The compound 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form may be used in mixtures with other active ingredients such as insecticides, attractants, Sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners (eg cloquintocet-mexyl, fenchlorazole-ethylester, isoxadifen-ethyl, mefenpyr-diethyl, fenclorim and cumyluron), fertilizers or semiochemicals or also with agents for improvement the plant properties are present. This applies in particular to their commercially available formulations and to the forms of use prepared from these formulations. The same applies to active ingredient combinations as well as to tank mix mixtures. Suitable mixing partners are in particular the following insecticides, acaricides and nematicides:
(1 ) Acetylcholinesterase (AChE) Inhibitoren, wie beispielsweise Carbamate, z.B. Alanycarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC und Xylylcarb; oder Organophosphate, z.B. Acephate, Azamethiphos, Azinpho s (-methyl, -ethyl), Cadusafos, Chlor ethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos (-methyl), Coumaphos, Cyanophos, Demeton-S-methyl, Diazinon, Dichlorvos/DDVP, Dicrotophos, Dimethoate, Dimethylvinphos, Disulfoton, EPN, Ethion, Ethoprophos, Famphur, Fen- amiphos, Fenitrothion, Fenthion , F o sthiazate, Heptenophos, Isofenphos, Isopropyl O- (methoxyaminothio-phosphoryl) salicylat, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion (- methyl), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimiphos (-methyl), Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Triclorfon und Vamidothion; (1) acetylcholinesterase (AChE) inhibitors such as carbamates, eg alanycarb, aldicarb, bendocarb, benfuracarb, butocarboxime, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, Pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb; or organophosphates, eg acephates, azamethiphos, azinophos (-methyl, -ethyl), cadusafos, chloroethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl), coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos , Dimethoates, dimethylvinphos, disulphoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, sthiazate, heptenophos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathione, malathion, mecarbam, methamidophos, methidathione , Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion (- methyl), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidone, Phoxim, Pirimiphos (-methyl), Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep . Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometone, Triazophos, Triclorfon and Vamidothion;
(2) GABA-gesteuerte Chlorid-Kanal-Antagonisten, wie beispielsweise Organochlorine, z.B. Chlordane und Endosulfan (alpha-); oder Fiprole (Phenylpyrazole), z.B. Ethiprole, Fipronil, Pyrafluprole und Pyriprole; (2) GABA-controlled chloride channel antagonists such as organochlorines, e.g. Chlordane and endosulfan (alpha); or fiproles (phenylpyrazoles), e.g. Ethiprole, fipronil, pyrafluprole and pyriprole;
(3) Natrium-Kanal-Modulatoren / Spannungsabhängige Natrium-Kanal-Blocker, wie beispielsweise Pyrethroide, z.B. Acrinathrin, Allethrin (d-cis-trans, d-trans), Bifenthrin, Bioallethrin, Bioallethrin- S-cyclopentenyl, Bioresmethrin, Cycloprothrin, Cyfluthrin (beta-), Cyhalothrin (gamma-, lambda-), Cypermethrin (alpha-, beta-, theta-, zeta-), Cyphenothrin [(lR)-trans-Isomere], Deltamethrin, Dimefluthrin, Empenthrin [ (EZ)-(lR)-Isomere], Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate (tau-), Halfenprox, Imiprothrin, Metofluthrin, Permethrin, Phenothrin [( lR)-trans-Isomer], Prallethrin, Profluthrin, Pyrethrine (pyrethrum), Res- methrin, RU 15525, Silafluofen, Tefluthrin, Tetramethrin [(1R)- Isomere], Tralomethrin, Transfluthrin und ZXI 8901 ; oder DDT; oder Methoxychlor; (3) sodium channel modulators / voltage dependent sodium channel blockers such as pyrethroids, e.g. Acrinathrin, allethrin (d-cis-trans, d-trans), bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin (beta), cyhalothrin (gamma, lambda), cypermethrin (alpha, beta , theta, zeta), cyphenothrin [(lR) trans isomers], deltamethrin, dimefluthrin, empenthrin [(EZ) (lR) isomers], esfenvalerates, etofenprox, fenpropathrin, fenvalerates, flucythrinates, flumethrin, fluvalinates (tau-), Halfenprox, Imiprothrin, Metofluthrin, Permethrin, Phenothrin [(lR) -trans-isomer], Prallethrin, Profluthrin, Pyrethrin (pyrethrum), Resmethrin, RU 15525, Silafluofen, Tefluthrin, Tetramethrin [(1R) - Isomers], tralomethrin, transfluthrin and ZXI 8901; or DDT; or methoxychlor;
(4) Nikotinerge Acetylcholin-Rezeptor-Agonisten, wie beispielsweise Neonikotinoide, z.B. Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam; oder Nikotin; (4) nicotinergic acetylcholine receptor agonists, such as neonicotinoids, e.g. Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; or nicotine;
(5) Allosterische Acetylcholin-Rezeptor-Modulatoren (Agonisten), wie beispielsweise Spinosyne, z.B. Spinetoram und Spinosad; (5) Allosteric acetylcholine receptor modulators (agonists), such as spinosyns, e.g. Spinetoram and spinosad;
(6) Chlorid-Kanal-Aktivatoren, wie beispielsweise Avermectine/Milbemycine, z.B. Abamectin, Emamectin-benzoate, Lepimectin und Milbemectin; (6) chloride channel activators, such as avermectins / milbemycins, e.g. Abamectin, Emamectin benzoate, Lepimectin and Milbemectin;
(7) Juvenilhormon-Analoge, z.B. Hydroprene, Kinoprene, Methoprene; oder Fenoxycarb; Pyri- proxyfen; (7) Juvenile hormone analogs, e.g. Hydroprene, kinoprene, methoprene; or fenoxycarb; Pyrimidines;
(8) Wirkstoffe mit unbekannten oder nicht spezifischen Wirkmechanismen, wie beispielsweise Begasungsmittel, z.B. Methylbromid und andere Alkylhalogenide; oder Chloropicrin; Sulfurylfluorid; Borax; Brechweinstein; (8) agents with unknown or nonspecific modes of action, such as fumigants, e.g. Methyl bromide and other alkyl halides; or chloropicrin; sulfuryl fluoride; Borax; Tartar emetic;
(9) Selektive Fraßhemmer, z.B. Pymetrozine; oder Flonicamid; (9) Selective feeding inhibitors, e.g. pymetrozine; or flonicamide;
(10) Milbenwachstumsinhibitoren, z.B. Clofentezine, Diflovidazin, Hexythiazox, Etoxazole; (11) Mikrobielle Disruptoren der Insektendarmmembran, wie beispielsweise Bacillus thuringiensis Subspezies israelensis, Bacillus sphaericus, Bacillus thuringiensis Subspezies aizawai, Bacillus thuringiensis Subspezies kurstaki, Bacillus thuringiensis Subspezies tenebrionis, und BT-Pflanzen- Proteine, z.B. CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl ; (12) Inhibitoren der oxidativen Phosphorylierung, ATP-Disruptoren, wie beispielsweise Diafenthiuron; oder Organozinnverbindungen, z.B. Azocyclotin, Cyhexatin, Fenbutatin oxide; oder Propargite; Tetradifon; (10) mite growth inhibitors, eg clofentezine, diflovidazine, hexythiazox, etoxazole; (11) Microbial disruptors of insect intestinal membrane, such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and BT plant proteins, eg, CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A , Cry3Ab, Cry3Bb, Cry34 / 35Abl; (12) inhibitors of oxidative phosphorylation, ATP disruptors such as diafenthiuron; or organotin compounds, eg azocyclotine, cyhexatin, fenbutatin oxide; or propargite; tetradifon;
(13) Entkoppler der oxidativen Phoshorylierung durch Unterbrechung des H-Protongradienten, wie beispielsweise Chlorfenapyr und DNOC; (14) Nikotinerge Acetylcholin-Rezeptor-Antagonisten, wie beispielsweise Bensultap, Cartap (- Hydrochlorid), Thiocylam, und Thiosultap (-sodium); (13) decoupling of oxidative phosphorylation by interruption of the H proton gradient, such as chlorfenapyr and DNOC; (14) nicotinergic acetylcholine receptor antagonists, such as Bensultap, Cartap (hydrochloride), thiocylam, and thiosultap (-sodium);
(15) Inhibitoren der Chitinbiosynthese, Typ 0, wie beispielsweise Benzoylharnstoffe, z.B. Bistrifluron, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Teflubenzuron und Triflumuron; (16) Inhibitoren der Chitinbiosynthese, Typ 1, wie beispielsweise Bupro fezin; (15) inhibitors of chitin biosynthesis, type 0, such as benzoylureas, e.g. Bistrifluron, chlorofluorazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron; (16) inhibitors of chitin biosynthesis, type 1, such as Bupro fezin;
(17) Häutungsstörende Wirkstoffe, wie beispielsweise Cyromazine; (17) Moulting agents, such as Cyromazine;
(18) EcdysonagonistenAdisruptoren, wie beispielsweise Diacylhydrazine, z.B. Chromafenozide, Halofenozide, Methoxyfenozide und Tebufenozide; (18) ecdysone agonists, such as diacylhydrazines, e.g. Chromafenozide, Halofenozide, Methoxyfenozide and Tebufenozide;
(19) Oktopaminerge Agonisten, wie beispielsweise Amitraz; (20) Komplex-III-Elektronentransportinhibitoren, wie beispielsweise Hydramethylnon; Acequinocyl; Fluacrypyrim; (19) octopaminergic agonists such as amitraz; (20) complex III electron transport inhibitors such as hydramethylnone; acequinocyl; fluacrypyrim;
(21) Komplex-I-Elektronentransportinhibitoren, beispielsweise aus der Gruppe der METI-Akarizide, z.B. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, Tolfenpyrad; oder Rotenone (Derris); (22) Spannungsabhängige Natriumkanal-Blocker, z.B. Indoxacarb; Metaflumizone; (21) Complex I electron transport inhibitors, for example from the group of the METI acaricides, e.g. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, Tolfenpyrad; or Rotenone (Derris); (22) voltage dependent sodium channel blockers, e.g. indoxacarb; metaflumizone;
(23) Inhibitoren der Acetyl-CoA-Carboxylase, wie beispielsweise Tetronsäure-Derivate, z.B. Spirodiclofen und Spiromesifen; oder Tetramsäure-Derivate, z.B. Spirotetramat; (24) Komplex-IV-Elektronentransportinhibitoren, wie beispielsweise Phosphine, z.B. (23) inhibitors of acetyl-CoA carboxylase, such as tetronic acid derivatives, eg, spirodiclofen and spiromesifen; or tetramic acid derivatives, eg spirotetramat; (24) complex IV electron transport inhibitors such as phosphines, eg
Aluminiumphosphid, Kalziumphosphid, Phosphin, Zinkphosphid; oder Cyanid; Aluminum phosphide, calcium phosphide, phosphine, zinc phosphide; or cyanide;
(25) Komplex-II-Elektronentransportinhibitoren, wie beispielsweise Cyenopyrafen; oder (25) complex II electron transport inhibitors such as cyenopyrafen; or
(28) Ryanodinrezeptor-Effektoren, wie beispielsweise Diamide, z.B. Chlorantraniliprole (28) ryanodine receptor effectors such as diamides, e.g. chlorantraniliprole
(Rynaxypyr), Cyantraniliprole (Cyazypyr) und Flubendiamide. (Rynaxypyr), Cyantraniliprole (Cyazypyr) and Flubendiamide.
Weitere Wirkstoffe mit unbekanntem Wirkmechanismus, wie beispielsweise Amidoflumet, Benz- oximate, Bifenazate, Chinomethionat, Cryolite, Cyflumetofen, Dicofol, Flufenerim, Pyridalyl und Pyrifluquinazon; oder folgende bekannte wirksame Verbindungen 4-{[(6-Brompyrid-3-yl)methyl](2- fluorethyl)amino}furan-2(5H)-on (b ekannt aus WO 2007/ 1 1 5644 ) , 4-{[(6-Fluorpyrid-3- yl)methyl](2,2-difluorethyl)amino}furan-2(5H)-on (bekannt aus WO 2007/1 15644), 4-{[(2-Chlor- l,3-thiazol-5-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on (bekannt aus WO 2007/1 15644), 4- {[(6-Chlo yrid-3-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on (bekannt aus WO 2007/ 115644), 4-{[(6-Chloφyrid-3-yl)methyl](2,2-difluorethyl)amino}furan-2(5H)-o n ( b e k a n n t a u s W O 2007/115644), 4-{[(6-Chlor-5-fluo yrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (bekannt aus WO 2007/115643), 4-{[(5,6-Dichloφyrid-3-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on (bekannt aus WO 2007/115646), 4-{[(6-Chlor-5-fluoφyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (bekannt aus WO 2007/1 15643), 4-{[(6-Chloφyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)- on (bekannt aus EP-A-0 539 588), 4-{[(6-Chloφyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (bekannt aus EP-A-0 539 588), [(6-Chloφyridin-3-yl)methyl](methyl)oxido-λ4- sulfanylidencyanamid (bekannt aus WO 2007/149134), [l-(6-Chloφyridin-3-yl)ethyl](methyl)oxido- 4- und seine Diastereomere (A) und (B) Other drugs with unknown mechanism of action, such as amidoflumet, benzoximes, bifenazates, quinomethionate, cryolites, cyflumetofen, dicofol, flufenerim, pyridalyl and pyrifluquinazone; or the following known effective compounds 4 - {[(6-bromopyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (b known from WO 2007/1 1 5644), 4- { [(6-fluoropyrid-3-yl) methyl] (2,2-difluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/1 15644), 4 - {[(2-chloro-1, 3-thiazol-5-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/1 15644), 4- {[(6-chloro-3-yl) methyl ] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[(6-chloropyrid-3-yl) methyl] (2,2-difluoroethyl) amino} furan -2 (5H) -one (known from WO 2007/115644), 4 - {[(6-chloro-5-fluoro-3-yl-3-yl) methyl] (methyl) amino} furan-2 (5H) -one (known WO 2007/115643), 4 - {[(5,6-dichloropyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115646), 4 {[(6-chloro-5-fluoropyrid-3-yl) methyl] (cyclopropyl) amino} furan-2 (5H) -one (known from WO 2007/1 15643), 4 - {[(6-chloropyrid-3 -yl) methyl] (cyclopropyl) amino} furan-2 (5H) -one (known from EP-A-0 539 588), 4 - {[(6-chloropyrid-3-yl) methyl] (methyl) amino} furan-2 (5H) -one (b known from EP-A-0 539 588), [(6-chloropyridin-3-yl) methyl] (methyl) oxido-λ 4 -sulfanylidenecyanoanamide (known from WO 2007/149134), [1- (6-chloropyridine-3 -yl) ethyl] (methyl) oxido-4- and its diastereomers (A) and (B)
(A) (B) (A) (B)
(ebenfalls bekannt aus WO 2007/149134), [(6-Trifluormethylpyridin-3-yl)methyl](methyl)oxido- 4-sulfanylidencyanamid (bekannt aus WO 2007/095229), Sulfoxaflor (also known from WO 2007/149134), [(6-trifluoromethylpyridin-3-yl) methyl] (methyl) oxido-4-sulfanylidenecyanoanamide (known from WO 2007/095229), sulfoxaflor
(ebenfalls bekannt aus WO 2007/149134), 1 l-(4-Chlor-2,6-dimethylphenyl)-12-hydroxy-l,4-dioxa- 9-azadispiro[4.2.4.2]tetradec-l l-en-10-on (b ekannt aus WO 2006/089633), 3-(4'-Fluor-2,4- dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-l-azaspiro[4.5]dec-3-en-2-o n ( b e k a n n t a u s WO 2 0 0 8 / 0 6 7 9 1 1 ) u n d l-{2,4-Dimethyl-5-[(2,2,2-trifluoroethyl)sulfmyl]phenyl}-3- (trifluoromethyl)-lH-l,2,4-triazol (bekannt aus WO 1999/55668). (also known from WO 2007/149134), 1 l- (4-chloro-2,6-dimethylphenyl) -12-hydroxy-1,4-dioxa-9-azadispiro [4.2.4.2] tetradec-1-ene 10-on (known from WO 2006/089633), 3- (4'-fluoro-2,4-dimethylbiphenyl-3-yl) -4-hydroxy-8-oxa-1-azaspiro [4.5] dec-3- en-2-on (known from WO 2 0 0 8/0 6 7 9 1 1) and 1- {2,4-dimethyl-5 - [(2,2,2-trifluoroethyl) sulfmyl] phenyl} -3- (trifluoromethyl) -1H-1, 2,4-triazole (known from WO 1999/55668).
