EP1047689A1 - Substituted guanidine derivatives - Google Patents

Substituted guanidine derivatives

Info

Publication number
EP1047689A1
EP1047689A1 EP98966405A EP98966405A EP1047689A1 EP 1047689 A1 EP1047689 A1 EP 1047689A1 EP 98966405 A EP98966405 A EP 98966405A EP 98966405 A EP98966405 A EP 98966405A EP 1047689 A1 EP1047689 A1 EP 1047689A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
spp
halogen
optionally substituted
formula
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Withdrawn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
EP98966405A
Other languages
German (de)
French (fr)
Inventor
Klaus Wagner
Christoph Erdelen
Wolfram Andersch
Ulrike Wachendorff-Neumann
Andreas Turberg
Norbert Mencke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Bayer 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 AG filed Critical Bayer AG
Publication of EP1047689A1 publication Critical patent/EP1047689A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • 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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present application relates to new guanidine derivatives, a process for their preparation and their use for controlling animal pests.
  • Rl represents a five- or six-membered heterocyclic grouping which 1,
  • R 3 stands for the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and -OSO 2 R 9 , where
  • R 4 , R5 and R ⁇ independently of one another are alkyl, alkoxyalkyl, haloalkyl, alkenyl, alkynyl, alkylaminoalkyl, dialkylaminoalkyl, optionally substituted cycloalkyl and in each case optionally substituted phenyl or benzyl,
  • R 7 and R 8 independently of one another represent hydrogen, alkyl, alkenyl and in each case optionally substituted phenyl or benzyl and
  • R9 represents alkyl or optionally substituted phenyl
  • Z represents cyano or nitro
  • R 2 and R 3 have the meaning given above and
  • X represents halogen (especially chlorine or bromine),
  • R preferably represents a five- to six-membered heterocyclic group from the series pyrazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrazinyl and pyrimidinyl, which is optionally by (which is optionally substituted by fluorine and / or chlorine) fluorine, chlorine, bromine, cyano, nitro, C j -C2 alkyl, C j -C2 -alkoxy (which is optionally substituted by fluorine and / or chlorine),
  • C 1 -C 2 -alkylthio (which is optionally substituted by fluorine and / or chlorine), or C 1 -C 2 -alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine) is substituted.
  • R 2 preferably represents hydrogen or C 1 -C 6 -alkyl.
  • R 3 preferably represents the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and -OSO 2 R 9 , where
  • R 4 , R5 and R 0 independently of one another are preferred for C ] -C] 2-alkyl, C1-C4-
  • R and R 8 independently of one another preferably represent hydrogen, C j -Cg- alkyl, C2-C4 alkenyl, or represent in each case monosubstituted to trisubstituted by identical or different substituents, phenyl or benzyl, are in each case preferably being mentioned as phenyl substituents halogen, C j - C4-alkyl, Cj-C4-alkoxy and C
  • R 9 preferably represents C1-C4-alkyl or phenyl which is monosubstituted to trisubstituted by identical or different substituents, the substituents which may be mentioned are halogen, C] -C4-alkyl, C 1 -C 4 -alkoxy and C1-C4-haloalkyl and C] -C4-Haloalkoxy, each with 1 to 5 identical or different halogen atoms, such as fluorine, chlorine and bromine atoms
  • Z preferably represents cyano or nitro
  • R particularly preferably represents 6-chloro-3-pyridyl (6-chloro-pyridin-3-yl) or 2-chloro-5-thiazolyl (2-chloro-thiazol-5-yl).
  • R2 particularly preferably represents hydrogen or C 5 -C 5 -alkyl.
  • R 3 particularly preferably represents the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and -OSO 2 R 9 , where
  • R 4 , R ⁇ and R ⁇ independently of one another are particularly preferred for C ] -Cg-
  • a phenyl substituent fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy and nitro.
  • R 7 and R 8 independently of one another, particularly preferably for hydrogen, C ] -
  • R 9 particularly preferably represents methyl, ethyl or phenyl which is monosubstituted or disubstituted by identical or different substituents, the following being mentioned as substituents: fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl and trifluoromethoxy.
  • a particularly preferably stands for the groupings -CH2CH2- and -CH CH-.
  • Preferred compounds according to the invention are substances of the formulas (I A) to (I D):
  • R2, R 3 and Z represent the general, preferred and particularly preferred meanings mentioned above.
  • Preferred compounds according to the invention are also substances of the formulas
  • hydrocarbon radicals such as alkyl - in each case straight-chain or branched - as far as possible - also in connection with heteroatoms such as alkoxy.
  • the compounds of the formula (II) required as starting materials for carrying out the process according to the invention are known (cf., for example, EP-A 0 192 060, EP-A 0 235 725, EP-A 0 259 738 and EP-A 0 315 826) and / or can be obtained in the manner described there
  • halogen compounds of the formula (III) which are also to be used as starting materials in the process according to the invention are generally known compounds of organic chemistry and / or can be obtained by generally known methods
  • diluents are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, Cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether and tetrahydrofuran, tetrahydrofuran , Methyl ethyl, methyl isopropyl and
  • Methyl isobutyl ketone esters such as methyl acetate and ethyl ester, nit ⁇ le such as acetonit ⁇ l and propionite, amides such as dimethylformamide, dimethyl acetamide and N-methylpyrrolidone and dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric acid
  • All customary proton acceptors can be used as bases in the process according to the invention.
  • Examples include sodium hydroxide, calcium hydroxide, sodium hydride, potassium carbonate, sodium hydrogen carbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclonones (DBN) and diazabicycloundecen (DBU).
  • reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between -40 ° C and + 200 ° C, preferably between -10 ° C and 100 ° C.
  • the end products are worked up and isolated in a generally known manner.
  • the active substances are suitable for controlling animal pests, especially insects,
  • the pests mentioned above include:
  • Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Thysanoptera for example Hercinoth ⁇ ps femora s, Th ⁇ ps tabaci
  • Homoptera for example Aleurodes brassicae, Bemisia tabaci,
  • Anthonomus spp Sitophilus spp, Otiorrhynchus sulcatus, Cosmopohtes sordidus, Ceuthorrhynchus assimi s, Hypera postica, Dermestes spp, Trogoderma spp, Anthrenus spp, Attagenus spp, Lyctus spp, Me gethes aeneus, Ptinus blumbum, Niptinusppole, Ptinus tolebum, Niptinusppole, Ptiptus soleol, sppylusppole b Teneb ⁇ o molitor, Ag ⁇ otes spp, Conoderus spp, Melolontha melolontha, Amphimallon solstitia s, Costelytra zealandica
  • Hymenoptera From the order of Hymenoptera, for example Dip ⁇ on spp, Hoplocampa spp, Lasius spp, Monomo ⁇ um pharaoms, Vespa spp
  • Diptera From the order of Diptera, for example Aedes spp, Anopheles spp, Culex spp, Drosophila melanogaster, Musca spp, Fannia spp, Calhphora erythrocephala, Luci a spp, Chrysomyia spp, Cuterebra spp, Gastrophilus spp, Hyppobosca spp Stoderestroxys spp, Hyderobox spp spp, Tabanus spp, Tannia spp, Bibio hortulanus, Oscinella f ⁇ t, Phorbia spp, Pegomyia hyoscyami, Ceratitis capitata,
  • Siphonaptera for example Xenopsylla cheopis
  • Ceratophyllus spp From the order of the Arachnida for example Scorpio maurus, Latrodectus mactans.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.,
  • Rhipicephalus spp. Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • Plant-parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..
  • the compounds of the formula (I) according to the invention are particularly notable for high insecticidal activity.
  • Onion fly (Hylemyia antiqua), against the peach aphid (Myzus persicae), against the green rice leafhopper (Nephotettix cincticeps), against the larvae of the horseradish beetle (Phaedon cochleariae), as well as against the larvae of the armyworm (Spodoptera frugiperda).
  • the compounds according to the invention also have a root systemic action.
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers Fabrics.
  • These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • alcohols such as butanol or glycol and their ethers and esters
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
  • strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • Possible solid carriers are: e.g. Ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene
  • Fatty alcohol ethers e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho- lipids such as cephalins and lecithins and synthetic phospholipids.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • Famoxadon Fenapanil, Fenarimol, Fenbuconazol, Fen Nameam, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimo ⁇ h, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconaziol, Flu ⁇ rimidol, Flusrimidol, Flusilimidol, Flusilimidol
  • Flutolanil Flutriafol, Folpet, Fosetyl-Alminium, Fosetyl-Sodium, Fthalid, Fuberidazol, Furalaxyl, Furametpyr, Furcarbonil, Furconazol, Furconazol-cis, Furmecyclox,
  • Imazalil Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
  • Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Meth tartroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen,
  • Thifluzamide Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol, Tridemo ⁇ h, Triflumizol, Triforin, Triticonazole,
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenatex, Fluufenate, Fluufenprox
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
  • Tebufenozid Tebufenpyrad
  • Tebupirimiphos Teflubenzuron, Tefluthrin, Temephos
  • the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active ingredient concentration of the Usage forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active ingredient When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
  • the active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas.
  • animal parasites ectoparasites
  • tick ticks leather ticks
  • mites running mites
  • flies stinging and licking
  • parasitic fly larvae lice, hair lice, Featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..
  • Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp ..
  • Nematocerina and Brachycerina for example 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., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp .. From the order of the Siphonaptrida, for example Pulex spp, Ctenocephalides spp, Xenopsylla spp, Ceratophyllus spp
  • 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, Pneumonyostus spp , Varroa spp.
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp Cheyletiella spp, Ornitrocheyletia spp, Myobia spp, Psorergates spp, Demodex spp.
  • Trombicula spp. Listrophorus spp, Acarus spp, Calrophogus spp, Calrophogus spp, Tyrophogus spp Hypodectes spp, Pterolichus spp., Psoroptes spp, Chorioptes spp, Otodectes spp, Sarcoptes spp, Notoedres spp, Knemidocoptes spp, Cytodites spp,
  • the compounds according to the invention show a good development-inhibiting action against fly larvae of Lucilia cuprina
  • the active compounds of the formula (I) according to the invention are also suitable for combating arthropods which are agricultural animals such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house bird, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and
  • the active compounds according to the invention are used in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, by dermal use in the form of, for example, diving or bathing ( Dipping), spraying (spray), pouring (pour-on and spot-on), washing, the
  • Powdering and with the help of shaped articles containing active ingredients such as collars, ear tags, tail tags, limb tapes, holsters, marking devices, etc.
  • formulations for example powders, emulsions, flowable agents
  • active compounds in an amount of 1 to 80% by weight, directly or after 100 to 10,000 times dilution, or use them as a chemical bath.
  • insects may be mentioned by way of example and preferably, but without limitation:
  • Kalotermes flavicollis Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucihegus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus
  • Bristle tail such as Lepisma sacca ⁇ na
  • non-living materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood and wood processing products and paints
  • the material to be protected against insect infestation is very particularly preferably wood and wood processing products
  • Means or mixtures containing them can be protected, is to be understood as exemplary construction timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden paneling, wooden windows and doors, plywood, chipboard, carpentry work or wooden products, the whole generally used in house construction or in carpentry
  • the active ingredients can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes
  • the formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersing and / or binding or fixing agent, water repellants, optionally desiccants and UV stabilizers and, if appropriate Dyes and pigments as well as other processing aids
  • the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight
  • the amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active ingredient, based on the material to be protected.
  • organic-chemical solvent or solvent mixture and / or an oily or oil-like difficult to volatile organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agents
  • oily or oil-like solvents preference is given to using oily or oil-like solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
  • Suitable mineral oils or their aromatic fractions or the like are difficultly volatile, water-insoluble, oily and oil-like solvents solvent mixtures containing mineral oil, preferably white spirit, petroleum and / or alkylbenzene
  • Mineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, turpentine oil are advantageous and the like
  • the organic slightly volatile oily or oil-like solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture
  • part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced.
  • aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups such as, for example, glycol ethers, esters or Like for application
  • the known organic-chemical binders are the water-thinnable and / or synthetic resins soluble or dispersible or emulsifiable in the organic chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, eg polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural substance - And / or synthetic resin used
  • the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution.
  • Bitumen or bituminous substances of up to 10% by weight can also be used as binders
  • Known dyes, pigments, water-repellent agents, odor agents and inhibitors or anticorrosive agents and the like are used
  • At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as organic-chemical binder.
  • binder mentioned can be replaced by a fixing agent (gem ⁇ sch) or a plasticizer (gem ⁇ sch). These additives are intended to prevent volatilization of the active ingredients and crystallization or failure. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used)
  • the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as t ⁇ butyl phosphate, adipic acid esters such as di (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate or oleates such as butyl glycol and oleates such as butyl glycol and oleates such as butyl glycol and oleates such as butyl glycol and oleates such as butyl glycol , Glyce ⁇ nester and p-toluenesulfonic acid ester
  • Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylene benzophenone
  • Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants
  • a particularly effective wood protection is achieved by large-scale impregnation processes, e.g. vacuum, double vacuum or printing processes
  • the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides
  • the insecticides and fungicides mentioned in Wo 94/29 268 are particularly suitable as additional mixing partners.
  • the compounds mentioned in this document are an integral part of the present application.
  • Insecticides such as chloropyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumazole, as well as fungazazole, as well as fungazazole, as well as fungazazole, as well as Fungazazole, as well as Fungazazole, like Fungazazole Tebuconazole, Cyproconazole, Metconazole, Imazalil, Dichlorfluanid, Tolylfluanid, 3-
  • logP The logP values were determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0, 1% aqueous phosphoric acid)
  • Mosquito larvae (Aedes aegypti) are placed in the active ingredient preparation of the desired concentration.
  • the effect on the larvae is determined. 100% means that all animals showed severe symptoms or were killed; 0% means that no animals have been killed.
  • Solvent 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Bean plants (Vicia faba), which are heavily infested with the black bean louse (Aphis fabae), are watered on with 20 ml of active compound preparation each, so that the active compound preparation penetrates into the soil without wetting the sprout.
  • the active ingredient is absorbed by the roots and in the
  • the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
  • Solvent 100 parts by weight of acetone 1900 parts by weight of methanol
  • a specified amount of active compound preparation of the desired concentration is pipetted onto a standardized amount of artificial feeder. After the methanol has evaporated, about 20 eggs of the onion fly (Hylemyia antiqua) are placed on the feed.
  • the death of the eggs or larvae is determined in%.
  • Cabbage leaves (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are treated by being dipped into the preparation of active compound of the desired concentration
  • the kill is determined in%. 100% means that all aphids have been killed, 0% means that no aphids have been killed
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Rice seedlings (Oryza sativa) are treated by dipping into the active ingredient preparation of the desired concentration and populated with larvae of the green rice leafhopper (Nephotettix cincticeps) while the seedlings are still moist
  • the kill is determined in%. 100% means that all cicadas have been killed, 0% means that no cicadas have been killed
  • Solvent 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist.
  • the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
  • Solvent 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the army worm (Spodoptera frugiperda) while the leaves are still moist.
  • the kill is determined in%. 100% means that all larvae have been killed; 0% means that no larvae have been killed.
  • Solvent 100 parts by weight of acetone 1900 parts by weight of methanol
  • a specified amount of active compound preparation of the desired concentration is pipetted onto a standardized amount of artificial feeder. After the methanol has evaporated, a larva (L2-L3) of the army worm (Spodoptera frugiperda) is placed in triple repetition on the feed.
  • L2-L3 of the army worm Spodoptera frugiperda
  • the kill is determined in%. 100% means that all animals have been killed; 0% means that no animals have been killed.
  • Test insect Aphis fabae solvent: 4 parts by weight of acetone
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • the active ingredient preparation is mixed intimately with soil.
  • the treated soil is filled into pots and planted with pre-germinated broad beans.
  • the active ingredient can be taken up from the soil by the plant roots and transported to the leaves.
  • the leaves are populated with the test animals mentioned above after 7 days. After a further 6 days, the evaluation is carried out by counting or estimating the dead animals.
  • the root systemic effect of the active ingredient is derived from the kill numbers. It is 100% when all test animals have been killed and 0% when as many test insects are still alive as in the untreated control.
  • Test animals Lucilia cuprina larvae
  • Solvent dimethyl sulfoxide
  • test tubes Contains 1 cm 3 horse meat and 0.5 ml of the active ingredient preparation to be tested. The effectiveness of the active substance preparation is determined after 24 hours and 48 hours.
  • the test tubes are transferred to beakers with a sand-covered bottom. After a further 2 days, the test tubes are removed and the dolls are counted.
  • the effect of the preparation of active substance is assessed according to the number of flies hatched after 1.5 times the development time of an untreated control. 100% means that no flies have hatched; 0% means that all flies hatched normally.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to novel guanidine derivatives of formula (1), wherein R<1> represents a five or six membered heterocyclic group containing 1, 2, 3 or 4 nitrogen atoms and/or one or two oxygen or sulphur atoms as heteroatom ring members, whereby the number of heteroatoms is 1, 2, 3 or 4 and is optionally substituted by halogen, cyano, nitro, alkyl, halogen alkane, alkenyl, halogen alkenyl, alkinyl, alkoxy, halogen alkoxy, alkenyloxy, halogen alkenyloxy, alkinyloxy, alkylthio, halogen alkanethio, alkenylthio, halogen alkenylthio, alkinylthio, alkylsulphinyl, halogen alkanesulphinyl, alkylsulphonyl, amino, alkylamino, dialkylamino, aryl, arylthio, arylamino, aralkyl, formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and or alkoxycarbonyl, R<2> represents hydrogen or alkyl, R<3> represents groups -OCR<4>, -OCOR<5>, OCOOR<6>, OCONR<7>R<8> and -OSO<2>R<9>, whereby R<4> and R<6> represent independently of each other alkyl, alkoxyalkyl, halogen alkane, alkenyl, alkinyl, alkylaminoalkyl, dialkylaminoalkyl, optionally substituted cycloalkyl and optionally substituted phenyl or benzyl, R<7> and R<8> represent independently of each other hydrogen, alkyl, alkenyl and optionally substituted phenyl or benzyl and R<9> represents alkyl or optionally substituted pheyl, A represents groups -CH2CH2-, (CH2)3 and -CH=CH- and Z represents cyano or nitro, with the proviso that when Z represents NO2 and A represents -CH2CH2, the radical R<2> represents hydrogen and the compound of formula (1), wherein R<1> corresponds to formula (II), R<2> = H, R<3> = OCH3, A = -CH2CH2- and Z = NO2, is excluded.

