EP2493881A1 - Nouvelle forme solide de 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5h)-one - Google Patents

Nouvelle forme solide de 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Withdrawn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)
English (en)
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/fr
Publication of EP2493881A1 publication Critical patent/EP2493881A1/fr
Withdrawn legal-status Critical Current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

La présente invention concerne une nouvelle forme solide de 4-[[(6-Chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5H)-one, son procédé de production et son utilisation dans des préparations agrochimiques.
EP10766065A 2009-10-26 2010-10-20 Nouvelle forme solide de 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5h)-one Withdrawn EP2493881A1 (fr)

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EP10766065A EP2493881A1 (fr) 2009-10-26 2010-10-20 Nouvelle forme solide de 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5h)-one

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EP09174046 2009-10-26
US25560009P 2009-10-28 2009-10-28
PCT/EP2010/065807 WO2011051151A1 (fr) 2009-10-26 2010-10-20 Nouvelle forme solide de 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5h)-one
EP10766065A EP2493881A1 (fr) 2009-10-26 2010-10-20 Nouvelle forme solide de 4-[[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino]furan-2(5h)-one

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EP2493881A1 true EP2493881A1 (fr) 2012-09-05

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US (2) US8324392B2 (fr)
EP (1) EP2493881A1 (fr)
JP (1) JP2013508339A (fr)
KR (1) KR20120102060A (fr)
CN (1) CN102741244A (fr)
BR (1) BR112012009808A2 (fr)
IL (1) IL219013A0 (fr)
MX (1) MX2012004796A (fr)
WO (1) WO2011051151A1 (fr)

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EP4295683A1 (fr) 2022-06-21 2023-12-27 Bayer Aktiengesellschaft Formulations agrochimiques comprenant une forme cristalline de 4-[(6-chloro-3-pyridylméthyl)(2,2-difluoroéthyl)amino]4-alkoxy(5h)-one
WO2023237444A1 (fr) 2022-06-06 2023-12-14 Bayer Aktiengesellschaft Formulations agrochimiques comprenant une forme cristalline a de 4-[(6-chloro-3-pyridylméthyl)(2,2-difluoroéthyl)amino]furan-2(5h)-one

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Publication number Publication date
BR112012009808A2 (pt) 2015-09-29
US20130059731A1 (en) 2013-03-07
US8324392B2 (en) 2012-12-04
CN102741244A (zh) 2012-10-17
KR20120102060A (ko) 2012-09-17
MX2012004796A (es) 2012-06-08
IL219013A0 (en) 2012-06-28
JP2013508339A (ja) 2013-03-07
US20110130288A1 (en) 2011-06-02
WO2011051151A1 (fr) 2011-05-05
US8476448B2 (en) 2013-07-02

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