Als Mischpartner eignen sich ferner die folgenden Fungizide Other suitable mixing partners are the following fungicides
(A) Inhibitoren der Nukleinsäuresynthese, wie beispielsweise Benalaxyl, Benalaxyl-M, Bupirimat, Clozylacon, Dimethirimol, Ethirimol, Furalaxyl, Hymexazol, Metalaxyl, Metalaxyl-M, Ofurace, Oxadixyl und Oxolinsäure; (A) inhibitors of nucleic acid synthesis such as benalaxyl, benalaxyl-M, bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazole, metalaxyl, metalaxyl-M, ofurace, oxadixyl and oxolic acid;
(B) Inhibitoren der Mitose und Zellteilung, wie beispielsweise Benomyl, Carbendazim, Chlorfenazol, Diethofencarb, Ethaboxam, Fuberidazol, Pencycuron, Thiabendazol, Thiophanat, Thiophanat-Methyl und Zoxamid; (B) Mitosis and cell division inhibitors such as benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fuberidazole, pencycuron, thiabendazole, thiophanate, thiophanate-methyl and zoxamide;
(C) Inhibitoren der Respiration (Atmungsketten-Inhibitoren), wie beispielsweise Diflumetorim als Inhibitor am Komplex I der Atmungskette; Bixafen, Boscalid, Carboxin, Fenfuram, Flutolanil, Fluopyram, Furametpyr, Furmecyclox, Isopyrazam (Mischung aus dem syn-epimeren Razemat 1RS,4SR,9RS und dem anti-epimeren Razemat 1RS,4SR,9SR), Isopyrazam (syn epimeres Razemat 1RS,4SR,9RS), Isopyrazam (syn-epimeres Enantiomer 1R,4S,9R), Isopyrazam (syn-epimeres Enantiomer 1 S,4R,9S), Isopyrazam (anti-epimeres Razemat 1RS,4SR,9SR), Isopyrazam (anti- epimeres Enantiomer 1R,4S,9S), Isopyrazam (anti-epimeres Enantiomer 1S,4R,9R),  (C) inhibitors of respiration (respiratory chain inhibitors), such as diflumetorim as an inhibitor at the complex I of the respiratory chain; Bixafen, boscalid, carboxin, fenfuram, flutolanil, fluopyram, furametpyr, furmecyclox, isopyrazam (mixture of the syn-epimeric racemate 1RS, 4SR, 9RS and the anti-epimeric racemate 1RS, 4SR, 9SR), isopyrazam (syn epimeric racemate 1RS, 4SR, 9RS), isopyrazam (syn-epimeric enantiomer 1R, 4S, 9R), isopyrazam (syn-epimeric enantiomer 1S, 4R, 9S), isopyrazam (anti-epimeric racemate 1RS, 4SR, 9SR), isopyrazam (anti-epimeric Enantiomer 1R, 4S, 9S), isopyrazam (anti-epimeric enantiomer 1S, 4R, 9R),
Mepronil, Oxycarboxin, Penflufen, Penthiopyrad, Sedaxane, Thifluzamid als Inhibitoren am Komplex II der Atmungskette; Amisulbrom, Azoxystrobin, Cyazofamid, Dimoxystrobin, Enestroburin, Famoxadon, Fenamidon, Fluoxastrobin, Kresoxim-Methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Pyraoxystrobin, Pyrametostrobin, Pyribencarb, Trifloxystrobin als Inhibitoren am Komplex III der Atmungskette;  Mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, thifluzamide as inhibitors of complex II of the respiratory chain; Amisulbrom, azoxystrobin, cyazofamide, dimoxystrobin, enestroburin, famoxadone, fenamidone, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyraoxystrobin, pyrametostrobin, pyribencarb, trifloxystrobin as inhibitors of complex III of the respiratory chain;
(D) Entkoppler, wie beispielsweise Binapacryl, Dinocap, Fluazinam und Meptyldinocap; (D) decouplers such as binapacryl, dinocap, fluazinam and meptyldinocap;
(E) Inhibitoren der ATP Produktion, wie beispielsweise Fentin Acetat, Fentin Chlorid, Fentin Hydroxid und Silthiofam; (E) inhibitors of ATP production, such as, for example, fentin acetate, fentin chloride, fentin hydroxide and silthiofam;
(F) Inhibitoren der Aminosäure- und Protein-Biosynthese, wie beispielsweise Andoprim, Blasticidin-S, Cyprodinil, Kasugamycin, Kasugamycin Hydrochlorid Hydrat, Mepanipyrim und Pyrimethanil; (F) inhibitors of amino acid and protein biosynthesis, such as andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim and pyrimethanil;
(G) Inhibitoren der Signaltransduktion, wie beispielsweise Fenpiclonil, Fludioxonil und Quinoxyfen; (G) signal transduction inhibitors such as fenpiclonil, fludioxonil and quinoxyfen;
(H) Inhibitoren der Lipid- und Membran-Synthese, wie beispielsweise Biphenyl, Chlozolinat, Edifenphos, Etridiazol, Iodocarb, Iprobenfos, Iprodion, Isoprothiolan, Procymidon, Propamocarb,(H) inhibitors of lipid and membrane synthesis, such as biphenyl, chlozolinate, edifenphos, etridiazole, iodocarb, Iprobenfos, iprodione, isoprothiolane, procymidone, propamocarb,
Propamocarb Hydrochlorid, Pyrazophos, Tolclofos-Methyl und Vinclozolin; (I) Inhibitoren der Ergosterol-Biosynthese, wie beispielsweise Aldimorph, Azaconazol, Bitertanol, Bromuconazol, Cyproconazol, Diclobutrazol, Difenoconazol, Diniconazol, Diniconazol-M, Dodemorph, Dodemorph Acetat, Epoxiconazol, Etaconazol, Fenarimol, Fenbuconazol, Fenhexamid, Fenpropidin, Fenpropimorph, Fluquinconazol, Flurprimidol, Flusilazol, Flutriafol, Furconazol, Furconazol-Cis, Hexaconazol, Imazalil, Imazalil Sulfat, Imibenconazol, Ipconazol, Metconazol, Myclobutanil, Naftifm, Nuarimol, Oxpoconazol, Paclobutrazol, Pefurazoat, Penconazol, Piperalin, Prochloraz, Propiconazol, Prothioconazol, Pyributicarb, Pyrifenox, Quinconazol, Simeconazol, Spiroxamin, Tebuconazol, Terbinafin, Tetraconazol, Triadimefon, Triadimenol, Tridemorph, Triflumizol, Triforin, Triticonazol, Uniconazol, Uniconazol-p, Viniconazol und Voriconazol; (J) Inhibitoren der Zellwandsynthese, wie beispielsweise Benthiavalicarb, Dimethomorph, Flumorph, Iprovalicarb, Mandipropamid, Polyoxins, Polyoxorim, Prothiocarb, Validamycin A und Valefenalat; Propamocarb hydrochloride, pyrazophos, tolclofos-methyl and vinclozolin; (I) inhibitors of ergosterol biosynthesis, such as aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamide, fenpropidin, fenpropimorph, Fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifm, nuarimol, oxpoconazole, paclobutrazole, pefurazoate, penconazole, piperaline, prochloraz, propiconazole, prothioconazole, pyributicarb , Pyrifenox, quinconazole, simeconazole, spiroxamine, tebuconazole, terbinafine, tetraconazole, triadimefon, triadimenol, tridemorph, triflumizole, triforin, triticonazole, uniconazole, uniconazole-p, viniconazole and voriconazole; (J) inhibitors of cell wall synthesis, such as benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamide, polyoxins, polyoxorim, prothiocarb, validamycin A and valefenalate;
(K) Inhibitoren der Melanin-Biosynthese, wie beispielsweise Carpropamid, Diclocymet, Fenoxanil, Fthalid, Pyroquilon und Tricyclazol; (L) Resistenzinduktoren, wie beispielsweise Acibenzolar-S-Methyl, Probenazol und Tiadinil. (K) inhibitors of melanin biosynthesis, such as carpropamide, diclocymet, fenoxanil, fthalide, pyroquilone and tricyclazole; (L) resistance inducers such as acibenzolar-S-methyl, probenazole and tiadinil.
(M) Verbindungen mit Multisite-Aktivität, wie beispielsweise Bordeauxmischung, Captafol, Captan, Chlorothalonil, Kupfernaphthenat, Kupferoxid, Kupferoxychlorid, Kupferzubereitungen, wie Kupferhydroxid, Kupfersulfat, Dichlofluanid, Dithianon, Dodine und dessen freie Base, Ferbam, Fluorofolpet, Folpet, Guazatin, Guazatinacetat, Iminoctadin, Iminoctadinalbesilat, Iminoctadintriacetat, Mankupfer, Mancozeb, Maneb, Metiram, Zinkmetiram, Kupfer-Oxin, Propamidin, Propineb, Schwefel und Schwefelzubereitungen wie beispielsweise Calciumpolysulfid, Thiram, Tolylfluanid, Zineb und Ziram; (M) Compounds with multisite activity, such as, for example, Bordeaux mixture, captafol, captan, chlorothalonil, copper naphthenate, copper oxide, copper oxychloride, copper preparations, such as copper hydroxide, copper sulfate, dichlofluanid, dithianone, dodine and its free base, Ferbam, Fluorofolpet, Folpet, Guazatine, Guazatine acetate, iminoctadine, iminoctadinal besylate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, zinc metiram, copper oxine, propamidine, propineb, sulfur and sulfur preparations such as calcium polysulfide, thiram, tolylfluanid, zineb and ziram;
(N) Weitere Verbindungen, wie beispielsweise 2,3-Dibutyl-6-chlorthieno[2,3-d]pyrimidin-4(3H)-on, (2Z)-3-Amino-2-cyano-3-phenylprop-2-ensäureethylester, 3-(Difluormethyl)-l-methyl-N-(3',4',5'- trifluorbiphenyl-2-yl)-lH-pyrazol-4-c a r b o x am i d , 3-(Difluormethyl)-N-[4-fluor-2-(l, 1,2, 3,3,3- hexafluorpropoxy)phenyl]-l-methyl-lH-pyrazol-4-c a r b o x a m i d , ( 2 E )-2-(2-{[6-(3-Chlor-2- methylphenoxy)-5-fluorpyrimidin-4-yl] oxy } phenyl)-2-(methoxyimino)-N-methylethanami d , ( 2 E )-2- {2-[({[(2E,3E)-4-(2,6-Dichlorphenyl)but-3-en-2-yliden]amino}oxy)methyl]phenyl}-2- (methoxyimino)-N-methylethanamid, 2-Chlor-N-( 1 , 1 ,3 -trimethyl-2,3 -dihydro- 1 H-inden-4-yl)pyridin- 3-carboxamid, N-(3-Ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamid, 5- Methoxy-2-methyl-4-(2-{[({(lE)-l-[3-(trifluormethyl)phenyl]ethyliden}amino)oxy]methyl}phenyl)- 2,4-dihydro-3H-l,2,4-triazol-3-o n , ( 2 E )-2-(Methoxyimino)-N-methyl-2-(2-{[({(lE)-l-[3- (trifluormethyl)phenyl]ethyliden}amino)oxy]methyl}phenyl)eth (2E)-2-(Methoxyimino)-N- methyl-2-{2-[(E)-({l-[3-(1rifluormethyl)phenyl]ethoxy}imino)methyl]p (2E)-2-{2- [( { [(1E)-1 -(3- { [(E)-l -Fluor-2-phenylethenyl]oxy}phenyl)ethyliden]amino} oxy)methyl]phenyl} -2- (methoxyimino)-N-methylethanamid, 1 -(4-Chlorphenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)cycloheptanol, 1 - (2,2-Dimethyl-2,3-dihydro-lH-inden-l-yl)-lH-imidazol-5-carbonsaeuremethylester