Description

Substituierte Guanidin-DerivateSubstituted guanidine derivatives
Die vorliegende Anmeldung betrifft neue Guanidin-Derivate, ein Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung von tierischen Schädlingen.The present application relates to new guanidine derivatives, a process for their preparation and their use for controlling animal pests.
Es ist bereits bekannt, daß bestimmte heterocyclische Verbindungen insektizide Eigenschaften aufweisen (vgl. z.B. EP-A 0 192 060, EP-A 0 277 317, Literaturstellen gemäß CA 125, 188 277; 12 255 796; Y2Λ, 157 642).It is already known that certain heterocyclic compounds have insecticidal properties (cf. e.g. EP-A 0 192 060, EP-A 0 277 317, references according to CA 125, 188 277; 12 255 796; Y2Λ, 157 642).
Die Wirksamkeit bzw. Wirkungsbreite dieser Verbindungen ist jedoch insbesondere bei niedrigen Aufwandmengen und Konzentrationen nicht immer in allen Anwendungsgebieten voll zufriedenstellend.However, the effectiveness or range of action of these compounds is not always completely satisfactory in all areas of application, in particular at low application rates and concentrations.
Es wurden neue Guanidin-Derivate der Formel (I) gefunden,New guanidine derivatives of the formula (I) have been found
in welcherin which
Rl für eine fünf- oder sechsgliedrige heterocyclische Gruppierung steht, welche 1,Rl represents a five- or six-membered heterocyclic grouping which 1,
2, 3 oder 4 Stickstoffatome und/oder ein oder zwei Sauerstoff- oder Schwefelatome als Heteroatom-Ringglieder enthält - wobei die Zahl der Heteroatome 1, 2, 3 ödere 4 beträgt - und welche gegebenenfalls durch Halogen, Cyano, Nitro, Alkyl, Halogenalkyl, Alkenyl, Halogenalkenyl, Alkinyl, Alkoxy, Halo- genalkoxy, Alkenyloxy, Halogenalkenyloxy, Alkinyloxy, Alkylthio, Halogen- alkylthio, Alkenylthio, Halogenalkenylthio, Alkinylthio, Alkylsulfinyl, Halo- genalkylsulfinyl, Alkylsulfonyl, Halogenalkylsulfonyl, Amino, Alkylamino, Di- alkylamino, Aryl, Arylthio, Arylamino, Aralkyl, Formylamino, Alkylcarbonyl- amino, Formyl, Carbamoyl, Alkylcarbonyl und/oder Alkoxycarbonyl substi- tuiert ist, R2 für Wasserstoff oder Alkyl steht,Contains 2, 3 or 4 nitrogen atoms and / or one or two oxygen or sulfur atoms as heteroatom ring members - the number of heteroatoms being 1, 2, 3 or 4 - and which may be halogen, cyano, nitro, alkyl, haloalkyl, Alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, alkynylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, amino, alkylamino, alkylamino, alkylamino Arylthio, arylamino, aralkyl, formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and / or alkoxycarbonyl is substituted, R 2 represents hydrogen or alkyl,
R3 für die Gruppierungen -OR4, -OCOR5, -OCOOR6, -OCONR7R8 und -OSO2R9 steht, wobeiR 3 stands for the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and -OSO 2 R 9 , where
R4, R5 und R^ unabhängig voneinander für Alkyl, Alkoxyalkyl, Halogenalkyl, Alkenyl, Alkinyl, Alkylaminoalkyl, Dialkylaminoalkyl, gegebenenfalls substituiertes Cycloalkyl und jeweils gegebenenfalls substituiertes Phenyl oder Benzyl stehen,R 4 , R5 and R ^ independently of one another are alkyl, alkoxyalkyl, haloalkyl, alkenyl, alkynyl, alkylaminoalkyl, dialkylaminoalkyl, optionally substituted cycloalkyl and in each case optionally substituted phenyl or benzyl,
R7 und R8 unabhängig voneinander für Wasserstoff, Alkyl, Alkenyl und jeweils gegebenenfalls substituiertes Phenyl oder Benzyl stehen undR 7 and R 8 independently of one another represent hydrogen, alkyl, alkenyl and in each case optionally substituted phenyl or benzyl and
R9 für Alkyl oder gegebenenfalls substituiertes Phenyl steht,R9 represents alkyl or optionally substituted phenyl,
A für die Gruppierungen -CH2CH2-, (CH2)3 und -CH=CH- steht undA stands for the groupings -CH2CH2-, (CH 2 ) 3 and -CH = CH- and
Z für Cyano oder Nitro steht,Z represents cyano or nitro,
mit der Maßgabe, daß wenn Z für NO2 und A für -CH2CH - stehen, der Rest R2 für Wasserstoff steht; sowie die Verbindung der Formel (I) in welcherwith the proviso that when Z is NO 2 and A is -CH 2 CH -, the radical R 2 is hydrogen; as well as the compound of formula (I) in which
R2 H,R 2 H,
R3 OCH3,R 3 OCH 3 ,
A -CH2CH2- undA -CH 2 CH 2 - and
Z NO2 Z NO 2
ausgenommen ist Weiterhin wurde gefunden, daß man die Verbindungen der Formel (I) erhält, wenn man Verbindungen der Formel (II)is excluded It has furthermore been found that the compounds of the formula (I) are obtained if compounds of the formula (II)
in welcherin which
Rl , A und Z die oben angegebene Bedeutung haben,Rl, A and Z have the meaning given above,
mit Halogenverbindungen der Formel (III)with halogen compounds of the formula (III)
RR
X-CH-R (HI)X-CH-R (HI)
in welcherin which
R2 und R3 die oben angegebene Bedeutung haben undR 2 and R 3 have the meaning given above and
X für Halogen (insbesondere Chlor oder Brom) steht,X represents halogen (especially chlorine or bromine),
in Gegenwart einer Base und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.in the presence of a base and optionally in the presence of a diluent.
Schließlich wurde gefunden, daß die neuen Verbindungen der Formel (I) stark ausgeprägte biologische Eigenschaften besitzen und vor allem zur Bekämpfung von tieri- sehen Schädlingen, insbesondere von Insekten, Spinnentieren und Nematoden, die in der Landwirtschaft, in den Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen, geeignet sind.Finally, it was found that the new compounds of the formula (I) have highly pronounced biological properties and above all to control animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in the forests, in the stock and Material protection as well as in the hygiene sector are suitable.
Die erfindungsgemäßen Verbindungen sind durch die Formel (I) allgemein definiert. Bevorzugte Substituenten bzw. Bereiche der in den oben und nachstehend erwähnten Formeln aufgeführten Reste werden im folgenden erläutert.The compounds according to the invention are generally defined by the formula (I). Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below.
R steht bevorzugt für eine fünf- bis sechsgliedrige heterocyclische Gruppierung aus der Reihe Pyrazolyl, 1,2,4-Triazolyl, Oxazolyl, Isoxazolyl, Thiazolyl, Isothiazolyl, 1,2,5-Thiadiazolyl, Pyridyl, Pyrazinyl und Pyrimidinyl steht, welche gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, Cj-C2- Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), Cj-C2- Alkoxy (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist),R preferably represents a five- to six-membered heterocyclic group from the series pyrazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrazinyl and pyrimidinyl, which is optionally by (which is optionally substituted by fluorine and / or chlorine) fluorine, chlorine, bromine, cyano, nitro, C j -C2 alkyl, C j -C2 -alkoxy (which is optionally substituted by fluorine and / or chlorine),
Cι-C2-Alkylthio (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), oder Cι -C2-Alkylsulfonyl (welches gegenenenfalls durch Fluor und/oder Chlor substituiert ist) substituiert ist.C 1 -C 2 -alkylthio (which is optionally substituted by fluorine and / or chlorine), or C 1 -C 2 -alkylsulfonyl (which is optionally substituted by fluorine and / or chlorine) is substituted.
R2 steht bevorzugt für Wasserstoff oder C \ -Cg-Alkyl.R 2 preferably represents hydrogen or C 1 -C 6 -alkyl.
R3 steht bevorzugt für die Gruppierungen -OR4, -OCOR5, -OCOOR6, -OCONR7R8 und -OSO2R9, wobeiR 3 preferably represents the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and -OSO 2 R 9 , where
R4, R5 und R0" unabhängig voneinander bevorzugt für C]-C]2-Alkyl, C1-C4-R 4 , R5 and R 0 " independently of one another are preferred for C ] -C] 2-alkyl, C1-C4-
Alkoxy-C]-C4-alkyl, C]-C4-Halogenalkyl mit 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- und Bromatomen; C2-C4- Alkenyl, C2-C4- Alkinyl, Cι-C4-Alkylamino-C1-C4-alkyl, Di- (Cι-C4)-alkylamino-C]-C4-alkyl, für gegebenenfalls einfach bis drei- fach, gleich oder verschieden substituiertes C3-C6-Cycloalkyl, wobei als Substituenten vorzugsweise genannt seien: Halogen, Cj-C^ Alkyl und C C^Halogenalkyl mit 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie F-, Cl- und Br-Atomen, oder für jeweils gegebenenfalls einfach bis dreifach, gleich oder verschieden substituiertes Phenyl oder Benzyl stehen, wobei jeweils als Phenylsubstituenten vorzugsweise genannt seien: Halogen, C]-C4- Alkyl, C1-C4- Alkoxy sowie Cι-C4-Halogenalkyl und Cj-C4-Halogenalkoxy mit jeweils 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- und Bromatomen und NitroAlkoxy-C ] -C4-alkyl, C] -C4-haloalkyl with 1 to 5 identical or different halogen atoms, such as fluorine, chlorine and bromine atoms; C2-C4-alkenyl, C 2 -C 4 -alkynyl, -C-C 4 -alkylamino-C 1 -C 4 -alkyl, di- (-C-C4) -alkylamino-C] -C4-alkyl, for optionally simply to three times by identical or different substituents, C 3 -C 6 cycloalkyl, may be preferably mentioned as substituents: halogen, C j ^ -C alkyl, and CC ^ halogenoalkyl having 1 to 5 identical or different halogen atoms, such as F, Cl and Br atoms, or in each case optionally monosubstituted to trisubstituted, identically or differently substituted, phenyl or benzyl, where the following are each preferably mentioned as phenyl substituents: halogen, C] -C4-alkyl, C1-C4-alkoxy and C 1 -C 4 -haloalkyl and Cj-C4 haloalkoxy each having 1 to 5 same or different halogen atoms, such as fluorine, chlorine and bromine atoms and nitro
R und R8 unabhängig voneinander bevorzugt für Wasserstoff, Cj-Cg- Alkyl, C2-C4- Alkenyl oder für jeweils einfach bis dreifach, gleich oder verschieden substituiertes Phenyl oder Benzyl stehen, wobei jeweils als Phenylsubstituenten vorzugsweise genannt seien Halogen, Cj-C4- Alkyl, Cj-C4-Alkoxy sowie C|-C4-Halogenalkyl und Cj-C4-Halogen- alkoxy mit jeweils 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- und Bromatomen, undR and R 8 independently of one another preferably represent hydrogen, C j -Cg- alkyl, C2-C4 alkenyl, or represent in each case monosubstituted to trisubstituted by identical or different substituents, phenyl or benzyl, are in each case preferably being mentioned as phenyl substituents halogen, C j - C4-alkyl, Cj-C4-alkoxy and C | -C4-haloalkyl and C j -C4-haloalkoxy each having 1 to 5 identical or different halogen atoms, such as fluorine, chlorine and bromine atoms, and
R9 bevorzugt für C1-C4- Alkyl oder für einfach bis dreifach, gleich oder verschieden substituiertes Phenyl steht, wobei als Substituenten genannt seien Halogen, C]-C4-Alkyl, Cι-C4-Alkoxy sowie C1-C4- Halogenalkyl und C]-C4-Halogenalkoxy mit jeweils 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- und BromatomenR 9 preferably represents C1-C4-alkyl or phenyl which is monosubstituted to trisubstituted by identical or different substituents, the substituents which may be mentioned are halogen, C] -C4-alkyl, C 1 -C 4 -alkoxy and C1-C4-haloalkyl and C] -C4-Haloalkoxy, each with 1 to 5 identical or different halogen atoms, such as fluorine, chlorine and bromine atoms
A steht bevorzugt für die Gruppierungen -CH2CH2-, -(CH )3- und -CH=CH-A preferably represents the groupings -CH2CH2-, - (CH) 3 - and -CH = CH-
Z steht bevorzugt für Cyano oder Nitro,Z preferably represents cyano or nitro,
mit der Maßgabe, daß wenn Z für NO2 und A für -CH2CH - stehen, der Rest R2 für Wasserstoff steht, sowie die Verbindung der Formel (I) in welcherwith the proviso that when Z is NO 2 and A is -CH 2 CH -, the radical R 2 is hydrogen, and the compound of the formula (I) in which
R2 H,R 2 H,
R3 OCH3,R 3 OCH 3 ,
A -CH2CH2- - undA -CH 2 CH 2 - - and
Z NO2 Z NO 2
ausgenommen ist R steht besonders bevorzugt für 6-Chlor-3-pyridyl (6-Chlor-pyridin-3-yl) oder für 2-Chlor-5-thiazolyl (2-Chlor-thiazol-5-yl).is excluded R particularly preferably represents 6-chloro-3-pyridyl (6-chloro-pyridin-3-yl) or 2-chloro-5-thiazolyl (2-chloro-thiazol-5-yl).
R2 steht besonders bevorzugt für Wasserstoff oder C \ -C5 -Alkyl.R2 particularly preferably represents hydrogen or C 5 -C 5 -alkyl.
R3 steht besonders bevorzugt für die Gruppierungen -OR4, -OCOR5, -OCOOR6, -OCONR7R8 und -OSO2R9, wobeiR 3 particularly preferably represents the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and -OSO 2 R 9 , where
R4, R^ und R^ unabhängig voneinander besonders bevorzugt für C]-Cg-R 4 , R ^ and R ^ independently of one another are particularly preferred for C ] -Cg-
Alkyl, Cι-C2-Alkoxy-Cι-C2-alkyl, C1-C2-Halogenalkyl mit 1 bis 2 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- und Bromatomen; Allyl, Propargyl, C]-C2-Alkylamino-C]-C2-alkyl, Di(Cι-C2)-alkylamino-Cι-C2-alkyl, Cyclopropyl, Cyclopentyl, Cyclo- hexyl oder für jeweils gegebenenfalls einfach bis zweifach, gleich oder verschieden substituiertes Phenyl oder Benzyl stehen, wobei jeweils als Phenylsubstituenten genannt seien: Fluor, Chlor, Brom, Methyl, Meth- oxy, Trifluormethyl, Trifluormethoxy und Nitro.Alkyl, -C-C2-alkoxy-Cι-C 2 alkyl, C 1 -C 2 haloalkyl having 1 to 2 identical or different halogen atoms, such as fluorine, chlorine and bromine atoms; Allyl, propargyl, C] -C2-alkylamino-C ] -C2-alkyl, di (Cι-C2) -alkylamino-Cι-C2-alkyl, cyclopropyl, cyclopentyl, cyclohexyl or for each optionally single to double, identical or differently substituted phenyl or benzyl, each of which may be mentioned as a phenyl substituent: fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl, trifluoromethoxy and nitro.
R7 und R8 unabhängig voneinander besonders bevorzugt für Wasserstoff, C ] -R 7 and R 8 independently of one another, particularly preferably for hydrogen, C ] -
C4- Alkyl, Vinyl, Allyl oder für jeweils gegebenenfalls einfach bis zweifach, gleich oder verschieden substituiertes Phenyl oder Benzyl stehen, wobei jeweils als Phenylsubstituenten genannt seien: Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl und Trifluormethoxy; undC4-alkyl, vinyl, allyl or phenyl or benzyl which are each mono- or disubstituted, identically or differently, where each may be mentioned as phenyl substituent: fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl and trifluoromethoxy; and
R9 besonders bevorzugt für Methyl, Ethyl oder gegebenenfalls einfach bis zweifach, gleich oder verschieden substituiertes Phenyl steht, wobei als Substituenten genannt seien: Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl und Trifluormethoxy.R 9 particularly preferably represents methyl, ethyl or phenyl which is monosubstituted or disubstituted by identical or different substituents, the following being mentioned as substituents: fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl and trifluoromethoxy.
A steht besonders bevorzugt für die Gruppierungen -CH2CH2- und -CH=CH-. Z steht besonders bevorzugt für Cyano oder Nitro;A particularly preferably stands for the groupings -CH2CH2- and -CH = CH-. Z particularly preferably represents cyano or nitro;
mit der Maßgabe, daß wenn Z für NO2 und A für -CH2CH2- stehen, der Rest R2 für Wasserstoff steht; sowie die Verbindung der Formel (I) in welcherwith the proviso that when Z is NO 2 and A is -CH 2 CH 2 -, the radical R 2 is hydrogen; as well as the compound of formula (I) in which
R2 H,R 2 H,
R3 OCH3,R 3 OCH 3 ,
A -CH2CH2- undA -CH 2 CH 2 - and
Z NO2 Z NO 2
ausgenommen ist.is excluded.
Bevorzugte erfindungsgemäße Verbindungen sind Stoffe der Formeln (I A) bis (I D):Preferred compounds according to the invention are substances of the formulas (I A) to (I D):
- R! ~LcH2-N. .N-CH-R3 ( I D )- R! ~ LcH 2 -N. .N-CH-R 3 (ID)
N^_N ^ _
in welchen R2, R3 und Z für die obengenannten allgemeinen, bevorzugten und besonders bevorzugten Bedeutungen stehen.in which R2, R 3 and Z represent the general, preferred and particularly preferred meanings mentioned above.
Bevorzugte erfindungsgemäße Verbindungen sind auch Stoffe der FormelnPreferred compounds according to the invention are also substances of the formulas
(I A-l), (I A-2), (I B-l), (I B-2), (I C-1), (I C-2), (I D-1) und (I D-2):(I Al), (I A-2), (I Bl), (I B-2), (I C-1), (I C-2), (I D-1) and (I D-2 ):
( I B-2 )(I B-2)
in welchenin which
R3 für die oben genannten allgemeinen, bevorzugten und besonders bevorzugtenR 3 for the above general, preferred and particularly preferred
Bedeutungen steht.Meanings.
Die oben aufgeführten allgemeinen oder in Vorzugsbereichen aufgeführten Restedefinitionen bzw. Erläuterungen gelten für die Endprodukte und für die Ausgangs- und Zwischenprodukte entsprechend. Diese Restedefinitionen können untereinander, also auch zwischen den jeweiligen Vorzugsbereichen, beliebig kombiniert werden.The general or preferred radical definitions or explanations listed above apply to the end products and to the starting and intermediate products accordingly. These residual definitions can be combined with one another, i.e. also between the respective preferred areas.
Erfindungsgemäß bevorzugt werden die Verbindungen der Formel (I), in welchen eine Kombination der vorstehend als bevorzugt (vorzugsweise) aufgeführten Bedeutungen vorliegt.According to the invention, preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as preferred (preferred).
Erfindungsgemäß besonders bevorzugt werden die Verbindungen der Formel (I), in welchen eine Kombination der vorstehend als besonders bevorzugt aufgeführten Bedeutungen vorliegt.According to the invention, particular preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred.
In den oben und nachstehend aufgeführten Restedefinitionen sind Kohlenwasserstoffreste, wie Alkyl - auch in Verbindung mit Heteroatomen wie Alkoxy - soweit möglich jeweils geradkettig oder verzweigt.In the radical definitions given above and below, hydrocarbon radicals, such as alkyl - in each case straight-chain or branched - as far as possible - also in connection with heteroatoms such as alkoxy.
Verwendet man beispielsweise l-(6-Chlor-pyridin-3-yl-methyl)-2-nitroimino-imid- azolin und i-Propoxymethylchlorid als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens durch das folgende Reaktionsschema wiedergegeben werden: If, for example, 1- (6-chloro-pyridin-3-yl-methyl) -2-nitroimino-imidazoline and i-propoxymethyl chloride are used as starting materials, the course of the process according to the invention can be represented by the following reaction scheme:
