WO1996014295A1 - Dithiocarbazonic acid butenyl esters and their use as pesticides - Google Patents

Dithiocarbazonic acid butenyl esters and their use as pesticides Download PDF

Info

Publication number
WO1996014295A1
WO1996014295A1 PCT/EP1995/004145 EP9504145W WO9614295A1 WO 1996014295 A1 WO1996014295 A1 WO 1996014295A1 EP 9504145 W EP9504145 W EP 9504145W WO 9614295 A1 WO9614295 A1 WO 9614295A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
spp
alkyl
compounds
optionally substituted
Prior art date
Application number
PCT/EP1995/004145
Other languages
German (de)
French (fr)
Inventor
Udo Kraatz
Jürgen Hartwig
Wolfram Andersch
Andreas Turberg
Norbert Mencke
Original Assignee
Bayer Aktiengesellschaft
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 Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU38064/95A priority Critical patent/AU3806495A/en
Publication of WO1996014295A1 publication Critical patent/WO1996014295A1/en

Links

Classifications

    • 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
    • A01N47/08—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 one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C337/02—Compounds containing any of the groups, e.g. thiocarbazates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C337/02—Compounds containing any of the groups, e.g. thiocarbazates
    • C07C337/04—Compounds containing any of the groups, e.g. thiocarbazates the other nitrogen atom being further doubly-bound to a carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/28—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

  • the present invention relates to new dithiocarbazonic acid butenyl esters, processes for their preparation and their use for controlling animal pests, in particular insects, arachnids and nematodes, which protect in agriculture, in forests, in the supply and material and in the hygiene sector.
  • R 1 represents hydrogen or halogen
  • R and R 3 independently of one another represent hydrogen or in each case optionally substituted alkyl, cycloalkyl, aminocarbonyl, alkoxycarbonyl, aryl, aralkyl, hetaryl or carboxyl or
  • R 2 and R 3 together with the carbon atom to which they are attached form an optionally substituted ring which optionally contains oxygen, sulfur or nitrogen, the nitrogen optionally being substituted by alkyl, aryl, aralkyl or hetaryl.
  • the compounds of the formula (I) can be in the form of geometric and / or optical isomers or isomer mixtures of different compositions.
  • the invention relates to both the pure isomers and the isomer mixtures. Furthermore, it was found that the dithiocarbazonic acid butenyl ester of the formula (I) is obtained when
  • R 1 has the meaning given above
  • R 2 and R 3 have the meaning given above
  • R 2 and R 3 have the meanings given above, in the presence of a base and in the presence of a diluent with carbon disulphide and then with a fluorobutenyl halide of the formula (V)
  • R 1 has the meaning given above and
  • the dithiocarbazone butenyl esters according to the invention are generally defined by the formula (I).
  • R 1 preferably represents hydrogen, fluorine, chlorine or bromine.
  • R 2 and R 3 independently of one another preferably represent hydrogen, C ⁇ C j, - alkyl, C r C 12 haloalkyl, C r C 8 alkoxy-C, -C 8 alkyl, C, -C 8 -alkylthio C, -C 8 alkyl, in each case optionally substituted by halogen, nitro, amino, C 1 -C 8 - alkylamino, di-C] -C 8 alkylamino, C j -C 8 haloalkyl, C, -C 8 - alkoxy, C, - C 8 haloalkoxy, C, -C 8 -alkylthio or C r C 8 haloalkylthio substitu ⁇ Clearlys phenyl, benzyl, phenoxy-C, -C 6 alkyl or phenylthio-C r C 6 alkyl, for carboxyl, C r C 8 alkoxycarbonyl,
  • R 2 and R together with the carbon atom to which they are attached form a 4- to 10-membered ring which optionally contains oxygen, sulfur or nitrogen (which is optionally substituted by C 1 -C 8 -alkyl, phenyl or benzyl) or
  • R 2 and R 3 together with the carbon atom to which they are attached represent one of the groups
  • R is halogen, nitro, C, -C 6 -alkyl, C, -C 6 -haloalkyl, C r C 6 -alkoxy, C r C 6 -haloalkoxy, C r C 6 -alkylthio or C, -C 6 -Halogen- alkylthio stands.
  • R 1 particularly preferably represents hydrogen, fluorine or chlorine.
  • R 2 and R 3 independently of one another particularly preferably represent hydrogen, C j -C 8 alkyl, C j -C ⁇ haloalkyl, each optionally by fluorine, chlorine, bromine, amino, C, -C 6 alkylamino, Di-C, -C 6 -alkylamino, C, -C 6 -alkoxy or C, -C 6 -haloalkoxy substituted phenyl or benzyl, for pyrryl, thienyl, furyl, pyrazolyl, thiazolyl, pyridyl or pyrimidyl or substituted by fluorine, chlorine, bromine or C r C 4 alkyl
  • R and R together with the carbon atom to which they are attached form a 5- to 8-membered ring which optionally contains oxygen or nitrogen (which is optionally substituted by C, -C 6 -Mky ⁇ ).
  • R 1 very particularly preferably represents fluorine.
  • R and R independently of one another very particularly preferably represent hydrogen, C r C 6 alkyl, C r C 4 haloalkyl, optionally by fluorine, chlorine, bromine, amino, C ] -C 4 alkylamino,
  • R 2 and R 3 together with the carbon atom to which they are attached form a 5- to 8-membered carbocycle.
  • Process A) described above for the preparation of compounds of the formula (I) is characterized in that the reactions are optionally carried out in
  • Halogenated aliphatic or aromatic hydrocarbons such as cyclohexane, toluene, xylene, dichloromethane, chloroform, dichloroethane or chlorobenzene, alcohols such as methanol, ethanol or are preferably usable
  • Isopropanol nitriles such as acetonitrile, ethers such as di isopropyl ether, tetrahydrofuran or dioxane or amides such as dimethylformamide.
  • the reaction can also be carried out in the absence of one of the solvents mentioned. In this case, it may be advantageous to use the carbonyl compound of the formula (III) in excess.
  • Suitable acidic catalysts are sulfonic acids such as p-toluenesulfonic acid.
  • reaction temperatures can be varied within a wide range in process A) described above. In general, temperatures between 0 ° C and 160 ° C, preferably between 20 ° C and 130 ° C.
  • the reaction is generally carried out at normal pressure.
  • the reaction mixture is worked up in a conventional manner, for example by distilling off the diluent.
  • Process B) described above for the preparation of compounds of the formula (I) is characterized in that the reactions are carried out in the presence of a base and in the presence of a diluent.
  • Alkali metal hydrides, alkali metal alcohols, alkali metal or alkaline earth metal carbonates or hydrogen carbonates or nitrogen bases can preferably be used.
  • Examples include sodium hydride, sodium methoxide, sodium trium hydroxide, calcium hydroxide, potassium carbonate, sodium hydrogen carbonate, triethylamine, dibenzylamine, diisopropyla in, pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclonones (DBN) and diazabicycloundecene (DBU).
  • Aromatic hydrocarbons such as benzene or toluene, alcohols such as methanol, ethanol, isopropanol or ethylene glycol, nitriles such as acetonitrile, ethers such as tetrahydrofuran or dioxane, amides such as dimethylformamide or other polar solvents such as dimethyl sulfoxide or sulfolane can preferably be used.
  • reaction temperatures can be varied within a wide range in process B) described above. In general, temperatures between 0 ° C and 140 ° C, preferably between 20 ° C and 80 ° C.
  • the starting materials of the formula (IV) and (V) are generally used in an approximately equimolar amount.
  • the reaction is generally carried out under normal pressure.
  • reaction mixture is diluted, for example, with water, extracted with an organic solvent such as toluene, ether or ethyl acetate and the organic phase is concentrated.
  • organic solvent such as toluene, ether or ethyl acetate
  • R 1 has the meaning given above
  • M represents an alkali metal, preferably sodium or potassium
  • Alcohols such as methanol, ethanol,
  • Isopropanol such as acetonitrile, ethers such as diethyl ether, tetrahydrofuran, dioxane, aliphatic or aromatic hydrocarbons such as cyclohexane, toluene or xylene or polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide or dimethylacetamide.
  • nitriles such as acetonitrile
  • ethers such as diethyl ether, tetrahydrofuran, dioxane, aliphatic or aromatic hydrocarbons such as cyclohexane, toluene or xylene or polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide or dimethylacetamide.
  • polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide or dimethylacetamide.
  • the reaction temperature can be varied within a wide range. In general, temperatures between 0 ° C and 140 ° C, preferably between 20 ° C and 100 ° C.
  • the ratio of the compounds of the formulas (V) and (VI) is generally between 2: 1 and 1: 2.
  • the reaction is generally carried out under normal pressure.
  • reaction mixture can be diluted with water and extracted with a suitable organic solvent. Then that will be described below.
  • the compounds of formula (II) have nematicidal properties.
  • the active substances are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species and against all or individual stages of development.
  • the pests mentioned above include:
  • Thysanura e.g. Lepisma saccharina.
  • Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus sppe, Phros
  • Empoasca spp. Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
  • Leptinotarsa decemlineata Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatordimidhmpphppm, spp. , Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,
  • Niptus hololeucus Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha elolontha, Amphimallon solstitialis, Costelytra zealandica.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Drosophila melanogaster Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tabanus spp.
  • Tannia spp. Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
  • 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.,. Chori ., 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.,
  • the compounds of the formula (I) according to the invention are distinguished in particular by an excellent nematicidal action, for example against Meloidogyne incognita.
  • 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 as well as very fine encapsulation in polymeric substances.
  • 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, if appropriate using surface-active agents, ie 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.
  • nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkyl aryl 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 powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example 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 compound 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 compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • active compounds 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.
  • copper preparations such as: copper hydroxide, copper naphthenate,
  • Mancopper Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
  • Tebuconazole Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,
  • Bactericides bronopol, dichlorophene, nitrapyrin, nickel-dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenproxatophon, Fufionphonophone, Fufionfox, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufone HCH, heptenophos, hexaflumuron
  • Imidacloprid Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
  • 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 substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active ingredient When used against hygiene 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.
  • 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 ..
  • Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodterol spp ., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, chickens, turkeys, ducks,
  • Combating these arthropods is said to result in deaths and reduced performance (in meat, milk, wool, skins, eggs, Honey, etc.) can be reduced, so that more economical and simple animal husbandry is possible through the use of the active compounds according to the invention.
  • the active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, and feed-through
  • suppositories by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray ), Pouring (pour-on and spot-on), washing, powdering and with the help of active ingredients
  • Shaped bodies such as collars, ear tags, tail tags, limb tapes, holsters, marking devices, etc.
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.
  • formulations for example powders, emulsions, flowable agents
  • Test nematode Meloidogyne incognita solvent: 3 parts by weight acetone
  • 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, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • the active ingredient preparation is mixed intimately with soil that is heavily contaminated with the test nematodes.
  • the treated soil is filled into pots, lettuce is sown and the pots are kept at a greenhouse temperature of 25 ° C.
  • the lettuce roots are examined for nematode infestation (root galls) and the effectiveness of the active ingredient is determined in%.
  • the efficiency is 100% if the infestation is completely avoided; it is 0% if the infestation is just as high as that of the control plants in untreated, but equally contaminated soil.
  • Test animals Lucilia cuprina larvae
  • Solvent 35 parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether
  • Lucilia cuprina larvae About 20 Lucilia cuprina larvae are placed in a test tube containing approx. 1 cm 3 horse meat and 0.5 ml of the active ingredient preparation to be tested. After 24 hours, the effectiveness of the active ingredient preparation is determined. 100% means that all Blowfly larvae have been killed; 0% means that no blowfly larvae have been killed.
  • the compound according to Preparation Example II-1 showed an activity of 100% at an exemplary active ingredient concentration of 1,000 ppm.
  • Test animals Adult suckled females
  • the test is carried out in 5-fold determination. 1 ⁇ l of the solutions is injected into the abdomen, the animals are transferred to dishes and stored in an air-conditioned room. The effect is determined by the inhibition of egg laying. 100% means that no tick has laid.
  • the compounds according to the preparation examples 1-1, 1-2, 1-8, 1-9, 1-10, 1-11, 1-13 and 1-14 showed an exemplary active ingredient concentration of 20 ⁇ g / Animal has an effect of 100%.
  • Solvent 35 parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether
  • a suitable formulation three parts by weight of active ingredient are mixed with seven parts of the solvent / emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the desired concentration.
  • the effectiveness of the active ingredient preparation is determined. 100% means that all cockroaches have been killed; 0% means that no cockroaches have been killed.
  • the compound according to the manufacturing example 1-9 with an exemplary active ingredient concentration of 1,000 ppm has an activity of 100%.