N-Ethyl-N- methyl-N'-{2-methyl-5-(1rifluormethyl^ N'-{5- (Difluormethyl)-2-methyl-4-[3-(1rimethylsilyl)propoxy]phenyl}-N-ethyl-N-m O- {l-[(4-Methoxyphenoxy)methyl]-2,2-dimethylpropyl} lH-imidazol-l-carbothioat, N-[2-(4-{[3-(4- Chlorphenyl)prop-2-yn-l -yl]oxy} -3-methoxyphenyl)ethyl]-N2-(methylsulfonyl)valinamid, 5-Chlor-7- (4-methylpiperidin-l-yl)-6-(2,4,6-1rifluoφh^ 5-Amino-l,3,4- thiadiazol-2-thiol, Propamocarb-Fosetyl, l-[(4-Methoxyphenoxy)methyl]-2,2-dimethylpropyl 1H- imidazol-l-c ar b o x y 1 at , l-Methyl-N-[2-(l,l,2,2-te1rafluorethoxy)phenyl]-3-(lTifluormethyl)-lH- pyrazol-4-carboxamid, 2,3,5,6-Tetrachlor-4-(methylsulfonyl)pyridin, 2-Butoxy-6-iod-3-propyl-4H- chromen-4-ο n , 2-Phenylphenol und dessen Salze, 3-(Difluormethyl)-l-methyl-N-[2-(l,l,2,2- tetrafluorethoxy)phenyl]-lH-pyrazol-4-carboxamid, 3,4,5-Trichlorpyridin-2,6-dicarbonitril, 3-[5-(4- Chlorphenyl)-2,3-dimethylisoxazolidin-3-y 1 ] p y r i d i n , 3-Chlor-5-(4-chlorphenyl)-4-(2,6- difluorphenyl)-6-methylpyridazin, 4-(4-Chloφhenyl)-5-(2,6-difluorphenyl)-3,6-dimethylpyridazin, 8- Hydroxychinolin, 8-Hydroxychinolinsulfat, Tebuf oquin, 2-[5-Methyl-3-(trifluormethyl)-lH- pyrazol-l-yl]-l-(4-{4-[(5R)-5-phenyl-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l- yl)ethanon Ametoctradin, Benthiazol, l-(4-{4-[(5R)-5-(2,6-Difluorphenyl)-4,5-dihydro-l,2-oxazol- 3 -yl] - 1 ,3 -thiazol-2-yl } piperidin- 1 -yl)-2- [5 -methyl-3 -(trifluormethyl)- 1 H-pyrazol- 1 -yl] ethanon, Bethoxazin, Capsimycin, Carvon, Chinomethionat, Chloroneb, Cufraneb, Cyflufenamid, Cymoxanil, Cyprosulfamide, Dazomet, Debacarb, Dichlorophen, Diclomezin, Dicloran, Difenzoquat, Difenzoquat Methylsulphat, Diphenylamin, Ecomat, Ferimzon, Flumetover, Fluopicolid, Fluoromid, Flusulfamid, Flutianil, Fosetyl-Aluminium, Fosetyl-Calcium, Fosetyl-Natrium, Hexachlorbenzol, I r u m a m y c i n , I s o t i a n i l , M e t h a sulfocarb, (2E)-2-{2-[({Cyclopropyl[(4- methoxyphenyl)imino]methyl}thio)methyl]phenyl}-3-methoxyacrylsaeuremethylester, (N) Other compounds such as 2,3-dibutyl-6-chlorothieno [2,3-d] pyrimidin-4 (3H) -one, (2Z) -3-amino-2-cyano-3-phenylprop-2 ethyl acetate, 3- (difluoromethyl) -1-methyl-N- (3 ', 4', 5'-trifluorobiphenyl-2-yl) -1H-pyrazole-4-carboxamide on the id, 3- (difluoromethyl) -N- [4-fluoro-2- (1,2,3,3,3,3-hexafluoropropoxy) phenyl] -1-methyl-1H-pyrazole-4-carboxamide, (2 E) -2- (2 - {[6 - (3-chloro-2-methylphenoxy) -5-fluoropyrimidin-4-yl] oxy} phenyl) -2- (methoxyimino) -N-methylethanediamine, (2E) -2- {2 - [({[( 2E, 3E) -4- (2,6-dichlorophenyl) but-3-en-2-ylidene] amino} oxy) methyl] phenyl} -2- (methoxyimino) -N-methylethaneamide, 2-chloro-N- ( 1, 1, 3 -trimethyl-2,3-dihydro-1H-inden-4-yl) pyridine-3-carboxamide, N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3- (formylamino) 2-hydroxybenzamide, 5-methoxy-2-methyl-4- (2 - {[({(1E) -1- [3- (trifluoromethyl) phenyl] ethylidene} amino) oxy] methyl} phenyl) -2,4 -dihydro-3H-l, 2,4-triazol-3-one, (2E) -2- (methoxyimino) -N-methyl-2- (2 - {[({(IE) -l- [3- (trifluoromethyl) phenyl] ethylidene} amino) oxy] methyl} phenyl) eth (2E) -2- (methoxyimino) -N-methyl-2- {2 - [(E) - ({1- [3- (1-fluoro-methyl) phenyl] ethoxy} imino) methyl] p (2E) -2- {2- [({[(1E) -1- (3 - {[(E) -1-fluoro-2-phenylethenyl] oxy} phenyl) ethylidene ] amino} oxy) methyl] phenyl} -2- (methoxyimino) -N-methylethaneamide, 1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol, 1 - (2,2-Dimethyl-2,3-dihydro-1H-inden-1-yl) -1H-imidazole-5-carboxylic acid methyl ester N-ethyl-N-methyl-N '- {2-methyl-5- (1-fluoromethyl) N '- {5- (Difluoromethyl) -2-methyl-4- [3- (1-trimethylsilyl) propoxy] phenyl} -N-ethylN.m O- {1- [(4-methoxyphenoxy) methyl] -2,2- dimethylpropyl} 1H-imidazole-1-carbothioate, N- [2- (4 - {[3- (4-chlorophenyl) -prop-2-yn-1-yl] oxy} -3-methoxyphenyl) ethyl] -N 2 - (methylsulfonyl) valinamide, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluoro-phthalo-5-amino-1,3,4-thiadiazole-2-thiol, propamocarboxylic acid) Fosetyl, 1 - [(4-methoxyphenoxy) methyl] -2,2-dimethylpropyl 1H-imidazole-1-arylcarboxylate, 1-methyl-N- [2- (1,1,2,2-tetrafluoroethoxy) phen yl] -3- (1-trifluoromethyl) -1H-pyrazole-4-carboxamide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2-butoxy-6-iodo-3-propyl-4H-chromo- 4-o, 2-phenylphenol and its salts, 3- (difluoromethyl) -1-methyl-N- [2- (1,1 -,2,2-tetrafluoroethoxy) phenyl] -1H-pyrazole-4-carboxamide, 3 , 4,5-trichloropyridine-2,6-dicarbonitrile, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine, 3-chloro-5- (4-chlorophenyl) -4 - (2,6-difluorophenyl) -6-methylpyridazine, 4- (4-chlorophenyl) -5- (2,6-difluorophenyl) -3,6-dimethylpyridazine, 8-hydroxyquinoline, 8-hydroxyquinoline sulphate, Tebufoquin, 2- [5-Methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl] -1- (4- {4 - [(5R) -5-phenyl-4,5-dihydro-1,2-oxazole-3 -yl] -1,3-thiazol-2-yl} piperidin-1-yl) ethanone Ametoctradin, Benthiazole, 1- (4- {4 - [(5R) -5- (2,6-Difluorophenyl) -4, 5-dihydro-l, 2-oxazol-3-yl] -1,3-thiazol-2-yl} piperidine-1-yl) -2- [5-methyl-3 - (trifluoromethyl) -1H-pyrazole 1 -yl] ethanone, bethoxazine, capsimycin, carvone, quinomethionate, chloroneb, cufraneb, cyflufenamid, cymoxanil, cypros ulfamides, dazomet, debacarb, dichlorophen, diclomethine, diclorane, difenzoquat, difenzoquat methylsulphate, diphenylamine, ecomat, ferimzone, flumetover, fluopicolide, fluoromide, flusulfamide, flutianil, fosetyl-aluminum, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, l rumamycin, Sotianil, M etha sulfocarb, (2E) -2- {2 - [({cyclopropyl [(4-methoxyphenyl) imino] methyl} thio) methyl] phenyl} -3-methoxyacrylic acid methyl ester,
Methylisothiocyanat, Metrafenon, (5-Chlor-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6- methylphenyl)methanon, Mildiomycin, Tolnifanid, N-(4-Chlorbenzyl)-3-[3-methoxy-4-(prop-2-yn-l- yloxy)phenyl] prop anamid, N-[(4-Chlorphenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-l- y l o x y ) p h e n y l ] p r o p an am i d , N-[(5-Brom-3-chlorpyridin-2-yl)methyl]-2,4-dichlorpyridin-3- carboxamid, N-[l-(5-Brom-3-chlorpyridin-2-yl)ethyl]-2,4-dichlorpyridin-3-carboxamid, N-[l-(5- Brom-3-chlorpyridin-2-yl)ethyl]-2-fluor-4-iodpyridin-3-c a r b o x a m i d , N-{(Z)- [(Cyclopropylmethoxy)imino][6-(difluormethoxy)-2,3-difluorphenyl]methyl}-2-phenylacetamid, N- {(E)-[(Cyclopropylmethoxy)imino][6-(difluormethoxy)-2,3-difluorphenyl]methyl}-2- phenylacetamid, Natamycin, Nickel Dimethyldithiocarbamat, Nitrothal-Isopropyl, Octhilinone, Oxamocarb, Oxyfenthiin, Pentachlorphenol und dessen Salze, Phenazin-1 -carbonsäure, Phenothrin, Phosphorsäure und deren Salze, Propamocarb Fosetylat, Propanosin-Natrium, Proquinazid, Pyrrolnitrin, Quintozen, S-Prop-2-en-l-yl 5-amino-2-(l-methylethyl)-4-(2-methylphenyl)-3-oxo-2,3- dihydro-lH-pyrazol-l-carbothioat, Tecloftalam, Tecnazene, Triazoxid, Trichlamid, 5-Chlor-N- phenyl-N'-prop-2-yn-l-ylthiophen-2-sulfonohydrazid, Zarilamid, N-Methyl-2-(l-{[5-methyl-3- (trifluormethyl)- 1 H-pyrazol- 1 -yljacetyl} piperidin-4-yl)-N-[( 1 R)- 1 ,2,3 ,4-tetrahydronaphthalen- 1 -yl]- l,3-thiazol-4-c a r b o x a m i d , N-Methyl-2-(l-{[5-methyl-3-(trifluormethyl)-lH-pyrazol-l- yljacetyl} piperidin-4-yl)-N-( 1 ,2,3 ,4-tetrahydronaphthalen- 1 -yl)- 1 ,3-thiazol-4-c arb o x am i d , un d Pentyl- { 6- [( { [( 1 -methyl- 1 H-tetrazol-5 -yl)(phenyl)methyliden]amino } oxy)methyl]pyridin-2- yl}carbamat. Methyl isothiocyanate, metrafenone, (5-chloro-2-methoxy-4-methylpyridin-3-yl) (2,3,4-trimethoxy-6-methylphenyl) methanone, Mildiomycin, Tolnifanide, N- (4-chlorobenzyl) -3- [3-methoxy-4- (prop-2-yn-1-yloxy) phenyl] propanamide, N - [(4-chlorophenyl) (cyano) methyl] -3- [3-methoxy-4- (prop-2 -yn-1-yloxy) phenyl] propane on id, N - [(5-bromo-3-chloropyridin-2-yl) methyl] -2,4-dichloropyridine-3-carboxamide, N- [1- (5 -Bromo-3-chloropyridin-2-yl) ethyl] -2,4-dichloropyridine-3-carboxamide, N- [1- (5-bromo-3-chloropyridin-2-yl) ethyl] -2-fluoro-4 -iodopyridine-3-carboxamide, N - {(Z) - [(cyclopropylmethoxy) imino] [6- (difluoromethoxy) -2,3-difluorophenyl] methyl} -2-phenylacetamide, N - {(E) - [(cyclopropylmethoxy ) imino] [6- (difluoromethoxy) -2,3-difluorophenyl] methyl} -2- phenylacetamide, natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, octhilinone, oxamocarb, oxyfenthiine, pentachlorophenol and its salts, phenazine-1-carboxylic acid, phenothrin, phosphoric acid and its salts, propamocarb fosetylate, propanosine sodium, proquinazide, pyrrolnitrin, quintozene, S- Prop-2-en-1-yl 5-Amino-2- (1-methylethyl) -4- (2-methylphenyl) -3-oxo-2,3-dihydro-1H-pyrazole-1-carbothioate, Tecloftalam, Tecnazene , Triazoxide, trichlamide, 5-chloro-N-phenyl-N'-prop-2-yn-1-yl-thiophene-2-sulfonohydrazide, zarilamide, N-methyl-2- (1 - {[5-methyl-3 ( trifluoromethyl) -1 H -pyrazole-1-yl-1-ylacetyl} piperidin-4-yl) -N - [(1 R) -1,3,3,4-tetrahydronaphthalene-1-yl] -1,3-thiazole-4 carboxamide, N-methyl-2- (1 - {[5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl-1-yl-1-yl-1-piperidin-4-yl) -N- (1,2,3,4-tetrahydronaphthalene 1 -yl) -1,3-thiazole-4-c arb ox on id, and pentyl {6- [({[(1-methyl-1 H-tetrazol-5-yl) (phenyl) methylidene] amino} oxy) methyl] pyridin-2-yl} carbamate.