+ Base jf j γN_CH2OC3H7-'+ Base jf j γ N_CH 2 OC 3 H 7- '
- HCI * cl N N lΛ - HCI * cl N N lΛ
NO,NO,
Die zur Durchführung des erfindungsgemaßen Verfahrens als Ausgangsstoffe benotigten Verbindungen der Formel (II) sind bekannt (vgl z B EP-A 0 192 060, EP-A 0 235 725, EP-A 0 259 738 und EP-A 0 315 826) und/oder können auf die dort beschriebene Art und Weise erhalten werdenThe compounds of the formula (II) required as starting materials for carrying out the process according to the invention are known (cf., for example, EP-A 0 192 060, EP-A 0 235 725, EP-A 0 259 738 and EP-A 0 315 826) and / or can be obtained in the manner described there
Die weiterhin beim erfindungsgemaßen Verfahren als Ausgangsstoffe zu verwendenden Halogenverbindungen der Formel (III) sind allgemein bekannte Verbindungen der Organischen Chemie und/oder nach allgemein bekannten Methoden erhältlichThe halogen compounds of the formula (III) which are also to be used as starting materials in the process according to the invention are generally known compounds of organic chemistry and / or can be obtained by generally known methods
Das erfindungsgemaße Verfahren zur Herstellung der neuen Verbindungen der Formel (I) wird vorzugsweise unter Verwendung von Verdünnungsmitteln durchgeführt Als Verdünnungsmittel kommen dabei praktisch alle inerten organischen Losungs- mittel in Frage Hierzu gehören vorzugsweise aliphatische und aromatische, gegebenenfalls halogemerte Kohlenwasserstoffe wie Pentan, Hexan, Heptan, Cyclohexan, Petrolether, Benzin, Ligroin, Benzol, Toluol, Xylol, Methylenchloπd, Ethylenchloπd, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol und o-Dichlorbenzol, Ether wie Di- ethyl- und Dibutylether, Glykoldimethylether und Diglykoldimethylether, Tetra- hydrofüran und Dioxan, Ketone wie Aceton, Methyl-ethyl-, Methyl-isopropyl- undThe process according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Suitable diluents are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, Cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether and tetrahydrofuran, tetrahydrofuran , Methyl ethyl, methyl isopropyl and
Methyl-isobutyl-keton, Ester wie Essigsauremethylester und -ethylester, Nitπle wie z B Acetonitπl und Propionitπl, Amide wie z B Dimethylformamid, Dimethyl- acetamid und N-Methylpyrrolidon sowie Dimethylsulfoxid, Tetramethylensulfon und HexamethylphosphorsauretπamidMethyl isobutyl ketone, esters such as methyl acetate and ethyl ester, nitπle such as acetonitπl and propionite, amides such as dimethylformamide, dimethyl acetamide and N-methylpyrrolidone and dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric acid
Als Basen können bei dem erfindungsgemaßen Verfahren alle üblichen Protonenakzeptoren eingesetzt werden Vorzugsweise verwendbar sind Alkali- oder Erdalkali- hydroxide, Alkali- oder Erdalkalihydride, Alkali- oder Erdalkalicarbonate oder -hy- drogencarbonate oder Stickstofrbasen. Genannt seien beispielsweise Natriumhydroxid, Calciumhydroxid, Natriumhydrid, Kaliumcarbonat, Natriumhydrogen- carbonat, Triethylamin, Dibenzylamin, Diisopropylamin, Pyridin, Chinolin, Diazabi- cyclooctan (DABCO), Diazabicyclononen (DBN) und Diazabicycloundecen (DBU).All customary proton acceptors can be used as bases in the process according to the invention. Alkali or alkaline earth hydroxides, alkali or alkaline earth hydrides, alkali or alkaline earth carbonates or hydrogen carbonates or nitrogen bases. Examples include sodium hydroxide, calcium hydroxide, sodium hydride, potassium carbonate, sodium hydrogen carbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclonones (DBN) and diazabicycloundecen (DBU).
Die Reaktionstemperaturen können bei dem erfindungsgemäßen Verfahren in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -40°C und +200°C, bevorzugt zwischen -10°C und 100°C.The reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between -40 ° C and + 200 ° C, preferably between -10 ° C and 100 ° C.
Bei der Durchführung des erfindungsgemäßen Verfahrens zur Herstellung der Verbindungen der Formel (I) setzt man im allgemeinen pro Mol Verbindungen der Formel (II) 1 bis 3 Mol, vorzugsweise 1 bis 2 Mol an Halogenverbindung der Formel (III) ein.When carrying out the process according to the invention for the preparation of the compounds of the formula (I), 1 to 3 mol, preferably 1 to 2 mol, of halogen compound of the formula (III) are generally employed per mole of compounds of the formula (II).
Aufarbeitung und Isolierung der Endprodukte erfolgen in allgemein bekannter Art und Weise.The end products are worked up and isolated in a generally known manner.
Die Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit und günstiger Warm- blütertoxizität zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten,With good plant tolerance and favorable warm-blooded toxicity, the active substances are suitable for controlling animal pests, especially insects,
Spinnentieren und Nematoden, die in der Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie können vorzugsweise als Pflanzenschutzmittel eingesetzt werden. Sie sind gegen normal sensible und resi- stente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:Arachnids and nematodes found in agriculture, in forests, in the protection of stocks and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
Aus der Ordnung der Isopoda z.B. Oniscus asellus, Armadillidium vulgäre, Porcellio scaber.From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus.From the order of the Diplopoda e.g. Blaniulus guttulatus.
Aus der Ordnung der Chilopoda z.B. Geophilus carpophagus, Scutigera spec. Aus der Ordnung der Symphyla z B Scutigerella immaculataFrom the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec. From the order of the Symphyla eg Scutigerella immaculata
Aus der Ordnung der Thysanura z B Lepisma saccharinaFrom the order of the Thysanura, for example Lepisma saccharina
Aus der Ordnung der Collembola z B Onychiurus armatusFrom the order of the Collembola, for example Onychiurus armatus
Aus der Ordnung der Orthoptera z B Blatta orienta s, Periplaneta ameπcana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp , Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregariaFrom the order of the Orthoptera, for example Blatta orienta s, Periplaneta ameπcana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp, Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria
Aus der Ordnung der Dermaptera z B Forficula auriculariaFrom the order of the Dermaptera e.g. Forficula auricularia
Aus der Ordnung der Isoptera z B Reticu termes sppFrom the order of the Isoptera, for example Reticu termes spp
Aus der Ordnung der Anoplura z B Pediculus humanus corpoπs, Haematopinus spp ,From the order of the Anoplura, e.g. Pediculus humanus corpoπs, Haematopinus spp,
Linognathus sppLinognathus spp
Aus der Ordnung der Mallophaga z B Tπchodectes spp , Damalinea sppFrom the order of the Mallophaga, for example Tπchodectes spp, Damalinea spp
Aus der Ordnung der Thysanoptera z B Hercinothπps femora s, Thπps tabaciFrom the order of the Thysanoptera, for example Hercinothπps femora s, Thπps tabaci
Aus der Ordnung der Heteroptera z B Eurygaster spp , Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma sppFrom the order of Heteroptera, for example Eurygaster spp, Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp
Aus der Ordnung der Homoptera z B Aleurodes brassicae, Bemisia tabaci,From the order of Homoptera, for example Aleurodes brassicae, Bemisia tabaci,
Trialeurodes vaporaπorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp , Macrosiphum avenae, Myzus spp , Phorodon humuh, Rhopalosiphum padi, Empoasca spp , Eusce s bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax stπatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp , Psylla spp Aus der Ordnung der Lepidoptera z B Pectinophora gossypiella, Bupalus piniaπus, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella macu pennis, Malacosoma neustπa, Euproctis chrysorrhoea, Lymantπa spp , Bucculatπx thurbeπella, Phyllocnistis citrella, Agrotis spp , Euxoa spp , Feltia spp , Earias insulana, Heliothis spp , Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera tura, Spodoptera spp , Tπchoplusia ni, Carpocapsa pomonella, Pieπs spp , Chilo spp , Pyrausta nubilalis, Ephestia kuehniella, Galleπa mellonella, Tmeola bisselhella, Tinea pel onella, Hofmannophila pseudospretella, Cacoecia po- dana, Capua reticulana, Choπstoneura fümiferana, Clysia ambiguella, Homona magnamma, Tortπx viπdanaTrialeurodes vaporaπorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp, Macrosiphum avenae, Myzus spp, Phoropaliphosumpp cincticeps, Lecanium corni, Saissetia oleae, Laodelphax stπatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp, Psylla spp From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniaπus, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella macu pennis, Malacosoma neustπa, Euproctis chrysorrhoea, Lymantπa spp thyllocella spp, Buurulbella spp, Bucculistis Earias insulana, Heliothis spp, Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera tura, Spodoptera spp, Tπchoplusia ni, Carpocapsa pomonella, Pieπs spp, Chilo spp, Pyrausta nubilalis, Ephestia kuehniella, Galleπa mellonella, Tmeola bisselhella, tinea pel Onella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choπstoneura fümiferana, Clysia ambiguella, Homona magnamma, Tortπx viπdana
Aus der Ordnung der Coleoptera z B Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthosce des obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleaπae, Diabrotica spp , Psyl odes chrysocephala, Epilachna vaπvestis, Atomaπa spp , Oryzaephilus suπnamensis,From the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthosce des obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleaπae, Diabrotica spp, Psyl odes Epysisaphala, sysalaaodes chrysoysappala
Anthonomus spp , Sitophilus spp , Otiorrhynchus sulcatus, Cosmopohtes sordidus, Ceuthorrhynchus assimi s, Hypera postica, Dermestes spp , Trogoderma spp , Anthrenus spp , Attagenus spp , Lyctus spp , Me gethes aeneus, Ptinus spp , Niptus hololeucus, Gibblum psylloides, Tπbolium spp , Tenebπo molitor, Agπotes spp , Conoderus spp , Melolontha melolontha, Amphimallon solstitia s, Costelytra zealandicaAnthonomus spp, Sitophilus spp, Otiorrhynchus sulcatus, Cosmopohtes sordidus, Ceuthorrhynchus assimi s, Hypera postica, Dermestes spp, Trogoderma spp, Anthrenus spp, Attagenus spp, Lyctus spp, Me gethes aeneus, Ptinus blumbum, Niptinusppole, Ptinus tolebum, Niptinusppole, Ptiptus soleol, sppylusppole b Tenebπo molitor, Agπotes spp, Conoderus spp, Melolontha melolontha, Amphimallon solstitia s, Costelytra zealandica
Aus der Ordnung der Hymenoptera z B Dipπon spp , Hoplocampa spp , Lasius spp , Monomoπum pharaoms, Vespa sppFrom the order of Hymenoptera, for example Dipπon spp, Hoplocampa spp, Lasius spp, Monomoπum pharaoms, Vespa spp
Aus der Ordnung der Diptera z B Aedes spp , Anopheles spp , Culex spp , Drosophila melanogaster, Musca spp , Fannia spp , Calhphora erythrocephala, Luci a spp , Chrysomyia spp , Cuterebra spp , Gastrophilus spp , Hyppobosca spp Stomoxys spp , Oestrus spp , Hypoderma spp , Tabanus spp , Tannia spp , Bibio hortulanus, Oscinella fπt, Phorbia spp , Pegomyia hyoscyami, Ceratitis capitata,From the order of Diptera, for example Aedes spp, Anopheles spp, Culex spp, Drosophila melanogaster, Musca spp, Fannia spp, Calhphora erythrocephala, Luci a spp, Chrysomyia spp, Cuterebra spp, Gastrophilus spp, Hyppobosca spp Stoderestroxys spp, Hyderobox spp spp, Tabanus spp, Tannia spp, Bibio hortulanus, Oscinella fπt, Phorbia spp, Pegomyia hyoscyami, Ceratitis capitata,
Dacus oleae, Tipula paludosaDacus oleae, Tipula paludosa
Aus der Ordnung der Siphonaptera z B Xenopsylla cheopis, Ceratophyllus spp Aus der Ordnung der Arachnida z.B. Scorpio maurus, Latrodectus mactans.From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp From the order of the Arachnida, for example Scorpio maurus, Latrodectus mactans.
Aus der Ordnung der Acarina z.B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.,From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.,
Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp..Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
Zu den pflanzenparasitären Nematoden gehören z.B. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp..Plant-parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp ..
Die erfindungsgemäßen Verbindungen der Formel (I) zeichnen sich insbesondere durch eine hohe insektizide Wirksamkeit aus.The compounds of the formula (I) according to the invention are particularly notable for high insecticidal activity.
Sie lassen sich mit besonders gutem Erfolg zur Bekämpfung pflanzenschädigender Blatt- und Bodeninsekten einsetzen, wie beispielsweise gegen Mückenlarven (Aedes aegypti), gegen die Schwarze Bohnenblattlaus (Aphis fabae), gegen die Eier derThey can be used with particularly good success to control plant-damaging leaf and soil insects, for example against mosquito larvae (Aedes aegypti), against black bean aphid (Aphis fabae), against the eggs of the
Zwiebelfliege (Hylemyia antiqua), gegen die Pfirsichblattlaus (Myzus persicae), gegen die Grüne Reiszikade (Nephotettix cincticeps), gegen die Larven des Meerrettich- Käfers (Phaedon cochleariae), sowie gegen die Larven des Heerwums (Spodoptera frugiperda).Onion fly (Hylemyia antiqua), against the peach aphid (Myzus persicae), against the green rice leafhopper (Nephotettix cincticeps), against the larvae of the horseradish beetle (Phaedon cochleariae), as well as against the larvae of the armyworm (Spodoptera frugiperda).
Darüber hinaus zeigen die erfindungsgemäßen Verbindungen auch eine wurzel- systemische Wirkung.In addition, the compounds according to the invention also have a root systemic action.
Die Wirkstoffe können in die üblichen Formulierungen überführt werden, wie Lö- sungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-imprägnierte Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymeren Stoffen. Diese 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 Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln.The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymers Fabrics. These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkyl- naphthaline, chlorierte Aromaten und chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser.If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
Als feste 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, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengeln; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Possible solid carriers are: e.g. Ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene
Fettalkohol-Ether, z.B. Alkylaryl-polyglykolether, Alkylsulfonate, Alkylsulfate, Aryl- sulfonate sowie Einweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.Fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospho- lipide, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho- lipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferro- cyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyanin- farbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gew.-% Wirk- stoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
Der erfindungsgemäße Wirkstoff kann in seinen handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit anderen Wirkstoffen, wie Insektiziden, Lockstoffen, Sterilantien, Bakteriziden, Akari- ziden, Nematiziden, Fungiziden, wachstumsregulierenden Stoffen oder Herbiziden vorliegen. Zu den Insektiziden zählen beispielsweise Phosphorsäureester, Carbamate, Carbonsäureester, chlorierte Kohlenwasserstoffe, Phenylharnstoffe, durch Mikroorganismen hergestellte Stoffe u.a.The active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
Besonders günstige Mischpartner sind z.B. die folgenden:Particularly cheap mixing partners are e.g. the following:
Fungizide:Fungicides:
Aldimorph, Ampropylfos, Ampropylfos-Kalium, Andoprim, Anilazin, Azaconazol, Azoxystrobin,Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, Benodanil, Benomyl, Benzamacril, Benzamacryl-isobutyl, Bialaphos, Binapacryl, Bip enyl, Bitertanol, Blasticidin-S, Bromuconazol, Bupirimat, Buthiobat,Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, bip enyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
Calciumpolysulfid, Capsimycin, Captafol, Captan, Carbendazim, Carboxin, Carvon, Chinomethionat (Quinomethionat), Chlobenthiazon, Chlorfenazol, Chloroneb, Chloro- picrin, Chlorothalonil, Chlozolinat, Clozylacon, Cufraneb, Cymoxanil, Cyproconazol, Cyprodinil, Cyprofüram, Debacarb, Dichlorophen, Diclobutrazol, Diclofluanid, Diclomezin, Dicloran, Diethofencarb, Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Diniconazol- M, Dinocap, Diphenylamin, Dipyrithione, Ditalimfos, Dithianon, Dodemorph, Dodine, Drazoxolon,Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazon, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyprodinconol, cypodinconol Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxinodonine, dithorphononine
Ediphenphos, Epoxiconazol, Etaconazol, Ethirimol, Etridiazol,Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadon, Fenapanil, Fenarimol, Fenbuconazol, Fenfüram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimoφh, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconaziol, Fluφrimidol, Flusilazol, Flusulfamid,Famoxadon, Fenapanil, Fenarimol, Fenbuconazol, Fenfüram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimoφh, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconaziol, Fluφrimidol, Flusrimidol, Flusilimidol, Flusilimidol
Flutolanil, Flutriafol, Folpet, Fosetyl-Alminium, Fosetyl-Natrium, Fthalid, Fuberidazol, Furalaxyl, Furametpyr, Furcarbonil, Furconazol, Furconazol-cis, Furmecyclox,Flutolanil, Flutriafol, Folpet, Fosetyl-Alminium, Fosetyl-Sodium, Fthalid, Fuberidazol, Furalaxyl, Furametpyr, Furcarbonil, Furconazol, Furconazol-cis, Furmecyclox,