Abstract

The invention relates to novel dithiocarbazonic acid butenyl esters of the formula (I) in which R1 is hydrogen or halogen, R?2 and R3¿ are mutually independently possibly substituted alkyl, cycloalkyl, aminocarbonyl, alkoxycarbonyl, aryl, aralkyl, hetaryl or carboxyl or R?2 and R3¿, together with the carbon atom to which they are bonded, form a possibly substituted ring possibly containing oxygen, sulphur or nitrogen, in which the nitrogen may be substituted by alkyl, aryl, aralkyl or hetaryl, a process and intermediate products for their production and their use against animal pests.

Description

DITHIOCARBAZONSXU EBUTENYLESTE UND IHRE VERWENDUNG ALS PESTIZIDEDITHIOCARBAZONSXU EBUTENYLESTE AND THEIR USE AS PESTICIDES
Die vorliegende Erfindung betrifft neue Dithiocarbazonsäurebutenylester, Ver- fahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung von tierischen Schädlingen, insbesondere von Insekten, Spinnentieren und Nematoden, die in der Landwirtschaft, in Forsten, im Vorrats- und Material schütz sowie auf dem Hygienesektor vorkommen.The present invention relates to new dithiocarbazonic acid butenyl esters, processes for their preparation and their use for controlling animal pests, in particular insects, arachnids and nematodes, which protect in agriculture, in forests, in the supply and material and in the hygiene sector.
Es ist bereits bekannt geworden, daß bestimmte Fluoralkenylverbindungen als Insektizide, Akarizide und Nematizide wirksam sind (vgl. z.B. WO 92/15 555, US-4 952 590, US-4 950 666, US-3 914 251). Die Wirksamkeit und Wirkungs¬ breite dieser Verbindungen ist jedoch insbesondere bei niedrigen Aufwandmengen und Konzentrationen nicht immer völlig zufriedenstellend.It has already been known that certain fluoroalkenyl compounds are effective as insecticides, acaricides and nematicides (see e.g. WO 92/15 555, US-4,952,590, US-4,950,666, US-3,914,251). However, the effectiveness and range of action of these compounds is not always completely satisfactory, especially at low application rates and concentrations.
Es wurden nun neue Dithiocarbazonsäurebutenylester der Formel (I) gefunden,New dithiocarbazonic acid butenyl esters of the formula (I) have now been found
Figure imgf000003_0001
Figure imgf000003_0001
in welcherin which
R1 für Wasserstoff oder Halogen steht,R 1 represents hydrogen or halogen,
R und R3 unabhängig voneinander für Wasserstoff oder jeweils gegebenenfalls substituiertes Alkyl, Cycloalkyl, Aminocarbonyl, Alkoxycarbonyl, Aryl, Aralkyl, Hetaryl oder Carboxyl stehen oderR and R 3 independently of one another represent hydrogen or in each case optionally substituted alkyl, cycloalkyl, aminocarbonyl, alkoxycarbonyl, aryl, aralkyl, hetaryl or carboxyl or
R2 und R3 gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, einen gegebenenfalls substituierten Ring bilden, der gegebenenfalls Sauerstoff, Schwefel oder Stickstoff enthält, wobei der Stickstoff gegebenenfalls durch Alkyl, Aryl, Aralkyl oder Hetaryl substituiert ist.R 2 and R 3 together with the carbon atom to which they are attached form an optionally substituted ring which optionally contains oxygen, sulfur or nitrogen, the nitrogen optionally being substituted by alkyl, aryl, aralkyl or hetaryl.
Die Verbindungen der Formel (I) können in Abhängigkeit von der Art der Substi- tuenten als geometrische und/oder optische Isomere oder Isomerengemische unter¬ schiedlicher Zusammensetzung vorliegen. Die Erfindung betrifft sowohl die reinen Isomeren als auch die Isomerengemische. Weiterhin wurde gefunden, daß man die Dithiocarbazonsäurebutenylester der For¬ mel (I) erthält, wenn manDepending on the nature of the substituents, the compounds of the formula (I) can be in the form of geometric and / or optical isomers or isomer mixtures of different compositions. The invention relates to both the pure isomers and the isomer mixtures. Furthermore, it was found that the dithiocarbazonic acid butenyl ester of the formula (I) is obtained when
A) Dithiocarbazinester der Formel (II)A) dithiocarbazine esters of the formula (II)
CF2 = C-CH2- -CH,— S-C— NH — NH, (II)CF 2 = C-CH 2 - -CH, - SC— NH - NH, (II)
R in welcherR in which
R1 die oben angegebene Bedeutung hat,R 1 has the meaning given above,
mit Carbonylverbindungen der Formel (III)with carbonyl compounds of the formula (III)
R2 o=c (HI) R 2 o = c ( HI )
\ 3 R3 \ 3 R 3
in welcherin which
R2 und R3 die oben angegebene Bedeutung haben,R 2 and R 3 have the meaning given above,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines sauren Katalysators umsetzt oderif appropriate in the presence of a diluent and if appropriate in the presence of an acidic catalyst or
B) Hydrazone der Formel (IV)B) hydrazones of the formula (IV)
R2 H3N-N=C (IV)R 2 H 3 NN = C ( IV )
\ 3\ 3
R in welcherR in which
R2 und R3 die oben angegebenen Bedeutungen haben, in Gegenwart einer Base und in Gegenwart eines Verdünnungsmittels mit Schwefelkohlenstoff und anschließend mit einem Fluorbutenylhalogenid der Formel (V)R 2 and R 3 have the meanings given above, in the presence of a base and in the presence of a diluent with carbon disulphide and then with a fluorobutenyl halide of the formula (V)
Figure imgf000005_0001
in welcher
Figure imgf000005_0001
in which
R1 die oben angegebene Bedeutung hat undR 1 has the meaning given above and
Hai für Halogen, insbesondere Chlor oder Brom steht,Shark represents halogen, especially chlorine or bromine,
umsetzt.implements.
Schließlich wurde gefunden, daß die neuen Dithiocarbazonsäurebutenylester der Formel (I) stark ausgeprägte biologische Eigenschaften besitzen und vor allem zur Bekämpfung von tierischen Schädlingen, insbesondere von Insekten, Spinnentieren und Nematoden, die in der Landwirtschaft, in den Forsten, im Vorrats- und Mate¬ rialschutz sowie auf dem Hygienesektor vorkommen, geeignet sind.Finally, it was found that the new dithiocarbazonic acid butenyl esters of the formula (I) have highly pronounced biological properties and above all to combat animal pests, in particular insects, arachnids and nematodes, which are used in agriculture, in the forests, in the stock and mate protection and in the hygiene sector.
Die erfindungsgemäßen Dithiocarbazonbutenylester sind durch die Formel (I) allgemein definiert.The dithiocarbazone butenyl esters according to the invention are generally defined by the formula (I).
Bevorzugte Substituenten bzw. Bereiche der in den oben und nachstehend erwähn¬ ten Formeln aufgeführten Reste werden im folgenden erläutert:Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:
R1 steht bevorzugt für Wasserstoff, Fluor, Chlor oder Brom.R 1 preferably represents hydrogen, fluorine, chlorine or bromine.
R2 und R3 stehen unabhängig voneinander bevorzugt für Wasserstoff, C^Cj,- Alkyl, CrC12-Halogenalkyl, CrC8-Alkoxy-C,-C8-alkyl, C,-C8-Alkylthio- C,-C8-alkyl, für jeweils gegebenenfalls durch Halogen, Nitro, Amino, C 1-C 8- Alkylamino, Di-C]-C8-alkylamino, Cj-C8-Halogenalkyl, C,-C8-Alkoxy, C,- C8-Halogenalkoxy, C,-C8-Alkylthio oder CrC8-Halogenalkylthio substitu¬ iertes Phenyl, Benzyl, Phenoxy-C,-C6-alkyl oder Phenylthio-CrC6-alkyl, für Carboxyl, CrC8-Alkoxycarbonyl, für gegebenenfalls einfach oder zweifach, gleich oder verschieden durch Cι-CI0-Alkyl oder Phenyl (welches gegebenenfalls durch Halogen, C,-C6- Alkyl, C,-C6-Halogenalkyl, C,-C6-Alkoxy oder C,-C6-Halogenalkoxy sub¬ stituiert ist) substituiertes Aminocarbonyl, für einen gegebenenfalls durch Halogen oder Cj-C6-Alkyl substituierten 5- oder 6-gliedrigen Heterocyclus, der ein bis drei Atome aus der Reihe Sauerstoff, Schwefel und Stickstoff enthält oderR 2 and R 3 independently of one another preferably represent hydrogen, C ^ C j, - alkyl, C r C 12 haloalkyl, C r C 8 alkoxy-C, -C 8 alkyl, C, -C 8 -alkylthio C, -C 8 alkyl, in each case optionally substituted by halogen, nitro, amino, C 1 -C 8 - alkylamino, di-C] -C 8 alkylamino, C j -C 8 haloalkyl, C, -C 8 - alkoxy, C, - C 8 haloalkoxy, C, -C 8 -alkylthio or C r C 8 haloalkylthio substitu¬ iertes phenyl, benzyl, phenoxy-C, -C 6 alkyl or phenylthio-C r C 6 alkyl, for carboxyl, C r C 8 alkoxycarbonyl, optionally mono- or disubstituted by identical or different substituents from Cι-C I0 alkyl or phenyl (which is optionally substituted by halogen, C, -C 6 - alkyl, C, -C 6 haloalkyl, C, -C 6 alkoxy or C -C 6 -Halogenalkoxy is substituted) substituted aminocarbonyl, for a 5- or 6-membered heterocycle optionally substituted by halogen or C j -C 6 alkyl, which contains one to three atoms from the series oxygen, sulfur and nitrogen or
R2 und R bilden gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind einen 4- bis 10-gliedrigen Ring, der gegebenenfalls Sauerstoff, Schwefel oder Stickstoff (welcher gegebenenfalls durch Cj-C8- Alkyl, Phenyl oder Benzyl substituiert ist) enthält oderR 2 and R together with the carbon atom to which they are attached form a 4- to 10-membered ring which optionally contains oxygen, sulfur or nitrogen (which is optionally substituted by C 1 -C 8 -alkyl, phenyl or benzyl) or
R2 und R3 stehen gemeinsam mit dem Kohlenstof atom, an das sie gebunden sind, für eine der GruppenR 2 and R 3 together with the carbon atom to which they are attached represent one of the groups
Figure imgf000006_0001
Figure imgf000006_0001
in welcherin which
R für Halogen, Nitro, C,-C6-Alkyl, C,-C6-Halogenalkyl, CrC6-Alk- oxy, CrC6-Halogenalkoxy, CrC6-Alkylthio oder C,-C6-Halogen- alkylthio steht.R is halogen, nitro, C, -C 6 -alkyl, C, -C 6 -haloalkyl, C r C 6 -alkoxy, C r C 6 -haloalkoxy, C r C 6 -alkylthio or C, -C 6 -Halogen- alkylthio stands.
R1 steht besonders bevorzugt für Wasserstoff, Fluor oder Chlor.R 1 particularly preferably represents hydrogen, fluorine or chlorine.
R2 und R3 stehen unabhängig voneinander besonders bevorzugt für Wasserstoff, Cj-C8-Alkyl, Cj-C^Halogenalkyl, für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Amino, C,-C6-Al- kylamino, Di-C,-C6-alkylamino, C,-C6-Alkoxy oder C,-C6-Halogenalkoxy substituiertes Phenyl oder Benzyl, für jeweils gegebenenfalls durch Fluor, Chlor, Brom oder CrC4-Alkyl substituiertes Pyrryl, Thienyl, Furyl, Pyrazolyl, Thiazolyl, Pyridyl oder Pyrimidyl oderR 2 and R 3 independently of one another particularly preferably represent hydrogen, C j -C 8 alkyl, C j -C ^ haloalkyl, each optionally by fluorine, chlorine, bromine, amino, C, -C 6 alkylamino, Di-C, -C 6 -alkylamino, C, -C 6 -alkoxy or C, -C 6 -haloalkoxy substituted phenyl or benzyl, for pyrryl, thienyl, furyl, pyrazolyl, thiazolyl, pyridyl or pyrimidyl or substituted by fluorine, chlorine, bromine or C r C 4 alkyl
R und R bilden gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, einen 5- bis 8-gliedrigen Ring, der gegebenenfalls Sauerstoff oder Stick¬ stoff (welcher gegebenenfalls durch C,-C6-Mky\ substituiert ist) enthält.R and R together with the carbon atom to which they are attached form a 5- to 8-membered ring which optionally contains oxygen or nitrogen (which is optionally substituted by C, -C 6 -Mky \).