Als Mischpartner eignen sich gleichfalls die folgenden Herbizide oder Pflanzenwachstumsregulatoren: Acetochlor, Acibenzolar, Acibenzolar-S-methyl, Acifluorfen, Acifluorfen-sodium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim-sodium, Ametryn, Amicarbazone, Amidochlor, Amidosulfuron, Aminopyralid, Amitrole, Ammoniumsulfamat, Ancymidol, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H, BAS-800H, Beflubutamid, Benazolin, Benazolin-ethyl, bencarbazone, Benfluralin, Benfuresate, Bensulide, Bensulfuron-methyl, Bentazone, Benzfendizone, Benzobicyclon, Benzofenap, Benzofluor, Benzoylprop, Bifenox, Bilanafos, Bilanafos-natrium, Bispyribac, Bispyribac-natrium, Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Bromuron, Buminafos, Busoxinone, Butachlor, Butafenacil, Butamifos, Butenachlor, Butralin, Butroxydim, Butylate, Cafenstrole, Carbetamide, Carfentrazone, Carfentrazone-ethyl, Chlomethoxyfen, Chloramben, Chlorazifop, Chlorazifop-butyl, Chlorbromuron, Chlorbufam, Chlorfenac, Chlorfenac-natrium,Also suitable as mixing partners are the following herbicides or plant growth regulators: acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, aminopyralid, amitrole , Ammonium Sulfamate, Ancymidol, Anilofos, Asulam, Atrazine, Azafenidine, Azimsulfuron, Aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H, BAS-800H, Beflubutamide, Benazoline, Benazoline -ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfuron-methyl, bentazone, benzofendizone, benzobicyclone, benzofenap, benzofluor, benzoylprop, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromoacil, bromobutide, bromofenoxime, bromoxynil, bromuron , Buminafos, Busoxinone, Butachlor, Butafenacil, Butamifos, Butenachlor, Butraline, Butroxydim, Butylates, Cafenstrole, Carbetamides, Carfentrazone, Carfentrazone-ethyl, Chlomethoxyfen, Chloramben, Chlorine azifop, chlorazifop-butyl, chlorobromuron, chlorobufam, chlorfenac, chlorfenac sodium,
Chlorfenprop, Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl, Chlormequat-chlorid, Chlornitrofen, Chlorophthalim, Chlorthal-dimethyl, Chlorotoluron, Chlorfenprop, Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl, Chlormequat-chloride, Chloronitrofen, Chlorophthalim, Chlorthal-dimethyl, Chlorotoluron,
Chlorsulfuron, Cinidon, Cinidon-ethyl, Cinmethylin, Cinosulfuron, Clethodim, Clodinafop Chlorsulfuron, cinidone, cinidon-ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop
Clodinafop-propargyl, Clofencet, Clomazone, Clomeprop, Cloprop, Clopyralid, Cloransulam, Cloransulam-methyl, Cumyluron, Cyanamide, Cyanazine, Cyclanilide, Cycloate, Cyclosulfamuron, Cycloxydim, Cycluron, Cyhalofop, Cyhalofop-butyl, Cyperquat, Cyprazine, Cyprazole, 2,4-D, 2,4- DB, Daimuron/Dymron, Dalapon, Daminozide, Dazomet, n-Decanol, Desmedipham, Desmetryn, Detosyl-Pyrazolate (DTP), Diallate, Dicamba, Dichlobenil, Dichlorprop, Dichlorprop-P, Diclofop, Diclofop-methyl, Diclofop-P-methyl, Diclosulam, Diethatyl, Diethatyl-ethyl, Difenoxuron, Difenzoquat, Diflufenican, Diflufenzopyr, Diflufenzopyr-natrium, Dimefuron, Dikegulac-sodium, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimethenamid-P, Dimethipin, Dimetrasulfuron, Dinitramine, Dinoseb, Dinoterb, Diphenamid, Dipropetryn, Diquat, Diquat-dibromide, Dithiopyr, Diuron, DNOC, Eglinazine-ethyl, Endothal, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron-methyl, Ethephon, Ethidimuron, Ethiozin, Ethofumesate, Ethoxyfen, Ethoxyfen-ethyl, Ethoxysulfuron, Etobenzanid, F-5331, d.h. N-[2-Chlor-4-fluor-5-[4-(3fluorpropyl)- 4,5-dihydro-5-oxo-lH-tetrazol-l-yl]-phenyl]-ethansulfonamid, Fenoprop, Fenoxaprop, Fenoxaprop- P, Fenoxaprop-ethyl, Fenoxaprop-P-ethyl, Fentrazamide, Fenuron, Flamprop, Flamprop-M- isopropyl, Flamprop-M-methyl, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-P, Fluazifop-butyl, Fluazifop-P -butyl, Fluazolate, Flucarbazone, Flucarbazone-sodium, Flucetosulfuron, Fluchloralin, Flufenacet (Thiafluamide), Flufenpyr, Flufenpyr-ethyl, Flumetralin, Flumetsulam, Flumiclorac, Flumiclorac-pentyl, Flumioxazin, Flumipropyn, Fluometuron, Fluorodifen, Fluoroglycofen, Fluoroglycofen-ethyl, Flupoxam, Flupropacil, Flupropanate, Flupyrsulfuron, Flupyrsulfuron-methyl- sodium, Flurenol, Flurenol-butyl, Fluridone, Flurochloridone, Fluroxypyr, Fluroxypyr-meptyl, Flurprimidol, Flurtamone, Fluthiacet, Fluthiacet-methyl, Fluthiamide, Fomesafen, Foramsulfuron, Forchlorfenuron, Fosamine, Furyloxyfen, Gibberellinsäure, Glufosinate, L-Glufosinate, L- Glufosinate-ammonium, Glufosinate-ammonium, Glyphosate, Glyphosate-isopropylammonium, H- 9201, Halosafen, Halosulfuron, Halosulfuron-methyl, Haloxyfop, Haloxyfop-P, Haloxyfop- ethoxyethyl, Haloxyfop-P-ethoxyethyl, Haloxyfop-methyl, Haloxyfop-P -methyl, Hexazinone, FTNPC-9908, HOK-201, HW-02, Imazamethabenz, Imazamethabenz -methyl, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Inabenfide, Indanofan, Indolessigsäure (IAA), 4- Indol-3-ylbuttersäure (IBA), Iodosulfuron, Iodosulfuron-methyl-natrium, Ioxynil, Isocarbamid, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, IDH-100, KUH-043, KUH-071, Karbutilate, Ketospiradox, Lactofen, Lenacil, Linuron, Maleinsäurehydrazid, MCPA, MCPB, MCPB-methyl, -ethyl und -natrium, Mecoprop, Mecoprop-natrium, Mecoprop- butotyl, Mecoprop-P-butotyl, Mecoprop-P-dimethylammonium, Mecoprop-P-2-ethylhexyl, Mecoprop-P-kalium, Mefenacet, Mefluidide, Mepiquat-chlorid, Mesosulfuron, Mesosulfuron- methyl, Mesotrione, Methabenzthiazuron, Metam, Metamifop, Metamitron, Metazachlor, Clodinafop-propargyl, Clofenac, Clomazone, Clomeprop, Cloprop, Clopyralid, Cloransulam, Cloransulam-methyl, Cumyluron, Cyanamide, Cyanazine, Cyclanilide, Cycloate, Cyclosulfamuron, Cycloxydim, Cycluron, Cyhalofop, Cyhalofop-butyl, Cyperquat, Cyprazine, Cyprazole, 2, 4-D, 2,4-DB, daimurone / dymron, dalapon, daminozide, dazomet, n-decanol, desmedipham, desmetryne, detosyl pyrazolates (DTP), dialkyls, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop -methyl, diclofop-P-methyl, diclosulam, diethatyl, diethyl-ethyl, difenoxuron, Difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dikegulac-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipine, dimetrasulfuron, dinitramine, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, diquat-dibromide, Dithiopyr, diuron, DNOC, eglinazine-ethyl, endothal, EPTC, esprocarb, etalfluralin, ethametsulfuron-methyl, ethephon, ethidimuron, ethiozine, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanide, F-5331, ie N- [2-] Chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide, fenoprop, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl , Fenoxaprop-P-ethyl, Fentrazamide, Fenuron, Flamprop, Flamprop-M-isopropyl, Flamprop-M-methyl, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-P, Fluazifop-butyl, Fluazifop-P-butyl, Fluazolate, Flucarbazone, Flucarbazone -sodium, flucetosulfuron, fluchloralin, flufenacet (thiafluamide), flufenpyr, flufenpyr-ethyl, flumetralin, F lumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazine, flumipropyne, fluometuron, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, flupoxam, flupropacil, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, fluroxypyr- meptyl, flurprimidol, flurtamone, fluthiacet, fluthiacet-methyl, fluthiamide, fomesafen, foramsulfuron, forchlorfenuron, fosamine, furyloxyfen, gibberellin, glufosinate, l-glufosinate, l-glufosinate-ammonium, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, H- 9201, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfopethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, FTNPC-9908, HOK-201, HW-02, Imazamethabenz, imazamethabenz -methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, inabenfide, indanofan, indoleacetic acid (IAA), 4-indol-3-yl-butyric acid (IBA), iodosulfuron, iodosulfuron-m ethyl-sodium, ioxynil, isocarbamide, isopropalin, isoproturon, isourone, isoxaben, isoxachlorotole, isoxaflutole, isoxapyrifop, IDH-100, KUH-043, KUH-071, carbutilate, ketospiradox, lactofen, lenacil, linuron, maleic hydrazide, MCPA, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium, mecopropbutotyl, mecoprop-p-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-potassium, mefenacet, mefluidides, Mepiquat chloride, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor,
Methazole, Methoxyphenone, Methyldymron, 1-Methylcyclopropen, Methylisothiocyanat, Methazoles, methoxyphenones, methyldymron, 1-methylcyclopropene, methyl isothiocyanate,
Metobenzuron, Metobenzuron, Metobromuron, Metolachlor, S-Metolachlor, Metosulam, Metobenzuron, Metobenzuron, Metobromuron, Metolachlor, S-Metolachlor, Metosulam,
Metoxuron, Metribuzin, Metsulfuron, Metsulfuron-methyl, Molinate, Monalide, Monocarbamide, Monocarbamide-dihydrogensulfat, Monolinuron, Monosulfuron, Monuron, MT 128, MT-5950, d. h. N-[3-Chlor-4-(l-methylethyl)-phenyl]-2-methylpentanamid, NGGC-011, Naproanilide,  Metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinates, monalides, monocarbamides, monocarbamide dihydrogen sulfate, monolinuron, monosulfuron, monuron, MT 128, MT-5950, d. H. N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide, NGGC-011, naproanilides,
Napropamide, Naptalam, NC-310, d.h. 4-(2,4-dichlorobenzoyl)-l-methyl-5-benzyloxypyrazole, Neburon, Nicosulfuron, Nipyraclofen, Nitralin, Nitrofen, Nitrophenolat-natrium (Isomerengemisch), Nitrofluorfen, Nonansäure, Norflurazon, Orbencarb, Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paclobutrazol, Paraquat, Paraquat- dichlorid, Pelargonsäure (Nonansäure), Pendimethalin, Pendralin, Penoxsulam, Pentanochlor, Pentoxazone, Perfluidone, Pethoxamid, Phenisopham, Phenmedipham, Phenmedipham-ethyl, Picloram, Picolinafen, Pinoxaden, Piperophos, Pirifenop, Pirifenop-butyl, Pretilachlor, Napropamide, naptalam, NC-310, ie 4- (2,4-dichlorobenzoyl) -l-methyl-5-benzyloxypyrazoles, neburon, nicosulfuron, nipyraclofen, nitrite, nitrofen, nitrophenolate sodium (mixture of isomers), Nitrofluorfen, nonanoic acid, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazone, oxasulfuron, oxaziclomefones, oxyfluorfen, paclobutrazole, paraquat, paraquat dichloride, pelargonic acid (nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamide, phenisopham , Phenmedipham, phenmedipham-ethyl, picloram, picolinafen, pinoxaden, piperophos, pirifenop, pirifenop-butyl, pretilachlor,
Primisulfuron, Primisulfuron-methyl, Probenazole, Profluazol, Procyazine, Prodiamine, Prifluraline, Profoxydim, Prohexadione, Prohexadione-calcium, Prohydrojasmone, Prometon, Prometryn, Propachlor, Propanil, Propaquizafop, Propazine, Propham, Propisochlor, Propoxycarbazone, Propoxycarbazone-natrium, Propyzamide, Prosulfalin, Prosulfocarb, Prosulfuron, Prynachlor, Pyraclonil, Pyraflufen, Pyraflufen-ethyl, Pyrasulfotole, Pyrazolynate (Pyrazolate), Pyrazosulfuron- ethyl, Pyrazoxyfen, Pyribambenz, Pyribambenz-isopropyl, Pyribenzoxim, Pyributicarb, Pyridafol, Pyridate, Pyriftalid, Pyriminobac, Pyriminobac-methyl, Pyrimisulfan, Pyrithiobac, Pyrithiobac- natrium, Pyroxasulfone, Pyroxsulam, Quinclorac, Quinmerac, Quinoclamine, Quizalofop,  Primisulfuron, Primisulfuron-methyl, Probenazole, Profluazole, Procyazine, Prodiamine, Prifluralin, Profoxydim, Prohexadione, Prohexadione-calcium, Prohydrojasmone, Prometon, Prometry, Propachlor, Propanil, Propaquizafop, Propazine, Propam, Propisochlor, Propoxycarbazone, Propoxycarbazone-Sodium, Propyzamide, Prosulfine, prosulfocarb, prosulfuron, prynachlor, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuronethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribenzoxime, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl , Pyrimisulfan, Pyrithiobac, Pyrithiobac Sodium, Pyroxasulfones, Pyroxsulam, Quinclorac, Quinmerac, Quinoclamine, Quizalofop,
Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, Rimsulfuron, Quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron,
Secbumeton, Sethoxydim, Siduron, Simazine, Simetryn, SN- 106279, Sulcotrione, SulfallateSecbumetone, sethoxydim, siduron, simazine, simetryn, SN-106279, sulctotrione, sulfallates
(CDEC), Sulfentrazone, Sulfometuron, Sulfometuron-methyl, Sulfosate (Glyphosate-trimesium), Sulfosulfuron, SYN-523, SYP-249, SYP-298, SYP-300, Tebutam, Tebuthiuron, Tecnazene, Tefuryltrione, Tembotrione, Tepraloxydim, Terbacil, Terbucarb, Terbuchlor, Terbumeton, Terbuthylazine, Terbutryn, TH-547, Thenylchlor, Thiafluamide, Thiazafluron, Thiazopyr, Thidiazimin, Thidiazuron, Thiencarbazone, Thiencarbazone-methyl, Thifensulfuron, Thifensulfuron- methyl, Thiobencarb, Tiocarbazil, Topramezone, Tralkoxydim, Triallate, Triasulfuron, Triaziflam, Triazofenamide, Tribenuron, Tribenuron-methyl, Trichloressigsäure (TCA), Triclopyr, Tridiphane, Trietazine, Trifloxysulfuron, Trifloxysulfuron-natrium, Trifluralin, Triflusulfuron, Triflusulfuron- methyl, Trimeturon, Trinexapac, Trinexapac-ethyl, Tritosulfuron, Tsitodef, Uniconazole, (CDEC), sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate-trimesium), sulfosulfuron, SYN-523, SYP-249, SYP-298, SYP-300, tebutam, tebuthiuron, tecnazene, tefuryltrione, tembotrione, tepraloxydim, terbacil , Terbucarb, terbuchlor, terbumetone, terbuthylazine, terbutryn, TH-547, thenylchloro, thiafluamides, thiazafluron, thiazopyr, thidiazimine, thidiazuron, thiencarbazones, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiocarbazil, toramezone, tralkoxydim, triallates, triasulfuron , Triazolyl, triazofenamide, tribenuron, tribenuron-methyl, trichloroacetic acid (TCA), triclopyr, tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron sodium, trifluralin, triflusulfuron, triflusulfuron-methyl, trimeturon, trinexapac, trinexapac-ethyl, tritosulfuron, tsitodef, uniconazole,
Uniconazole-P, Vernolate, ZJ-0166, ZJ-0270, ZJ-0543, oder ZJ-0862 sowie die folgenden Uniconazole-P, Vernolate, ZJ-0166, ZJ-0270, ZJ-0543, or ZJ-0862 and the following
Verbindungen links
Die genannten Wirkstoffe sind entweder mit dem "common name" nach der International Organization for Standardization (ISO) oder mit ihrem chemischen Namen oder Codenummer bezeichnet und umfassen stets sämtliche Anwendungsformen wie Säuren, Salze, Ester oder Modifikationen, wie Isomere, Stereoisomere und optische Isomere. Beispielhaft sind eine oder auch mehrere Anwendungsformen oder Modifikationen genannt. The active substances mentioned are denoted either by the "common name" according to the International Organization for Standardization (ISO) or by their chemical name or code number and always include all forms of use, such as acids, salts, esters or modifications, such as isomers, stereoisomers and optical isomers. By way of example, one or more application forms or modifications are mentioned.
Die Erfindung bezieht sich gleichfalls auf Mittel zur Bekämpfung tierischer Schädlinge, insbesondere Schädlinge, die in der Landwirtschaft und in Forsten vokommen, enthaltend die neue feste Form von 4- [[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on werden und mindestens eines der vorgenannten Wirkstoffe. The invention also relates to compositions for combating animal pests, in particular pests which are found in agriculture and in forests, containing the new solid form of 4- [[(6-chloropyridin-3-yl) methyl] (2,2-) difluoroethyl) amino] furan-2 (5H) -one and at least one of the aforementioned active ingredients.
Die Verbindung 4-[[(6-Chlo yridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on in der neuen festen Form kann ferner beim Einsatz als Insektizid in ihren handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit Synergisten vorliegen. Synergisten sind Verbindungen, durch die die Wirkung der Wirkstoffe gesteigert wird, ohne dass der zugesetzte Synergist selbst aktiv wirksam sein muss. The compound 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the novel solid form may also be used as an insecticide in its commercial formulations and in the formulations prepared from these formulations in admixture with synergists available. Synergists are compounds that increase the effect of the active ingredients without the added synergist itself having to be active.
Die Verbindung 4-[[(6-Chlo yridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on in der neuen festen Form kann ebenso beim Einsatz als Insektizide in ihren handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischungen mit Hemmstoffen vorliegen, die einen Abbau des Wirkstoffes nach Anwendung in der Umgebung der Pflanze, auf der Oberfläche von Pflanzenteilen oder in pflanzlichen Geweben vermindern. The compound 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in the new solid form may also be used as insecticides in their commercial formulations and in the forms of use prepared from these formulations in mixtures with inhibitors which reduce degradation of the active ingredient after application in the environment of the plant, on the surface of plant parts or in plant tissues.
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten An wendungs formen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen kann von 0,00000001 bis zu 95 Gew.-% Wirkstoff, vorzugsweise zwischen 0,00001 und 1 Gew.-% liegen. The active ingredient content of the application forms prepared from the commercial formulations can vary widely. The active ingredient concentration of the use forms may be from 0.00000001 up to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.