Guazatin,Guazatin,
Hexachlorobenzol, Hexaconazol, Hymexazol,Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobenfos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoxim-methyl, Kupfer-Zubereitungen, wie: Kupferhydroxid, Kupfer- naphthenat, Kupferoxychlorid, Kupfersulfat, Kupferoxid, Oxin-Kupfer und Bordeaux- Mischung,Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfüroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfüroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel-dimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol,Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofürace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin, Paclobutrazol, Pefürazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Polyoxorim, Probenazol, Prochloraz, Procymidon, Propamocarb, Propanosine- Natrium, Propiconazol, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon, Pyroxyfür,Ofürace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin, Paclobutrazol, Pefürazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Polyoxorim, probenazole, Prochloraz, Procymidon, Propamocarb, Propanosine-Sodium, Propiconazole, Propineb, Pyrazophos, Pyrifen, Pyifen, Pyroyilonil
Quinconazol, Quintozen (PCNB),Quinconazole, quintozen (PCNB),
Schwefel und Schwefel-Zubereitungen,Sulfur and sulfur preparations,
Tebuconazol, Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazol, Thiabendazol, Thicyofen,Tebuconazole, tecloftalam, tecnazen, tetcyclacis, tetraconazole, thiabendazole, thicyofen,
Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol, Tridemoφh, Triflumizol, Triforin, Triticonazol,Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutil, Triazoxid, Trichlamid, Tricyclazol, Tridemoφh, Triflumizol, Triforin, Triticonazole,
Uniconazol,Uniconazole,
Validamycin A, Vinclozolin, Viniconazol,Validamycin A, vinclozolin, viniconazole,
Zarilamid, Zineb, Ziram sowieZarilamid, Zineb, Ziram as well
Dagger G,Dagger G,
OK-8705,OK-8705,
OK-8801,OK-8801,
α-(l , 1 -Dimethylethyl)-ß-(2-phenoxyethyl)- 1 H- 1 ,2,4-triazol- 1 -ethanol,α- (1,1-dimethylethyl) -ß- (2-phenoxyethyl) -1 H-1, 2,4-triazole-1-ethanol,
α-(2,4-Dichloφhenyl)-ß-fluor-b-propyl- 1 H- 1 ,2,4-triazol- 1 -ethanol,α- (2,4-dichlorophenyl) -ß-fluoro-b-propyl-1 H-1, 2,4-triazole-1-ethanol,
α-(2,4-Dichloφhenyl)-ß-methoxy-a-methyl- 1 H- 1 ,2,4-triazol- 1 -ethanol, α-(5-Methyl- 1 ,3-dioxan-5-yl)-ß-[[4-(trifluormethyl)-phenyl]-methylen]- IH- 1 ,2,4-triazol- 1 -ethanol,α- (2,4-dichloφhenyl) -ß-methoxy-a-methyl-1 H-1, 2,4-triazole-1-ethanol, α- (5-methyl-1,3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) phenyl] methylene] - IH-1, 2,4-triazol-1-ethanol,
(5RS,6RS)-6-Hydroxy-2,2,7,7-tetramethyl-5-(lH-l,2,4-triazol-l-yl)-3-octanon,(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (lH-l, 2,4-triazol-l-yl) -3-octanone,
(E)-a-(Methoxyimino)-N-methyl-2-phenoxy-phenylacetamid,(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
{2-Methyl- 1 -[[[ 1 -(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbaminsäure- 1 - isopropylester{2-Methyl- 1 - [[[1 - (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester
1 -(2,4-Dichloφhenyl)-2-( IH- 1 ,2,4-triazol- 1 -yl)-ethanon-O-(phenylmethyl)-oxim,1 - (2,4-dichloφhenyl) -2- (IH- 1, 2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) -oxime,
1 -(2-Methyl- 1 -naphthalenyl)- 1 H-pyπol-2, 5-dion,1 - (2-methyl-1-naphthalenyl) - 1 H-pyπol-2, 5-dione,
1 -(3 , 5 -Dichloφhenyl)-3 -(2-propenyl)-2, 5 -pyπolidindion,1 - (3, 5 -Dichloφhenyl) -3 - (2-propenyl) -2, 5 -pyπolidindione,
l-[(Diiodmethyl)-sulfonyl]-4-methyl-benzol,l - [(diiodomethyl) sulfonyl] -4-methyl-benzene,
1 -[[2-(2,4-Dichlθφhenyl)- 1 ,3-dioxolan-2-yl]-methyl]- 1 H-imidazol,1 - [[2- (2,4-dichlorothenyl) -1,3-dioxolan-2-yl] methyl] -1 H-imidazole,
1 -[[2-(4-Chlθφhenyl)-3-phenyloxiranyl]-methyl]- 1 H- 1 ,2,4-triazol,1 - [[2- (4-Chlθφhenyl) -3-phenyloxiranyl] methyl] - 1 H- 1, 2,4-triazole,
1 -[ 1 -[2-[(2,4-Dichloφhenyl)-methoxy]-phenyl]-ethenyl]- 1 H-imidazol,1 - [1 - [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] - 1 H-imidazole,
1 -Methyl-5-nonyl-2-(phenylmethyl)-3-pyπolidinol,1-methyl-5-nonyl-2- (phenylmethyl) -3-pyπolidinol,
2',6'-Dibrom-2-methyl-4'-trifluormethoxy-4l-trifluor-methyl-l,3-thiazol-5-carboxanilid,2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4 l -trifluoromethyl-l, 3-thiazole-5-carboxanilide,
2,2-Dichlor-N-[ 1 -(4-chloφhenyl)-ethyl]- 1 -ethyl-3 -methyl-cyclopropancarboxamid,2,2-dichloro-N- [1 - (4-chloro-phenyl) ethyl] - 1-ethyl-3-methylcyclopropanecarboxamide,
2,6-Dichlor-5-(methylthio)-4-pyrimidinyl-thiocyanat, 2,6-Dichlor-N-(4-trifluormethylbenzyl)-benzamid,2,6-dichloro-5- (methylthio) -4-pyrimidinyl thiocyanate, 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide,
2,6-Dichlor-N-[[4-(trifluoπnethyl)-phenyl]-methyl]-benzamid,2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,
2-(2,3,3-Triiod-2-propenyl)-2H-tetrazol,2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2-[( 1 -Methylethyl)-sulfonyl]-5-(trichlormethyl)- 1 ,3 ,4-thiadiazol,2 - [(1-methylethyl) sulfonyl] -5- (trichloromethyl) - 1, 3, 4-thiadiazole,
2-[[6-Deoxy-4-O-(4-O-methyl-ß-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4- methoxy-lH-pyπolo[2,3-d]pyrimidin-5-carbonitril,2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -aD-glucopyranosyl] amino] -4- methoxy-lH-pyπolo [2,3-d] pyrimidine- 5-carbonitrile,
2-Aminobutan,2-aminobutane,
2-Brom-2-(brommethyl)-pentandinitril,2-bromo-2- (bromomethyl) pentandinitrile,
2-Chlor-N-(2,3 -dihydro- 1,1,3 -trimethyl- 1 H-inden-4-yl)-3 -pyridincarboxamid,2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1 H-inden-4-yl) -3-pyridinecarboxamide,
2-Chlor-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamid,2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide,
2-Phenylphenol(OPP),2-phenylphenol (OPP),
3,4-Dichlor- 1 -[4-(difluormethoxy)-phenyl]- 1 H-pyrrol-2,5-dion,3,4-dichloro-1 - [4- (difluoromethoxy) phenyl] -1 H-pyrrole-2,5-dione,
3,5-Dichlor-N-[cyan[( 1 -methyl-2-propynyl)-oxy]-methyl]-benzamid,3,5-dichloro-N- [cyan [(1-methyl-2-propynyl) oxy] methyl] benzamide,
3 -( 1 , 1 -Dimethylpropyl- 1 -oxo- 1 H-inden-2-carbonitril,3 - (1,1-dimethylpropyl-1-oxo-1 H-indene-2-carbonitrile,
3-[2-(4-Chloφhenyl)-5-ethoxy-3-isoxazolidinyl]-pyridin,3- [2- (4-chloro-phenyl) -5-ethoxy-3-isoxazolidinyl] pyridine,
4-Chlor-2-cyan-N,N-dimethyl-5-(4-methylphenyl)- 1 H-imidazol- 1 -sulfonamid,4-chloro-2-cyan-N, N-dimethyl-5- (4-methylphenyl) -1 H-imidazole-1-sulfonamide,
4-Methyl-tetrazolo[ 1 , 5-a]quinazolin-5(4H)-on, 8-( 1 , 1 -Dimethylethyl)-N-ethyl-N-propyl- 1 ,4-dioxaspiro[4.5]decan-2-methanamin,4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one, 8- (1, 1-dimethylethyl) -N-ethyl-N-propyl-1, 4-dioxaspiro [4.5] decane-2-methanamine,
8-Hydroxychinolinsulfat,8-hydroxyquinoline sulfate,
9H-Xanthen-9-carbonsäure-2-[(phenylamino)-carbonyl]-hydrazid,9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide,
bis-(l-Methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophendicarboxylat,bis- (l-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) -oxy] -2,5-thiophene dicarboxylate,
eis- 1 -(4-Chloφhenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-cycloheptanol,ice 1 - (4-chloro-phenyl) -2- (1 H-1, 2,4-triazol-1-yl) -cycloheptanol,
cis-4-[3-[4-(l,l-Dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-moφholin- hydrochlorid,cis-4- [3- [4- (l, l-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethyl-moφholin hydrochloride,
Ethyl-[(4-chloφhenyl)-azo]-cyanoacetat,Ethyl - [(4-chloro-phenyl) -azo] cyanoacetate,
Kaliumhydrogencarbonat,Potassium hydrogen carbonate,
Methantetrathiol-Natriumsalz,Methane tetrathiol sodium salt,
Methyl- 1 -(2,3-dihydro-2,2-dimethyl- 1 H-inden- 1 -yl)- 1 H-imidazol-5-carboxylat,Methyl 1 - (2,3-dihydro-2,2-dimethyl-1 H-inden-1-yl) - 1 H-imidazole-5-carboxylate,
Methyl-N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninat,Methyl N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl-N-(chloracetyl)-N-(2,6-dimethylphenyl)-DL-alaninat,Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N-(2,3 -Dichlor-4-hydroxyphenyl)- 1 -methyl-cyclohexancarboxamid.N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexane carboxamide.
N-(2,6-Dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-füranyl)-acetamid,N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N-(2, 6-Dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3 -thienyl)-acetamid,N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N-(2-Chlor-4-nitrophenyl)-4-methyl-3-nitro-benzolsulfonamid, N-(4-Cyclohexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidinamin,N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide, N- (4-cyclohexylphenyl) -l, 4,5,6-tetrahydro-2-pyrimidinamine,
N-(4-Hexylphenyl)- 1,4,5, 6-tetrahydro-2-pyrimidinamin,N- (4-hexylphenyl) - 1,4,5,6-tetrahydro-2-pyrimidinamine,
N-(5-Chlor-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamid,N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide,
N-(6-Methoxy)-3-pyridinyl)-cyclopropancarboxamid,N- (6-methoxy) -3-pyridinyl) cyclopropanecarboxamide,
N-[2,2,2-Trichlor- 1 -[(chloracetyl)-amino]-ethyl]-benzamid,N- [2,2,2-trichloro-1 - [(chloroacetyl) amino] ethyl] benzamide,
N-[3-Chlor-4,5-bis-(2-propinyloxy)-phenyl]-N'-methoxy-methanimidamid,N- [3-chloro-4,5-bis (2-propynyloxy) phenyl] -N'-methoxymanimidamide,
N-Formyl-N-hydroxy-DL-alani -Natriumsalz,N-formyl-N-hydroxy-DL-alani sodium salt,
O,O-Diethyl-[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioat,O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate,
O-Methyl-S-phenyl-phenylpropylphosphoramidothioate,O-methyl-S-phenyl-phenylpropylphosphoramidothioate,
S-Methyl-l,2,3-benzothiadiazol-7-carbothioat,S-methyl-l, 2,3-benzothiadiazole-7-carbothioate,
spiro[2H]-l-Benzopyran-2, (3'H)-isobenzofüran]-3'-on,spiro [2H] -l-benzopyran-2, (3'H) -isobenzofüran] -3'-one,
Bakterizide:Bactericides:
Bronopol, Dichlorophen, Nitrapyrin, Nickel-Dimethyldithiocarbamat, Kasugamycin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insektizide / Akarizide / Nematizide:Insecticides / acaricides / nematicides:
Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectine, AZ 60541, Azadirachtin, Azinphos A, Azinphos M,Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectine, AZ 60541, Azadirachtin, Azinphos A, Azinphos M,
Azocyclotin, AKD 1022, Bacillus thuringiensis, Bendiocarb, Benfüracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,Azocyclotin, AKD 1022, Bacillus thuringiensis, Bendiocarb, Benfüracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxim, Butylpyridaben,
Cadusafos, Carbaryl, Carbofüran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184 699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor- fluazuron, Chlormephos, Chlorpyrifos, Chloφyrifos M, Cis-Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,Cadusafos, Carbaryl, Carbofüran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184 699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorofluazuron, Chlormephos, Chlorpyrifos, Chloφyrifos M, Cis-Resmethrin, Clofenthrin, Clocenthrinflin, Clocenthrinflinin , Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diaeloden, Diafen- thiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diaeloden, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,
Ethoprophos, Etrimphos,Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate,Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenatex, Fluufenate, Fluufenprox
Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,
HCH, Heptenophos, Hexaflumuron, Hexythiazox,HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda-cyhalothrin, Lufenuron,Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyd, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin,Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin,
Monocrotophos, Moxidectin,Monocrotophos, moxidectin,
Naled, NC 184, NI 25, Nitenpyram Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,Naled, NC 184, NI 25, Nitenpyram Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,Quinalphos,
RH 5992,RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos,Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temephos,
Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio- methon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb, TI 435,Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio- methon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb, TI 435,
Vamidothion, XMC, Xylylcarb, YI 5301 / 5302, Zetamethrin.Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Herbiziden oder mit Düngemitteln und Wachstumsregulatoren ist möglich.A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.
Die erfindungsgemäßen Wirkstoffe können ferner beim Einsatz als Insektizide 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.When used as insecticides, the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren. Die Wirkstoff onzentration der An- wendungsformen kann von 0,0000001 bis zu 95 Gew.-% Wirkstoff, vorzugsweise zwischen 0,0001 und 1 Gew. -% liegen.The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active ingredient concentration of the Usage forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
Die Anwendung geschieht in einer den Anwendungsformen angepaßten üblichen Weise.The application takes place in a customary manner adapted to the application forms.
Bei der Anwendung gegen Hygiene- und Vorratsschädlinge zeichnet sich der Wirkstoff durch eine hervorragende Residualwirkung auf Holz und Ton sowie durch eine gute Alkalistabilität auf gekalkten Unterlagen aus.When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
Die erfindungsgemäßen Wirkstoffe wirken nicht nur gegen Pflanzen-, Hygiene- und Vorratsschädlinge, sondern auch auf dem veterinärmedizinischen Sektor gegen tierische Parasiten (Ektoparasiten) wie Schildzecken, Lederzecken, Räudemilben, Laufmilben, Fliegen (stechend und leckend), parasitierende Fliegenlarven, Läuse, Haarlinge, Federlinge und Flöhe. Zu diesen Parasiten gehören:The active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas. These parasites include:
Aus der Ordnung der Anoplurida z.B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp..From the order of the Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..
Aus der Ordnung der Mallophagida und den Unterordnungen Amblycerina sowieFrom the order of the Mallophagida and the subordinates Amblycerina as well
Ischnocerina z.B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp..Ischnocerina e.g. 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 Nematocerina sowie Brachycerina 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., Lucilia 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..From the order Diptera and the subordinates Nematocerina and Brachycerina, for example 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., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp .. From the order of the Siphonapterida, for example 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 the 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 the Blattarida e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp ..
Aus der Unterklasse der Acaria (Acarida) und den Ordnungen der Meta- sowieFrom the subclass of Acaria (Acarida) and the orders of the Meta and
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 .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, Pneumonyostus 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 ,From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example Acarapis spp, Cheyletiella spp, Ornithocheyletia spp, Myobia spp, Psorergates spp, Demodex spp., Trombicula spp., Listrophorus spp, Acarus spp, Calrophogus spp, Calrophogus spp, Tyrophogus spp Hypodectes spp, Pterolichus spp., Psoroptes spp, Chorioptes spp, Otodectes spp, Sarcoptes spp, Notoedres spp, Knemidocoptes spp, Cytodites spp,
Laminosioptes sppLaminosioptes spp
Beispielsweise zeigen die erfindungsgemaßen Verbindungen eine gute entwicklungshemmende Wirkung gegen Fliegenlarven von Lucilia cuprinaFor example, the compounds according to the invention show a good development-inhibiting action against fly larvae of Lucilia cuprina
Die erfindungsgemaßen Wirkstoffe der Formel (I) eignen sich auch zur Bekämpfung von Arthropoden, die landwirtschaftliche Nutztiere, wie z.B Rinder, Schafe, Ziegen, Pferde, Schweine, Esel, Kamele, Büffel, Kaninchen, Huhner, Puten, Enten, Gänse, Bienen, sonstige Haustiere wie z B Hunde, Katzen, Stubenvogel, Aquarienfische sowie sogenannte Versuchstiere, wie z B Hamster, Meerschweinchen, Ratten undThe active compounds of the formula (I) according to the invention are also suitable for combating arthropods which are agricultural animals such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house bird, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and
Mause befallen Die Anwendung der erfindungsgemäßen Wirkstoffe geschieht im Veterinärsektor in bekannter Weise durch enterale Verabreichung in Form von beispielsweise Tabletten, Kapseln, Tränken, Drenchen, Granulaten, Pasten, Boli, des feed-through- Verfahrens, durch dermale Anwendung in Form beispielsweise des Tauchens oder Badens (Dippen), Sprühens (Spray), Aufgießens (Pour-on und Spot-on), des Waschens, desInfested mouse In the veterinary sector, the active compounds according to the invention are used in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, by dermal use in the form of, for example, diving or bathing ( Dipping), spraying (spray), pouring (pour-on and spot-on), washing, the
Einpuderns sowie mit Hilfe von wirkstofϊhaltigen Formkörpern, wie Halsbändern, Ohrmarken, Schwanzmarken, Gliedmaßenbändern, Halftern, Markierungsvorrichtungen usw.Powdering and with the help of shaped articles containing active ingredients, such as collars, ear tags, tail tags, limb tapes, holsters, marking devices, etc.
Bei der Anwendung für Vieh, Geflügel, Haustiere etc. kann man die Wirkstoffe derWhen used for cattle, poultry, pets etc., you can use the active ingredients in