R1 steht ganz besonders bevorzugt für Fluor.R 1 very particularly preferably represents fluorine.
R und R stehen unabhängig voneinander ganz besonders bevorzugt für Wasserstoff, CrC6-Alkyl, CrC4-Halogenalkyl, für gegebenenfalls durch Fluor, Chlor, Brom, Amino, C]-C4-Alkylamino,R and R independently of one another very particularly preferably represent hydrogen, C r C 6 alkyl, C r C 4 haloalkyl, optionally by fluorine, chlorine, bromine, amino, C ] -C 4 alkylamino,
Di-C,-C4-alkylamino,
Figure imgf000007_0001
oder Cj-C.j-Halogenalkoxy substituier¬ tes Phenyl, für jeweils gegebenenfalls durch Fluor, Chlor, Brom oder Cj- j-Alkyl sub¬ stituiertes Thienyl, Furyl oder Pyridyl oderDi-C, -C 4 -alkylamino,
Figure imgf000007_0001
or C j -C. j haloalkoxy substituier¬ tes phenyl, optionally substituted by fluorine, chlorine, bromine or C j respectively - j alkyl sub¬ stituiertes thienyl, furyl or pyridyl, or
R2 und R3 bilden gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, einen 5- bis 8-gliedrigen Carbocyclus.R 2 and R 3 together with the carbon atom to which they are attached form a 5- to 8-membered carbocycle.
Die oben aufgeführten allgemeinen oder in Vorzugsbereichen aufgeführten Reste¬ definitionen bzw. Erläuterungen gelten für die Endprodukte und für die Ausgangs¬ und Zwischenprodukte entsprechend. Diese Restedefintionen können untereinander, also auch zwischen den jeweiligen Vorzugsbereichen, beliebig kombiniert werden.The general definitions or explanations or explanations given above, or in preferred areas, apply correspondingly to the end products and to the starting and intermediate products. These residual definitions can be combined with one another as desired, 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 aufgeführtenAccording to the invention, particular preference is given to the compounds of the formula (I) in which a combination of those listed as particularly preferred above
Bedeutungen vorliegt.Meanings exist.
Erfindungsgemäß ganz besonders bevorzugt werden die Verbindungen der Formel (I), in welchen eine Kombination der vorstehend als ganz besonders bevorzugt aufgeführten Bedeutungen vorliegt. In den oben und nachstehend aufgeführten Restedefinitionen sind Kohlenwasser¬ stoffreste, wie Alkyl oder Alkenyi, - auch in Verbindung mit Heteroatomen wie Alkoxy oder Alkylthio - soweit möglich geradkettig oder verzweigt.According to the invention, very particular preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as being very particularly preferred. In the radical definitions listed above and below, hydrocarbon radicals, such as alkyl or alkenyl, are straight-chain or branched as far as possible, even in conjunction with heteroatoms such as alkoxy or alkylthio.
Verwendet man bei der Herstellung von Verbindungen der Formel (I) gemäß Verfahren A) z.B. Dithiocarbazinsäure-(3,4,4-trifluorbut-3-enyl)-ester und Aceton als Ausgangsstoffe, so kann der Reaktionsverlauf durch folgendes Reaktions¬ schema wiedergegeben werden:Is used in the preparation of compounds of formula (I) according to process A) e.g. Dithiocarbazinic acid (3,4,4-trifluorobut-3-enyl) ester and acetone as starting materials, the course of the reaction can be represented by the following reaction scheme:
CF,=CF-CH7-CH2-S-C-NH-NH7 0=C(CH3)2 CF, = CF-CH 7 -CH 2 -SC-NH-NH 7 0 = C (CH 3 ) 2
SS
IIII
CF2=CF-CH2-CH2-S-C-NH-N=C(CH3)2 CF 2 = CF-CH 2 -CH 2 -SC-NH-N = C (CH 3 ) 2
Verwendet man bei der Herstellung von Verbindungen der Formel (I) gemäß Verfahren B) z.B. Benzophenonhydrazon und 3,4,4-Trifluorbut-3-enylbromid alsIs used in the preparation of compounds of formula (I) according to process B) e.g. Benzophenone hydrazone and 3,4,4-trifluorobut-3-enyl bromide as
Ausgangsstoffe, so kann der Reaktionsverlauf durch folgendes Reaktionsschema wiedergegeben werden:Starting materials, the course of the reaction can be represented by the following reaction scheme:
Figure imgf000008_0001
Figure imgf000008_0001
Das oben beschriebene Verfahren A) zur Herstellung von Verbindungen der Formel (I) ist dadurch gekennzeichnet, daß die Umsetzungen gegebenenfalls inProcess A) described above for the preparation of compounds of the formula (I) is characterized in that the reactions are optionally carried out in
Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines sauren Katalysators durchgeführt werden. Als Verdünnungsmittel können bei diesem Verfahren alle üblichen Lösungsmittel eingesetzt werden.In the presence of a diluent and optionally in the presence of an acidic catalyst. All customary solvents can be used as diluents in this process.
Vorzugsweise verwendbar sind gegebenenfalls halogenierte aliphatische oder aro¬ matische Kohlenwasserstoffe wie Cyclohexan, Toluol, Xylol, Dichlormethan, Chloroform, Dichlorethan oder Chlorbenzol, Alkohole wie Methanol, Ethanol oderHalogenated aliphatic or aromatic hydrocarbons such as cyclohexane, toluene, xylene, dichloromethane, chloroform, dichloroethane or chlorobenzene, alcohols such as methanol, ethanol or are preferably usable
Isopropanol, Nitrile wie Acetonitril, Ether wie Di isopropy lether, Tetrahydrofuran oder Dioxan oder Amide wie Dimethylformamid.Isopropanol, nitriles such as acetonitrile, ethers such as di isopropyl ether, tetrahydrofuran or dioxane or amides such as dimethylformamide.
Die Umsetzung kannn auch in Abwesenheit eines der genannten Lösungsmittel durchgeführt werden. In diesem Fall kann es vorteilhaft sein, die Carbonylver- bindung der Formel (III) im Überschuß einzusetzen.The reaction can also be carried out in the absence of one of the solvents mentioned. In this case, it may be advantageous to use the carbonyl compound of the formula (III) in excess.
Als saurer Katalysator kommen beispielsweise Sulfonsäuren wie p-Toluolsulfon- säure in Frage.Examples of suitable acidic catalysts are sulfonic acids such as p-toluenesulfonic acid.
Die Reaktionstemperaturen können bei dem oben beschriebenen Verfahren A) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Tempe- raturen zwischen 0°C und 160°C, bevorzugt zwischen 20°C und 130°C.The reaction temperatures can be varied within a wide range in process A) described above. In general, temperatures between 0 ° C and 160 ° C, preferably between 20 ° C and 130 ° C.
Im allgemeinen setzt man beim Verfahren A) die Ausgangsstoffe der Formeln (II) und (III) in etwa äquimolaren Mengen ein. Es kann jedoch vorteilhaft sein, die Carbonylverbindung der Formel (III) im Überschuß zu verwenden.In general, in process A) the starting materials of the formulas (II) and (III) are used in approximately equimolar amounts. However, it may be advantageous to use the carbonyl compound of the formula (III) in excess.
Die Umsetzung wird im allgemeinen bei Normaldruck durchgeführt.The reaction is generally carried out at normal pressure.
Das Reaktionsgemisch wird auf übliche Weise, beispielsweise durch Abdestillieren des Verdünnungsmittels, aufgearbeitet.The reaction mixture is worked up in a conventional manner, for example by distilling off the diluent.
Das oben beschriebene Verfahren B) zur Herstellung von Verbindungen der Formel (I) ist dadurch gekennzeichnet, daß die Umsetzungen in Gegenwart einer Base und in Gegenwart eines Verdünnungsmittels durchgeführt werden.Process B) described above for the preparation of compounds of the formula (I) is characterized in that the reactions are carried out in the presence of a base and in the presence of a diluent.
Als Basen können beim Verfahren B) alle üblichen Protonenakzeptoren eingesetzt werden. Vorzugsweise verwendbar sind Alkalimetallhydride, Alkalimetallalkoho- late, Alkali- oder Erdalkalimetallcarbonate oder -hydrogencarbonate oder Stick¬ stoffbasen. Genannt seien beispielsweise Natriumhydrid, Natriummethanolat, Na- triumhydroxid, Calciumhydroxid, Kaliumcarbonat, Natriumhydrogencarbonat, Tri- ethylamin, Dibenzylamin, Diisopropyla in, Pyridin, Chinolin, Diazabicyclooctan (DABCO), Diazabicyclononen (DBN) und Diazabicycloundecen (DBU).All conventional proton acceptors can be used as bases in method B). Alkali metal hydrides, alkali metal alcohols, alkali metal or alkaline earth metal carbonates or hydrogen carbonates or nitrogen bases can preferably be used. Examples include sodium hydride, sodium methoxide, sodium trium hydroxide, calcium hydroxide, potassium carbonate, sodium hydrogen carbonate, triethylamine, dibenzylamine, diisopropyla in, pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclonones (DBN) and diazabicycloundecene (DBU).
Als Verdünnungsmittel können bei diesem Verfahren alle üblichen Lösungsmittel verwendet werden.All customary solvents can be used as diluents in this process.
Vorzugsweise verwendbar sind aromatische Kohlenwasserstoffe wie Benzol oder Toluol, Alkohole wie Methanol, Ethanol, Isopropanol oder Ethylenglykol, Nitrile wie Acetonitril, Ether wie Tetrahydrofuran oder Dioxan, Amide wie Dime- thylformamid oder andere polare Lösungsmittel wie Dimethylsulfoxid oder Sulfolan.Aromatic hydrocarbons such as benzene or toluene, alcohols such as methanol, ethanol, isopropanol or ethylene glycol, nitriles such as acetonitrile, ethers such as tetrahydrofuran or dioxane, amides such as dimethylformamide or other polar solvents such as dimethyl sulfoxide or sulfolane can preferably be used.
Die Reaktionstemperaturen können bei dem oben beschriebenen Verfahren B) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Tem¬ peraturen zwischen 0°C und 140°C, bevorzugt zwischen 20°C und 80°C.The reaction temperatures can be varied within a wide range in process B) described above. In general, temperatures between 0 ° C and 140 ° C, preferably between 20 ° C and 80 ° C.
Die Ausgangsstoffe der Formel (IV) und (V) werden im allgemeinen in angenähert äquimolarer Menge eingesetzt. Die Umsetzung wird im allgemeinen unter Normal¬ druck durchgeführt.The starting materials of the formula (IV) and (V) are generally used in an approximately equimolar amount. The reaction is generally carried out under normal pressure.
Beispielsweise kann man so vorgehen, daß man die Verbindung der Formel (IV) in einem Verdünnungsmittel vorlegt, Schwefelkohlenstoff und anschließend die Base zugibt, gegebenenfalls eine gewisse Zeit rührt und dann die Verbindung der Formel (V) zudosiert. Anschließend wird bis zum Ende der Umsetzung bei der erforderlichen Temperatur gerührt.For example, one can proceed in such a way that the compound of formula (IV) is placed in a diluent, carbon disulfide and then the base are added, optionally stirred for a certain time and then the compound of formula (V) is metered in. The mixture is then stirred at the required temperature until the end of the reaction.