Erfindungsgemäß können alle Pflanzen und Pflanzenteile behandelt werden. Unter Pflanzen werden hierbei alle Pflanzen und Pflanzenpopulationen verstanden, wie erwünschte und unerwünschte Wildpflanzen oder Kulturpflanzen (einschließlich natürlich vorkommender Kulturpflanzen). Kulturpflanzen können Pflanzen sein, die durch konventionelle Züchtungs- und Optimierungsmethoden oder durch biotechnologische und gentechnologische Methoden oder Kombinationen dieser Methoden erhalten werden können, einschließlich der transgenen Pflanzen und einschließlich der durch Sortenschutzrechte schützbaren oder nicht schützbaren Pflanzensorten. Unter Pflanzenteilen sollen alle oberirdischen und unterirdischen Teile und Organe der Pflanzen, wie Spross, Blatt, Blüte und Wurzel verstanden werden, wobei beispielhaft Blätter, Nadeln, Stängel, Stämme, Blüten, Fruchtkörper, Früchte und Saatgut sowie Wurzeln, Knollen und Rhizome aufgeführt werden. Zu den Pflanzenteilen gehört auch Erntegut sowie vegetatives und generatives Vermehrungsmaterial, beispielsweise Stecklinge, Knollen, Rhizome, Ableger und Saatgut. According to the invention, all plants and parts of plants can be treated. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop 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 varieties which can or can not be protected by plant breeders' rights. Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
Die erfindungsgemäße Behandlung der Pflanzen und Pflanzenteile mit dem neuen festen Wirkstoff oder den Wirkstoffkombinationen enthaltend den neuen festen Wirkstoff erfolgt direkt oder durch Einwirkung auf deren Umgebung, Lebensraum oder Lagerraum nach den üblichen Behandlungsmethoden, z.B. durch Tauchen, Sprühen, Verdampfen, Vernebeln, Streuen, Aufstreichen, Injizieren und bei Vermehrungsmaterial, insbesondere bei Saatgut, weiterhin durch ein- oder mehrschichtiges Umhüllen. Als Pflanzen, welche erfindungsgemäß behandelt werden können, seien folgende erwähnt: Baumwolle, Flachs, Weinrebe, Obst, Gemüse, wie Rosaceae sp. (beispielsweise Kernfrüchte wie Apfel und Birne, aber auch Steinfrüchte wie Aprikosen, Kirschen, Mandeln und Pfirsiche und Beerenfrüchte wie Erdbeeren), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (beispielsweise Bananenbäume und - plantagen), Rubiaceae sp. (beispielsweise Kaffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (beispielsweise Zitronen, Organen und Grapefruit); Solanaceae sp. (beispielsweise Tomaten), Liliaceae sp., Asteraceae sp. (beispielsweise Salat), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (beispielsweise Gurke), Alliaceae sp. (beispielsweise Lauch, Zwiebel), Papilionaceae sp. (beispielsweise Erbsen); Hauptnutzpflanzen, wie Gramineae sp. (beispielsweise Mais, Rasen, Getreide wie Weizen, Roggen, Reis, Gerste, Hafer, Hirse und Triticale), Asteraceae sp. (beispielsweise Sonnenblume), Brassicaceae sp. (beispielsweise Weißkohl, Rotkohl, Brokkoli, Blumenkohl, Rosenkohl, Pak Choi, Kohlrabi, Radieschen sowie Raps, Senf, Meerrettich und Kresse), Fabacae sp. (beispielsweise Bohne, Erdnüsse), Papilionaceae sp. (beispielsweise Sojabohne), Solanaceae sp. (beispielsweise Kartoffeln), Chenopodiaceae sp. (beispielsweise Zuckerrübe, Futterrübe, Mangold, Rote Rübe); Nutzpflanzen und Zierpflanzen in Garten und Wald; sowie jeweils genetisch modifizierte Arten dieser Pflanzen. Die erfindungsgemäße Behandlung der Pflanzen und Pflanzenteile mit dem neuen festen Wirkstoff oder den erfindungsgemäßen Wirkstoffkombinationen erfolgt direkt oder durch Einwirkung auf deren Umgebung, Lebensraum oder Lagerraum nach den üblichen Behandlungsmethoden, z.B. durch Tauchen, Sprühen, Verdampfen, Vernebeln, Streuen, Aufstreichen und bei Vermehrungsmaterial, insbesondere bei Saatgut, weiterhin durch ein- oder mehrschichtiges Umhüllen. Ein großer Teil des durch Schädlinge verursachten Schadens an Kulturpflanzen erfolgt bereits durch den Befall des Saatguts während der Lagerung und nach dem Einbringen des Saatguts in den Boden sowie während und unmittelbar nach der Keimung der Pflanzen. Diese Phase ist besonders kritisch, da die Wurzeln und Sprosse der wachsenden Pflanze besonders empfindlich sind und bereits ein geringer Schaden zum Absterben der ganzen Pflanze führen kann. Es besteht daher ein insbesondere großes Interesse daran, das Saatgut und die keimende Pflanze durch den Einsatz geeigneter Mittel zu schützen. The treatment according to the invention of the plants and plant parts with the new solid active substance or the active substance combinations containing the new solid active ingredient takes place directly or by acting on their environment, habitat or storage space according to the usual treatment methods, for example by dipping, spraying, evaporating, atomizing, spreading, painting , Injecting and propagating material, in particular seed, continue by single or multi-layer wrapping. As plants which can be treated according to the invention, mention may be made of the following: cotton, flax, grapevine, fruits, vegetables, such as Rosaceae sp. (for example, pomes such as apple and pear, but also drupes such as apricots, cherries, almonds and peaches, and soft fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for example, banana trees and plantations), Rubiaceae sp. (for example, coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for example, lemons, organs and grapefruit); Solanaceae sp. (for example tomatoes), Liliaceae sp., Asteraceae sp. (for example, lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (for example cucumber), Alliaceae sp. leek, onion), Papilionaceae sp. (for example, peas); Main crops, such as Gramineae sp. (for example corn, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (for example sunflower), Brassicaceae sp. (for example, white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes and rapeseed, mustard, horseradish and cress), Fabacae sp. (for example, bean, peanuts), Papilionaceae sp. (for example, soybean), Solanaceae sp. (for example potatoes), Chenopodiaceae sp. (for example, sugar beet, fodder beet, Swiss chard, beet); Useful plants and ornamental plants in the garden and forest; and each genetically modified species of these plants. The treatment according to the invention of the plants and plant parts with the new solid active ingredient or the active compound combinations according to the invention is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, eg by dipping, spraying, evaporating, atomizing, spreading, spreading and in the case of propagation material, especially in seeds, further by single or multi-layer wrapping. Much of the damage to crops caused by pests occurs as early as the infestation of the seed during storage and after the seed has been introduced into the soil and during and immediately after the germination of the plants. This phase is particularly critical, as the roots and shoots of the growing plant are particularly sensitive and even minor damage can lead to the death of the entire plant. There is therefore a particular interest in protecting the seed and the germinating plant by the use of suitable agents.
Die vorliegende Erfindung bezieht sich daher insbesondere auch auf ein Verfahren zum Schutz von Saatgut und keimenden Pflanzen vor dem Befall von Schädlingen, indem das Saatgut mit einem erfindungsgemäßen Mittel behandelt wird. Die Erfindung bezieht sich ebenfalls auf die Verwendung der erfindungsgemäßen Mittel zur Behandlung von Saatgut zum Schutz des Saatguts und der daraus entstehenden Pflanze vor Schädlingen. Weiterhin bezieht sich die Erfindung auf Saatgut, welches zum Schutz vor Schädlingen mit einem erfindungsgemäßen Mittel behandelt wurde. Unter Saatgut wird konventionelles Saatgut oder transgenes Saatgut verstanden. Bei transgenem Saatgut sind die aus diesem Saatgut hervorgehenden Pflanzen zur Expression eines gegen Schädlinge gerichteten Proteins befähigt sind. Dabei handelt es sich um das Saatgut von Pflanzen, die in der Regel zumindest ein heterologes Gen enthalten, das die Expression eines Polypeptids mit insbesondere Insektiziden Eigenschaften steuert. Die heterologen Gene in transgenem Saatgut können dabei aus Mikroorganismen wie Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus oder Gliocladium stammen. Die vorliegende Erfindung eignet sich besonders für die Behandlung von transgenem Saatgut, das zumindest ein heterologes Gen enthält, das aus Bacillus sp. stammt und dessen Genprodukt Wirksamkeit gegen Maiszünsler und/oder Mais wurzel-B ohrer zeigt. Besonders bevorzugt handelt es sich dabei um ein heterologes Gen, das aus Bacillus thuringiensis stammt. The present invention therefore more particularly relates to a method of protecting seed and germinating plants from infestation by pests by treating the seed with an agent according to the invention. The invention also relates to the use of the agents according to the invention for the treatment of seeds for the protection of the seed and the resulting plant from pests. Furthermore, the invention relates to seed which has been treated with an agent according to the invention for protection against pests. Seed is understood to be conventional seed or transgenic seed. In transgenic seeds, the plants resulting from this seed are capable of expressing a pest-targeted protein. These are the seeds of plants, which usually contain at least one heterologous gene which controls the expression of a polypeptide, in particular insecticidal properties. The heterologous genes in transgenic seed can come from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. The present invention is particularly useful for the treatment of transgenic seed containing at least one heterologous gene derived from Bacillus sp. and whose gene product shows efficacy against European corn borer and / or corn rootworm. Most preferably, this is a heterologous gene derived from Bacillus thuringiensis.
Durch die Behandlung solchen Saatguts mit den erfindungsgemäßen Mitteln können bestimmte Schädlinge bereits durch die Expression des z.B. Insektiziden Proteins kontrolliert werden, und zusätzlich durch die erfindungsgemäßen Mittel vor Schäden bewahrt werden. By treating such seeds with the agents of the invention, certain pests may already be affected by the expression of e.g. Insecticidal protein can be controlled, and also be protected by the means of the invention from damage.
Die erfindungsgemäßen Mittel eignen sich zum Schutz von Saatgut jeglicher Pflanzensorte wie bereits vorstehend genannt, die in der Landwirtschaft, im Gewächshaus, in Forsten oder im Gartenbau eingesetzt wird. Insbesondere handelt es sich dabei um Saatgut von Mais, Erdnuss, Canola, Raps, Mohn, Soja, Baumwolle, Rübe (z.B. Zuckerrübe und Futterrübe), Reis, Hirse, Weizen, Gerst e , Hafer, Roggen, Sonnenblume, Tabak, Kartoffeln oder Gemüse (z.B. Tomaten, Kohlgewächs). Die erfindungsgemäßen Mittel eignen sich ebenfalls zur Behandlung des Saatguts von Obstpflanzen und Gemüse wie vorstehend bereits genannt. Besondere Bedeutung kommt der Behandlung des Saatguts von Mais, Soja, Baumwolle, Weizen und Canola oder Raps zu. The compositions of the invention are suitable for the protection of seed of any plant variety as mentioned above, which is used in agriculture, in the greenhouse, in forests or in horticulture. In particular, these are seeds of corn, peanut, canola, rapeseed, poppy seeds, soybean, cotton, turnip (eg sugar beet and fodder beet), rice, millet, wheat, barley, oats, rye, sunflower, tobacco, potatoes or vegetables (eg tomatoes, cabbages). The compositions according to the invention are likewise suitable for the treatment of the seed of fruit plants and vegetables as already mentioned above. Of particular importance is the treatment of the seeds of maize, soya, cotton, wheat and canola or rapeseed.
Im Rahmen der vorliegenden Erfindung wird das erfindungsgemäßes Mittel alleine oder in einer geeigneten Formulierung auf das Saatgut aufgebracht. Vorzugsweise wird das Saatgut in einem Zustand behandelt, in dem so stabil ist, dass keine Schäden bei der Behandlung auftreten. Im Allgemeinen kann die Behandlung des Saatguts zu jedem Zeitpunkt zwischen der Ernte und der Aussaat erfolgen. Üblicherweise wird Saatgut verwendet, das von der Pflanze getrennt und von Kolben, Schalen, Stängeln, Hülle, Wolle oder Fruchtfleisch befreit wurde. In the context of the present invention, the agent according to the invention is applied to the seed alone or in a suitable formulation. Preferably, the seed is treated in a condition that is so stable that no damage occurs during the treatment. In general, the treatment of the seed can be done at any time between harvesting and sowing. Usually, seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp.
Im Allgemeinen muss bei der Behandlung des Saatguts darauf geachtet werden, dass die Menge des auf das Saatgut aufgebrachten erfindungsgemäßen Mittels und/oder weiterer Zusatzstoffe so gewählt wird, dass die Keimung des Saatguts nicht beeinträchtigt bzw. die daraus hervorgehende Pflanze nicht geschädigt wird. Dies ist vor allem bei Wirkstoffen zu beachten, die in bestimmten Aufwandmengen phytotoxische Effekte zeigen können. Die erfindungsgemäßen Mittel können unmittelbar aufgebracht werden, also ohne weitere Komponenten zu enthalten und ohne verdünnt worden zu sein. In der Regel ist es vorzuziehen, die Mittel in Form einer geeigneten Formulierung auf das Saatgut aufzubringen. Geeignete Formulierungen und Verfahren für die Saatgutbehandlung sind dem Fachmann bekannt und werden z.B. in den folgenden Dokumenten beschrieben: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 AI, WO 2002/080675 AI, WO 2002/028186 A2. In general, care must be taken in the treatment of the seed that the amount of the agent and / or other additives applied to the seed is chosen so that germination of the seed is not impaired or the resulting plant is not damaged. This is especially important for active ingredients, which can show phytotoxic effects in certain application rates. The agents according to the invention can be applied directly, ie without containing further components and without being diluted. In general, it is preferable to apply the agents to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 Al, WO 2002/080675 Al, WO 2002 / 028186 A2.
Die neue feste Form von 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on kann in die üblichen Beizmittel-Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Slurries oder andere Hüllmassen für Saatgut, sowie ULV- Formulierungen. Diese Formulierungen werden in bekannter Weise hergestellt, indem man die Wirkstoffe mit üblichen Zusatzstoffen vermischt, wie zum Beispiel übliche Streckmittel sowie Lösungs- oder Verdünnungsmittel, Farbstoffe, Netzmittel, Dispergiermittel, Emulgatoren, Entschäumer, Konservierungsmittel, sekundäre Verdickungsmittel, Kleber, Gibberelline und auch Wasser. Als Farbstoffe, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle für derartige Zwecke üblichen Farbstoffe in Betracht. Dabei sind sowohl in Wasser wenig lösliche Pigmente als auch in Wasser lösliche Farbstoffe verwendbar. Als Beispiele genannt seien die unter den Bezeichnungen Rhodamin B, C.I. Pigment Red 112 und C.I. Solvent Red 1 bekannten Farbstoffe. Als Netzmittel, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle zur Formulierung von agrochemischen Wirkstoffen üblichen, die Benetzung fördernden Stoffe in Frage. Vorzugsweise verwendbar sind Alkylnaphthalin-Sulfonate, wie Diiso- propyl- oder Diisobutylnaphthalin-Sulfonate. The new solid form of 4 - [[(6-chloro-pyridin-3-yl) -methyl] (2,2-difluoroethyl) -amino] -furan-2 (5H) -one can be converted into the usual seed-dressing formulations, such as solutions, Emulsions, suspensions, powders, foams, slurries or other coating materials for seeds, as well as ULV formulations. These formulations are prepared in a known manner by mixing the active ingredients with conventional additives, such as conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and water. Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1 known dyes. Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds. Preference is given to using alkylnaphthalene sulfonates, such as diisopropyl or diisobutylnaphthalene sulfonates.