Formel (I) als Formulierungen (beispielsweise Pulver, Emulsionen, fließfähige Mittel), die die Wirkstoffe in einer Menge von 1 bis 80 Gew.-% enthalten, direkt oder nach 100 bis 10 000-facher Verdünnung anwenden oder sie als chemisches Bad verwenden.Use formula (I) as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or after 100 to 10,000 times dilution, or use them as a chemical bath.
Außerdem wurde gefunden, daß die erfindungsgemäßen Verbindungen der Formel (I) eine hohe insektizide Wirkung gegen Insekten zeigen, die technische Materialien zerstören.It has also been found that the compounds of the formula (I) according to the invention have a high insecticidal action against insects which destroy industrial materials.
Beispielhaft und vorzugsweise - ohne jedoch zu limitieren - seien die folgenden Insekten genannt:The following insects may be mentioned by way of example and preferably, but without limitation:
Käfer wieBeetle like
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 minutusHylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces rugus, Lyctus pubescescus, Lyctus pubis linearis, Lyctus linearesces rug Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus
Hautflügler wieSkin wings like
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur Termiten wieSirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifügus, Mastotermes darwinien- sis, Zootermopsis nevadensis, Coptotermes formosanusKalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifügus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus
Borstenschwanze, wie Lepisma saccaπnaBristle tail, such as Lepisma saccaπna
Unter technischen Materialien sind im vorliegenden Zusammenhang nicht-lebende Materialien zu verstehen, wie vorzugsweise Kunststoffe, Klebstoffe, Leime, Papiere und Kartone, Leder, Holz und Holzverarbeitungsprodukte und AnstrichmittelIn the present context, technical materials are to be understood as non-living materials, such as preferably plastics, adhesives, glues, papers and cartons, leather, wood and wood processing products and paints
Ganz besonders bevorzugt handelt es sich bei dem vor Insektenbefall zu schutzenden Material um Holz und HolzverarbeitungsprodukteThe material to be protected against insect infestation is very particularly preferably wood and wood processing products
Unter Holz und Holzverarbeitungsprodukten, welche durch das erfindungsgemaßeAmong wood and wood processing products, which by the inventive
Mittel bzw dieses enthaltende Mischungen geschützt werden kann, ist beispielhaft zu verstehen Bauholz, Holzbalken, Eisenbahnschwellen, Bruckenteile, Bootsstege, Holzfahrzeuge, Kisten, Paletten, Container, Telefonmasten, Holzverkleidungen, Holzfenster und- turen, Sperrholz, Spanplatten, Tischlerarbeiten oder Holzprodukte, die ganz allgemein beim Hausbau oder in der Bautischlerei Verwendung findenMeans or mixtures containing them can be protected, is to be understood as exemplary construction timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden paneling, wooden windows and doors, plywood, chipboard, carpentry work or wooden products, the whole generally used in house construction or in carpentry
Die Wirkstoffe können als solche, in Form von Konzentraten oder allgemein üblichen Formulierungen wie Pulver, Granulate, Losungen, Suspensionen, Emulsionen oder Pasten angewendet werdenThe active ingredients can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes
Die genannten Formulierungen können in an sich bekannter Weise hergestellt werden, z B durch Vermischen der Wirkstoffe mit mindestens einem Losungs- bzw Verdünnungsmittel, Emulgator, Dispergier- und/oder Binde- oder Fixiermitteis, Wasser- Repellent, gegebenenfalls Sikkative und UV- Stabilisatoren und gegebenenfalls Farb- Stoffen und Pigmenten sowie weiteren Verarbeitungshilfsmitteln Die zum Schutz von Holz und Holzwerkstoffen verwendeten insektiziden Mittel oder Konzentrate enthalten den erfindungsgemaßen Wirkstoff in einer Konzentration von 0,0001 bis 95 Gew.-%, insbesondere 0,001 bis 60 Gew -%The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersing and / or binding or fixing agent, water repellants, optionally desiccants and UV stabilizers and, if appropriate Dyes and pigments as well as other processing aids The insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight
Die Menge der eingesetzten Mittel bzw Konzentrate ist von der Art und dem Vorkommen der Insekten und von dem Medium abhangig. Die optimale Einsatzmenge kann bei der Anwendung jeweils durch Testreihen ermittelt werden. Im allgemeinen ist es jedoch ausreichend 0,0001 bis 20 Gew.-%, vorzugsweise 0,001 bis 10 Gew.-%, des Wirkstoffs, bezogen auf das zu schutzende Material, einzusetzen.The amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active ingredient, based on the material to be protected.
Als Losungs- und/oder Verdünnungsmittel dient ein organisch-chemisches Losungsmittel oder Losungsmittelgemisch und/oder ein öliges oder olartiges schwer fluchtiges organisch-chemisches Losungsmittel oder Losungsmittelgemisch und/oder ein polares organisch-chemisches Losungsmittel oder Lόsungsmittelgemisch und/oder Wasser und gegebenenfalls einen Emulgator und/oder NetzmittelAn organic-chemical solvent or solvent mixture and / or an oily or oil-like difficult to volatile organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agents
Als organisch-chemische Losungsmittel werden vorzugsweise ölige oder olartige Losungsmittel mit einer Verdunstungszahl über 35 und einem Flammpunkt oberhalb 30°C, vorzugsweise oberhalb 45°C, eingesetzt Als derartige schwerfluchtige, wasser- unlösliche, ölige und olartige Losungsmittel werden entsprechende Mineralole oder deren Aromatenfraktionen oder mineralolhaltige Losungsmittelgemische, vorzugsweise Testbenzin, Petroleum und/oder Alkylbenzol verwendetAs organic-chemical solvents, preference is given to using oily or oil-like solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. Suitable mineral oils or their aromatic fractions or the like are difficultly volatile, water-insoluble, oily and oil-like solvents solvent mixtures containing mineral oil, preferably white spirit, petroleum and / or alkylbenzene
Vorteilhaft gelangen Mineralole mit einem Siedebereich von 170 bis 220°C, Test- benzin mit einem Siedebereich von 170 bis 220°C, Spindelol mit einem Siedebereich von 250 bis 350°C, Petroleum bzw Aromaten vom Siedebereich von 160 bis 280°C, Terpentinöl und dgl. zum EinsatzMineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, turpentine oil are advantageous and the like
In einer bevorzugten Ausführungsform werden flussige aliphatische Kohlenwasser- Stoffe mit einem Siedebereich von 180 bis 210°C oder hochsiedende Gemische von aromatischen und aliphatischen Kohlenwasserstoffen mit einem Siedebereich von 180 bis 220°C und/oder Spindeol und/oder Monochlornaphtha n, vorzugsweise α-Mono- chlornaphthalin, verwendetIn a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 up to 220 ° C and / or spindeol and / or monochloronaphthalene, preferably α-monochloronaphthalene, used
Die organischen schwerfluchtigen öligen oder olartigen Losungsmittel mit einer Verdunstungszahl über 35 und einem Flammpunkt oberhalb 30°C, vorzugsweise oberhalb 45°C, können teilweise durch leicht oder mittelfluchtige organisch-chemische Losungsmittel ersetzt werden, mit der Maßgabe, daß das Losungsmittelgemisch ebenfalls eine Verdunstungszahl über 35 und einen Flammpunkt oberhalb 30°C, vorzugsweise oberhalb 45°C, aufweist und daß das Insektizid-Fungizid-Gemisch in diesem Losungsmittelgemisch loslich oder emulgierbar istThe organic slightly volatile oily or oil-like solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture
Nach einer bevorzugten Ausführungsform wird ein Teil des organisch-chemischen Losungsmittel oder Losungsmittelgemisches oder ein aliphatisches polares organischchemisches Losungsmittel oder Losungsmittelgemisch ersetzt Vorzugsweise ge- langen Hydroxyl- und/oder Ester- und/oder Ethergruppen enthaltende aliphatische organisch-chemische Losungsmittel wie beispielsweise Glycolether, Ester oder dgl zur AnwendungAccording to a preferred embodiment, part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced. Preferably, aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or Like for application
Als organisch-chemische Bindemittel werden im Rahmen der vorliegenden Erfindung die an sich bekannten wasserverdunnbaren und/oder in den eingesetzten organischchemischen Losungsmitteln loslichen oder dispergier- bzw emulgierbaren Kunstharze und/oder bindende trocknende Ole, insbesondere Bindemittel bestehend aus oder enthaltend ein Acrylatharz, ein Vinylharz, z B Polyvinylacetat, Polyesterharz, Poly- kondensations- oder Polyadditionsharz, Polyurethanharz, Alkydharz bzw modifizier- tes Alkydharz, Phenolharz, Kohlenwasserstoffharz wie Inden-Cumaronharz, Siliconharz, trocknende pflanzliche und/oder trocknende Ole und/oder physikalisch trocknende Bindemittel auf der Basis eines Natur- und/oder Kunstharzes verwendetIn the context of the present invention, the known organic-chemical binders are the water-thinnable and / or synthetic resins soluble or dispersible or emulsifiable in the organic chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, eg polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural substance - And / or synthetic resin used
Das als Bindemittel verwendete Kunstharz kann in Form einer Emulsion, Dispersion oder Losung, eingesetzt werden Als Bindemittel können auch Bitumen oder bituminöse Substanzen bis zu 10 Gew -%, verwendet werden Zusatzlich können an sich bekannte Farbstoffe, Pigmente, wasserabweisende Mittel, Geruchskorπgentien und Inhibitoren bzw Korrosionsschutzmittel und dgl eingesetzt werdenThe synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances of up to 10% by weight can also be used as binders Known dyes, pigments, water-repellent agents, odor agents and inhibitors or anticorrosive agents and the like are used
Bevorzugt ist gemäß der Erfindung als organisch-chemische Bindemittel mindestens ein Alkydharz bzw modifiziertes Alkydharz und/oder ein trocknendes pflanzliches Ol im Mittel oder im Konzentrat enthalten Bevorzugt werden gemäß der Erfindung Alkydharze mit einem Olgehalt von mehr als 45 Gew -%, vorzugsweise 50 bis 68 Gew -%, verwendetAccording to the invention, at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as organic-chemical binder. According to the invention, alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68%, are preferred % By weight used
Das erwähnte Bindemittel kann ganz oder teilweise durch ein Fixierungs- mιttel(gemιsch) oder ein Weιchmacher(gemιsch) ersetzt werden Diese Zusätze sollen einer Verflüchtigung der Wirkstoffe sowie einer Kristallisation bzw Ausfallem vorbeugen Vorzugsweise ersetzen sie 0,01 bis 30 % des Bindemittels (bezogen auf 100 % des eingesetzten Bindemittels)All or part of the binder mentioned can be replaced by a fixing agent (gemιsch) or a plasticizer (gemιsch). These additives are intended to prevent volatilization of the active ingredients and crystallization or failure. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used)
Die Weichmacher stammen aus den chemischen Klassen der Phthalsaureester wie Dibutyl-, Dioctyl- oder Benzylbutylphthalat, Phosphorsaureester wie Tπbutylphos- phat, Adipinsaureester wie Dι-(2-ethylhexyl)-adιpat, Stearate wie Butylstearat oder Amylstearat, Oleate wie Butyloleat, Glyceπnether oder hohermolekulare Glykolether, Glyceπnester sowie p-ToluolsulfonsaureesterThe plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tπbutyl phosphate, adipic acid esters such as di (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate or oleates such as butyl glycol and oleates such as butyl glycol and oleates such as butyl glycol and oleates such as butyl glycol , Glyceπnester and p-toluenesulfonic acid ester
Fixierungsmittel basieren chemisch auf Polyvinylalkylethern wie z B Polyvinyl- methylether oder Ketonen wie Benzophenon, EthylenbenzophenonFixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylene benzophenone
Als Losungs- bzw Verdünnungsmittel kommt insbesondere auch Wasser in Frage, gegebenenfalls in Mischung mit einem oder mehreren der obengenannten organischchemischen Losungs- bzw Verdünnungsmittel, Emulgatoren und DispergatorenWater is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants
Ein besonders effektiver Holzschutz wird durch großtechnische Impragmerverfahren, z B Vakuum, Doppelvakuum oder Druckverfahren, erzieltA particularly effective wood protection is achieved by large-scale impregnation processes, e.g. vacuum, double vacuum or printing processes
Die anwendungsfertigen Mittel können gegebenenfalls noch weitere Insektizide und gegebenenfalls noch ein oder mehrere Fungizide enthalten Als zusätzliche Zumischpartner kommen vorzugsweise die in der Wo 94/29 268 genannten Insektizide und Fungizide in Frage. Die in diesem Dokument genannten Verbindungen sind ausdrücklicher Bestandteil der vorliegenden Anmeldung.The ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides The insecticides and fungicides mentioned in Wo 94/29 268 are particularly suitable as additional mixing partners. The compounds mentioned in this document are an integral part of the present application.
Als ganz besonders bevorzugte Zumischpartner können Insektizide, wie Chlor- pyriphos, Phoxim, Silafluofin, Alphamethrin, Cyfluthrin, Cypermethrin, Deltamethrin, Permethrin, Imidacloprid, NI-25, Flufenoxuron, Hexaflumuron und Triflumuron, sowie Fungizide wie Epoxyconazole, Hexaconazole, Azaconazole, Propiconazole, Tebuconazole, Cyproconazole, Metconazole, Imazalil, Dichlorfluanid, Tolylfluanid, 3-Insecticides, such as chloropyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumazole, as well as fungazazole, as well as fungazazole, as well as fungazazole, as well as Fungazazole, as well as Fungazazole, like Fungazazole Tebuconazole, Cyproconazole, Metconazole, Imazalil, Dichlorfluanid, Tolylfluanid, 3-
Iod-2-propinyl-butylcarbamat, N-Octyl-isothiazolin-3-on und 4,5-Dichlor-N-octyliso- thiazolin-3-on, sein.Iodo-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octyl-isothiazolin-3-one.
Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe gehen aus den nachfolgenden Beispielen hervor. The preparation and use of the active compounds according to the invention can be seen from the examples below.
HerstellungsbeispieleManufacturing examples
Beispiel 1example 1
1,5 g (0,0063 mol) l-(6-Chlor-pyπdιn-3-yl-methyl)-2-cyammιno-ιmιdazohdιn in 25 ml absolutem Dimethylformamid werden unter Ruhren bei 5°C portionsweise mit 0,25 g (0,0063 mol) Natriumhydrid versetzt Nach 1 Stunde Ruhren bei Raumtemperatur werden bei 0°C 0,7 ml (0,0063 mol) l-Propoxymethylchloπd zugegeben und über1.5 g (0.0063 mol) of l- (6-chloro-pyπdιn-3-yl-methyl) -2-cyammιno-ιmιdazohdιn in 25 ml of absolute dimethylformamide are added in portions with 0.25 g ( 0.0063 mol) sodium hydride added After 1 hour of stirring at room temperature, 0.7 ml (0.0063 mol) of l-propoxymethylchloride are added at 0 ° C. and the mixture is poured over
Nacht gerührt Das Reaktionsgemisch wird durch Ab destillieren des Losungsmittels eingeengt, der Ruckstand in Petrolether aufgenommen und filtriert Das Filtrat wird saulenchromatographisch an Kieselgel (Methylenchlorid / Methanol 15 / 0,5) gerei¬Stirred overnight. The reaction mixture is concentrated by distilling off the solvent, the residue is taken up in petroleum ether and filtered. The filtrate is purified by column chromatography on silica gel (methylene chloride / methanol 15 / 0.5)
Man erhalt 0,57 g (29 % der Theoπe) l-(6-Chlor-pyπdιn-3-yl-methyl)-2-cyanιmιno-3- ι-propoxymethyl-ιmιdazolιdιn vom Schmelzpunkt 85-87°CYou get 0.57 g (29% of Theoπe) l- (6-chloro-pyπdιn-3-yl-methyl) -2-cyanιmιno-3- ι-propoxymethyl-ιmιdazolιdιn melting point 85-87 ° C.
Beispiel 2Example 2
1,5 g (5,7 mmol) l-(2-Chlor-thιazol-5-yl-methyl)-2-mtroιmιno-ιmιdazohdιn in 5 ml absolutem Dimethylformamid werden unter Ruhren portionsweise mit 0,26 g (6,5 mmol) Natriumhydrid versetzt Nach kurzzeitigem Ruhren bei Raumtemperatur werden unter Kühlung 0,70 g (6,5 mmol) n-Propoxymethylchloπd zugegeben und über Nacht gerührt Das Reaktionsgemisch wird im Vakuum eingeengt, der Ruckstand mit Wasser versetzt und mit Methylenchloπd extrahiert Die organische Phase wird über Natriumsulfat getrocknet, eingeengt, der Rückstand mit Diisopropylether verrührt und erneut eingeengt.1.5 g (5.7 mmol) of l- (2-chloro-thιazol-5-yl-methyl) -2-mtroιmιno-ιmιdazohdιn in 5 ml of absolute dimethylformamide are added in portions with 0.26 g (6.5 mmol ) Sodium hydride added After briefly stirring at room temperature, 0.70 g (6.5 mmol) of n-propoxymethylchloride are added with cooling and the mixture is stirred overnight. The reaction mixture is concentrated in vacuo, the residue is mixed with water and extracted with methylene chloride. The organic phase is dried over sodium sulfate, concentrated, the residue is stirred with diisopropyl ether and concentrated again.
Man erhält 1,54 g (76 % der Theorie) l-(2-Chlor-thiazol-5-yl-methyl)-2-nitroimino-3-1.54 g (76% of theory) of 1- (2-chlorothiazol-5-yl-methyl) -2-nitroimino-3- are obtained.
20 n-propoxymethyl-imidazolidin vom Berechnungsindex n^ = 1.5781.20 n-propoxymethyl-imidazolidine with calculation index n ^ = 1.5781.
Beispiel 3Example 3
2,54 g (0,01 mol) l-(6-Chlor-pyridin-3-yl-methyl)-2-nitroimino-imidazolin in 10 ml absolutem Dimethylformamid werden bei Raumtemperatur portionsweise mit 0,44 g (0,011 mol) Natriumhydrid versetzt. Nach kurzzeitigem Rühren werden unter Kühlung 2,17 g (0,0125 mol) Bromethoxymethylchlorid zugegeben und über Nacht bei Raumtemperatur gerührt. Das Reaktionsgemisch wird im Vakuum eingeengt, der2.54 g (0.01 mol) of l- (6-chloro-pyridin-3-yl-methyl) -2-nitroimino-imidazoline in 10 ml of absolute dimethylformamide are added in portions at room temperature with 0.44 g (0.011 mol) of sodium hydride transferred. After briefly stirring, 2.17 g (0.0125 mol) of bromoethoxymethyl chloride are added with cooling and the mixture is stirred at room temperature overnight. The reaction mixture is concentrated in vacuo