Zur Aufarbeitung wird das Reaktionsgemisch beispielsweise mit Wasser verdünnt, mit einem organischen Lösungsmittel wie Toluol, Ether oder Essigsäureethylester extrahiert und die organische Phase eingeengt.For working up, the reaction mixture is diluted, for example, with water, extracted with an organic solvent such as toluene, ether or ethyl acetate and the organic phase is concentrated.
Die beim Herstellungsverfahren A) als Ausgangsstoffe verwendeten Verbindungen der Formel (II)The compounds of the formula (II) used as starting materials in production process A)
CF2 = C-CH2— CH2— S — C — NH NH2 (II) in welcherCF 2 = C-CH 2 - CH 2 - S - C - NH NH 2 (II) in which
R1 die oben angegebene Bedeutung hat,R 1 has the meaning given above,
sind neu.are new.
Man erhält die Verbindungen, der Formel (II), wenn man Verbindungen der Formel (VI)The compounds of the formula (II) are obtained if compounds of the formula (VI)
SS
II (vi) S-C-NH-NH2 II (vi) SC-NH-NH 2
in welcherin which
M für ein Alkalimetall, bevorzugt Natrium oder Kalium, steht,M represents an alkali metal, preferably sodium or potassium,
mit Fluorbutenylhalogeniden der Formel (V)with fluorobutenyl halides of the formula (V)
Figure imgf000011_0001
Figure imgf000011_0001
in welcherin which
R1 und Hai die oben angegebene Bedeutung haben,R 1 and shark have the meaning given above,
in Gegenwart eines Verdünnungsmittels umsetzt.in the presence of a diluent.
Als Verdünnungsmittel kommen hierbei alle üblichen organischen Lösungsmittel in Frage. Vorzugsweise verwendbar sind Alkohole wie Methanol, Ethanol,All customary organic solvents are suitable as diluents. Alcohols such as methanol, ethanol,
Isopropanol, Nitrile wie Acetonitril, Ether wie Diethylether, Tetrahydrofuran, Dioxan, aliphatische oder aromatische Kohlenwasserstoffe wie Cyclohexan, Toluol oder Xylol oder polare Lösungsmittel wie Dimethylsulfoxid, Sulfolan, Dimethylformamid oder Dimethylacetamid.Isopropanol, nitriles such as acetonitrile, ethers such as diethyl ether, tetrahydrofuran, dioxane, aliphatic or aromatic hydrocarbons such as cyclohexane, toluene or xylene or polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide or dimethylacetamide.
Die Reaktionstemperatur kann in einem größeren Bereich variiert werden. Im all¬ gemeinen arbeitet man bei Temperaturen zwischen 0°C und 140°C, bevorzugt zwi¬ schen 20°C und 100°C. Das Verhältnis der Verbindungen der Formeln (V) und (VI) liegt im allgemeinen zwischen 2: 1 und 1:2. Die Reaktion wird im allgemeinen unter Normaldruck durchgeführt.The reaction temperature can be varied within a wide range. In general, temperatures between 0 ° C and 140 ° C, preferably between 20 ° C and 100 ° C. The ratio of the compounds of the formulas (V) and (VI) is generally between 2: 1 and 1: 2. The reaction is generally carried out under normal pressure.
Zur Aufarbeitung kann das Reaktionsgemisch mit Wasser verdünnt und mit einem geeigneten organischen Lösungsmittel extrahiert werden. Anschließend wird dasFor working up, the reaction mixture can be diluted with water and extracted with a suitable organic solvent. Then that will
Lösungsmittel abdestilliert.Distilled off solvent.
Die Verbindungen der Formel (II) weisen nematizide Eigenschaften auf.The compounds of formula (II) have nematicidal properties.
Die Wirkstoffe eignen sich zur Bekämpfung von tierischen Schädlingen, insbeson¬ dere Insekten, 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 resistente Arten sowie gegen alle oder einzelne Entwick¬ lungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:The active substances are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species and against all or individual stages of development. The pests mentioned above include:
Aus der Ordnung der Isopoda z.B. Oniscus asellus, Armadillidium vulgäre, Por- cellio scaber.From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgäre, 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.From the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spec.
Aus der Ordnung der Symphyla z.B. Scutigerella immaculata.From the order of the Symphyla e.g. Scutigerella immaculata.
Aus der Ordnung der Thysanura z.B. Lepisma saccharina.From the order of the Thysanura e.g. Lepisma saccharina.
Aus der Ordnung der Collembola z.B. Onychiurus armatus.From the order of the Collembola e.g. Onychiurus armatus.
Aus der Ordnung der Orthoptera z.B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.From the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
Aus der Ordnung der Dermaptera z.B. Forficula auricularia.From the order of the Dermaptera e.g. Forficula auricularia.
Aus der Ordnung der Isoptera z.B. Reticulitermes spp.. Aus der Ordnung der Anoplura z.B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.From the order of the Isoptera, for example Reticulitermes spp .. From the order of the anoplura, for example Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
Aus der Ordnung der Mallophaga z.B. Trichodectes spp., Damalinea spp.From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.
Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci.From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
Aus der Ordnung der Heteroptera z.B. Eurygaster spp., Dysdercus intermedius,From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius,
Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
Aus der Ordnung der Homoptera z.B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus sppe, Phrosiphodumonum., Macrosiphodumon. Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
Aus der Ordnung der Lepidoptera z.B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata. Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata. Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia sppana, Heliodia spp. Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophana piferosellaella, pellellaella pianosella pellaella, Hofmannophila pseudosella , Clysia ambiguella, Homona magnanima, Tortrix viridana.
Aus der Ordnung der Coleoptera z.B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,
Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatordimidhmpphppm, spp. , Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,
Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha elolontha, Amphimallon solstitialis, Costelytra zealandica.Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha elolontha, Amphimallon solstitialis, Costelytra zealandica.
Aus der Ordnung der Hymenoptera z.B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
Aus der Ordnung der Diptera z.B. Aedes spp., Anopheles spp., Culex spp.,From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp.,
Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tabanus spp. Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
Aus der Ordnung der Siphonaptera z.B. Xenopsylla cheopis, Ceratophyllus spp..From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp ..
Aus der Ordnung der Arachnida z.B. Scorpio maurus, Latrodectus mactans.From the order of the Arachnida e.g. 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., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus 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.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
Zu den pflanzenparasitären Nematoden gehören z.B. Pratylenchus spp., Radopho- lus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus 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..Xiphinema spp., Trichodorus spp ..
Die erfindungsgemäßen Verbindungen der Formel (I) zeichnen sich insbesondere durch eine hervorragende nematizide Wirkung aus, beispielsweise gegen Meloido¬ gyne incognita.The compounds of the formula (I) according to the invention are distinguished in particular by an excellent nematicidal action, for example against Meloidogyne incognita.
Die Wirkstoffe können in die üblichen Formulierungen überführt werden, wie Lö¬ sungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lös¬ liche Pulver, Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-impräg¬ nierte 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 oberflächen¬ aktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaum- erzeugenden 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 as well as very fine encapsulation in polymeric substances. 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, if appropriate using surface-active agents, ie 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 Alkylnaphthaline, chlorierte Aromaten und chlorierte aliphatische Kohlenwasser- Stoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Koh¬ lenwasserstoffe, 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 Cyclo- hexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethyl- sulfoxid, 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-Fett- säure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkyl aryl -poly glykol ether, Al- kylsulfonate, Alkylsulfate, Arylsulfonate sowie Einweißhydrolysate; als Dispergier¬ mittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.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. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkyl aryl 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, natür- liehe und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein. Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metall phthalo- cyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils. Dyes such as inorganic pigments, for example 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.-% Wirkstoff, 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, Akariziden, Nematiziden, Fungiziden, wachstumsregulierenden Stof¬ fen oder Herbiziden vorliegen. Zu den Insektiziden zählen beispielsweise Phos¬ phorsäureester, Carbamate, Carbonsäureester, chlorierte Kohlenwasserstoffe, Phe- nylharnstoffe, durch Mikroorganismen hergestellte Stoffe u.a.The active compound 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 compounds, 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:
2-Aminobutan; 2-Anilino-4-methyl-6-cyclopropyl-pyrimidin; 2',6'-Dibromo-2-me- thyl^'-trifluoromethoxy^'-trifluoro-methyl-l^-thiazol-S-carboxanilid; 2,6-Di- chloroN-(4-trifluoromethylbenzyl)-benzamid; (E)-2-Methoxyimino-N-methyl-2-(2- phenoxyphenyl)-acetamid; 8-Hydroxyquinolinsulfat; Methyl-(E)-2- { 2-[6-(2-cyano- phenoxy)-pyrimidin-4-yloxy ]-phenyl }-3-methoxyacrylat; Methyl-(E)-methoximino-2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl ^' - trifluoromethoxy ^ '- trifluoro-methyl-l ^ -thiazole-S-carboxanilide; 2,6-dichloroN- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyano-phenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl- (E) -methoximino-
[alpha-(o-tolyloxy)-o-tolyl]acetat; 2-Phenylphenol (OPP), Aldimorph, Ampropylfos, Anilazin, Azaconazol,[alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate, Calciumpolysulfid, Captafol, Captan, Carbendazim, Carboxin, ChinomethionatBenalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate, Calciumpolysulfid, Captafol, Captan, Carbendazim, Carboxin, Chinomethionate