Als Dispergiermittel und/oder Emulgatoren, die in den erfindungsgemäß verwendbaren Beizmittel- Formulierungen enthalten sein können, kommen alle zur Formulierung von agrochemischen Wirkstoffen üblichen nichtionischen, anionischen und kationischen Dispergiermittel in Betracht. Vorzugsweise verwendbar sind nichtionische oder anionische Dispergiermittel oder Gemische von nichtionischen oder anionischen Dispergiermitteln. Als geeignete nichtionische Dispergiermittel sind insbesondere Ethylenoxid-Propylenoxid Blockpolymere, Alkylphenolpolyglykolether sowie Tri- stryrylphenolpolyglykolether und deren phosphatierte oder sulfatierte Derivate zu nennen. Geeignete anionische Dispergiermittel sind insbesondere Ligninsulfonate, Polyacrylsäuresalze und Aryl- sulfonat-Formaldehydkondensate. Als Entschäumer können in den ernndungsgemäß verwendbaren Beizmittel-Formulierungen alle zur Formulierung von agrochemischen Wirkstoffen üblichen schaumhemmenden Stoffe enthalten sein. Vorzugsweise verwendbar sind Silikonentschäumer und Magnesiumstearat. Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds. Preferably usable are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide, block polymers, alkylphenol polyglycol ethers and tri-stryrylphenol polyglycol ethers and their phosphated or sulfated derivatives. Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates. Defoamers which may be present in the seed dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds. Preferably usable are silicone defoamers and magnesium stearate.
Als Konservierungsmittel können in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen alle für derartige Zwecke in agrochemischen Mitteln einsetzbaren Stoffe vorhanden sein. Beispielhaft genannt seien Dichlorophen und Benzylalkoholhemiformal. Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal.
Als sekundäre Verdickungsmittel, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle für derartige Zwecke in agrochemischen Mitteln einsetzbaren Stoffe in Frage. Vorzugsweise in Betracht kommen Cellulosederivate, Acrylsäure- derivate, Xanthan, modifizierte Tone und hochdisperse Kieselsäure. Suitable secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and highly dispersed silicic acid.
Als Kleber, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle üblichen in Beizmitteln einsetzbaren Bindemittel in Frage. Vorzugsweise genannt seien Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol und Tylose. Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents. Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
Als Gibberelline, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen vorzugsweise die Gibberelline AI , A3 (= Gibberellinsäure), A4 und A7 infrage, besonders bevorzugt verwendet man die Gibberellinsäure. Die Gibberelline sind bekannt (vgl. R. Wegler„Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel", Bd. 2, Springer Verlag, 1970, S. 401-412). Gibberellins which may be present in the seed dressing formulations which can be used in accordance with the invention are preferably the gibberellins AI, A3 (= gibberellic acid), A4 and A7, particularly preferably gibberellic acid. The gibberellins are known (see R. Wegler "Chemie der Pflanzenschutz- und Schädlingsbekungsmittel", Vol. 2, Springer Verlag, 1970, pp. 401-412).
Die erfindungsgemäß verwendbaren Beizmittel-Formulierungen können entweder direkt oder nach vorherigem Verdünnen mit Wasser zur Behandlung von Saatgut der verschiedensten Art, auch von Saatgut transgener Pflanzen, eingesetzt werden. Dabei können im Zusammenwirken mit den durch Expression gebildeten Substanzen auch zusätzliche synergistische Effekte auftreten. The seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds, including seed of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression.
Zur Behandlung von Saatgut mit den erfindungsgemäß verwendbaren Beizmittel-Formulierungen oder den daraus durch Zugabe von Wasser hergestellten Zubereitungen kommen alle üblicherweise für die Beizung einsetzbaren Mischgeräte in Betracht. Im einzelnen geht man bei der Beizung so vor, dass man das Saatgut in einen Mischer gibt, die jeweils gewünschte Menge an Beizmittel-Formulierungen entweder als solche oder nach vorherigem Verdünnen mit Wasser hinzufügt und bis zur gleichmäßigen Verteilung der Formulierung auf dem Saatgut mischt. Gegebenenfalls schließt sich ein Trocknungsvorgang an. For the treatment of seed with the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water, all mixing devices customarily usable for the dressing can be considered. Specifically, in the pickling procedure, the seed is placed in a mixer which adds either desired amount of seed dressing formulations either as such or after prior dilution with water and mixes until evenly distributed the formulation on the seed. Optionally, a drying process follows.
Wie bereits oben erwähnt, können erfindungsgemäß alle Pflanzen und deren Teile behandelt werden. In einer bevorzugten Ausführungsform werden wild vorkommende oder durch konventionelle biologische Zuchtmethoden, wie Kreuzung oder Protoplastenfusion erhaltenen Pflanzenarten und Pflanzensorten sowie deren Teile behandelt. In einer weiteren bevorzugten Ausführungsform werden transgene Pflanzen und Pflanzensorten, die durch gentechnologische Methoden gegebenenfalls in Kombination mit konventionellen Methoden erhalten wurden (Genetically Modified Organisms) und deren Teile behandelt. Die Begriffe "Teile" bzw. "Teile von Pflanzen" oder "Pflanzenteile" wurden oben erläutert. As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, wild or conventional biological breeding methods, such as crossing or protoplast fusion obtained plant species and plant varieties and their parts treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms "parts" or "parts of plants" or "plant parts" have been explained above.
Besonders bevorzugt werden erfindungsgemäß Pflanzen der jeweils handelsüblichen oder in Gebrauch befindlichen Pflanzensorten behandelt. Unter Pflanzensorten versteht man Pflanzen mit neuen Eigenschaften ("Traits"), die sowohl durch konventionelle Züchtung, durch Mutagenese oder durch rekombinante DNA-Techniken gezüchtet worden sind. Dies können Sorten, Bio- und Genotypen sein. It is particularly preferred according to the invention to treat plants of the respective commercially available or in use plant cultivars. Plant varieties are understood as meaning plants having new traits which have been bred by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.
Je nach Pflanzenarten bzw. Pflanzensorten, deren Standort und Wachstumsbedingungen (Böden, Klima, Vegetationsperiode, Ernährung) können durch die erfindungsgemäße Behandlung auch überadditive ("synergistische") Effekte auftreten. So sind beispielsweise erniedrigte Aufwandmengen und/oder Erweiterungen des Wirkungsspektrums und/oder eine Verstärkung der Wirkung der erfindungsgemäß verwendbaren Stoffe und Mittel, besseres Pflanzenwachstum, erhöhte Toleranz gegenüber hohen oder niedrigen Temperaturen, erhöhte Toleranz gegen Trockenheit oder gegen Wasser- bzw. Bodensalzgehalt, erhöhte Blühleistung, erleichterte Ernte, Beschleunigung der Reife, höhere Ernteerträge, höhere Qualität und/oder höherer Ernährungswert der Ernteprodukte, höhere Lagerfähigkeit und/oder Bearbeitbarkeit der Ernteprodukte möglich, die über die eigentlich zu erwartenden Effekte hinausgehen. Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also give rise to superadditive ("synergistic") effects. Thus, for example, reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents usable in 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 power facilitated harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products, which exceed the actual expected effects.
Zu den bevorzugten erfindungsgemäß zu behandelnden transgenen (gentechnologisch erhaltenen) Pflanzen bzw. Pflanzensorten gehören alle Pflanzen, die durch die gentechnologische Modifikation genetisches Material erhielten, welches diesen Pflanzen besondere vorteilhafte wertvolle Eigenschaften ( "Traits ") verleiht. B eispiele für solche Eigenschaften sind besseres Pflanzenwachstum, erhöhte Toleranz gegenüber hohen oder niedrigen Temperaturen, erhöhte Toleranz gegen Trockenheit oder gegen Wasser- bzw. Bodensalzgehalt, erhöhte Blühleistung, erleichterte Ernte, Beschleunigung der Reife, höhere Ernteerträge, höhere Qualität und/oder höherer Ernährungswert der Ernteprodukte, höhere Lagerfähigkeit und/oder Bearbeitbarkeit der Ernte- produkte. Weitere und besonders hervorgehobene Beispiele für solche Eigenschaften sind eine erhöhte Abwehr der Pflanzen gegen tierische und mikrobielle Schädlinge, wie gegenüber Insekten, Milben, pflanzenpathogenen Pilzen, Bakterien und/oder Viren sowie eine erhöhte Toleranz der Pflanzen gegen bestimmte herbizide Wirkstoffe. Als Beispiele transgener Pflanzen werden die wichtigen Kulturpflanzen, wie Getreide (Weizen, Reis), Mais, Soja, Kartoffel, Zuckerrüben, Tomaten, Erbsen und andere Gemüsesorten, Baumwolle, Tabak, Raps, sowie Obstpflanzen (mit den Früchten Äpfel, Birnen, Zitrusfrüchten und Weintrauben) erwähnt, wobei Mais, Soja, Kartoffel, Baumwolle, Tabak und Raps besonders hervorgehoben werden. Als Eigenschaften ("Traits") werden besonders hervorgehoben die erhöhte Abwehr der Pflanzen gegen Insekten, Spinnentiere, Nematoden und Schnecken durch in den Pflanzen entstehende Toxine, insbesondere solche, die durch das genetische Material aus Bacillus Thuringiensis (z.B. durch die Gene CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb und CrylF sowie deren Kombinationen) in den Pflanzen erzeugt werden (im folgenden "Bt Pflanzen"). Als Eigenschaften ("Traits") werden auch besonders hervorgehoben die erhöhte Abwehr von Pflanzen gegen Pilze, Bakterien und Viren durch Systemische Akquirierte Resistenz (SAR), Systemin, Phytoalexine, Elicitoren sowie Resistenzgene und entsprechend exprimierte Proteine und Toxine. Als Eigenschaften ("Traits") werden weiterhin besonders hervorgehoben die erhöhte Toleranz der Pflanzen gegenüber bestimmten herbiziden Wirkstoffen, beispielsweise Imidazolinonen, Sulfonylharnstoffen, Glyphosate oder Phosphinotricin (z.B. "PAT"-Gen). Die jeweils die gewünschten Eigenschaften ("Traits") verleihenden Gene können auch in Kombinationen miteinander in den transgenen Pflanzen vorkommen. Als Beispiele für "Bt Pflanzen" seien Maissorten, Baumwollsorten, Sojasorten und Kartoffelsorten genannt, die unter den Handelsbezeichnungen YIELD GARD® (z.B. Mais, Baumwolle, Soja), KnockOut® (z.B. Mais), StarLink® (z.B. Mais), Bollgard® (Baumwolle), Nucotn® (Baumwolle) und NewLeaf® (Kartoffel) vertrieben werden. Als Beispiele für Herbizid-tolerante Pflanzen seien Maissorten, Baumwollsorten und Sojasorten genannt, die unter den Handelsbezeichnungen Roundup Ready® (Toleranz gegen Glyphosate z.B. Mais, Baumwolle, Soja), Liberty Link® (Toleranz gegen Phosphinotricin, z.B. Raps), IMI® (Toleranz gegen Imidazolinone) und STS® (Toleranz gegen Sulfonylharnstoffe z.B. Mais) vertrieben werden. Als Herbizid- resistente (konventionell auf Herbizid-Toleranz gezüchtete) Pflanzen seien auch die unter der Bezeichnung Clearfield® vertriebenen Sorten (z.B. Mais) erwähnt. Selbstverständlich gelten diese Aussagen auch für in der Zukunft entwickelte bzw. zukünftig auf den Markt kommende Pflanzensorten mit diesen oder zukünftig entwickelten genetischen Eigenschaften ("Traits"). The preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits"). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value Harvested products, higher shelf life and / or workability of the harvested products. Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants against certain herbicidal active substances. Examples of transgenic plants are the important crops, such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, oilseed rape, as well as fruit plants (with the fruits apples, pears, citrus fruits and grapes) Soya, potato, cotton, tobacco and oilseed rape are particularly emphasized. Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins produced in the plants, in particular those produced by the genetic material from Bacillus thuringiensis (eg by the genes CrylA (a) , CrylA (b), CrylA (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) in the plants (hereinafter "Bt plants"). Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene). The genes which confer the desired properties ("traits") can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soybean varieties and potato varieties which are sold under the trade names YIELD GARD® (eg corn, cotton, soya), KnockOut® (eg maize), StarLink® (eg maize), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties, which are sold under the trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), IMI® (tolerance against imidazolinone) and STS® (tolerance to sulfonylureas eg corn). As herbicide-resistant (grown on conventional herbicide tolerance) plants are also sold under the name Clearfield® varieties (eg corn) mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.
Die neue feste Form von 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on kann auch auf dem veterinärmedizinischen Sektor gegen tierische Parasiten (Ekto- und Endoparasiten) wie Schildzecken, Lederzecken, Räudemilben, Laufmilben, Fliegen (stechend und leckend), parasitierende Fliegenlarven, Läuse, Haarlinge, Federlinge und Flöhe eingesetzt werden. Zu diesen Parasiten gehören: Aus der Ordnung der Anoplurida z.B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.. The new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one can also be used in the veterinary sector against animal parasites (ecto- and Endoparasites) such as ticks, leather ticks, mange mites, running mites, flies (stinging and licking), parasitizing fly larvae, lice, hair pieces, featherlings and fleas. These parasites include: From the order of the Anoplurida eg Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
Aus der Ordnung der Mallophagida und den Unterordnungen Amblycerina sowie Ischnocerina z.B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.. From the order of Mallophagida and suborders Amblycerina and Ischnocerina, for example. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
Aus der Ordnung Diptera und den Unterordnungen Nematocenna sowie Brachycenna z.B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilla spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.. From the order Diptera and the suborders Nematocenna and Brachycenna e.g. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp , Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilla spp., Chrysomyia spp. Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
Aus der Ordnung der Siphonapterida z.B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.. Aus der Ordnung der Heteropterida z.B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.. From the order of siphonapterida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp. From the order of Heteropterida, e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
Aus der Ordnung der Blattarida z.B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.. From the order of Blattarida e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.
Aus der Unterklasse der Acari (Acarina) und den Ordnungen der Meta- sowie Mesostigmata z.B. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.. From the subclass of Acari (Acarina) and the orders of Meta and Mesostigmata e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp ., Sternostoma spp., Varroa spp.
Aus der Ordnung der Actinedida (Prostigmata) und Acaridida (Astigmata) z.B. Acarapis spp., Cheyletiella spp., Ornithocheyletia 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.. From the order of Actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia 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.
Die neue feste Form von 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on eignet sich auch zur Bekämpfung von Arthropoden, die landwirtschaftliche Nutztiere, wie z.B. Rinder, Schafe, Ziegen, Pferde, Schweine, Esel, Kamele, Büffel, Kaninchen, Hühner, Puten, Enten, Gänse, Bienen, sonstige Haustiere wie z.B. Hunde, Katzen, Stubenvögel, Aquarienfische sowie sogenannte Versuchstiere, wie z.B. Hamster, Meerschweinchen, Ratten und Mäuse befallen. Durch die Bekämpfung dieser Arthropoden sollen Todesfälle und Leistungsminderungen (bei Fleisch, Milch, Wolle, Häuten, Eiern, Honig usw.) vermindert werden, so daß durch den Einsatz der erfindungsgemäßen Wirkstoffe eine wirtschaftlichere und einfachere Tierhaltung möglich ist. The new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is also useful in the control of arthropods such as livestock eg cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, Geese, bees, other pets such as dogs, cats, caged birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice infested. By controlling these arthropods deaths and reductions in performance (in meat, milk, wool, hides, eggs, honey, etc.) are reduced, so that a more economical and easier animal husbandry is possible by the use of the active compounds according to the invention.
