WO1996014295A1 - Esters de butenyle d'acide dithiocarbazonique et leur utilisation comme pesticides - Google Patents

Esters de butenyle d'acide dithiocarbazonique et leur utilisation comme pesticides Download PDF

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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
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formula
spp
alkyl
compounds
optionally substituted
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PCT/EP1995/004145
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German (de)
English (en)
Inventor
Udo Kraatz
Jürgen Hartwig
Wolfram Andersch
Andreas Turberg
Norbert Mencke
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Bayer Aktiengesellschaft
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Priority to AU38064/95A priority Critical patent/AU3806495A/en
Publication of WO1996014295A1 publication Critical patent/WO1996014295A1/fr

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    • 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%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne de nouveaux esters de butényle d'acide dithiocarbazonique de la formule (I) dans laquelle R1 désigne hydrogène ou halogène, R2 et R3 désignent indépendamment l'un de l'autre hydrogène ou alkyle, cycloalkyle, aminocarbonyle, alcoxycarbonyle, aryle, aralkyle, hétaryle ou carboxyle éventuellement substitué, ou bien R2 et R3 désignent, conjointement avec l'atome de carbone auquel ils sont liés, un cycle éventuellement substitué qui contient éventuellement de l'oxygène, du soufre ou de l'azote, l'azote étant éventuellement substitué par alkyle, aryle, aralkyle ou hétaryle. L'invention concerne en outre des procédés et des intermédiaires permettant de les préparer, ainsi que leur utilisation pour lutter contre les parasites animaux.
PCT/EP1995/004145 1994-11-04 1995-10-23 Esters de butenyle d'acide dithiocarbazonique et leur utilisation comme pesticides WO1996014295A1 (fr)

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 (de) 1994-11-04 1994-11-04 Dithiocarbazonsäurebutenylester
DEP4439334.2 1994-11-04

Publications (1)

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

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PCT/EP1995/004145 WO1996014295A1 (fr) 1994-11-04 1995-10-23 Esters de butenyle d'acide dithiocarbazonique et leur utilisation comme pesticides

Country Status (3)

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

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 (it) * 2018-06-06 2019-12-06 Processo per la preparazione di derivati tiadiazolici

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 (fr) * 1978-03-01 1979-09-05 Fbc Limited Derivés d'hydrazone de benzophenone, procédés pour leur préparation et compositions et méthodes pesticides
WO1986007590A1 (fr) * 1985-06-20 1986-12-31 Fmc Corporation Derives de polyhaloalcene a effet pesticide
DE4207400A1 (de) * 1992-03-09 1993-09-16 Bayer Ag Hydrazone

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 (fr) * 1978-03-01 1979-09-05 Fbc Limited Derivés d'hydrazone de benzophenone, procédés pour leur préparation et compositions et méthodes pesticides
WO1986007590A1 (fr) * 1985-06-20 1986-12-31 Fmc Corporation Derives de polyhaloalcene a effet pesticide
DE4207400A1 (de) * 1992-03-09 1993-09-16 Bayer Ag Hydrazone

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
AU3806495A (en) 1996-05-31
DE4439334A1 (de) 1996-05-09

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