(Quinomethionat), Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinat, Cufraneb, Cymoxanil, Cyproconazole, Cyprofuram,(Quinomethionate), Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinate, Cufraneb, Cymoxanil, Cyproconazole, Cyprofuram,
Dichlorophen, Diclobutrazol, Diclofluanid, Diclomezin, Dicloran, Diethofencarb, Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Dinocap, Diphenyl- amin, Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon,Dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, Epoxyconazole, Ethirimol, Etridiazol,Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, F'enitropan, Fenpiclonil, Fenpropidin, Fen- propimo h, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Flu- dioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flu- triafol, Folpet, Fosetyl-Aluminium, Fthalide, Fuberidazol, Furalaxyl, Furmecyclox,Fenarimol, Fenbuconazole, Fenfuram, F'enitropan, Fenpiclonil, Fenpropidin, Fen- propimo h, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Flu- dioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, fluotriafol, folpet, fosetyl aluminum, fthalide, fuberidazole, furalaxyl, furmecyclox,
Guazatine,Guazatine,
Hexachlorobenzol, Hexaconazol, Hymexazol, Imazalil, Imibenconazol, Iminoctadin, Iprobenfos (IBP), Iprodion, Isoprothiolan,Hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, Iprobefos (IBP), iprodione, isoprothiolan,
Kasugamycin, Kupfer-Zubereitungen, wie: Kupferhydroxid, Kupfernaphthenat,Kasugamycin, copper preparations, such as: copper hydroxide, copper naphthenate,
Kupferoxychlorid, Kupfersulfat, Kupferoxid, Oxin-Kupfer und Bordeaux-Mi¬ schung,Copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel-dimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol,Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Phthalid, Pimaricin, Piperalin,Pefurazoate, penconazole, pencycuron, phosdiphene, phthalide, pimaricin, piperalin,
Polycarbamate, Polyoxin, Probenazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,Polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilone,
Quintozen (PCNB),Quintozen (PCNB),
Schwefel und Schwefel-Zubereitungen,Sulfur and sulfur preparations,
Tebuconazol, Tecloftalam, Tecnazen, Tetraconazol, Thiabendazol, Thicyofen,Tebuconazole, tecloftalam, tecnazen, tetraconazole, thiabendazole, thicyofen,
Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadi- menol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Tri- ticonazol,Thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforin, triticonazole,
Validamycin A, Vinclozolin,Validamycin A, vinclozolin,
Zineb, Ziram.Zineb, ziram.
Bakterizide: Bronopol, Dichlorophen, Nitrapyrin, Nickel-Dimethyldithiocarbamat, Kasugamy¬ cin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.Bactericides: 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, Alpha- methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M,Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alpha-methrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,
Azocyclotin,Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifen- thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor- fluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocy- thrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorofluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocyentoshrinhrin, Cloferthrin, Cloferthrin, Cyan Cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Di- azinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu- benzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho- prophos, Etrimphos,Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinone, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu- benzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphi furnace, Edifenphi furnace, Emifenphi furnace, Ethion, Ethofenprox, Ethoprophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluva- linate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox,Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenproxatophon, Fufionphonophone, Fufionfox, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufone HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Iver- mectin, Lambda-cyhalothrin, Lufenuron,Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyd, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, NI 25, Nitenpyram,Naled, NC 184, NI 25, Nitenpyram,
Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos,Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos,
Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,
Quinalphos,Quinalphos,
RH 5992,RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos,Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos,
Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio- methon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Tri- azuron, Trichlorfon, Triflumuron, Trimethacarb,Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb,
Vamidothion, XMC, Xylylcarb, YI 5301 / 5302, Zetamethrin.Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Herbiziden oder mitA mixture with other known active ingredients, such as herbicides or with
Düngemitteln und Wachstumsregulatoren ist möglich. Die erfindungsgemäßen Wirkstoffe können ferner in ihren handelsüblichen Formu¬ lierungen 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.Fertilizers and growth regulators are possible. 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 An¬ wendungsformen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen 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 substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
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.,From the order of the Anoplurida e.g. Haematopinus spp., Linognathus spp.,
Pediculus spp., Phtirus spp., Solenopotes spp..Pediculus spp., Phtirus spp., Solenopotes spp ..
Aus der Ordnung der Mallophagida und den Unterordnungen Amblycerina sowie Ischnocerina z.B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp..From the order of the Mallophagida and the subordinates Amblycerina and 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..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 ..
Aus der Ordnung der Siphonapterida z.B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..From the order of the Siphonapterida e.g. 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- sowie Mesostigmata z.B. Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneu- monyssus spp., Sternostoma spp., Varroa spp..From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillneu- spp., Pill monyssus spp., Sternostoma spp., Varroa spp ..
Aus der Ordnung der Actinedida (Prostigmata) und Acaridida (Astigmata) z.B.From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) e.g.
Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp..Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodterol spp ., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..
Beispielsweise zeigen sie eine hervorragende Wirksamkeit gegen Boophilus microplus, Lucilia cuprina und Musca domestica.For example, they show excellent effectiveness against Boophilus microplus, Lucilia cuprina and Musca domestica.
Die erfindungsgemäßen Wirkstoffe der Formel (I) eignen sich auch zur Bekämp¬ fung von Arthropoden, die landwirtschaftliche Nutztiere, wie z.B. Rinder, Schafe, Ziegen, Pferde, Schweine, Esel, Kamele, Büffel, Kaninchen, Hühner, Puten, Enten,The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, chickens, turkeys, ducks,
Gänse, Bienen, sonstige Haustiere wie z.B. Hunde, Katzen, Stubenvögel, Aqua¬ rienfische sowie sogenannte Versuchstiere, wie z.B. Hamster, Meerschweinchen, Ratten und Mäuse befallen. Durch die Bekämpfung dieser Arthropoden sollen Todesfälle und Leistungsminderungen (bei Fleisch, Milch, Wolle, Häuten, Eiern, Honig usw.) vermindert werden, so daß durch den Einsatz der erfindungsgemäßen Wirkstoffe eine wirtschaftlichere und einfachere Tierhaltung möglich ist.Geese, bees, other domestic animals such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice are attacked. Combating these arthropods is said to result in deaths and reduced performance (in meat, milk, wool, skins, eggs, Honey, etc.) can be reduced, so that more economical and simple animal husbandry is possible through the use of the active compounds according to the invention.
Die Anwendung der erfindungsgemäßen Wirkstoffe geschieht im Veterinärsektor in bekannter Weise durch enterale Verabreichung in Form von beispielsweise Tab- letten, Kapseln, Tränken, Drenchen, Granulaten, Pasten, Boli, des feed-through-The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, and feed-through
Verfahrens, von Zäpfchen, durch parenterale Verabreichung, wie zum Beispiel durch Injektionen (intramuskulär, subcutan, intravenös, intraperitonal u.a.), Implan¬ tate, durch nasale Applikation, durch dermale Anwendung in Form beispielsweise des Tauchens oder Badens (Dippen), Sprühens (Spray), Aufgießens (Pour-on und Spot-on), des Waschens, des Einpuderns sowie mit Hilfe von wirkstoffhaltigenMethod, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray ), Pouring (pour-on and spot-on), washing, powdering and with the help of active ingredients
Formkörpern, wie Halsbändern, Ohrmarken, Schwanzmarken, Gliedmaßenbändern, Halftern, Markierungsvorrichtungen usw.Shaped bodies, 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 der 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.When used for cattle, poultry, pets, etc., the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.
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 1-1Example 1-1
Figure imgf000022_0001
Figure imgf000022_0001
In 50 ml Ethanol werden 6,5 g (30 mMol) Dithiocarbazinsäure-(3,4,4-trifluorbut-3- enyl)-ester und 4,9 g (50 mMol) Cyclohexanon unter Zusatz von 100 mg p-In 50 ml of ethanol 6.5 g (30 mmol) of dithiocarbazinic acid (3,4,4-trifluorobut-3-enyl) ester and 4.9 g (50 mmol) of cyclohexanone are added with the addition of 100 mg of p-
Toluolsulfonsäure über Nacht unter Rückfluß erhitzt. Anschließend verdünnt man mit Wasser und extrahiert das Produkt mit Methylenchlorid. Im Vakuum wird die organische Phase eingedampft und der Rückstand an Kieselgel mit Chloroform Chromatographien.Toluene sulfonic acid heated under reflux overnight. Then diluted with water and the product extracted with methylene chloride. The organic phase is evaporated in vacuo and the residue on silica gel using chloroform chromatography.
Ausbeute: 1,1 g (12,4 % der Theorie).Yield: 1.1 g (12.4% of theory).
Fp.: 56-58°CMp: 56-58 ° C
Beispiel 1-2Example 1-2
Figure imgf000022_0002
Figure imgf000022_0002