Die Anwendung der neuen festen Form von 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on erfolgt im Veterinärsektor und bei der Tierhaltung in bekannter Weise durch enterale Verabreichung in Form von beispielsweise Tabletten, Kapseln, Tränken, Drenchen, Granulaten, Pasten, Boli, des feed-through- Verfahrens, von Zäpfchen, durch parenterale Verabreichung, wie zum Beispiel durch Injektionen (intramuskulär, subcutan, intravenös, intraperitonal u.a.), Implantate, durch nasale Applikation, durch dermale Anwendung in Form beispielsweise des Tauchens oder Badens (Dippen), Sprühens (Spray), Aufgießens (Pour-on und Spot-on), des Waschens, des Einpuderns sowie mit Hilfe von wirkstoffhaltigen Formkörpern, wie Halsbändern, Ohrmarken, Schwanzmarken, Gliedmaßenbändern, Halftern, Markierungsvor- richtungen usw. The use of the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is carried out in the veterinary and animal husbandry in a known manner enteral administration in the form of, for example, tablets, capsules, infusions, drenches, granules, pastes, boluses, the feed-through procedure, suppositories, by parenteral administration, such as 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 (pour-on and spot-on), washing, powdering and with the aid of active substance-containing moldings, such as collars , Ear tags, tail tags, limb bands, holsters, markers, etc.
Bei der erfindungsgemäßen Anwendung in der Tierhaltung, beispielsweise Haltung von Vieh, Geflügel, Haustiere können die Wirkstoffe oder Zusammensetzungen als geeignete Formulierungen, beispielsweise Pulver, Emulsionen, fließfähige Mittel verwendet werden. Gewöhnlicherweise enthalten geeignete Formulierungen die Wirkstoffe in einer Konzentration im Bereich von 0,1 bis 80 Gew.-%, bevorzugt im Bereich von 1- 60 Gew.-%, besonders bevorzugt im Bereich von 5 bis 30 Gew.-% enthalten. Die Formulierungen können direkt oder verdünnt, bevorzugt nach 100- bis 10 000-facher Verdünnung angewendet werden. Die Wirkstoffe bzw. die Zusammensetzungen können auch als chemisches Bad verwendet werden. In animal use according to the present invention, for example, livestock, poultry, and domestic animals, the active ingredients or compositions may be used as suitable formulations, for example, powders, emulsions, flowables. Usually, suitable formulations contain the active ingredients in a concentration in the range of 0.1 to 80 wt .-%, preferably in the range of 1- 60 wt .-%, particularly preferably in the range of 5 to 30 wt .-%. The formulations may be applied directly or diluted, preferably after 100 to 10,000 fold dilution. The active compounds or the compositions can also be used as a chemical bath.
Außerdem wurde gefunden, dass die neue feste Form von 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on und die erfindungsgemäßen Mittel auch im Materialschutz einsetzbar sind. In addition, it has been found that the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one and the agents according to the invention can also be used in the protection of materials are.
Beispielhaft und vorzugsweise - ohne jedoch zu limitieren - seien die folgenden Insekten genannt: By way of example and preferably without limiting however, the following insects are mentioned:
Käfer wie Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus; Hautflügler wie Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur; Beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus; Hymenoptera such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
Termiten wie Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus; Borstenschwänze wie Lepisma saccharina. Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus; Bristle tails like Lepisma saccharina.
Unter technischen Materialien sind im vorliegenden Zusammenhang nicht-lebende Materialien zu verstehen, wie vorzugsweise Kunststoffe, Klebstoffe, Leime, Papiere und Kartone, Leder, Holz, Holzverarbeitungsprodukte und Anstrichmittel. Technical materials in the present context are non-living materials, such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood, wood processing products and paints.
Zugleich k a n n d i e n e u e f e s t e F o r m v o n 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on zum Schutz vor Bewuchs von Gegenständen, insbesondere von Schiffskörpern, Sieben, Netzen, Bauwerken, Kaianlagen und Signalanlagen, welche mit See- oder Brackwasser in Verbindung kommen, eingesetzt werden. At the same time, the most recent form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one can be used to protect against fouling of objects, particularly hulls, sieves, nets , Structures, quays and signal systems, which come into contact with seawater or brackish water.
Weiter können die erfindungsgemäßen Verbindungen allein oder in Kombinationen mit anderen Wirkstoffen als Antifouling-Mittel eingesetzt werden. Die neue feste Form von 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on eignet sich auch zur Bekämpfung von tierischen Schädlingen im Haushalts-, Hygiene- und Vorratsschutz, insbesondere von Insekten, Spinnentieren und Milben, die in geschlossenen Räumen, wie beispielsweise Wohnungen, Fabrikhallen, Büros, Fahrzeugkabinen u.ä. vorkommen. Sie können zur Bekämpfung dieser Schädlinge allein oder in Kombination mit anderen Wirk- und Hilfsstoffen in Haushaltsinsektizid-Produkten verwendet werden. Sie sind gegen sensible und resistente Arten sowie gegen alle Entwicklungsstadien wirksam. Zu diesen Schädlingen gehören: Furthermore, the compounds according to the invention can be used alone or in combinations with other active substances as antifouling agents. The new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one is also useful for controlling domestic pests in household hygiene and stored product protection, in particular of insects, arachnids and mites, in enclosed spaces, such as apartments, factory buildings, offices, vehicle cabins, etc. occurrence. They can be used to control these pests, alone or in combination with other active ingredients and adjuvants in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
Aus der Ordnung der Scorpionidea z.B. Buthus occitanus. From the order of Scorpionidea e.g. Buthus occitanus.
Aus der Ordnung der Acarina z.B. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae. From the order of Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
Aus der Ordnung der Araneae z.B. Aviculariidae, Araneidae. From the order of the Araneae e.g. Aviculariidae, Araneidae.
Aus der Ordnung der Opiliones z.B. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium. Aus der Ordnung der Isopoda z.B. Oniscus asellus, Porcellio scaber. From the order of the Opiliones eg Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium. From the order of the Isopoda eg Oniscus asellus, Porcellio scaber.
Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus, Polydesmus spp.. From the order of diplopoda e.g. Blaniulus guttulatus, Polydesmus spp ..
Aus der Ordnung der Chilopoda z.B. Geophilus spp.. From the order of Chilopoda e.g. Geophilus spp ..
Aus der Ordnung der Zygentoma z.B. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus. From the order of Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
Aus der Ordnung der Blattaria z.B. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplan eta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa. From the order of the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplan eta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
Aus der Ordnung der Saltatoria z.B. Acheta domesticus. Aus der Ordnung der Dermaptera z.B. Forficula auricularia. From the order of Saltatoria e.g. Acheta domesticus. From the order of the Dermaptera e.g. Forficula auricularia.
Aus der Ordnung der Isoptera z.B. Kalotermes spp., Reticulitermes spp. From the order of Isoptera e.g. Kalotermes spp., Reticulitermes spp.
Aus der Ordnung der Psocoptera z.B. Lepinatus spp., Liposcelis spp. From the order of Psocoptera e.g. Lepinatus spp., Liposcelis spp.
Aus der Ordnung der Coleoptera z.B. Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum. From the order of Coleoptera e.g. Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
Aus der Ordnung der Diptera z.B. 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. Aus der Ordnung der Lepidoptera z.B. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella. From the order of Diptera e.g. 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. From the order of Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
Aus der Ordnung der Siphonaptera z.B. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis. From the order of siphonaptera e.g. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
Aus der Ordnung der Hymenoptera z.B. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum. From the order of Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
Aus der Ordnung der Anoplura z.B. Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis. Aus der Ordnung der Heteroptera z.B. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans. From the order of Anoplura eg Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis. From the order of Heteroptera eg Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
Die Anwendung im Bereich der Haushaltsinsektizide erfolgt allein oder in Kombination mit anderen geeigneten Wirkstoffen wie Phosphorsäureestern, Carbamaten, Pyrethroiden, Neo-nicotinoiden, Wachstumsregulatoren oder Wirkstoffen aus anderen bekannten Insektizidklassen. The application in the field of household insecticides is carried out alone or in combination with other suitable active ingredients such as phosphoric acid esters, carbamates, pyrethroids, neo-nicotinoids, growth regulators or agents from other known insecticide classes.
Die Anwendung erfolgt in Aerosolen, drucklosen Sprühmitteln, z.B. Pump- und Zerstäubersprays, Nebelautomaten, Foggern, Schäumen, Gelen, Verdampferprodukten mit Verdampferplättchen aus Cellulos e oder Kunststoff, Flüssigverdampfern, Gel- und Membranverdampfern, propellergetriebenen Verdampfern, energielosen bzw. passiven Verdampfungssystemen, Mottenpapieren, Mottensäckchen und Mottengelen, als Granulate oder Stäube, in Streuködern oder Köderstationen. Application is in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, misting machines, foggers, foams, gels, evaporator products with evaporator plates of cellulosic or plastic, liquid evaporators, gel and membrane evaporators, propeller driven evaporators, energyless or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in Litter or bait stations.
Die folgenden Abbildungen und Beispiele erläutern die Erfindung ohne sie einzuschränken. Die in den folgenden Beispielen eingesetzten Lösungsmittelsysteme sind besonders bevorzugt. The following figures and examples illustrate the invention without limiting it. The solvent systems used in the following examples are particularly preferred.
Beschreibung der Abbildungen Abbildung la: Röntgen- Pulverdiffraktogramm der neuen festen Form von 4-[[(6-Chlorpyridin-3- yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on. Description of the figures Figure la: X-ray powder diffractogram of the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one.
Abbildung lb: Röntgen-Pulverdiffraktogramm von amorphen 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on hergestellt nach WO 2009/036899. Figure lb: X-ray powder diffractogram of amorphous 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one prepared according to WO 2009/036899.
Abbildung 2a: Infrarot (IR) Spektren der neuen festen Form von 4-[[(6-Chlorpyridin-3- yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on. Figure 2a: Infrared (IR) spectra of the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one.
Abbildung 2b: Infrarot (IR) Spektren der amorphen F orm von 4-[[(6-Chlorpyridin-3- yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on. Figure 2b: Infrared (IR) spectra of the amorphous form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one.
Abbildung 3a: Raman Spektren der neuen festen Form von 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on. Abbildung 3b: Raman Spektren der amorphen Form von 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on. Figure 3a: Raman spectra of the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one. Figure 3b: Raman spectra of the amorphous form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one.
Röntgen-Pulverdiffraktometrie-Spektren wurden mit einem XPERT-PRO Diffraktometer unter Verwendung einer Cu-Ka-Strahlung (1.54060 Ä Wellenlänge) bei 25 °C aufgenommen, wobei der 2 Θ-Wert im Bereich von 2 - 38° liegen kann. Die Aufnahme wurde bei bei einer Schrittweite von 0, 0130 °2 Θ durchgeführt. X-ray powder diffractometry spectra were taken with an XPERT-PRO diffractometer using Cu-Ka radiation (1.54060 A wavelength) at 25 ° C, the 2 Θ value can be in the range of 2 - 38 °. The recording was carried out at a step size of 0, 0130 ° 2 Θ.
Infrarot (IR)-Spektren wurden mit einem FT-IR-Spektrometer Bruker Tensor 37, enhaltend eine Diamond ATR Unit der Firma Specac, über einen Wellenlängenbereich von 550 - 4000 cm"1 aufgenommen. Die Auflösung des Geräts beträgt 2 cm"1. Pro Spektrum wurden 64 Scans durchgeführt. Infrared (IR) spectra were recorded with a FT-IR spectrometer Bruker Tensor 37, enhaltend a Diamond ATR unit Company Specac, over a wavelength range from 550 to 4000 cm ". Recorded 1 The resolution of the device is 2 cm" 1. 64 scans were performed per spectrum.
Raman-Spektren wurden mit einem FT-Raman-Spektrometer Bruker RFS/100, dessen Laser eine Wellenzahl (Laser Wave Number) von 15798.7 cm"1 aufweist, aufgenommen. Die Auflösung des Geräts beträgt 1 cm"1. Pro Spektrum wurden 128 Scans durchgeführt. Raman spectra were recorded on a Bruker RFS / 100 FT Raman spectrometer whose laser has a wave wave number (Laser Wave Number) of 15798.7 cm -1 and the resolution of the device is 1 cm -1 . 128 scans were performed per spectrum.
A: Herstellung von 4-[[(6-Chlorpyridin-3-vUmethyll(2.,2-difluorethvnaininolfuran-2(5HVon nach WO 2009/036899 (in amorphen Zustand) Zu einer Suspension von 10,4 g 4-(Ethoxycarbonyl)-5-oxo-2,5-dihydrofuran-3-olat-Kaliumsalz und 7,5 g N-[(6-Chlorpyridin-3-yl)methyl)-2,2-difluorethylamin in 68 ml Butyronitril werden bei Raumtemperatur 11,5 g Kaliumhydrogensulfat zugesetzt. Die Mischung wird bei einer Temperatur von 90 bis 95 °C 3 Stunden gerührt. Anschließend wird auf Raumtemperatur abgekühlt, 120 ml Wasser und 120 ml Dichlormethan zugegeben, die organische Phase abgetrennt und die wässrige Phase wird zweimal mit je 120 ml Methylenchlorid extrahiert. Die vereinigten organischen Phasen werden zur Trockene eingeengt. Man erhält 11,4 g des amorphen 4-[[(6-Chloφyridin-3yl)methyl](2,2-difluorethyl)amino]flιran-2(5H)-on in einer Reinheit von 84 % (dies entspricht 92 % Ausbeute). A: Preparation of 4 - [[(6-chloropyridine-3-vymethyl] (2, 2-difluoroethvnaininolfuran-2 (5HVon according to WO 2009/036899 (in amorphous state) to a suspension of 10.4 g of 4- (ethoxycarbonyl) 5-oxo-2,5-dihydrofuran-3-olate potassium salt and 7.5 g of N - [(6-chloropyridin-3-yl) methyl] -2,2-difluoroethylamine in 68 ml of butyronitrile are stirred at room temperature 11, The mixture is stirred for 3 hours at a temperature of 90 ° to 95 ° C. It is then cooled to room temperature, 120 ml of water and 120 ml of dichloromethane are added, the organic phase is separated off and the aqueous phase is washed twice with 120 ml each time The combined organic phases are concentrated to dryness, giving 11.4 g of the amorphous 4 - [[(6-chloro-pyridin-3-yl) methyl] (2,2-difluoroethyl) -amino] -fluoro-2 (5H) -one in a purity of 84% (this corresponds to 92% yield).
Ή-NMR (CDC13, 298K) δ: 3,53 (td, 2H), 4,52 (s, 2H), 4,82 (s, 2H), 4,83 (s, 1H), 5,96 (tt, 1H), 7,37 (d, 1H), 7,55 (dd, 1H), 8,27( d, 1H) B: Herstellung der neuen feste Form Ή-NMR (CDC1 3 , 298K) δ: 3.53 (td, 2H), 4.52 (s, 2H), 4.82 (s, 2H), 4.83 (s, 1H), 5.96 (tt, 1H), 7.37 (d, 1H), 7.55 (dd, 1H), 8.27 (d, 1H) B: Preparation of the new solid form
Herstellungsbeispiel 1 : Production Example 1
20 g des amorphen 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on werden mit 27 ml Methyl-tert.-butylether und 3 ml Essigsäure-n-butylester versetzt und auf 60°C erhitzt. Anschließend wird mit 0,5°C/min auf 40°C abgekühlt und 8 h bei 40°C gerührt. Dann wird innerhalb von 1 h auf 35°C abgekühlt und anschließend auf 25°C gekühlt. Die ausgefallenen Kristalle werden abgesaugt und mit 5 ml Methyl-tert.-butylether gewaschen. Die Kristalle werden bei Temperaturen kleiner 40°C im Vakuum getrocknet. Man erhält 19 g kristallines -[[(6- Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on mit einem Schmelzpunkt im Bereich von 72- 74 °C. 20 g of the amorphous 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one are mixed with 27 ml of methyl tert-butyl ether and 3 ml of acetic acid added n-butyl ester and heated to 60 ° C. It is then cooled at 0.5 ° C / min to 40 ° C and stirred at 40 ° C for 8 h. It is then cooled to 35 ° C within 1 h and then cooled to 25 ° C. The precipitated crystals are filtered off with suction and washed with 5 ml of methyl tert-butyl ether. The crystals will be dried at temperatures below 40 ° C in a vacuum. This gives 19 g of crystalline - [[(6-chloφyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one having a melting point in the range of 72-74 ° C.