Rückstand mit Wasser versetzt und mit Methylenchlorid extrahiert. Die organische Phase wird über Natriumsulfat getrocknet, eingeengt, der Rückstand in Diisopropylether verrührt und filtriert. Das Filtrat wird säulenchromatographisch an Kieselgel (Methylenchlorid / Methanol: 10 / 1) gereinigt.The residue is mixed with water and extracted with methylene chloride. The organic phase is dried over sodium sulfate, concentrated, the residue is stirred in diisopropyl ether and filtered. The filtrate is purified by column chromatography on silica gel (methylene chloride / methanol: 10/1).
Man erhält 2,3 g (53 % der Theorie) l-(6-Chlor-pyridin-3-yl-methyl)-2-nitroimino-3- bromethoxymethyl-imidazolin vom Schmelzpunkt 90-92°C.2.3 g (53% of theory) of l- (6-chloro-pyridin-3-yl-methyl) -2-nitroimino-3-bromethoxymethyl-imidazoline with a melting point of 90-92 ° C. are obtained.
Analog den Herstellungsbeispielen 1 bis 3 und gemäß den allgemeinen Angaben zur Herstellung der Verbindungen der Formel (I) werden die in der folgenden Tabelle 1 aufgeführten Verbindungen erhalten: The compounds listed in Table 1 below are obtained analogously to Preparation Examples 1 to 3 and according to the general information on the preparation of the compounds of the formula (I):
[logP = Die Bestimmung der logP -Werte erfolgte gemäß EEC-Directive 79/831 Annex V. A8 durch HPLC (Gradientenmethode, Acetonitril/0, 1 % wäßrige Phosphorsäure] [logP = The logP values were determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0, 1% aqueous phosphoric acid)
AnwendungsbeispieleExamples of use
Beispiel A Aedes-TestExample A Aedes test
Lösungsmittel: 1000 Gewichtsteile MethanolSolvent: 1000 parts by weight of methanol
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und verdünnt das Konzentrat mit Wasser auf die gewünschten Konzentrationen.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water to the desired concentrations.
Mückenlarven (Aedes aegypti) werden in die Wirkstoffzubereitung der gewünschten Konzentration gesetzt.Mosquito larvae (Aedes aegypti) are placed in the active ingredient preparation of the desired concentration.
Nach der gewünschten Zeit wird die Wirkung auf die Larven bestimmt. Dabei bedeutet 100 %, daß alle Tiere schwere Symptome zeigten oder abgetötet wurden; 0 % bedeutet, daß keine Tiere getötet wurden.After the desired time, the effect on the larvae is determined. 100% means that all animals showed severe symptoms or were killed; 0% means that no animals have been killed.
In diesem Test bewirkten bei einer beispielhaften Wirkstofϊkonzentration von 0,0016 % die Verbindungen gemäß den Herstellungsbeispielen 4, 5 und 7 eine Ab- tötung von 100 %, jeweils nach 4 Stunden. In this test, at an exemplary active ingredient concentration of 0.0016%, the compounds according to Preparation Examples 4, 5 and 7 caused a kill of 100%, in each case after 4 hours.
Beispiel BExample B
Aphis-Test (systemische Wirkung)Aphis test (systemic effect)
Lösungsmittel: 7 Gewichtsteile Dimethylformamid Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherSolvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Mit je 20 ml Wirkstoffzubereitung der gewünschten Konzentration werden Bohnenpflanzen (Vicia faba), die stark von der schwarzen Bohnenlaus (Aphis fabae) befallen sind, angegossen, so daß die Wirkstoffzubereitung in den Boden eindringt, ohne den Sproß zu benetzen. Der Wirkstoff wird von den Wurzeln aufgenommen und in denBean plants (Vicia faba), which are heavily infested with the black bean louse (Aphis fabae), are watered on with 20 ml of active compound preparation each, so that the active compound preparation penetrates into the soil without wetting the sprout. The active ingredient is absorbed by the roots and in the
Sproß weitergeleitet.Sprout forwarded.
Nach der gewünschten Zeit wird die Abtötung in % bestimmt. Dabei bedeutet 100 %, daß alle Blattläuse abgetötet wurden; 0 % bedeutet, daß keine Blattläuse abgetötet wurden.After the desired time, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
In diesem Test bewirkten bei einer beispielhaften Wirkstoffkonzentration von 0,01 % die Verbindungen gemäß:In this test, at an exemplary active ingredient concentration of 0.01%, the compounds according to:
den Herstellungsbeispielen 4 und 9 eine Abtötung von 100 % dem Herstellungsbeispiel 5 eine Abtötung von 95 %Production Examples 4 and 9 a kill of 100% Production Example 5 a kill of 95%
jeweils nach 4 Tagen. Beispiel C Hylemyia-Testevery 4 days. Example C Hylemyia test
Lösungsmittel: 100 Gewichtsteile Aceton 1900 Gewichtsteile MethanolSolvent: 100 parts by weight of acetone 1900 parts by weight of methanol
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und verdünnt das Konzentrat mit Methanol auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with methanol to the desired concentration.
Auf eine genormte Menge Kunstfütter wird eine angegebene Menge Wirkstoffzubereitung der gewünschten Konzentration pipettiert. Nachdem das Methanol verdunstet ist, werden ca. 20 Eier der Zwiebelfliege (Hylemyia antiqua) auf das Futter gesetzt.A specified amount of active compound preparation of the desired concentration is pipetted onto a standardized amount of artificial feeder. After the methanol has evaporated, about 20 eggs of the onion fly (Hylemyia antiqua) are placed on the feed.
Nach der gewünschten Zeit wird die Abtötung der Eier bzw. Larven in % bestimmt.After the desired time, the death of the eggs or larvae is determined in%.
Dabei bedeutet 100 %, daß alle Tiere abgetötet wurden; 0 % bedeutet, daß keine Tiere abgetötet wurden.100% means that all animals have been killed; 0% means that no animals have been killed.
In diesem Test bewirkte bei einer beispielhaften Wirkstoffkonzentration von 0,05 % die Verbindung gemäß Herstellungsbeispiel 4 eine Abtötung von 100 % nach 7In this test, at an exemplary active ingredient concentration of 0.05%, the compound according to Preparation Example 4 caused 100% destruction according to FIG. 7
Tagen. Days.
Beispiel D Myzus-TestExample D Myzus test
Losungsmittel 7 Gewichtsteile Dimethylformamid Emulgator. 1 Gewichtsteil AlkylarylpolyglykoletherSolvent 7 parts by weight of dimethylformamide emulsifier. 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Losungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Kon- zentrationTo produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration
Kohlblatter (Brassica oleracea), die stark von der Pfirsichblattlaus (Myzus persicae) befallen sind, werden durch Tauchen in die Wirkstoffzubereitung der gewünschten Konzentration behandeltCabbage leaves (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are treated by being dipped into the preparation of active compound of the desired concentration
Nach der gewünschten Zeit wird die Abtötung in % bestimmt Dabei bedeutet 100 %, daß alle Blattlause abgetötet wurden, 0 % bedeutet, daß keine Blattlause abgetötet wurdenAfter the desired time, the kill is determined in%. 100% means that all aphids have been killed, 0% means that no aphids have been killed
In diesem Test bewirkten bei einer beispielhaften Wirkstoffkonzentration von 0, 1 % die Verbindungen gemäß den Herstellungsbeispielen 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 20, 25 und 36 eine Abtötung von 100 %, jeweils nach 6 Tagen In this test, at an exemplary active ingredient concentration of 0.1%, the compounds according to Preparation Examples 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 25 and 36 caused 100% kill, each after 6 days
Beispiel E Nephotettix-TestExample E Nephotettix test
Losungsmittel 7 Gewichtsteile Dimethylformamid Emulgator 1 Gewichtsteil AlkylarylpolyglykoletherSolvent 7 parts by weight of dimethylformamide emulsifier 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Losungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Kon- zentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Reiskeimlinge (Oryza sativa) werden durch Tauchen in die Wirkstoffzubereitung der gewünschten Konzentration behandelt und mit Larven der Grünen Reiszikade (Nephotettix cincticeps) besetzt, solange die Keimlinge noch feucht sindRice seedlings (Oryza sativa) are treated by dipping into the active ingredient preparation of the desired concentration and populated with larvae of the green rice leafhopper (Nephotettix cincticeps) while the seedlings are still moist
Nach der gewünschten Zeit wird die Abtötung in % bestimmt Dabei bedeutet 100 %, daß alle Zikaden abgetötet wurden, 0 % bedeutet, daß keine Zikaden abgetötet wurdenAfter the desired time, the kill is determined in%. 100% means that all cicadas have been killed, 0% means that no cicadas have been killed
In diesem Test bewirkten bei einer beispielhaften Wirkstoffkonzentration von 0,1 % die Verbindungen gemäß den Herstellungsbeispielen 4, 10, 12, 13, 14, 15, 18, 19, 21, 24, 25, 26, 33 und 36 eine Abtötung von 100 %, jeweils nach 6 Tagen In this test, the compounds according to Preparation Examples 4, 10, 12, 13, 14, 15, 18, 19, 21, 24, 25, 26, 33 and 36 caused 100% kill at an exemplary active ingredient concentration of 0.1%. every 6 days
Beispiel F Phaedon-Larven-TestExample F Phaedon larval test
Lösungsmittel: 7 Gewichtsteile Dimethylformamid Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherSolvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Kon- zentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
Kohlblätter (Brassica oleracea) werden durch Tauchen in die Wirkstoffzubereitung der gewünschten Konzentration behandelt und mit Meerrettichblattkäfer-Larven (Phaedon cochleariae) besetzt, solange die Blätter noch feucht sind.Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist.
Nach der gewünschten Zeit wird die Abtötung in % bestimmt. Dabei bedeutet 100%, daß alle Käfer-Larven abgetötet wurden; 0% bedeutet, daß keine Käfer-Larven abgetötet wurden.After the desired time, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
In diesem Test bewirkten bei einer beispielhaften Wirkstoffkonzentration von 0, 1 % die Verbindungen gemäß den Herstellungsbeispielen 4, 10, 12, 17, 18, 19, 21, 25, 33, 34, 35 und 36 eine Abtötung von 100, jeweils nach 7 Tagen. In this test, at an exemplary active ingredient concentration of 0.1%, the compounds according to Preparation Examples 4, 10, 12, 17, 18, 19, 21, 25, 33, 34, 35 and 36 caused a kill of 100, in each case after 7 days .
Beispiel GExample G
Spodoptera frugiperda-TestSpodoptera frugiperda test
Lösungsmittel: 7 Gewichtsteile Dimethylformamid Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherSolvent: 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
Kohlblätter (Brassica oleracea) werden durch Tauchen in die Wirkstoffzubereitung der gewünschten Konzentration behandelt und mit Larven des Heerwurms (Spodoptera frugiperda) besetzt, solange die Blätter noch feucht sind.Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the army worm (Spodoptera frugiperda) while the leaves are still moist.
Nach der gewünschten Zeit wird die Abtötung in % bestimmt. Dabei bedeutet 100 %, daß alle Larven abgetötet wurden; 0 % bedeutet, daß keine Larven abgetötet wurden.After the desired time, the kill is determined in%. 100% means that all larvae have been killed; 0% means that no larvae have been killed.
In diesem Test bewirkten bei einer beispielhaften Wirkstoffkonzentration von 0, 1 % die Verbindungen gemäß den Herstellungsbeispielen 2, 10, 12, 13, 17, 18, 20, 25, 33, 35 und 36 eine Abtötung von 100, jeweils nach 7 Tagen. In this test, at an exemplary active ingredient concentration of 0.1%, the compounds according to Preparation Examples 2, 10, 12, 13, 17, 18, 20, 25, 33, 35 and 36 caused 100 deaths, in each case after 7 days.
Beispiel HExample H
Spodoptera frugiperda-Test / KunstfutterSpodoptera frugiperda test / artificial feed
Lösungsmittel: 100 Gewichtsteile Aceton 1900 Gewichtsteile MethanolSolvent: 100 parts by weight of acetone 1900 parts by weight of methanol
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und verdünnt das Konzentrat mit Methanol auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with methanol to the desired concentration.
Auf eine genormte Menge Kunstfütter wird eine angegebene Menge Wirkstoffzubereitung der gewünschten Konzentration pipettiert. Nachdem das Methanol verdunstet ist, werden in 3-facher Wiederholung je eine Larve (L2-L3) des Heerwurms (Spodoptera frugiperda) auf das Futter gesetzt.A specified amount of active compound preparation of the desired concentration is pipetted onto a standardized amount of artificial feeder. After the methanol has evaporated, a larva (L2-L3) of the army worm (Spodoptera frugiperda) is placed in triple repetition on the feed.
Nach der gewünschten Zeit wird die Abtötung in % bestimmt. Dabei bedeutet 100 %, daß alle Tiere abgetötet wurden; 0 % bedeutet, daß keine Tiere abgetötet wurden.After the desired time, the kill is determined in%. 100% means that all animals have been killed; 0% means that no animals have been killed.
In diesem Test bewirkte bei einer beispielhaften Wirkstoffkonzentration von 0,05 % die Verbindung gemäß Herstellungsbeispiel 4 eine Abtötung von 100 % nach 7In this test, at an exemplary active ingredient concentration of 0.05%, the compound according to Preparation Example 4 caused 100% destruction according to FIG. 7
Tagen. Days.
Beispiel IExample I
Grenzkonzentrations-Test / Wurzelsystemische WirkungLimit concentration test / root systemic effect
Testinsekt: Aphis fabae Lösungsmittel: 4 Gewichtsteile AcetonTest insect: Aphis fabae solvent: 4 parts by weight of acetone
Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherEmulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschteTo produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired level
Konzentration.Concentration.
Die Wirkstoffzubereitung wird innig mit Boden vermischt. Dabei spielt die Konzentration des Wirkstoffs in der Zubereitung praktisch keine Rolle, entscheidend ist allein die Wirkstoffgewichtsmenge pro Volumeneinheit Boden, welche in ppm (= mg/1) angegeben wird. Man füllt den behandelten Boden in Töpfe und bepflanzt diese mit vorgekeimten Dicken Bohnen. Der Wirkstoff kann so von den Pflanzenwurzeln aus dem Boden aufgenommen und in die Blätter transportiert werden.The active ingredient preparation is mixed intimately with soil. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the weight of the active ingredient per unit volume of soil, which is given in ppm (= mg / 1). The treated soil is filled into pots and planted with pre-germinated broad beans. The active ingredient can be taken up from the soil by the plant roots and transported to the leaves.
Für den Nachweis des wurzelsystemischen Effektes werden nach 7 Tagen die Blätter mit den obengenannten Testtieren besetzt. Nach weiteren 6 Tagen erfolgt die Auswertung durch Zählen oder Schätzen der toten Tiere. Aus den Abtötungszahlen wird die wurzelsystemische Wirkung des Wirkstoffs abgeleitet. Sie ist 100 %, wenn alle Testtiere abgetötet sind und 0 %, wenn noch genau so viele Testinsekten leben wie bei der unbehandelten Kontrolle.To demonstrate the root systemic effect, the leaves are populated with the test animals mentioned above after 7 days. After a further 6 days, the evaluation is carried out by counting or estimating the dead animals. The root systemic effect of the active ingredient is derived from the kill numbers. It is 100% when all test animals have been killed and 0% when as many test insects are still alive as in the untreated control.
In diesem Test bewirkten bei einer beispielhaften Wirkstoffkonzentration von 20 ppm die Verbindungen gemäß den Herstellungsbeispielen 4 und 5 eine Abtötung von 100 %. Beispiel JIn this test, the compounds according to Preparation Examples 4 and 5 caused 100% destruction at an exemplary active ingredient concentration of 20 ppm. Example J
Blowfly- Larven-Test/Entwicklungshemmende WirkungBlowfly larva test / development-inhibiting effect
Testtiere: Lucilia cuprina-Larven Lösungsmittel: DimethylsulfoxidTest animals: Lucilia cuprina larvae Solvent: dimethyl sulfoxide
20 mg Wirkstoff werden in 1 ml Dimethylsulfoxid gelöst, geringere Konzentrationen werden durch verdünnen mit Dest H2O hergestellt.20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide, lower concentrations are made by diluting with Dest H2O.
Etwa 20 Lucilia cuprina-Larven werden in ein Teströhrchen gebracht, welches ca.About 20 Lucilia cuprina larvae are placed in a test tube, which contains approx.
1 cm3 Pferdefleisch und 0,5 ml der zu testenden Wirkstoffzubereitung enthält. Nach 24 Stunden und 48 Stunden wird die Wirksamkeit der Wirkstoffzubereitung ermittelt. Die Teströhrchen werden in Becher mit Sand-bedecktem Boden überführt. Nach weiteren 2 Tagen werden die Teströhrchen entfernt und die Puppen ausgezählt.Contains 1 cm 3 horse meat and 0.5 ml of the active ingredient preparation to be tested. The effectiveness of the active substance preparation is determined after 24 hours and 48 hours. The test tubes are transferred to beakers with a sand-covered bottom. After a further 2 days, the test tubes are removed and the dolls are counted.
Die Wirkung der Wirkstoffzubereitung wird nach der Zahl der geschlüpften Fliegen nach 1,5-facher Entwicklungsdauer einer unbehandelten Kontrolle beurteilt. Dabei bedeutet 100 %, daß keine Fliegen geschlüpft sind; 0 % bedeutet, daß alle Fliegen normal geschlüpft sind.The effect of the preparation of active substance is assessed according to the number of flies hatched after 1.5 times the development time of an untreated control. 100% means that no flies have hatched; 0% means that all flies hatched normally.
In diesem Test zeigten bei einer beispielhaften Wirkstoffkonzentration von 100 ppm die Verbindungen gemäß den Herstellungsbeispielen 9, 10, 11, 12 und 13 eine entwicklungshemmende Wirkung von 100 %. In this test, the compounds according to Preparation Examples 9, 10, 11, 12 and 13 showed an development-inhibiting effect of 100% at an exemplary active ingredient concentration of 100 ppm.