Zur Lösung von 1 1 g (56 mMol) Benzophenonhydrazon in 60 ml Dimethylform- amid gibt man 5,1 g (67 mMol) Schwefelkohlenstoff und anschließend bei5.1 g (67 mmol) of carbon disulfide are added to the solution of 1 g (56 mmol) of benzophenone hydrazone in 60 ml of dimethylformamide and then added
Raumtemperatur 3,1 g (56 mMol) Kaliumhydroxid-Pulver. Nach 1 Stunde Rührzeit tropft man 10,6 g (56 mMol) 3,4,4-Trifluor-but-3-enylbromid zu und läßt über Nacht rühren. Der Reaktionsansatz wird mit Wasser verdünnt und 2 mal mit Methylenchlorid extrahiert. Die organischen Extrakte werden im Vakuum einge- dampft und der Rückstand an Kieselgel mit Chloroform chromatographiert.Room temperature 3.1 g (56 mmol) potassium hydroxide powder. After stirring for 1 hour, 10.6 g (56 mmol) of 3,4,4-trifluoro-but-3-enylbromide are added dropwise and the mixture is stirred overnight. The reaction mixture is diluted with water and extracted twice with methylene chloride. The organic extracts are evaporated in vacuo and the residue is chromatographed on silica gel with chloroform.
Ausbeute: 6,5 g (30,5 % der Theorie). Fp.: 78-80°CYield: 6.5 g (30.5% of theory). Mp .: 78-80 ° C
In analoger Weise und gemäß den allgemeinen Angaben zur Herstellung erhält man die folgenden Verbindungen der Formel (I)The following compounds of the formula (I) are obtained in an analogous manner and in accordance with the general information on the preparation
CF, -C-CH — CH— S-C- -NH-N = CR2R3 (I)CF, -C-CH - CH— SC- -NH-N = CR 2 R 3 (I)
Tabelletable
Figure imgf000023_0001
Figure imgf000024_0001
log p Logarithmus des Verteilungskoeffizienten p der Substanz zwischen den Lösungsmitteln Octanol und Wasser, experimentell ermittelt aus reversed phase HPLC. Herstellung der Ausgangsstoffe
Figure imgf000023_0001
Figure imgf000024_0001
log p Logarithm of the partition coefficient p of the substance between the solvents octanol and water, experimentally determined from reversed phase HPLC. Production of raw materials
Beispiel II- 1Example II-1
Figure imgf000025_0001
Figure imgf000025_0001
Zu einer Suspension von 8,8 g (60 mMol) Kaliumdithiocarbazat in 100 ml Acetonitiil tropft man bei 40°C 10,4 g (55 mMol) 3,4,4-Trifluorbut-3-enylbromid und läßt anschließend noch 6 h bei 50°C rühren. Nach dem Abkühlen gießt man auf Wasser und extrahiert das Produkt mit Methylenchlorid. Das Lösungsmittel wird im Vakuum entfernt und der Rückstand an Kieselgel im System Chloro- form/Cyclohexan (2: 1) chromatographiert. Man erhält von dem gewünschten Pro- dukt 2,4 g als hellgelbes Öl.10.4 g (55 mmol) of 3,4,4-trifluorobut-3-enyl bromide are added dropwise to a suspension of 8.8 g (60 mmol) of potassium dithiocarbazate in 100 ml of acetoneitiil at 40 ° C., and the mixture is then left at 50 for a further 6 h Stir ° C. After cooling, the mixture is poured onto water and the product is extracted with methylene chloride. The solvent is removed in vacuo and the residue is chromatographed on silica gel in the chloroform / cyclohexane (2: 1) system. 2.4 g of the desired product are obtained as a light yellow oil.
Ausbeute: 2,4 g (20,2 % der Theorie). nß0 = 1.4820 Yield: 2.4 g (20.2% of theory). nß 0 = 1.4820
AnwendungsbeispielApplication example
Beispiel AExample A
Grenzkonzentrations-Test / NematodenLimit concentration test / nematodes
Testnematode: Meloidogyne incognita Lösungsmittel: 3 Gewichtsteile AcetonTest nematode: Meloidogyne incognita solvent: 3 parts by weight acetone
Emulgator: 1 Gewichtsteil Alkylarylpolyglykol etherEmulsifier: 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge¬ wichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angege¬ bene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die ge- wünschte Konzentration.To 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 concentration.
Die Wirkstoffzubereitung wird innig mit Boden vermischt, der mit den Test- nematoden stark verseucht ist. Dabei spielt die Konzentration des Wirkstoffs in der Zubereitung praktisch keine Rolle, entscheidend ist allein die Wirkstoffmenge pro Volumeneinheit Boden, welche in ppm (= mg/1) angegeben wird. Man füllt den behandelten Boden in Töpfe, sät Salat ein und hält die Töpfe bei einer Gewächs¬ haus-Temperatur von 25°C.The active ingredient preparation is mixed intimately with soil that is heavily contaminated with the test nematodes. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (= mg / 1). The treated soil is filled into pots, lettuce is sown and the pots are kept at a greenhouse temperature of 25 ° C.
Nach drei Wochen werden die Salatwurzeln auf Nematodenbefall (Wurzelgallen) untersucht und der Wirkungsgrad des Wirkstoffs in % bestimmt. Der Wirkungsgrad ist 100 %, wenn der Befall vollständig vermieden wird, er ist 0 %, wenn der Befall genau so hoch ist wie bei den Kontroll pflanzen in unbehandeltem, aber in gleicher Weise verseuchtem Boden.After three weeks, the lettuce roots are examined for nematode infestation (root galls) and the effectiveness of the active ingredient is determined in%. The efficiency is 100% if the infestation is completely avoided; it is 0% if the infestation is just as high as that of the control plants in untreated, but equally contaminated soil.
Bei diesem Test besaßen z.B. die Verbindungen gemäß den Herstellungsbeispielen II- 1, 1-10 und 1-1 bei einer beispielhaften Wirkstoffkonzentration von 20 ppm einen Wirkungsgrad von 100 %. Beispiel BIn this test, for example, the compounds according to Preparation Examples II-1, 1-10 and 1-1 had an efficiency of 100% at an exemplary active ingredient concentration of 20 ppm. Example B
Blowfly-Larven-Test / Entwicklungshemmende WirkungBlowfly larva test / development-inhibiting effect
Testtiere: Lucilia cuprina-LarvenTest animals: Lucilia cuprina larvae
Lösungsmittel: 35 Gewichtsteile Ethylenglykolmonomethyl ether 35 Gewichtsteile NonylphenolpolyglykoletherSolvent: 35 parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether
Zwecks Herstellung einer geeigneten Formulierung vermischt man 3 Gewichtsteile Wirkstoff mit 7 Teilen des oben angegebenen Lösungsmittel-Emulgator-Gemisches und verdünnt das so erhaltene Emulsionskonzentrat mit Wasser auf die jeweils gewünschte Konzentration.In order to produce a suitable formulation, 3 parts by weight of active ingredient are mixed with 7 parts of the solvent-emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the concentration desired in each case.
Etwa 20 Lucilia cuprina-Larven werden in ein Teströhrchen gebracht, welches ca. 1 cm3 Pferdefleisch und 0,5 ml der zu testenden Wirkstoffzubereitung enthält. Nach 24 Stunden wird die Wirksamkeit der Wirkstoffzubereitung ermittelt. Dabei bedeutet 100 %, daß alle Blowfly-Larven abgetötet wurden; 0 % bedeutet, daß keine Blowfly-Larven abgetötet wurden.About 20 Lucilia cuprina larvae are placed in a test tube containing approx. 1 cm 3 horse meat and 0.5 ml of the active ingredient preparation to be tested. After 24 hours, the effectiveness of the active ingredient preparation is determined. 100% means that all Blowfly larvae have been killed; 0% means that no blowfly larvae have been killed.
In diesem Test zeigte die Verbindung gemäß Herstellungsbeispiel II-l bei einer beispielhaften Wirkstoffkonzentration von 1 000 ppm eine Wirkung von 100 %. In this test, the compound according to Preparation Example II-1 showed an activity of 100% at an exemplary active ingredient concentration of 1,000 ppm.
Beispiel CExample C
Test mit Boophilus microplus resistent / SP resistenter Parkhurst-StammTest with Boophilus microplus resistant / SP resistant Parkhurst strain
Testtiere: Adulte gesogene WeibchenTest animals: Adult suckled females
Lösungsmittel: DimethylsulfoxidSolvent: dimethyl sulfoxide
20 mg Wirkstoff werden in 1 ml Dimethylsulfoxid gelöst, geringere Konzentra¬ tionen werden durch Verdünnen mit dem gleichen Lösungsmittel hergestellt.20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide; lower concentrations are produced by dilution with the same solvent.
Der Test wird in 5-fach Bestimmung durchgeführt. 1 μl der Lösungen wird in das Abdomen injiziert, die Tiere in Schalen überführt und in einem klimatisierten Raum aufbewahrt. Die Wirkung wird über die Hemmung der Eiablage bestimmt. Dabei bedeutet 100 %, daß keine Zecke gelegt hat.The test is carried out in 5-fold determination. 1 μl of the solutions is injected into the abdomen, the animals are transferred to dishes and stored in an air-conditioned room. The effect is determined by the inhibition of egg laying. 100% means that no tick has laid.
In diesem Test zeigten z.B. die Verbindungen gemäß den Herstellungsbeispielen 1- 1 , 1-2, 1-8, 1-9, 1- 10, 1- 1 1 , 1- 13 und 1- 14 bei einer beispielhaften Wirkstoffkonzentration von 20 μg/Tier jeweils eine Wirkung von 100 %. In this test, for example, the compounds according to the preparation examples 1-1, 1-2, 1-8, 1-9, 1-10, 1-11, 1-13 and 1-14 showed an exemplary active ingredient concentration of 20 μg / Animal has an effect of 100%.
Beispiel DExample D
SchabentestCockroach test
Testtiere: Periplaneta americanaTest animals: Periplaneta americana
Lösungsmittel: 35 Gewichtsteile Ethylenglykolmonomethylether 35 Gewichtsteile Nonylphenolpolyglykol etherSolvent: 35 parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether
Zwecks Herstellung einer geeigneten Formulierung vermischt man drei Gewichts¬ teile Wirkstoff mit sieben Teilen des oben angegebenen Lösungsmittel-Emulgator- Gemisches und verdünnt das so erhaltene Emulsionskonzentrat mit Wasser auf die jeweils gewünschte Konzentration.To produce a suitable formulation, three parts by weight of active ingredient are mixed with seven parts of the solvent / emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the desired concentration.
2 ml dieser Wirkstoffzubereitung werden auf Filterpapierscheiben (Θ 9,5 cm) pipettiert, die sich in Petrischalen entsprechender Größe befinden. Nach Trocknung der Filterscheiben werden 5 Testtiere bei B. germanica bzw. P. americana über¬ führt und abgedeckt.2 ml of this active ingredient preparation are pipetted onto filter paper discs (Θ 9.5 cm), which are located in Petri dishes of the appropriate size. After the filter disks have dried, 5 test animals are transferred and covered in B. germanica or P. americana.
Nach 3 Tagen wird die Wirksamkeit der Wirkstoffzubereitung bestimmt. Dabei bedeutet 100 %, daß alle Schaben abgetötet wurden; 0 % bedeutet, daß keine Schaben abgetötet wurden.After 3 days, the effectiveness of the active ingredient preparation is determined. 100% means that all cockroaches have been killed; 0% means that no cockroaches have been killed.
In diesem Test besaß z.B. die Verbindung gemäß Herstellungsb ei spiel 1-9 bei einer beispielhaften Wirkstoffkonzentration von 1 000 ppm eine Wirksamkeit von 100 %. In this test e.g. the compound according to the manufacturing example 1-9 with an exemplary active ingredient concentration of 1,000 ppm has an activity of 100%.