Das Ή-NMR (CDC13, 298K) enspri cht dem v on 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on in amorphem Zustand wie oben angegeben. The Ή-NMR (CDC1 3 , 298K) corresponds to that of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in an amorphous state as you can read above.
Herstellungsbeispiel 2: Production Example 2
20 g des amorphen 44-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on werden mit 22,5 ml Toluol und 7,5 ml Essigsäure-n-butylester versetzt und auf 60°C erhitzt. Anschließend wird mit 0,5°C/min auf 40°C abgekühlt und 8 h bei 40°C gerührt. Dann wird innerhalb von 1 h auf 35°C abgekühlt und anschließend auf 25°C gekühlt. Die ausgefallenen Kristalle werden abgesaugt und mit 5 ml Methyl-tert.-butylether gewaschen. Die Kristalle werden bei Temperaturen kleiner 40°C im Vakuum getrocknet. Man erhält 19,3 g kristallines -[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on mit einem Schmelzpunkt im Bereich von 72- 74 °C. Das Ή-NMR (CDC13, 298K) enspricht dem von 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on in amorphem Zustand wie oben angegeben. 20 g of the amorphous 44 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one are mixed with 22.5 ml of toluene and 7.5 ml of acetic acid. n-butyl ester and heated to 60 ° C. It is then cooled at 0.5 ° C / min to 40 ° C and stirred at 40 ° C for 8 h. It is then cooled to 35 ° C within 1 h and then cooled to 25 ° C. The precipitated crystals are filtered off with suction and washed with 5 ml of methyl tert-butyl ether. The crystals are dried at temperatures below 40 ° C in a vacuum. This gives 19.3 g of crystalline - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one having a melting point in the range of 72-74 ° C. The Ή-NMR (CDC1 3 , 298K) corresponds to that of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in amorphous state as above specified.
Herstellungsbeispiel 3: Production Example 3
20 g des amorphen 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on werden in 20 g Ethanol bei 50°C gelöst. Anschließend wird auf 40°C abgekühlt und 16 h bei 40°C gerührt. Dann wird innerhalb von 4 h auf 5°C abgekühlt. Die ausgefallenen Kristalle werden abgesaugt und bei Temperaturen kleiner 40°C im Vakuum getrocknet. Man erhält 17,2 g kristallines -[[(6- Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on, mit einem Schmelzpunkt im Bereich von 72- 74 °C. 20 g of the amorphous 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one are dissolved in 20 g of ethanol at 50 ° C. It is then cooled to 40 ° C and stirred at 40 ° C for 16 h. Then it is cooled to 5 ° C within 4 h. The precipitated crystals are filtered off and dried at temperatures below 40 ° C in a vacuum. There are obtained 17.2 g of crystalline - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one having a melting point in the range of 72-74 ° C ,
Das Ή-NMR (CDC13, 298K) enspri cht dem v on 4-[[(6-Ch^yridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on in amoφhem Zustand wie oben angegeben. The Ή NMR (CDC1 3 , 298K) corresponds to that of 4 - [[(6-chloro-3-yl-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one amoφhem state as stated above.
Herstellungsbeispiel 4: Production Example 4
20 g 4-[[(6-Chlo yridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on werden in 20 g 1- Propanol bei 50°C gelöst. Anschließend wird auf 40°C abgekühlt und 16 h bei 40°C gerührt. Dann wird innerhalb von 4 h auf 5°C abgekühlt. Die ausgefallenen Kristalle werden abgesaugt und bei Temperaturen kleiner 40°C im Vakuum getrocknet. Man erhält 15, 1 g kristallines -[[(6- Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on, mit einem Schmelzpunkt im Bereich von 72- 74 °C. 20 g of 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one are dissolved in 20 g of 1-propanol at 50 ° C. It is then cooled to 40 ° C and stirred at 40 ° C for 16 h. Then it is cooled to 5 ° C within 4 h. The precipitated crystals are sucked off and at Temperatures less than 40 ° C dried in vacuo. 15. 1 g of crystalline - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one having a melting point in the range of 72-74 ° C. is obtained ,
Das Ή-NMR (CDC13, 298K) enspricht dem von 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on in amorphem Zustand wie oben angegeben. The Ή-NMR (CDC1 3 , 298K) corresponds to that of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in amorphous state as above specified.
Formulierungsbeispiele: Formulation Examples:
L Herstellung eines Suspensionskonzentrats der neuen festen Form von 4-rr(6-Chlorpyridin-3- yl)methyl1(2,2-difluorethyl)amino1furan-2(5H)-on L Preparation of a suspension concentrate of the new solid form of 4-rr (6-chloropyridin-3-yl) methyl 1 (2,2-difluoroethyl) amino-1-furan-2 (5H) -one
Zur Herstellung eines Suspensionskonzentrates werden zunächst alle flüssigen Komponenten und danach die Feststoffe sowie die neue feste Form von 4-[[(6-Chlorpyridin-3-yl)methyl](2,2- difluorethyl)amino]furan-2(5H)-on ins Wasser gegeben und so lange gerührt, bis eine homogene Suspension entsteht. Diese wird zunächst einer Grob- und dann einer Feinmahlung in einer Perlmühle unterworfen, so dass man eine Suspension erhält, in der 90% der Feststoffpartikel eine Teilchengröße kleiner 10 μηι aufweisen. Anschließend fügt man unter Rühren bei Raumtemperatur eine Lösung von Kelzan® S, (Kelzan® S enthält Xanthangummi (CAS-Nr. 1 1 138-66-2) und Glyoxal (CAS-Nr. 1 07-22-2)) Gummi) und Wasser hinzu. Es wird ein homogenes Suspensionskonzentrat erhalten. Während der Herstellung wird darauf geachtet, dass die Produkttemperatur bei den einzelnen Formulierschritten 40°C nicht übersteigt. Zur Untersuchung der Lagerstabilität wird das Suspensionskonzentrat über acht Wochen bei 40°C aufbewahrt. Die anschließende Überprüfung der chemischen und physikalischen Eigenschaften ergab nur geringfügige tolerierbare Abweichungen der Werte im Vergleich zu den Ausgangswerten. Das Produkt ist auch nach Lagerung uneingeschränkt anwendbar und wirksam. To prepare a suspension concentrate, first all liquid components and then the solids and the new solid form of 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) - is added to the water and stirred until a homogeneous suspension is formed. This is first subjected to a coarse and then a fine grinding in a bead mill, so that a suspension is obtained in which 90% of the solid particles have a particle size of less than 10 μm. A solution of Kelzan® S is then added with stirring at room temperature (Kelzan® S contains xanthan gum (CAS No. 1 1 138-66-2) and glyoxal (CAS No. 1 07-22-2)) Rubber) and water. There is obtained a homogeneous suspension concentrate. During the production, care is taken that the product temperature does not exceed 40 ° C in the individual formulation steps. To test the storage stability, the suspension concentrate is stored for eight weeks at 40 ° C. The subsequent verification of the chemical and physical properties revealed only minor tolerable deviations of the values compared to the initial values. The product is fully applicable and effective even after storage.
2. Herstellung eines wasserdispergierbaren Granulates der neuen festen Form von 4-ΓΙΥ6- Chlorpyridin-3-yl)methyl1(2,2-difluorethyl)amino1furan-2(5H)-on 2. Preparation of a water-dispersible granulate of the new solid form of 4-ΓΙΥ6-chloropyridin-3-yl) methyl 1 (2,2-difluoroethyl) amino-1-furan-2 (5H) -one
Zur Herstellung eines wasserdispergierbaren Granulates werden alle festen Rezepturbestandteile sowie die neue feste Form von 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)- on in einem Mischer (z.B. Pflugscharmischer mit Zerhacker) gemischt und vorzerkleinert. Anschließend wird die Feststoffmischung einer Luftstrahlmahlung unterworfen, so dass 90% der Feststoffpartikel eine Teilchengröße unterhalb von 20 μηι aufweisen. In die Feststoffmischung wird nun mit einem schnell laufenden Mischer ca. 15 Wasser eingearbeitet. Die angefeuchtete Feststoffmischung wird unter möglichst geringem Druck und Energieeintrag durch einen geeigneten Extruder in Produktstränge überführt, die beim Austritt aus der Matrize und während der Trocknung in die stäbchenförmigen wasserdispergierbaren Granulate zerfallen. Während der Herstellung wird darauf geachtet, dass die Produkttemperatur bei den einzelnen Formulierschritten 40°C nicht übersteigt. To prepare a water-dispersible granule, all solid formulation ingredients and the new solid form of 4 - [[(6-chloro-pyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one are mixed (eg ploughshare mixer with chopper) mixed and pre-shredded. Subsequently, the solid mixture is subjected to an air jet milling, so that 90% of the solid particles have a particle size below 20 μηι. In the solid mixture is now incorporated with a fast-running mixer about 15 water. The moistened Solid mixture is transferred under the lowest possible pressure and energy input through a suitable extruder in product strands, which disintegrate on exit from the die and during drying in the rod-shaped water-dispersible granules. During the production, care is taken that the product temperature does not exceed 40 ° C in the individual formulation steps.
Zur Untersuchung der Lagerstabilität wird das wasserdispergierbare Granulat über acht Wochen bei 40°C aufbewahrt. Die anschließende Überprüfung der chemischen und physikalischen Eigenschaften ergab nur geringfügige tolerierbare Abweichungen der Werte im Vergleich zu den Ausgangswerten. Das Produkt ist auch nach Lagerung uneingeschränkt anwendbar und wirksam. To test the storage stability, the water-dispersible granules are stored for eight weeks at 40 ° C. The subsequent verification of the chemical and physical properties revealed only minor tolerable deviations of the values compared to the initial values. The product is fully applicable and effective even after storage.

Claims

Patentansprüche claims
1. Feste Form von 4-[[(6-Chlo yridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on, dadurch gekennzeichnet, dass ihr Röntgen-Pulverdiffraktogramm bei 25 °C mindestens 3 der folgenden charakteristischen 2Θ (2 Theta)-Werte aufweist: 1. Solid form of 4 - [[(6-chloro-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one, characterized in that its X-ray powder diffractogram at 25 ° C has at least 3 of the following characteristic 2Θ (2 theta) values:
2Θ = 16,8°  2Θ = 16.8 °
2Θ = 17,8°  2Θ = 17.8 °
2Θ = 20,2°  2Θ = 20.2 °
2Θ = 21,7°  2Θ = 21,7 °
2Θ = 23,6°  2Θ = 23.6 °
2Θ = 23,9°  2Θ = 23.9 °
2Θ = 24,7°  2Θ = 24.7 °
2Θ = 25,3°.  2Θ = 25.3 °.
2. Feste Form nach Anspruch 1, dadurch gekennzeichnet, dass ihr Röntgenpulverdiffraktogramm bei 25 °C mindestens 4 der in Anspruch 1 genannten charakteristischen 2Θ -Werte aufweist. 2. Solid form according to claim 1, characterized in that its X-ray powder diffractogram at 25 ° C has at least 4 of the characteristic 2Θ values mentioned in claim 1.
3. Zusammensetzung umfassend die neue feste Form nach Anspruch 1 oder 2 und geeignete Hilfsstoffe. A composition comprising the novel solid form of claim 1 or 2 and suitable adjuvants.
4. Verwendung der neuen festen Form nach Anspruch 1 oder 2 oder der Zusammensetzung nach Anspruch 3 zur Herstellung von Mitteln zur Bekämpfung von Schädlingen 4. Use of the novel solid form according to claim 1 or 2 or the composition according to claim 3 for the preparation of agents for combating pests
5. Verwendung nach Anspruch 4, wobei die Schädlinge Pflanzenschädlinge, tierische Parasiten oder Insekten sind, die technische Materialien zerstören. 5. Use according to claim 4, wherein the pests are plant pests, animal parasites or insects that destroy engineering materials.
6. Verwendung der neuen festen Form nach Anspruch 1 oder 2 oder der Zusammensetzung nach Anspruch 3 zur Behandlung von Saatgut. 6. Use of the novel solid form according to claim 1 or 2 or the composition according to claim 3 for the treatment of seed.
7. Verfahren zur Bekämpfung von Schädlingen, dadurch gekennzeichnet, dass die neue feste Form nach Anspruch 1 oder 2 oder die Zusammensetzung nach Anspruch 3 auf die Schädlinge und/oder ihren Lebensraum und/oder Saatgut ausgebracht wird. 7. A method for controlling pests, characterized in that the new solid form according to claim 1 or 2 or the composition according to claim 3 is applied to the pests and / or their habitat and / or seed.
8. Verfahren zur Herstellung der Verbindung wie in Anspruch 1 oder 2 definiert, das die folgenden Schritte umfasst: A process for the preparation of the compound as defined in claim 1 or 2, which comprises the following steps:
(a) Lösen von 4-[[(6-Chloφyridin-3-yl)methyl](2,2-difluorethyl)amino]furan-2(5H)-on in einem Lösungsmittel oder Lösungsmittelgemisch bei Temperaturen von mindestens 30 °C und (b) langsames Abkühlen der Lösung. (a) dissolving 4 - [[(6-chloropyridin-3-yl) methyl] (2,2-difluoroethyl) amino] furan-2 (5H) -one in a solvent or solvent mixture at temperatures of at least 30 ° C and (b) slowly cooling the solution.
9. Verfahren nach Anspruch 8, in dem das langsame Abkühlen stufenweise vorgenommen wird. 9. The method of claim 8, wherein the slow cooling is carried out in stages.
10. Verfahren nach Anspruch 8 oder 9, in dem das verwendete Lösungsmittel oder Lösungsmittelgemisch ausgewählt ist unter Isopropanol, Toluol, Methyl-THF Diethylcarbonat, Chlorbenzol, n-Butylacetat und i-Butylacetat, n-Butanol, Ethanol,10. The method according to claim 8 or 9, in which the solvent or solvent mixture used is selected from isopropanol, toluene, methyl THF diethyl carbonate, chlorobenzene, n-butyl acetate and i-butyl acetate, n-butanol, ethanol,
Malonsäureethylester, Methyl-t.butylether, Mischungen aus Toluol und Butanol, Toluol und n-Butylacetat, Malonsäureethylester und Methyl-t.-butylether, und Butylacetat und Methyl- t.-butylether. Malonic acid ethyl ester, methyl t-butyl ether, mixtures of toluene and butanol, toluene and n-butyl acetate, ethyl malonate and methyl t-butyl ether, and butyl acetate and methyl t-butyl ether.
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CN102741244A (en) 2012-10-17
IL219013A0 (en) 2012-06-28
US8324392B2 (en) 2012-12-04
US20110130288A1 (en) 2011-06-02
US8476448B2 (en) 2013-07-02
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