Claims

Patentansprüche claims
1. Verbindungen der Formel (I)1. Compounds of formula (I)
in welcherin which
Rl für eine fünf- oder sechsgliedrige heterocyclische Gruppierung steht, welche 1, 2, 3 oder 4 Stickstoffatome und/oder ein oder zwei Sauerstoff- oder Schwefelatome als Heteroatom-Ringglieder enthält - wobei die Zahl der Heteroatome 1, 2, 3 ödere 4 beträgt - und welche gegebenenfalls durch Halogen, Cyano, Nitro, Alkyl, Halogenalkyl, Alkenyl, Halogenalkenyl, Alkinyl, Alkoxy, Halogenalkoxy, Alkenyloxy, Halo- genalkenyloxy, Alkinyloxy, Alkylthio, Halogenalkylthio, Alkenylthio,Rl represents a five- or six-membered heterocyclic grouping which contains 1, 2, 3 or 4 nitrogen atoms and / or one or two oxygen or sulfur atoms as heteroatom ring members - the number of heteroatoms being 1, 2, 3 or 4 - and which are optionally substituted by halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, alkylthio, haloalkylthio, alkenylthio,
Halogenalkenylthio, Alkinylthio, Alkylsulfinyl, Halogenalkylsulfinyl, Alkylsulfonyl, Halogenalkylsulfonyl, Amino, Alkylamino, Dialkyl- amino, Aryl, Arylthio, Arylamino, Aralkyl, Formylamino, Alkylcarbo- nylamino, Formyl, Carbamoyl, Alkylcarbonyl und/oder Alkoxycarbonyl substituiert ist,Haloalkenylthio, alkynylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, amino, alkylamino, dialkylamino, aryl, arylthio, arylamino, aralkyl, formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and / or alkoxycarbonyl substituted
R2 für Wasserstoff oder Alkyl steht,R 2 represents hydrogen or alkyl,
R3 für die Gruppierungen -OR4, -OCOR5, -OCOOR6, -OCONR7R8 und -OSO2R9 steht, wobeiR 3 stands for the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and -OSO 2 R 9 , where
R"4, R^ und R^ unabhängig voneinander für Alkyl, Alkoxyalkyl, Halogenalkyl, Alkenyl, Alkinyl, Alkylaminoalkyl, Dialkylamino- alkyl, gegebenenfalls substituiertes Cycloalkyl und jeweils gegebenenfalls substituiertes Phenyl oder Benzyl stehen, R' und R° unabhängig voneinander für Wasserstoff, Alkyl, Alkenyl und jeweils gegebenenfalls substituiertes Phenyl oder Benzyl stehen undR " 4 , R ^ and R ^ independently of one another represent alkyl, alkoxyalkyl, haloalkyl, alkenyl, alkynyl, alkylaminoalkyl, dialkylaminoalkyl, optionally substituted cycloalkyl and in each case optionally substituted phenyl or benzyl, R 'and R ° are independently hydrogen, alkyl, alkenyl and each optionally substituted phenyl or benzyl and
R9 für Alkyl oder gegebenenfalls substituiertes Phenyl steht,R9 represents alkyl or optionally substituted phenyl,
A für die Gruppierungen -CH2CH2-, (CH2)3 und -CH=CH- steht undA stands for the groupings -CH2CH2-, (CH 2 ) 3 and -CH = CH- and
Z für Cyano oder Nitro steht,Z represents cyano or nitro,
mit der Maßgabe, daß wenn Z für NO2 und A für -CH2CH2- stehen, der Rest R2 für Wasserstoff steht; sowie die Verbindung der Formel (I) in welcherwith the proviso that when Z is NO 2 and A is -CH 2 CH 2 -, the radical R 2 is hydrogen; as well as the compound of formula (I) in which
R2 H,R 2 H,
R3 OCH3,R 3 OCH 3 ,
A -CH2CH2- - undA -CH 2 CH 2 - - and
Z NO2 Z NO 2
ausgenommen ist.is excluded.
2. Verfahren zur Herstellung der Verbindungen der Formel (I) gemäß Anspruch 12. A process for the preparation of the compounds of formula (I) according to claim 1
in welcher R! für eine fünf- oder sechsgliedrige heterocyclische Gruppierung steht, welche 1, 2, 3 oder 4 Stickstoffatome und/oder ein oder zwei Sauerstoff- oder Schwefelatome als Heteroatom-Ringglieder enthält - wobei die Zahl der Heteroatome 1, 2, in which R! represents a five- or six-membered heterocyclic grouping which contains 1, 2, 3 or 4 nitrogen atoms and / or one or two oxygen or sulfur atoms as heteroatom ring members - the number of heteroatoms 1, 2,
3 ödere 4 beträgt - und welche gegebe- nenfalls durch Halogen, Cyano, Nitro, Alkyl, Halogenalkyl, Alkenyl,3 or 4 is - and which, if appropriate, by halogen, cyano, nitro, alkyl, haloalkyl, alkenyl,
Halogenalkenyl, Alkinyl, Alkoxy, Halogenalkoxy, Alkenyloxy, Halo- genalkenyloxy, Alkinyloxy, Alkylthio, Halogenalkylthio, Alkenylthio, Halogenalkenylthio, Alkinylthio, Alkylsulfinyl, Halogenalkylsulfinyl, Alkylsulfonyl, Halogenalkylsulfonyl, Amino, Alkylamino, Dialkyl- amino, Aryl, Arylthio, Arylamino, Aralkyl, Formylamino, Alkylcarbo- nylamino, Formyl, Carbamoyl, Alkylcarbonyl und/oder Alkoxycarbonyl substituiert ist.Haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkenyloxy, haloalkenyloxy, alkynyloxy, alkylthio, haloalkylthio, alkenylthio, haloalkenylthio, alkynylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, amino, alkylamino, arylkylamino, aryl, aryl, aryl, aryl, aryl, arylthio Formylamino, alkylcarbonylamino, formyl, carbamoyl, alkylcarbonyl and / or alkoxycarbonyl is substituted.
R2 für Wasserstoff oder Alkyl steht,R 2 represents hydrogen or alkyl,
R3 für die Gruppierungen -OR4, -OCOR5, -OCOOR6, -OCONR7R8 und -OSO2R9 steht, wobeiR 3 stands for the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and -OSO 2 R 9 , where
R4, R^ und R6 unabhängig voneinander für Alkyl, Alkoxyalkyl, Halogenalkyl, Alkenyl, Alkinyl, Alkylaminoalkyl, Dialkylamino- alkyl, gegebenenfalls substituiertes Cycloalkyl und jeweils gegebenenfalls substituiertes Phenyl oder Benzyl stehen,R 4 , R ^ and R6 independently of one another represent alkyl, alkoxyalkyl, haloalkyl, alkenyl, alkynyl, alkylaminoalkyl, dialkylaminoalkyl, optionally substituted cycloalkyl and in each case optionally substituted phenyl or benzyl,
R7 und R8 unabhängig voneinander für Wasserstoff, Alkyl, Alkenyl und jeweils gegebenenfalls substituiertes Phenyl oder Benzyl stehen undR 7 and R 8 independently of one another represent hydrogen, alkyl, alkenyl and in each case optionally substituted phenyl or benzyl and
R9 für Alkyl oder gegebenenfalls substituiertes Phenyl steht,R 9 represents alkyl or optionally substituted phenyl,
A für die Gruppierungen -CH2CH2-, (CH2)3 und -CH=CH- steht undA stands for the groupings -CH 2 CH 2 -, (CH 2 ) 3 and -CH = CH- and
Z für Cyano oder Nitro steht, mit der Maßgabe, daß wenn Z für NO2 und A für -CH2CH - stehen, der Rest R2 für Wasserstoff steht; sowie die Verbindung der Formel (I) in welcherZ represents cyano or nitro, with the proviso that when Z is NO 2 and A is -CH 2 CH -, the radical R 2 is hydrogen; as well as the compound of formula (I) in which
RlRl
>>
R2 H,R 2 H,
R3 OCH3,R 3 OCH 3 ,
A -CH2CH2- - undA -CH 2 CH 2 - - and
Z NO2 Z NO 2
ausgi enommen ist,except
dadurch gekennzeichnet, daß man Verbindungen der Formel (II)characterized in that compounds of the formula (II)
in welcherin which
R , A und Z die oben angegebene Bedeutung haben,R, A and Z have the meaning given above,
mit Halogenverbindungen der Formel (III)with halogen compounds of the formula (III)
R2 X-CH-R3 (III)R 2 X-CH-R 3 (III)
in welcherin which
R2 und R3 die oben angegebene Bedeutung haben undR 2 and R 3 have the meaning given above and
X für Halogen (insbesondere Chlor oder Brom) steht, in Gegenwart einer Base und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.X represents halogen (especially chlorine or bromine), in the presence of a base and optionally in the presence of a diluent.
Verbindungen der Formel (I) gemäß Anspruch 1 , wobeiCompounds of formula (I) according to claim 1, wherein
R für eine fünf- bis sechsgliedrige heterocyclische Gruppierung aus der Reihe Pyrazolyl, 1,2,R for a five- to six-membered heterocyclic grouping from the series pyrazolyl, 1,2,
4-Triazolyl, Oxazolyl, Isoxazolyl, Thiazolyl, Isothiazolyl, 1,2,5-Thiadiazolyl, Pyridyl, Pyrazinyl und Pyrimidinyl steht, welche gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrazinyl and pyrimidinyl, which may be replaced by fluorine, chlorine, bromine, cyano, nitro,
C1 -C2- Alkyl (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C1-C2- Alkoxy (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), C \ -C2-Alkylthio (welches gegebenenfalls durch Fluor und/oder Chlor substituiert ist), oder Cι -C2-Alkyl- sulfonyl (welches gegenenenfalls durch Fluor und/oder Chlor substituiert ist) substituiert ist,C1 -C2 alkyl (which is optionally substituted by fluorine and / or chlorine), C1-C2 alkoxy (which is optionally substituted by fluorine and / or chlorine), C \ -C2 alkylthio (which is optionally substituted by fluorine and / or Chlorine is substituted), or -C -C-alkyl sulfonyl (which is optionally substituted by fluorine and / or chlorine) is substituted,
R2 für Wasserstoff oder C j -Cg- Alkyl,R 2 represents hydrogen or C j -Cg alkyl,
R3 für die Gruppierungen -OR4, -OCOR5, -OCOOR6, -OCONR7R8 undR 3 for the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and
-OSO2R9 steht, wobei-OSO 2 R 9 , where
R4, R5 und R0" unabhängig voneinander für Cj-C \2~ Alkyl, C1-C4-AI- koxy-Ci-C/j-alkyl, Cj-C4-Halogenalkyl mit 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- undR 4 , R 5 and R 0 " independently of one another for C 1 -C 6 -alkyl, C 1 -C 4 -alkoxy-Ci-C / C-1-alkyl, Cj-C4-haloalkyl having 1 to 5 identical or different halogen atoms, such as fluorine, chlorine and
Bromatomen; C2-C4 -Alkenyl, C2-C4- Alkinyl, Cj-C4-Alkyl- amino-Cj-C4-alkyl, Di(Cι-C4)-alkylamino-Cι-C4-alkyl, für gegebenenfalls einfach bis dreifach, gleich oder verschieden substituiertes C3-Cg-Cycloalkyl, wobei als Substituenten vor- zugsweise genannt seien: Halogen, C1-C4-Alkyl und C1-C4-Bromine atoms; C2-C4-alkenyl, C2-C4-alkynyl, Cj-C4-alkylamino-Cj-C4-alkyl, di (Cι-C4) alkylamino-Cι-C4-alkyl, for optionally single to triple, the same or different Substituted C 3 -Cg cycloalkyl, the preferred substituents being: halogen, C 1 -C 4 alkyl and C 1 -C 4 -
Halogenalkyl mit 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie F-, Cl- und Br-Atomen, oder für jeweils gegebenenfalls einfach bis dreifach, gleich oder verschieden substi- tuiertes Phenyl oder Benzyl stehen, wobei jeweils als Phenylsubstituenten genannt seien: Halogen, C]-C4-Alkyl, C1-C4- Alkoxy sowie Cj-C4-Halogenalkyl und C \ -C4-Halogenalkoxy mit jeweils 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- und Bromatomen und Nitro.Haloalkyl with 1 to 5 identical or different halogen atoms, such as F, Cl and Br atoms, or for each optionally one to three times, identical or different substances. tuated phenyl or benzyl, where each may be mentioned as a phenyl substituent: halogen, C ] -C4-alkyl, C1-C4-alkoxy and Cj-C4-haloalkyl and C \ -C4-haloalkoxy each having 1 to 5 identical or different halogen atoms, such as fluorine, chlorine and bromine atoms and nitro.
R7 und R8 unabhängig voneinander für Wasserstoff, C\-C - Alkyl, C2-R 7 and R 8 independently of one another for hydrogen, C \ -C - alkyl, C2-
C4-Alkenyl oder für jeweils einfach bis dreifach, gleich oder verschieden substituiertes Phenyl oder Benzyl stehen, wobei je- weils als Phenylsubstituenten genannt seien: Halogen, C1-C4-C4-alkenyl or phenyl or benzyl which is monosubstituted to trisubstituted by identical or different substituents, the following in each case being mentioned as phenyl substituents: halogen, C1-C4-
Alkyl, Cj-C4-Alkoxy sowie Cj-C4-Halogenalkyl und C1-C4- Halogenalkoxy mit jeweils 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- und Bromatomen; undAlkyl, Cj-C4-alkoxy and Cj-C4-haloalkyl and C1-C4-haloalkoxy each having 1 to 5 identical or different halogen atoms, such as fluorine, chlorine and bromine atoms; and
R9 für C1-C4- Alkyl oder für einfach bis dreifach, gleich oder verschieden substituiertes Phenyl steht, wobei als Substituenten genannt seien: Halogen, C1-C4- Alkyl, Cj-C4-Alkoxy sowie Cj- C4-Halogenalkyl und Cj-C4-Halogenalkoxy mit jeweils 1 bis 5 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- und Bromatomen,R 9 represents C1-C4-alkyl or phenyl which is monosubstituted to trisubstituted by identical or different substituents, and the following may be mentioned as substituents: halogen, C1-C4-alkyl, Cj-C4-alkoxy and Cj-C4-haloalkyl and Cj-C4 Haloalkoxy each having 1 to 5 identical or different halogen atoms, such as fluorine, chlorine and bromine atoms,
A für die Gruppierungen -CH2CH2-, -(CH2)3- und -CH=CH- steht,A stands for the groupings -CH2CH2-, - (CH 2 ) 3 - and -CH = CH-,
Z für Cyano oder Nitro steht,Z represents cyano or nitro,
mit der Maßgabe, daß wenn Z für NO2 und A für -CH2CH - stehen, der Rest R2 für Wasserstoff steht; sowie die Verbindung der Formel (I) in welcherwith the proviso that when Z is NO 2 and A is -CH 2 CH -, the radical R 2 is hydrogen; as well as the compound of formula (I) in which
R2 H,R 2 H,
R3 OCH3,R3 OCH 3 ,
A -CH2CH2- und Z NO2 A -CH 2 CH 2 - and Z NO 2
ausgenommen ist.is excluded.
Verbindungen der Formel (I) gemäß Anspruch 1, wobeiCompounds of formula (I) according to claim 1, wherein
R1 für 6-Chlor-3-pyridyl (6-Chlor-pyridin-3-yl) oder für 2-Chlor-5- thiazolyl (2-Chlor-thiazol-5-yl) steht,R 1 represents 6-chloro-3-pyridyl (6-chloro-pyridin-3-yl) or 2-chloro-5-thiazolyl (2-chloro-thiazol-5-yl),
R2 für Wasserstoff oder C j -C5 -Alkyl steht,R 2 represents hydrogen or C j -C 5 alkyl,
R3 für die Gruppierungen -OR4, -OCOR5, -OCOOR6, -OCONR7R8 und -OSO2R9 steht, wobeiR 3 stands for the groupings -OR 4 , -OCOR 5 , -OCOOR 6 , -OCONR 7 R 8 and -OSO2R 9 , where
R4, R^ und R^ unabhängig voneinander für Ci -Cg-Alkyl, C1-C2-R 4 , R ^ and R ^ independently of one another for Ci -Cg-alkyl, C1-C2-
Alkoxy-Cj-C2-alkyl, C}-C2-Halogenalkyl mit 1 bis 2 gleichen oder verschiedenen Halogenatomen, wie Fluor-, Chlor- und Bromatomen; Allyl, Propargyl, Cι-C2-Alkylamino-Cι-C2- alkyl, Di(C^-C2)-alkylamino-Cι-C2-alkyl, Cyclopropyl, Cyclo- pentyl, Cyclohexyl oder für jeweils gegebenenfalls einfach bis zweifach, gleich oder verschieden substituiertes Phenyl oder Benzyl stehen, wobei jeweils als Phenylsubstituenten genannt seien: Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl und Trifluormethoxy und Nitro.Alkoxy-Cj-C2-alkyl, C} -C2-haloalkyl with 1 to 2 identical or different halogen atoms, such as fluorine, chlorine and bromine atoms; Allyl, propargyl, -C-C2-alkylamino -CC-C2-alkyl, di (C ^ -C2) -alkylamino -CC-C2-alkyl, cyclopropyl, cyclopentyl, cyclohexyl or for each optionally one to two times, identical or different Substituted phenyl or benzyl, each of which may be mentioned as a phenyl substituent: fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl and trifluoromethoxy and nitro.
R7 und R8 unabhängig voneinander für Wasserstoff, Cι -C4-Alkyl, Vinyl, Allyl oder für jeweils gegebenenfalls einfach bis zweifach, gleich oder verschieden substituiertes Phenyl oder Benzyl stehen, wobei jeweils als Phenylsubstituenten genannt seien: Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl und Trifluormethoxy; und R9 für Methyl, Ethyl oder gegebenenfalls einfach bis zweifach, gleich oder verschieden substituiertes Phenyl steht, wobei als Substituenten genannt seien: Fluor, Chlor, Brom, Methyl, Methoxy, Trifluormethyl und Trifluormethoxy,R 7 and R 8 independently of one another are hydrogen, C 4 -C 4 -alkyl, vinyl, allyl or for phenyl or benzyl which are monosubstituted or disubstituted in the same way or differently, each of which may be mentioned as a phenyl substituent: fluorine, chlorine, bromine, methyl , Methoxy, trifluoromethyl and trifluoromethoxy; and R 9 represents methyl, ethyl or phenyl which is monosubstituted or disubstituted by identical or different substituents, the following being mentioned as substituents: fluorine, chlorine, bromine, methyl, methoxy, trifluoromethyl and trifluoromethoxy,
A für die Gruppierungen -CH2CH2- und -CH=CH- steht,A stands for the groupings -CH2CH2- and -CH = CH-,
Z für Cyano oder Nitro steht,Z represents cyano or nitro,
mit der Maßgabe, daß wenn Z für NO2 und A für -CH2CH2- stehen, der Restwith the proviso that when Z is NO 2 and A is -CH 2 CH 2 -, the rest
R2 für Wasserstoff steht; sowie die Verbindung der Formel (I) in welcherR 2 represents hydrogen; as well as the compound of formula (I) in which
R2 H, R 2 H,
R3 OCH3,R 3 OCH 3 ,
A -CH2CH2- - undA -CH 2 CH 2 - - and
Z NO2 Z NO 2
ausg enommen ist.is taken out.
5. Mittel zur Bekämpfung tierischer Schädlinge, dadurch gekennzeichnet, daß sie mindestens eine Verbindung der Formel (I) gemäß Anspruch 1 enthalten.5. Agents for controlling animal pests, characterized in that they contain at least one compound of the formula (I) according to Claim 1.
6. Verwendung von Verbindungen der Formel (I) gemäß Anspruch 1 zur Bekämpfung tierischer Schädlinge.6. Use of compounds of formula (I) according to claim 1 for controlling animal pests.
7. Herstellung von Mitteln zur Bekämpfung tierischer Schädlinge, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) gemäß Anspruch 1 mit Verdünnungs- und/oder oberflächenaktiven Stoffen vermischt. 7. Production of agents for controlling animal pests, characterized in that compounds of the formula (I) according to Claim 1 are mixed with diluents and / or surface-active substances.
EP98966405A 1998-01-08 1998-12-24 Substituted guanidine derivatives Withdrawn EP1047689A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19800400A DE19800400A1 (en) 1998-01-08 1998-01-08 Substituted guanidine derivatives
DE19800400 1998-01-08
PCT/EP1998/008444 WO1999035141A1 (en) 1998-01-08 1998-12-24 Substituted guanidine derivatives

Publications (1)

Publication Number Publication Date
EP1047689A1 true EP1047689A1 (en) 2000-11-02

Family

ID=7854139

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98966405A Withdrawn EP1047689A1 (en) 1998-01-08 1998-12-24 Substituted guanidine derivatives

Country Status (9)

Country Link
US (2) US6503912B1 (en)
EP (1) EP1047689A1 (en)
JP (1) JP2002500222A (en)
KR (1) KR20010033372A (en)
CN (3) CN1550498A (en)
AU (1) AU2275999A (en)
BR (1) BR9813241A (en)
DE (1) DE19800400A1 (en)
WO (1) WO1999035141A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376548B1 (en) 2000-01-28 2002-04-23 Rohm And Haas Company Enhanced propertied pesticides
EP1940282B1 (en) * 2005-10-26 2009-06-10 REBUFFAT, Carlo Anoscope for ano-rectal diagnostic and surgery
DE602007012771D1 (en) 2007-03-07 2011-04-07 Covidien Ag CLAMP DEVICE FOR MUCOSEKTOMY
US8181838B2 (en) 2008-09-10 2012-05-22 Tyco Healthcare Group Lp Surgical stapling device
US9204789B2 (en) 2009-10-08 2015-12-08 Covidien Lp Asymmetrical anoscope
US20180360040A1 (en) * 2015-12-03 2018-12-20 Syngenta Participations Ag Pesticidal compounds and their uses
DE102016108551B3 (en) * 2016-05-09 2017-11-02 Fritz Egger Gmbh & Co. Og Fibrous plate with increased resistance to fungal attack and process for their preparation
CN108440519B (en) * 2018-04-03 2020-10-23 青岛科技大学 Oxadiazole o-phenylethoxy compound and application thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3681465D1 (en) * 1985-02-04 1991-10-24 Nihon Bayer Agrochem K.K., Tokio/Tokyo, Jp
JPH0784461B2 (en) * 1986-12-19 1995-09-13 日本バイエルアグロケム株式会社 Insecticidal nitroimino or cyanoimino compounds
JPH0717621B2 (en) * 1986-03-07 1995-03-01 日本バイエルアグロケム株式会社 New heterocyclic compound
JPH07121909B2 (en) 1986-09-10 1995-12-25 日本バイエルアグロケム株式会社 Novel heterocyclic compound and insecticide
JP2583429B2 (en) * 1987-11-06 1997-02-19 日本バイエルアグロケム株式会社 Imidazolines and insecticides
US5192778A (en) * 1990-04-03 1993-03-09 Mitsui Toatsu Chemicals, Inc. Dialkoxymethylimidazolidine derivatives, preparation thereof, insecticides containing same as an effective ingredient and intermediates therefor
JPH06100557A (en) * 1992-09-21 1994-04-12 Mitsui Toatsu Chem Inc Substituted nitroguanidine derivative, its production, insecticide containing the same as active ingredient and intermediate thereof and their production
JPH06122680A (en) * 1992-10-12 1994-05-06 Mitsui Toatsu Chem Inc Substituted nitroguanidine derivatives, their production, insecticide comprising the same derivatives as active ingredient, intermediate and its production
JPH06122681A (en) * 1992-10-12 1994-05-06 Mitsui Toatsu Chem Inc Substituted nitroguanidine derivative, its production, insecticide comprising the same derivative as active ingredient, intermediate and its production
WO1994029268A1 (en) 1993-06-07 1994-12-22 Bayer Aktiengesellschaft Iodopropargyl carbamates and their use as biocides in the protection of plants and materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9935141A1 *

Also Published As

Publication number Publication date
WO1999035141A1 (en) 1999-07-15
BR9813241A (en) 2001-01-02
CN1550498A (en) 2004-12-01
CN1191247C (en) 2005-03-02
US20030119828A1 (en) 2003-06-26
AU2275999A (en) 1999-07-26
KR20010033372A (en) 2001-04-25
US6667310B2 (en) 2003-12-23
DE19800400A1 (en) 1999-07-15
US6503912B1 (en) 2003-01-07
CN1285827A (en) 2001-02-28
JP2002500222A (en) 2002-01-08
CN1810807A (en) 2006-08-02

Similar Documents

Publication Publication Date Title
EP0880505A1 (en) Acylated 4-amino- and 4-hydrazinopyrimidines and their use as pesticides
EP0877741B1 (en) Acylated 5-amino-1,2,4-thiadiazoles as pesticides and fungicides
WO2002085870A1 (en) Novel azoles having an insecticidal action
EP1047689A1 (en) Substituted guanidine derivatives
WO1999062886A1 (en) Substituted 3-thiocarbamoylpyrazoles
EP0912532A1 (en) Substituted n-(5-isothiazolyl) thioamides
EP1097128B1 (en) Imidamide derivatives
EP1144407B1 (en) Cyclic guanidine derivatives and their use as pesticides
WO2003095418A1 (en) N&#39;-cyano-n-methyl-imidamide derivatives
DE19924273A1 (en) New nitro- or cyano-imideamide derivatives, used as insecticides, acaricides, ectoparasiticides or especially nematocides
WO1999010334A1 (en) Acylated 5-aminoisothiazoles as pesticides and fungicides
WO1997048280A1 (en) Use of pyrrolopyrimidines to combat pests
EP0944608B1 (en) 4-cyclohexylphenyl-oxazolines and their use for controlling animal pests
DE19629463A1 (en) New well tolerated glyoxylic acid thioamide derivatives
WO1998038172A1 (en) Phenyl-amino-sulfonyl-urea derivatives as fungicides and pesticides
DE19629466A1 (en) New alkyl glyoxylic acid oxime derivatives to control pests,
MXPA00006416A (en) Substituted guanidine derivatives
WO1999025692A1 (en) Acylated 4-aminopyridines as pesticides and fungicides
EP1037879A1 (en) Condensed pyridine derivatives

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20000808

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI NL

17Q First examination report despatched

Effective date: 20020612

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BAYER CROPSCIENCE AG

18D Application deemed to be withdrawn

Effective date: 20040608

RTI1 Title (correction)

Free format text: SUBSTITUTED GUANIDINE DERIVATIVES AND THEIR USE FOR COMBATING ANIMAL PESTS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20070905