Claims

Patentansprüche:Claims:
1. Verbindungen der Formel (I),1. Compounds of formula (I)
S CF2 = C-CH2— CH — S— C — NH-N = CR J (I)S CF 2 = C-CH 2 - CH - S— C - NH-N = CR J (I)
R1 in welcherR 1 in which
R1 für Wasserstoff oder Halogen steht,R 1 represents hydrogen or halogen,
R2 und R3 unabhängig voneinander für Wasserstoff oder jeweils gegebenenfalls substituiertes Alkyl, Cycloalkyl, Aminocarbonyl, Alkoxycarbonyl, Aryl, Aralkyl, Hetaryl oder Carboxyl stehen oderR 2 and R 3 independently of one another represent hydrogen or in each case optionally substituted alkyl, cycloalkyl, aminocarbonyl, alkoxycarbonyl, aryl, aralkyl, hetaryl or carboxyl or
R2 und R3 gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, einen gegebenenfalls substituierten Ring bilden, der gegebenenfallsR 2 and R 3 together with the carbon atom to which they are attached form an optionally substituted ring which, if appropriate
Sauerstoff, Schwefel oder Stickstoff enthält, wobei der Stickstoff gegebenenfalls durch Alkyl, Aryl, Aralkyl oder Hetaryl substituiert ist.Contains oxygen, sulfur or nitrogen, the nitrogen being optionally substituted by alkyl, aryl, aralkyl or hetaryl.
2. Verbindungen der Formel (I) gemäß Anspruch 1, in welcher2. Compounds of formula (I) according to claim 1, in which
R1 für Wasserstoff, Fluor, Chlor oder Brom steht,R 1 represents hydrogen, fluorine, chlorine or bromine,
R2 und R3 unabhängig voneinander für Wasserstoff, C]-C12-Alkyl,R 2 and R 3 independently of one another are hydrogen, C ] -C 12 alkyl,
CrC]2-Halogenalkyl, CrC8-Alkoxy-CrC8-alkyl, CrC8-Alkylthio-CrC8- alkyl, für jeweils gegebenenfalls durch Halogen, Nitro, Amino, C,-C8- Alkylamino, Di-Cj-C^alkylamino, Cj-C8-Halogenalkyl, C,-C8-Alkoxy, C,-C r C ] 2 -haloalkyl, C r C 8 -alkoxy-C r C 8 -alkyl, C r C 8 -alkylthio-C r C 8 -alkyl, for each optionally by halogen, nitro, amino, C, -C 8 - alkylamino, di-C j -C ^ alkylamino, C j -C 8 haloalkyl, C, -C 8 alkoxy, C, -
C8-Halogenalkoxy, C,-C8-Alkylthio oder C,-C8-Halogenalkylthio substitu¬ iertes Phenyl, Benzyl, Phenoxy-Cj-C6-alkyl oder Phenylthio-Cj-C8-alkyl, für Carboxyl, Cj-C8-Alkoxycarbonyl, für gegebenenfalls einfach oder zweifach, gleich oder verschieden durch C,-C10-Alkyl oder Phenyl (welches gegebenenfalls durch Halogen, C,-C6- Alkyl, C1-C6-Halogenalkyl, CrC6-Alkoxy oder C,-C6-Halogenalkoxy sub¬ stituiert ist) substituiertes Aminocarbonyl, für einen gegebenenfalls durch Halogen oder C C^Alkyl substituierten 5- oder 6-gliedrigen Heterocyclus stehen, der ein bis drei Atome aus der Reihe Sauerstoff, Schwefel und Stickstoff enthält oderC 8 haloalkoxy, C, -C 8 alkylthio or C, -C 8 haloalkylthio substitu¬ iertes phenyl, benzyl, phenoxy-C j to C 6 alkyl or phenylthio-C j -C 8 -alkyl, carboxyl, C j -C 8 alkoxycarbonyl, for optionally single or double, identical or different by C, -C 10 alkyl or phenyl (which optionally by halogen, C, -C 6 - Alkyl, C 1 -C 6 haloalkyl, C r C 6 alkoxy or C, -C 6 haloalkoxy is substituted) substituted aminocarbonyl, are a 5- or 6-membered heterocycle optionally substituted by halogen or CC ^ alkyl , which contains one to three atoms from the series oxygen, sulfur and nitrogen or
R2 und R3 gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind einen 4- bis 10-gliedrigen Ring bilden, der gegebenenfalls Sauerstoff, Schwefel oder Stickstoff (welcher gegebenenfalls durch Cj-C8-Alkyl, Phenyl oder Benzyl substituiert ist) enthält oderR 2 and R 3 together with the carbon atom to which they are attached form a 4- to 10-membered ring which optionally contains oxygen, sulfur or nitrogen (which is optionally substituted by C j -C 8 alkyl, phenyl or benzyl) contains or
R und R gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, für eine der GruppenR and R together with the carbon atom to which they are attached for one of the groups
Figure imgf000031_0001
Figure imgf000031_0001
stehen.stand.
in welcherin which
R4 für Halogen, Nitro, CrC6-Alkyl, CrC6-Halogenalkyl, Cr C6-Alkoxy, CrC6-Halogenalkoxy, Cj-C8-Alkylthio oder C,- C6-Halogenalkylthio steht.R 4 is halogen, nitro, C r C 6 -alkyl, C r C 6 -haloalkyl, C r C 6 -alkoxy, C r C 6 -haloalkoxy, C j -C 8 -alkylthio or C, - C 6 -haloalkylthio stands.
Verbindungen der Formel (I) gemäß Anspruch 1 , in welcherCompounds of formula (I) according to claim 1, in which
für Wasserstoff, Fluor oder Chlor steht,represents hydrogen, fluorine or chlorine,
R2 und R3 unabhängig voneinander besonders bevorzugt für Wasserstoff, CrC8-Alkyl, CrC8-Halogenalkyl, für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Amino, C,-C6- Alkylamino, Di-CrC6-alkylamino, CrC6-Alkoxy oder C,-C6- Halogenalkoxy substituiertes Phenyl oder Benzyl, für jeweils gegebenenfalls durch Fluor, Chlor, Brom oder C,-C4- Alkyl substituiertes Pyrryl, Thienyl, Furyl, Pyrazolyl, Thiazolyl,R 2 and R 3 independently of one another are particularly preferably hydrogen, C r C 8 alkyl, C r C 8 haloalkyl, for phenyl or benzyl optionally substituted by fluorine, chlorine, bromine, amino, C, -C 6 -alkylamino, di-C r C 6 -alkylamino, C r C 6 -alkoxy or C, -C 6 - haloalkoxy, for each pyrryl, thienyl, furyl, pyrazolyl, thiazolyl optionally substituted by fluorine, chlorine, bromine or C 1 -C 4 -alkyl,
Pyridyl oder Pyrimidyl stehen oderPyridyl or pyrimidyl or
R2 und R3 gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, einen 5- bis 8-gliedrigen Ring bilden, der gegebenenfalls Sauerstoff oder Stickstoff (welcher gegebenenfalls durch C C6-Alkyl substituiert ist) enthält.R 2 and R 3 together with the carbon atom to which they are attached form a 5- to 8-membered ring which optionally contains oxygen or nitrogen (which is optionally substituted by CC 6 -alkyl).
4. Verbindungen der Formel (I) gemäß Anspruch 1, in welcher4. Compounds of formula (I) according to claim 1, in which
R1 für Fluor steht,R 1 represents fluorine,
R2 und R3 unabhängig voneinander für Wasserstoff, Cj-C8- Alkyl, C , -C4-Halogenalky 1, für gegebenenfalls durch Fluor, Chlor, Brom, Amino, Cj- j-Alkyl- amino, Di-C1-C4-alkylamino, Cj-C4-Alkoxy oder C,-C4-Halogenal- koxy substituiertes Phenyl, für jeweils gegebenenfalls durch Fluor, Chlor, Brom oder C,-C4- Alkyl substituiertes Thienyl, Furyl oder Pyridyl stehen oderR 2 and R 3 independently of one another for hydrogen, C j -C 8 alkyl, C, -C 4 haloalky 1, for optionally by fluorine, chlorine, bromine, amino, C j - j alkylamino, di-C 1 -C 4 alkylamino, C j -C 4 alkoxy or C, -C 4 haloalkoxy substituted phenyl, for each optionally substituted by fluorine, chlorine, bromine or C, -C 4 alkyl thienyl, furyl or pyridyl stand or
R2 und R3 gemeinsam mit dem Kohlenstoffatom, an das sie gebunden sind, einen 5- bis 8-gliedrigen Carbocyclus bilden.R 2 and R 3 together with the carbon atom to which they are attached form a 5- to 8-membered carbocycle.
5. Verfahren zur Herstellung von Verbindungen der Formel (I) gemäß5. A process for the preparation of compounds of formula (I) according to
Anspruch 1, dadurch gekennzeichnet, daß manClaim 1, characterized in that one
A) Verbindungen der Formel (II)A) compounds of the formula (II)
CF2 = C-CH2- -CH — S — C — NH NH2 (II)CF 2 = C-CH 2 - -CH - S - C - NH NH 2 (II)
in welcher R1 die oben angegebene Bedeutung hat,in which R 1 has the meaning given above,
mit Carbonylverbindungen der Formel (III)with carbonyl compounds of the formula (III)
R2 o=c ( n) R 2 o = c (n )
\ 3\ 3
R3 in welcherR 3 in which
R und R die oben angegebene Bedeutung haben,R and R have the meaning given above,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines sauren Katalysators umsetzt oderif appropriate in the presence of a diluent and if appropriate in the presence of an acidic catalyst or
Hydrazone der Formel (IV)Hydrazones of the formula (IV)
R2 H,N-N=C (Iγ)R 2 H, NN = C (I γ )
\ 3\ 3
RR
in welcherin which
R2 und R3 die oben angegebenen Bedeutungen haben,R 2 and R 3 have the meanings given above,
in Gegenwart einer Base und in Gegenwart eines Verdünnungs¬ mittels mit Schwefelkohlenstoff und anschließend mit einem Fluor- butenylhalogenid der Formel (V)in the presence of a base and in the presence of a diluent with carbon disulphide and then with a fluorobutenyl halide of the formula (V)
Figure imgf000033_0001
in welcher
Figure imgf000033_0001
in which
R1 die oben angegebene Bedeutung hat undR 1 has the meaning given above and
Hai für HalogenShark for halogen
umsetzt. 6. Verbindungen der Formel (II)implements. 6. Compounds of formula (II)
CF2 = C-CH2— CH — S-C — NH NH2 (H)CF 2 = C-CH 2 - CH - SC - NH NH 2 (H)
R1 R 1
in welcherin which
R1 die in Anspruch 1 angegebene Bedeutung hat.R 1 has the meaning given in claim 1.
7. Verfahren zur Herstellung von Verbindungen der Formel (II) gemäß Anspruch 6, dadurch gekennzeichnet, daß man Verbindungen der Formel7. A process for the preparation of compounds of formula (II) according to claim 6, characterized in that compounds of the formula
SS
II (VI)II (VI)
MS-C-NH-NH2 MS-C-NH-NH 2
in welcherin which
M für ein Alkalimetall steht,M represents an alkali metal,
mit Fluorbutenylhalogeniden der Formel (V)with fluorobutenyl halides of the formula (V)
Figure imgf000034_0001
Figure imgf000034_0001
in welcherin which
R1 die in Anspruch 1 angegebene Bedeutung hat undR 1 has the meaning given in claim 1 and
Hai für Halogen steht,Shark represents halogen,
in Gegenwart eines Verdünnungsmittels umsetzt.in the presence of a diluent.
8 Schädlingsbekämpfungsmittel, gekennzeichnet durch einen Gehalt an mindestens einer Verbindung der Formel (I) gemäß Anspruch 1. 9. Verwendung von Verbindungen der Formel (I) gemäß Anspruch zur Be¬ kämpfung von Schädlingen.8 pesticide, characterized by a content of at least one compound of the formula (I) according to claim 1. 9. Use of compounds of formula (I) according to claim for combating pests.
10. Verfahren zur Bekämpfung von Schädlingen, dadurch gekennzeichnet, daß man von Verbindungen der Formel (I) gemäß Anspruch 1 auf Schädlinge und/oder ihren Lebensraum einwirken läßt.10. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.
11. Verfahren zur Herstellung von Schädlingsbekämpfungsmitteln, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Mittlen vermischt.11. A process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active agents.
12. Verwendung von Verbindungen der Formel (I) gemäß Anspruch 1 zur Herstellung von Schädlingsbekämpfungsmitteln. 12. Use of compounds of formula (I) according to claim 1 for the preparation of pesticides.
PCT/EP1995/004145 1994-11-04 1995-10-23 Dithiocarbazonic acid butenyl esters and their use as pesticides WO1996014295A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU38064/95A AU3806495A (en) 1994-11-04 1995-10-23 Dithiocarbazonic acid butenyl esters and their use as pesticides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4439334A DE4439334A1 (en) 1994-11-04 1994-11-04 Butenyl dithiocarbazonate
DEP4439334.2 1994-11-04

Publications (1)

Publication Number Publication Date
WO1996014295A1 true WO1996014295A1 (en) 1996-05-17

Family

ID=6532426

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/004145 WO1996014295A1 (en) 1994-11-04 1995-10-23 Dithiocarbazonic acid butenyl esters and their use as pesticides

Country Status (3)

Country Link
AU (1) AU3806495A (en)
DE (1) DE4439334A1 (en)
WO (1) WO1996014295A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8895556B2 (en) 2007-12-26 2014-11-25 Critical Outcome Technologies Inc. Compounds and method for treatment of cancer
US8987272B2 (en) 2010-04-01 2015-03-24 Critical Outcome Technologies Inc. Compounds and method for treatment of HIV
US9284275B2 (en) 2007-01-11 2016-03-15 Critical Outcome Technologies Inc. Inhibitor compounds and cancer treatment methods

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9708903D0 (en) * 1997-05-02 1997-06-25 Agrevo Uk Ltd Fungicides
IT201800006066A1 (en) * 2018-06-06 2019-12-06 Process for the preparation of thiadiazole derivatives

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3914251A (en) * 1971-12-08 1975-10-21 Stauffer Chemical Co Certain trifluorobutenyl compounds and their utility as nematocides
EP0003913A1 (en) * 1978-03-01 1979-09-05 Fbc Limited Pesticidally active benzophenone hydrazone derivatives, methods for their production and pesticidal compositions and methods
WO1986007590A1 (en) * 1985-06-20 1986-12-31 Fmc Corporation Pesticidal polyhaloalkene derivatives
DE4207400A1 (en) * 1992-03-09 1993-09-16 Bayer Ag New hydrazone cpds. - useful as antimicrobial agents, insecticides, acaricides and fungicides, etc., for plant and wood protection, antibacterial therapy, etc.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3914251A (en) * 1971-12-08 1975-10-21 Stauffer Chemical Co Certain trifluorobutenyl compounds and their utility as nematocides
EP0003913A1 (en) * 1978-03-01 1979-09-05 Fbc Limited Pesticidally active benzophenone hydrazone derivatives, methods for their production and pesticidal compositions and methods
WO1986007590A1 (en) * 1985-06-20 1986-12-31 Fmc Corporation Pesticidal polyhaloalkene derivatives
DE4207400A1 (en) * 1992-03-09 1993-09-16 Bayer Ag New hydrazone cpds. - useful as antimicrobial agents, insecticides, acaricides and fungicides, etc., for plant and wood protection, antibacterial therapy, etc.

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 90, no. 7, 12 February 1979, Columbus, Ohio, US; abstract no. 54750, page 592; *
COLLECT. CZECH. CHEM. COMMUN., vol. 43, no. 10, pages 2643 - 8 *
PEDERSEN, LARS ERIK K. ET AL.: "Synthesis and insect growth regulating activity of", PESTIC. SCI., vol. 15, no. 5, pages 462 - 70 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9284275B2 (en) 2007-01-11 2016-03-15 Critical Outcome Technologies Inc. Inhibitor compounds and cancer treatment methods
US8895556B2 (en) 2007-12-26 2014-11-25 Critical Outcome Technologies Inc. Compounds and method for treatment of cancer
US8987272B2 (en) 2010-04-01 2015-03-24 Critical Outcome Technologies Inc. Compounds and method for treatment of HIV
US9422282B2 (en) 2010-04-01 2016-08-23 Critical Outcome Technologies Inc. Compounds and method for treatment of HIV
US9624220B2 (en) 2010-04-01 2017-04-18 Critical Outcome Technologies Inc. Compounds and method for treatment of HIV

Also Published As

Publication number Publication date
DE4439334A1 (en) 1996-05-09
AU3806495A (en) 1996-05-31

Similar Documents

Publication Publication Date Title
EP0861241B1 (en) Acylated 5-aminoisothiazoles with insecticidal properties, intermediate products and process for producing them
WO1997028133A1 (en) Acylated 4-amino- and 4-hydrazinopyrimidines and their use as pesticides
AU702938B2 (en) Fluorobutenyl(thio)ethers used as pesticides
EP0861239B1 (en) Biphenyl ether oxazolines and their use as pest-control agents
EP0848698A1 (en) Fluorobutene acid amides
EP0859767B1 (en) Fluoropropenyl oxadiazoles and the use thereof as pest control agents
EP0846099A1 (en) 4,4-difluoro-3-butenylester derivatives or 4,4-difluoro-3-halogen-3-butenylester derivatives and the use thereof as pesticides
WO1996014295A1 (en) Dithiocarbazonic acid butenyl esters and their use as pesticides
EP0970059B1 (en) Disubstituted biphenyloxazolines
DE19500789A1 (en) Acylated 5-aminopyrazoles
US5929118A (en) Fluorobutenic acid hydrazides
EP0797574B1 (en) 1,3,4-oxadiazine derivatives having a pesticide effect
WO1997002238A1 (en) Fluorobutenoic acid hydrazones
WO1997019051A1 (en) Fluorobutenoyloxyacetamides
EP0863867A2 (en) Aminocarboxylic acid fluorobutenyl esters
WO1997002237A1 (en) Fluorobutenic acid oxime esters
DE19638047A1 (en) Biphenyl ether oxazolines
EP0944608B1 (en) 4-cyclohexylphenyl-oxazolines and their use for controlling animal pests
DE19750403A1 (en) New pesticidal and fungicidal acylated 4-aminopyridine derivatives
DE19750402A1 (en) New pesticidal and fungicidal acylated 4-aminopyridine derivatives
DE19544798A1 (en) New 3-thiocarbamoyl-5-anilino-pyrazole derivatives
DE19750401A1 (en) New pesticidal and fungicidal bicyclic 4-aminopyridine derivatives
DE19757223A1 (en) New 2-phenyl-4-bi:phenyl-oxazoline derivatives
DE19718522A1 (en) New 2-phenyl-4-bi:phenyl-oxazoline derivatives

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR BY CA CN CZ FI HU JP KR KZ LK MX NO NZ PL RO RU SK UA US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA