WO1997046101A1 - Pesticides based on cyclic polysiloxanes - Google Patents

Pesticides based on cyclic polysiloxanes Download PDF

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Publication number
WO1997046101A1
WO1997046101A1 PCT/EP1997/002622 EP9702622W WO9746101A1 WO 1997046101 A1 WO1997046101 A1 WO 1997046101A1 EP 9702622 W EP9702622 W EP 9702622W WO 9746101 A1 WO9746101 A1 WO 9746101A1
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Prior art keywords
spp
alkyl
methyl
stands
halogen
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PCT/EP1997/002622
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German (de)
French (fr)
Inventor
Jochen Kalbe
Andreas Turberg
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Bayer Aktiengesellschaft
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Priority to AU30914/97A priority Critical patent/AU3091497A/en
Publication of WO1997046101A1 publication Critical patent/WO1997046101A1/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N55/00Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur

Definitions

  • the present invention relates to pesticides based on cyclic polysiloxanes mixed with arthropodicidal active ingredients
  • Cyclic polysiloxanes with 4 and 5 siloxane units of insecticide were known to be effective. It was also known that polysiloxanes can be used to spray insects by spraying (US Pat. No. 4,654,328). However, these active compounds do not show any lasting action
  • the invention therefore relates to the following mixtures and agents
  • R for identical or different radicals of the group methyl, ethyl,
  • n stands for integers from 3 to 6
  • R for identical or different radicals of the group methyl, ethyl,
  • n stands for integers from 3 to 6
  • Preferred arthropodicidal agents for the agents according to the invention are preferred.
  • insects especially parasiticides for use on animals.
  • the insecticides include agonists or antagonists of the nicotinergic acetylcholine receptors of insects, ivermectins and avermectins as well as phosphorus-containing compounds such as phosphoric or phosphonic acid esters, natural and synthetic pyrethroids, carbamates, amidines, juvenile hormones and juvenoid synthetic
  • the agonists or antagonists of the nicotinergic acetylcholine receptors of insects include the compounds known from the following publications:
  • R represents hydrogen, optionally substituted radicals from the group acyl, al yl, aryl, aralkyl, heteroaryl or heteroarylalkyl;
  • E represents an electron withdrawing group
  • Atom can be linked to the radical Z;
  • Z for a monofunctional group from the series alkyl, -OR, -SR, RN stands for a bifunctional group that is associated with the
  • Radical A or the radical X is linked
  • R represents hydrogen and also optionally substituted radicals from the
  • alkyl which may be mentioned are C 1 -C 4 -alkyl, in particular C 4 -C 4 alkyl
  • Phenyl, naphthyl, in particular phenyl, may be mentioned as aryl
  • Phenylmethyl and phenethyl may be mentioned as aralkyl
  • heteroaryl alkyl examples include heteroarylmethyl, heteroarylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms
  • Optionally substituted alkylene with 1-4, in particular 1-2, carbon atoms may be mentioned, the substituents listed above being the substituents and the alkylene groups being heteroatoms from the series N, O, S can be interrupted
  • a and Z together with the atoms to which they are attached, form a saturated or unsaturated heterocyclic ring.
  • the heterocyclic ring may contain a further 1 or 2 identical or different hetero atoms and / or hetero groups.
  • Oxygen is preferably a hetero atom , Sulfur or nitrogen and, as hetero groups, N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms.
  • the heterocych ring contains 5 to 7, preferably 5 or 6 ring members
  • Examples of the heterocyclic ring are pyrrolidine, piperidine, piperazine, hexamethyleneimine, hexahydro-l, 3,5-triazione, morpholine, which may optionally be substituted by methyl
  • E stands for an electron-withdrawing radical, in particular NO 2 , CN, haloalkylcarbonyl such as 1,5-halogeno-carbonyl, in particular COCF
  • Z stands for optionally substituted radicals alkyl, -OR, -SR, -NRR, where
  • R and the substituents preferably have the meaning given above
  • the heterocychic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups.
  • the hetero atoms are preferably oxygen, sulfur or nitrogen and as
  • the alkyls are methyl, ethyl, n- and l-propyl and n-, I- and t-butyl
  • the heterocych ring contains 5 to 7, preferably 5 or 6 ring members
  • heterocyclic ring examples include pyrrolidine, piperidine,
  • n 1 or 2
  • the phosphoric or phosphoric acid esters include:
  • the carbamates include
  • R 1 and R 2 represent halogen, optionally halogen-substituted alkyl, optionally halogen-substituted phenyl,
  • R ' represents hydrogen or CN
  • R represents hydrogen or halogen
  • R 1 represents hydrogen or halogen
  • R 2 for halogen in particular fluorine, chlorine, bromine, t ⁇ halomethyl
  • R ⁇ represents hydrogen or CN
  • R 4 represents hydrogen or fluorine
  • R "1 represents hydrogen
  • R 1 represents chlorine
  • R 2 represents chlorine, trifluoromethyl, p-chlorophenyl
  • R * stands for CN
  • R 4 represents hydrogen or fluorine
  • R- stands for hydrogen
  • R 1 represents chlorine
  • R 2 represents chlorine or p-chlorophenyl
  • R 4 represents fluorine in the 4-position
  • R 5 represents hydrogen
  • amidines include:
  • Juvenile hormones or juvenile hormone-like substances include substituted diaryl ethers, benzoyl ureas and triazine derivatives. Juvenile hormones and juvenile hormone-like substances include in particular compounds of the following formulas:
  • the substituted diaryl ethers include, in particular, substituted alkoxydiphenyl ethers or diphenyl methanes of the general formula VI
  • R 1 represents hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, dioxyalkylene, dioxyhalogenalkylene, CN, NO 2 , alkenyl, alkynyl, alkoxyalkyl, alkoxyalkoxy, hydroxyalkoxy,
  • R 2 represents the radicals specified for R 1 ,
  • R 3 represents the radicals specified for R 1 ,
  • R 4 represents hydrogen, alkyl, haloalkyl or halogen
  • R -1 represents the radicals specified for R 4 .
  • Het stands for optionally substituted heteroaryl, which does not have the
  • Hetero atom is bound to the rest of the rest
  • X, Y independently of one another represent -O-, -S-
  • Z represents -O-, -S-, -CH 2 -, -CHCH 3 -, -C (CH 3 ) 2 -,
  • n and n independently of one another represent 0, 1, 2, 3 but their sum is equal to or greater than 2.
  • R 1 is hydrogen, methyl, trifluoromethyl, methoxy, trifluoromethoxy, chlorine, fluorine R ⁇ stands for hydrogen
  • R 1 represents hydrogen, fluorine, chlorine, methyl
  • R 4 represents hydrogen or methyl
  • R 5 represents methyl, ethyl, trifluoromethyl or hydrogen
  • Het is pyridyl or pyridazinyl which are optionally substituted by
  • Z represents O, CH 2 or -C (CH 3 ) 2 -
  • n 1,
  • n 1
  • Benzoylureas include compounds of the formula VII
  • R represents halogen
  • R 1 represents hydrogen or halogen
  • R 3 represents hydrogen, halogen or C 1 -C 4 -alkyl
  • the triazines include compounds of the formula (VIII)
  • R represents cyclopropyl or isopropyl
  • R- hydrogen, halogen, C ] -C 12 alkylcarbonyl ; Cyclopropylcarbonyl, C, -C p - alkyl carbamoyl, C, -C p alkylthiocarbamoyl or C 2 -C 6 alkenyl carbamoyl means, and
  • R 3 for hydrogen, C r C 12 alkyl, cyclopropyl, C 2 -C 6 alkenyl, C, -C ] 2 alkylcarbonyl, cyclopropylcarbonyl, C j -Cp alkylcarbamoyl, C r C p alkylthio carbamoyl or C 2 -C -alkenylcarbamoyl and their acid addition salts, which are non-toxic to warm-blooded animals.
  • arthropodicidal active ingredients with the comnon names Propoxur, Cyfluth ⁇ n, Flumeth ⁇ n, Py ⁇ proxyfen, Methoprene, Diazinon, Amitraz, Fenthion, Imidaclop ⁇ d, Ti 435, AKD 1022, Ti 304, T ⁇ flumuron, Ivermectin, Avermectin
  • the active substances are present in the compositions in m concentrations of 0.1 to 20% by weight, preferably between 1 to 10% by weight.
  • the agents according to the invention have considerable practical advantages. Their action on pests is immediate, that is, the consumer sees them
  • control measure is carried out directly
  • compositions according to the invention are suitable for controlling animal pests, preferably arthropods, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are resistant to normally sensitive and resistant species and to all or some of them Developmental stages effective
  • animal pests preferably arthropods, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are resistant to normally sensitive and resistant species and to all or some of them Developmental stages effective
  • the pests mentioned above include arthropods, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are resistant to normally sensitive and resistant species and to all or some of them Developmental stages effective
  • the pests mentioned above include
  • Isopoda for example Oniscus asellus, Armadillidium vulgare,
  • Diplopoda e.g. Blaniulus guttulatus From the order of the Chilopoda eg Geophilus carpophagus, Scutigera spec
  • Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp,
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lamgerum, Hyalopterus arundinis,
  • Leptinotarsa decemlineata Phaedon cochleariae, Diabrotica spp, Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp, Sitophilus spp, Otiorrhynchus Sulcatushidpphidpphidispphppisidpphidisidpphidispphidispphidispphcpphc, spp spp, Lyctus spp., Meligethes aeneus, Ptinus spp,
  • Niptus hololeucus Gibbium psylloides, Tribolium spp, Tenebno mohtor, Agriotes spp, Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica
  • Hymenoptera e.g. Diprion spp, Hoplocampa spp, Lasius spp, Monomorium pharaonis, Vespa spp
  • Dacus oleae Tipula paludosa.
  • Siphonaptera e.g. Xenopsylla cheopis
  • Ceratophyllus spp From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans From the order of the Aca ⁇ na z B Acarus siro, Argas spp, Ornithodoros spp, Dermanyssus gallinae, Eriophyes ribis, Phyllivoraopilil, Phyllivoraopil
  • the agents are suitable for controlling animal pests, such as arthropods, preferably insects, arachnids, which occur in livestock farming and animal breeding in farm animals, breeding, zoo, laboratory, experimental and hobby animals. They are against all or individual stages of development of the pests and against resistant and normally sensitive types of
  • the pests include:
  • Eomenacanthus spp. Menacanthus spp., Trichodectes spp., Felicola spp.,
  • Hydrotaea spp. Muscina spp., Haematobosca spp., Haematobia spp., Stomoxys spp., Fannia spp., Glossina spp., Lucilia spp., Calliphora spp., Auchmeromyia spp.,
  • Oestrus spp. Rhinoestrus spp., Melophagus spp., Hippobosca spp.
  • Siphonaptera e.g. Ctenocephalides spp., Echidnophaga spp., Ceratophyllus spp.
  • Domestic and farm animals include mammals such as cattle, sheep, goats, "horses, pigs, dogs, cats, camels, water buffalo, donkeys, rabbits, Fallow deer, reindeer, fur animals such as mink, chinchilla, raccoon, birds such as chickens, turkeys, pheasants, geese, ducks.
  • Laboratory and experimental animals include e.g. Mice, rats, guinea pigs, golden hamsters, dogs and cats.
  • Hobby animals include e.g. Dogs and cats.
  • the agents according to the invention can also be used in closed rooms such as apartments, halls or the like. deploy. They are particularly suitable for controlling animal pests and nuisances that occur in the household.
  • agents according to the invention are used directly or in the form of suitable preparations dermally or by treating their environment.
  • the dermal application happens e.g. in the form of bathing, diving (dipping), spraying (spraying), pouring on (pour-on or spot-on), washing, shampooing, watering, powdering.
  • Suitable preparations are:
  • Emulsions and suspensions for dermal use and semi-solid preparations are Emulsions and suspensions for dermal use and semi-solid preparations
  • Solid preparations such as powder or dusts, also through microencapsulation of the liquid ingredients. In addition to use on animals, these preparations can also be used in the home, in hygiene or in agriculture
  • Solutions for use on the skin are dripped on, spread on, rubbed in, sprayed on, sprayed on or applied by dipping (dipping), bathing or washing
  • the solutions are prepared by dissolving the active ingredients in the cyclic silicones and / or suitable solvents and possibly adding additives such as solubilizers, acids, bases, buffer salts, antioxidants and preservatives
  • Alcohols such as ethanol, butanol, benzyl alcohol, glycols, hydrocarbons, propylene glycol, polyethylene glycols, N-methyl-pyrrohdon, and mixtures thereof
  • the active ingredients can optionally also be dissolved in physiologically acceptable vegetable or synthetic oils
  • Solvents which may be mentioned are solvents which require the active ingredient to be dissolved in the main solvent or prevent it from precipitating out. Examples are polyvinylpyrrohdon, polyoxyethylated castor oil, polyoxyethylated sorbitan esters
  • Preservatives are benzyl alcohol, chlorobutanol, p-hydroxybenzoic acid ester, n-butanol
  • Thickeners are inorganic thickeners such as bentonites, colloidal silica, aluminum monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers.
  • Gels that are applied or spread on the skin are produced by adding enough thickening agent to solutions that have been prepared as described above to produce a clear mass with an ointment-like consistency.
  • the thickeners specified above are used as thickeners
  • pour-on formulations are poured or sprayed onto limited areas of the skin, the active ingredients being distributed over the surface of the body
  • Pour-on formulations are prepared by dissolving, suspending or emulsifying the active ingredients in suitable solvents or solvent mixtures that are compatible with the skin.
  • Solvents which may be mentioned are water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol and glycol monoethyl ether , Methyl ethyl ketone, aromatic and / or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, N-methylpyrrolidone, 2-dimethyl-4-oxy-methylene-1, 3-d ⁇ oxolan
  • Dyes are all dyes approved for use on animals, which can be dissolved or suspended
  • Excipients are also spreading oils such as isopropyl mypstat, dipropylene glycol pelargonate, silicone oils, fatty acid esters, triglycerides, fatty alcohols
  • Antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylated hydroxytoluene, butylated hydroxyanisole, tocopherol
  • Light stabilizers are, for example, substances from the class of the benzophenones or
  • Novantisol acidic Adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates, natural polymers such as alginates, gelatin.
  • Emulsions are either water in oil or oil in water.
  • Emulsifiers and optionally other auxiliaries such as dyes, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-increasing substances, homogenized with the solvent of the other phase
  • hydrophobic phase paraffin oils, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as
  • Fatty acid esters such as ethyl stearate, di-n-butyryl adipate, lauric acid hexyl ester, dipropylene glycol pelargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C 16 -C 18 , isopropyl myristate, isopropyl palmitate, caprylic / capric acid esters of saturated fatty alcohol the chain length Cp-C ) 8 , isopropyl stearate, oleic acid oleyl ester, oleic acid decyl ester, ethyl oleate, lactic acid ethyl ester, waxy fatty acid esters such as dibutyl phthalate, diisopropyl adipate, the latter related ester mixtures including fatty alcohols such as isotridecyl alcohol alcohol, 2-octyl alcohol alcohol, 2-octyl alcohol alcohol
  • Fatty acids such as Oleic acid and its mixtures.
  • hydrophilic phase water, alcohols, e.g. Propylene glycol, glycerin, sorbitol and their mixtures.
  • nonionic surfactants for example polyoxyethylated ⁇ castor oil, polyoxyethylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, Pol yoxy ethyl stearate, alkylphenol; ampholytic surfactants such as di-Na-N-lauryl- ⁇ -iminodipropionate or lecithin,
  • anionic surfactants such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono / dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt, cationic surfactants such as cetyl methyl methyl ammonium chloride
  • auxiliaries which may be mentioned are substances which increase viscosity and stabilize the emulsion, such as carboxymethyl cellulose, methyl cellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrodone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, silica glycols, waxes, polyethylene glycols, waxes, polyethylene glycols, waxes, polyethylene glycols, waxes, polyethylene glycols, waxes, and ethylene glycols or mixtures of the listed substances
  • Suspensions are produced by suspending the active ingredients in a carrier liquid, optionally with the addition of further auxiliaries such as wetting agents, dyes, absorption-promoting substances, preservatives, antioxidants, light stabilizers
  • surfactants specified above may be mentioned as wetting agents (dispersants)
  • the active ingredients are mixed with suitable carriers, if appropriate with the addition of auxiliaries, and brought into the desired shape
  • suitable carriers if appropriate with the addition of auxiliaries
  • All physiologically compatible solid inert substances may be mentioned as carrier substances. All such serve inorganic and organic substances.
  • Inorganic substances are, for example, table salt, carbonates such as calcium carbonate, hydrogen carbonates, aluminum oxides, silicas, clays, precipitated or colloidal silicon dioxide, phosphates
  • Excipients are preservatives, antioxidants, dyes, which have already been listed above
  • auxiliaries are lubricants and lubricants such as magnesium stearate, stearic acid, talc, bentonite
  • Ready-to-use preparations contain the active ingredients in concentrations of
  • Preparations which are diluted before use contain the active compounds in concentrations of 0.5 to 90 percent by weight, preferably from 1 to 50 percent by weight
  • Agents according to the invention in which the arthropodicidal active ingredient is present in solution in the cyclic polysiloxane are particularly preferred

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Abstract

The invention concerns pesticides based on cyclic polysiloxanes and arthropodicidal active substances.

Description

Schädlingsbekämpfungsmittel auf Basis cyclischer PoiysiloxanePesticide based on cyclic poysiloxanes
Die vorliegende Erfindung betrifft Schädlingsbekämpfungsmittel auf der Basis von cyclischen Polysiloxanen in Mischung mit arthropodiziden WirkstoffenThe present invention relates to pesticides based on cyclic polysiloxanes mixed with arthropodicidal active ingredients
Es war bekannt, daß cyclische Poiysiloxane mit 4 und 5 Siloxaneinheiten Insektizid wirksam sind Es war auch bekannt, daß man mit Polysiloxanen Insekten durch Besprühen abtoten kann (US-P 4 654 328) Diese Wirkstoffe zeigen jedoch keine DauerwirkungCyclic polysiloxanes with 4 and 5 siloxane units of insecticide were known to be effective. It was also known that polysiloxanes can be used to spray insects by spraying (US Pat. No. 4,654,328). However, these active compounds do not show any lasting action
Gegenstand der Erfindung sind daher folgende Mischungen und MittelThe invention therefore relates to the following mixtures and agents
1 Schädlingsbekämpfungsmittel auf Basis cyclischer Poiysiloxane der Formel1 pesticide based on cyclic poysiloxanes of the formula
(I)(I)
-(S,R — O)-- (S, R - O) -
in welcherin which
R für gleiche oder verschiedene Reste der Gruppe Methyl, Ethyl,R for identical or different radicals of the group methyl, ethyl,
Propyl steht,Propyl stands,
n für ganze Zahlen von 3 bis 6 steht,n stands for integers from 3 to 6,
in Mischung mit arthropodiziden Wirkstoffenin a mixture with arthropodicidal agents
2 Mittel gemäß 1 (oben), dadurch gekennzeichnet, daß es überwiegend als Bestandteil der Formel (I) Verbindungen enthalt, in denen der Index n = 5
Figure imgf000003_0001
2 agents according to 1 (above), characterized in that it contains predominantly as part of the formula (I) compounds in which the index n = 5
Figure imgf000003_0001
3 Mittel gemäß 1 (oben), dadurch gekennzeichnet, daß in den cyclischen Polysiloxanen der Formel (I)3 agents according to 1 (above), characterized in that in the cyclic polysiloxanes of the formula (I)
(-(SiR -o,.-, - ? .(- (SiR -o, .-, -? ,
in welcherin which
R für gleiche oder verschiedene Reste der Gruppe Methyl, Ethyl,R for identical or different radicals of the group methyl, ethyl,
Propyl stehtPropyl stands
n für ganze Zahlen von 3 bis 6 steht,n stands for integers from 3 to 6,
die Bestandteile der Formel (I) mit den Indices 4 und 5 im Gewichtsver¬ hältnisthe constituents of the formula (I) with the indices 4 and 5 in the weight ratio
n = 4 < 85 % (Gewicht) n = 5 > 15 % (Gewicht)n = 4 <85% (weight) n = 5> 15% (weight)
vorliegen.available.
4. Mischung gemäß 3 (oben), dadurch gekennzeichnet, daß die Bestandteile der Formel (I) mit den Indices 4 und 5 im Gewichtsverhältnis4. Mixture according to 3 (above), characterized in that the constituents of the formula (I) with the indices 4 and 5 in the weight ratio
n = 4 75 Gew.-% n = 5 25 Gew.-%n = 4 75% by weight n = 5 25% by weight
vorliegen.available.
Als arthropodizide Wirkstoffe für die erfmdungsgemäßen Mittel seien bevorzugtPreferred arthropodicidal agents for the agents according to the invention are preferred
Insektizide insbesondere Parasitizide zur Verwendung an Tieren genannt. Zu den Insektiziden gehören Agonisten oder Antagonisten der nicotinergen Acetylcholinre¬ zeptoren von Insekten, Ivermectine und Avermectine sowie phosphorhaltige Ver¬ bindungen wie Phosphor- oder Phosphonsäureester, natürliche und synthetische Pyrethroide, Carbamate, Amidine, Juvenilhormone und juvenoide synthetischeInsecticides, especially parasiticides for use on animals. The insecticides include agonists or antagonists of the nicotinergic acetylcholine receptors of insects, ivermectins and avermectins as well as phosphorus-containing compounds such as phosphoric or phosphonic acid esters, natural and synthetic pyrethroids, carbamates, amidines, juvenile hormones and juvenoid synthetic
Wirkstoffe.Active ingredients.
Zu den Agonisten oder Antagonisten der nicotinergen Acetylcholinrezeptoren von Insekten zählen die aus den folgenden Publikationen bekannten Verbindungen:The agonists or antagonists of the nicotinergic acetylcholine receptors of insects include the compounds known from the following publications:
Europäische Offenlegungsschriften Nr. 464 830, 428 941 , 425 978, 386 565, 383 091 , 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600,European Patent Application Nos. 464 830, 428 941, 425 978, 386 565, 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600,
192 060, 163 855, 154 178, 136 636, 303 570, 302 833, 306 696, 189 972, 455 000, 135 956, 471 372, 302 389; Deutsche Offenlegungsschriften Nr. 3 639 877, 3 712 307; Japanische Offenlegungsschriften Nr. 03 220 176,192 060, 163 855, 154 178, 136 636, 303 570, 302 833, 306 696, 189 972, 455,000, 135,956, 471,372, 302,389; German Offenlegungsschriften No. 3 639 877, 3 712 307; Japanese Patent Application Laid-Open No. 03 220 176,
02 207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371 , 03 279 359,02 207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359,
03 255 072; US-Patentschriften Nr. 5 034 524, 4 948 798, 4 918 086, 5 039 686, 5 034 404; PCT-Anmeldungen Nr. WO 91 /17 659, 91 /4965 ; Französische03 255 072; U.S. Patent Nos. 5,034,524, 4,948,798, 4,918,086, 5,039,686, 5,034,404; PCT applications No. WO 91/17659, 91/4965; French
Anmeldung Nr. 2 61 1 1 14; Brasilianische Anmeldung Nr. 88 03 621.Application No. 2 61 1 1 14; Brazilian application No. 88 03 621.
Auf die in diesen Publikationen beschriebenen Methoden, Verfahren, Formeln und Definitionen sowie auf die darin beschriebenen einzelnen Präparationen und Ver¬ bindungen wird hiermit ausdrücklich Bezug genommen.Reference is hereby expressly made to the methods, processes, formulas and definitions described in these publications and to the individual preparations and compounds described therein.
Diese Verbindungen lassen sich bevorzugt durch die allgemeine Formel (II) wiedergebenThese compounds can preferably be represented by the general formula (II)
Figure imgf000005_0001
Figure imgf000005_0001
in welcherin which
R für Wasserstoff, gegebenenfalls substituierte Reste der Gruppe Acyl, Al yl, Aryl, Aralkyl, Heteroaryl oder Heteroarylalkyl steht;R represents hydrogen, optionally substituted radicals from the group acyl, al yl, aryl, aralkyl, heteroaryl or heteroarylalkyl;
A für eine monofunktionelle Gruppe aus der Reihe Wasserstoff, Acyl, Alkyl,A for a monofunctional group from the series hydrogen, acyl, alkyl,
Aryl steht oder für eine bifunktionelle Gruppe steht, die mit dem Rest Z verknüpft ist,Aryl or a bifunctional group which is linked to the radical Z,
E für einen elektronenziehenden Rest steht;E represents an electron withdrawing group;
X für die Reste -CH= oder =N- steht, wobei der Rest -CH= anstelle eines H-X represents the radicals -CH = or = N-, the radical -CH = instead of an H-
Atoms mit dem Rest Z verknüpft sein kann;Atom can be linked to the radical Z;
Z für eine monofunktionelle Gruppe aus der Reihe Alkyl, -O-R, -S-R, R N steht oder für eine bifunktionelle Gruppe steht, die mit demZ for a monofunctional group from the series alkyl, -OR, -SR, RN stands for a bifunctional group that is associated with the
RR
Rest A oder dem Rest X verknüpft istRadical A or the radical X is linked
Besonders bevorzugt sind Verbindungen der Formel (II), in welcher die Reste fol¬ gende Bedeutung habenCompounds of the formula (II) in which the radicals have the following meaning are particularly preferred
R steht für Wasserstoff sowie für gegebenenfalls substituierte Reste aus derR represents hydrogen and also optionally substituted radicals from the
Reihe Acyl, Alkyl, Aryl, Aralkyl, Heteroaryl, Heteroaryl alkylSeries acyl, alkyl, aryl, aralkyl, heteroaryl, heteroaryl alkyl
Als Acylreste seien genannt Formyl, Alkylcarbonyl, Arylcarbonyl, Alkyl- sulfonyl, Arylsulfonyl, (Alkyl-)-(Aryl-)-phosphoryl, die ihrerseits substitu¬ iert sein könnenFormyl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, (alkyl-) - (aryl-) - phosphoryl, which in turn can be substituted, may be mentioned as acyl radicals
Als Alkyl seien genannt C,_]0-Alkyl, insbesondere C,.4-Alkyl, im einzelnenExamples of alkyl which may be mentioned are C 1 -C 4 -alkyl, in particular C 4 -C 4 alkyl
Methyl, Ethyl, l-Propyl, sec - oder t -Butyl, die ihrerseits substituiert sein können.Methyl, ethyl, l-propyl, sec - or t-butyl, which in turn can be substituted.
Als Aryl seien genannt Phenyl, Naphthyl, insbesondere PhenylPhenyl, naphthyl, in particular phenyl, may be mentioned as aryl
Als Aralkyl seien genannt Phenylmethyl, PhenethylPhenylmethyl and phenethyl may be mentioned as aralkyl
Als Heteroaryl seien genannt Heteroaryl mit bis zu 10 Ringatomen und N,Heteroaryl with up to 10 ring atoms and N,
O, S insbesondere N als Heteroatomen Im einzelnen seien genannt Thio- phenyl, Furyl, Thiazolyl, Imidazolyl, Pyridyl, BenzthiazolylO, S, in particular N, as heteroatoms. Thiophenyl, furyl, thiazolyl, imidazolyl, pyridyl, benzthiazolyl may be mentioned individually
Als Heteroaryl alkyl seien genannt Heteroarylmethyl, Heteroarylethyl mit bis zu 6 Ringatomen und N, O, S, insbesondere N als HeteroatomenExamples of heteroaryl alkyl are heteroarylmethyl, heteroarylethyl having up to 6 ring atoms and N, O, S, in particular N, as heteroatoms
Als Substituenten seien beispielhaft und vorzugsweise aufgeführtExamples of substituents which may be mentioned are preferred
Alkyl mit vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen, wie Methyl, Ethyl, n- und i-Propyl und n-, i- und t-Butyl, Alkoxy mit vor¬ zugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen, wie Methoxy, Ethoxy, n- und i-Propyloxy und n-, I- und t-Butyloxy, Alkylthio mit vor- zugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen, wie Methyl- thio, Ethylthio, n- und i-Propylthio und n-, i- und t-Butylthio, Halogenalkyl mit vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen und vorzugsweise 1 bis 5, insbesondere I bis 3 Halogenatomen, wobei die Halogenatome gleich oder verschieden sind und als Halogenatome, vor- zugsweise Fluor, Chlor oder Brom, insbesondere Fluor stehen, wie Tri- fluormethyl; Hydroxy; Halogen, vorzugsweise Fluor, Chlor, Brom und Jod, insbesondere Fluor, Chlor und Brom; Cyano, Nitro, Amino, Monoalkyl- und Dialkylamino mit vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlen¬ stoffatomen je Alkylgruppe, wie Methylamino, Methyl-ethyl-amino, n- und i-Propylamino und Methyl-n-butylamino, Carboxyl, Carbalkoxy mit vor¬ zugsweise 2 bis 4, insbesondere 2 oder 3 Kohlenstoffatomen, wie Carbo- methoxy und Carboethoxy, Sulfo (-SO3H); Alkylsulfonyl mit vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen, wie Methylsulfonyl und Ethylsulfonyl, Arylsulfonyl mit vorzugsweise 6 oder 10 Arylkohlenstoff- atomen, wie Phenylsulfonyl sowie Heteroarylamino und Heteroarylalkyl- amino wie Chlorpyridylamino und ChlorpyridylmethylaminoAlkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl, alkoxy with preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n- and i-propyloxy and n-, I- and t-butyloxy, alkylthio with preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl thio, ethylthio, n- and i-propylthio and n-, i- and t-butylthio, haloalkyl preferably having 1 to 4, in particular 1 or 2, carbon atoms and preferably 1 to 5, in particular I to 3, halogen atoms, the halogen atoms being identical or are different and stand as halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl; Hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; Cyano, nitro, amino, monoalkyl and dialkylamino with preferably 1 to 4, in particular 1 or 2 carbon atoms per alkyl group, such as methylamino, methylethylamino, n- and i-propylamino and methyl-n-butylamino, carboxyl, Carbalkoxy with preferably 2 to 4, in particular 2 or 3 carbon atoms, such as carbomethoxy and carboethoxy, sulfo (-SO 3 H); Alkylsulfonyl with preferably 1 to 4, especially 1 or 2 carbon atoms, such as methylsulfonyl and ethylsulfonyl, arylsulfonyl with preferably 6 or 10 aryl carbon atoms, such as phenylsulfonyl, and also heteroarylamino and heteroarylalkylamino such as chloropyridylamino and chloropyridylmethylamino
A steht besonders bevorzugt für Wasserstoff sowie für gegebenenfalls sub¬ stituierte Reste aus der Reihe Acyl, Alkyl, Aryl, die bevorzugt die bei R angegebenen Bedeutungen haben. A steht ferner für eine bifunktionelle Gruppe Genannt sei gegebenenfalls substituiertes Alkylen mit 1-4, insbe¬ sondere 1-2 C-Atomen, wobei als Substituenten die weiter oben aufgezahl¬ ten Substituenten genannt seien und wobei die Alkylengruppen durch Heteroatome aus der Reihe N, O, S unterbrochen sein könnenA particularly preferably represents hydrogen and optionally substituted radicals from the series acyl, alkyl, aryl, which preferably have the meanings given for R. A furthermore stands for a bifunctional group. Optionally substituted alkylene with 1-4, in particular 1-2, carbon atoms may be mentioned, the substituents listed above being the substituents and the alkylene groups being heteroatoms from the series N, O, S can be interrupted
A und Z können gemeinsam mit den Atomen, an welche sie gebunden sind, einen gesattigten oder ungesättigten heterocyclischen Ring bilden Der hetero- cyclische Ring kann weitere 1 oder 2 gleiche oder verschiedene Hetero¬ atome und/oder Heterogruppen enthalten Als Heteroatome stehen vorzugs¬ weise Sauerstoff, Schwefel oder Stickstoff und als Heterogruppen N- Alkyl, wobei Alkyl der N-Alkyl-Gruppe vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatome enthalt Als Alkyl seien Methyl, Ethyl, n- und I-A and Z, together with the atoms to which they are attached, form a saturated or unsaturated heterocyclic ring. The heterocyclic ring may contain a further 1 or 2 identical or different hetero atoms and / or hetero groups. Oxygen is preferably a hetero atom , Sulfur or nitrogen and, as hetero groups, N-alkyl, alkyl of the N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. Alkyl, methyl, ethyl, n- and I-
Propyl und n-, i- und t-Butyl genannt Der heterocychsche Ring enthalt 5 bis 7, vorzugsweise 5 oder 6 Ringglieder Als Beispiele für den heterocychschen Ring seien Pyrrolidin, Piperidin, Piperazin, Hexamethylenimin, Hexahydro-l,3,5-triazιn, Morpholin genannt, die gegebenenfalls bevorzugt durch Methyl substituiert sein könnenPropyl and n-, i- and t-butyl called The heterocych ring contains 5 to 7, preferably 5 or 6 ring members Examples of the heterocyclic ring are pyrrolidine, piperidine, piperazine, hexamethyleneimine, hexahydro-l, 3,5-triazione, morpholine, which may optionally be substituted by methyl
E steht für einen elektronentziehenden Rest, wobei insbesondere NO2, CN, Halogenalkylcarbonyl wie l ,5-Halogen-C -carbonyl, insbesondere COCF genannt seienE stands for an electron-withdrawing radical, in particular NO 2 , CN, haloalkylcarbonyl such as 1,5-halogeno-carbonyl, in particular COCF
X steht für -CH= oder -N=X stands for -CH = or -N =
Z steht für gegebenenfalls substituierte Reste Alkyl, -OR, -SR, -NRR, wobeiZ stands for optionally substituted radicals alkyl, -OR, -SR, -NRR, where
R und die Substituenten bevorzugt die oben angegebene Bedeutung habenR and the substituents preferably have the meaning given above
Z kann außer dem obengenannten Ring gemeinsam mit dem Atom, anIn addition to the ring mentioned above, Z can be attached together with the atom
__ l _ welches es gebunden ist und dem Rest__ l _ which it is bound and the rest
an der Stelle von X einen gesattigten oder ungesättigten heterocyclischen Ring bilden Der heterocychsche Ring kann weitere 1 oder 2 gleiche oder verschiedene Heteroatome und/oder Heterogruppen enthalten. Als Hetero- atome stehen vorzugsweise Sauerstoff, Schwefel oder Stickstoff und alsform a saturated or unsaturated heterocyclic ring in the place of X. The heterocychic ring can contain a further 1 or 2 identical or different heteroatoms and / or hetero groups. The hetero atoms are preferably oxygen, sulfur or nitrogen and as
Heterogruppen N-Alkyl, wobei die Alkyl oder N-Alkyl-Gruppe vorzugs¬ weise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatome enthalt Als Alkyl seien Methyl, Ethyl, n- und l-Propyl und n-, I- und t-Butyl genannt Der heterocychsche Ring enthalt 5 bis 7, vorzugsweise 5 oder 6 RinggliederHetero groups N-alkyl, the alkyl or N-alkyl group preferably containing 1 to 4, in particular 1 or 2, carbon atoms. The alkyls are methyl, ethyl, n- and l-propyl and n-, I- and t-butyl The heterocych ring contains 5 to 7, preferably 5 or 6 ring members
Als Beispiele für den heterocyclischen Ring seien Pyrrolidin, Piperidin,Examples of the heterocyclic ring are pyrrolidine, piperidine,
Piperazin, Hexamethylenimin, Morpholin und N-Methylpiperazin genanntPiperazine, hexamethyleneimine, morpholine and N-methylpiperazine called
Als ganz besonders bevorzugt erfindungsgemaß verwendbare Verbindungen seien Verbindungen der allgemeinen Formeln (III) und (IV) genanntCompounds of the general formulas (III) and (IV) may be mentioned as very particularly preferred compounds which can be used according to the invention
Figure imgf000008_0001
Subst.
Figure imgf000008_0001
Subst.
Figure imgf000009_0001
Figure imgf000009_0001
in welchenin which
n für 1 oder 2 steht,n represents 1 or 2,
Subst für einen der oben aufgeführten Substituenten, insbesonders für Halogen, ganz besondere für Chlor, steht,Subst stands for one of the substituents listed above, in particular for halogen, very particularly for chlorine,
A, Z, X und E die oben angegebenen Bedeutungen haben,A, Z, X and E have the meanings given above,
Im einzelnen seien folgende Verbindungen genannt:The following connections are specifically mentioned:
Figure imgf000009_0002
Figure imgf000009_0002
ImidaclopridImidacloprid
CH.CH.
Figure imgf000009_0003
Figure imgf000009_0003
AKD 1022AKD 1022
Figure imgf000009_0004
Figure imgf000010_0001
Figure imgf000009_0004
Figure imgf000010_0001
Figure imgf000010_0002
Figure imgf000010_0002
Figure imgf000010_0003
Figure imgf000010_0003
Figure imgf000010_0004
Figure imgf000010_0004
CH3 CH 3
Figure imgf000010_0005
Figure imgf000010_0005
Ti3 04
Figure imgf000011_0001
Ti3 04
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0002
Figure imgf000011_0003
Figure imgf000011_0003
Figure imgf000011_0004
Figure imgf000011_0004
Zu den Phosphor- oder Phosphorsäureestern gehören:The phosphoric or phosphoric acid esters include:
0-Ethyl-0-(8-chinolyl)phenyl-thiophosphat (Quintiofos),0-ethyl-0- (8-quinolyl) phenylthiophosphate (Quintiofos),
0,0-Diethyl-0-(3-chloro-4-methyl-7-coumarinyl)-thiophosphat (Coumaphos),0.0-diethyl-0- (3-chloro-4-methyl-7-coumarinyl) thiophosphate (Coumaphos),
0,0-Diethyl-O-phenylglyoxylonitril-oxim-thiophosphat (Phoxim),0,0-diethyl-O-phenylglyoxylonitrile oxime thiophosphate (phoxime),
0,0-Diethyl-O-cyanochlorbenzaldoxim-thiophosphat (Chlorphoxim), ,0-DιethyI-0-(4-bromo-2,5-dιchlorophenyl)-phosphorothιonat (Bromophos-ethyl),0.0-diethyl-O-cyanochlorobenzaldoxime thiophosphate (chlorophoxime), , 0-DιethyI-0- (4-bromo-2,5-dιchlorophenyl) phosphorothionate (bromophos-ethyl),
,0,0',0'-Tetraethyl-S,S'-methylene-di(phosphorodιthιonat) (Ethion),, 0,0 ', 0'-tetraethyl-S, S'-methylene-di (phosphorodionothonate) (ethion),
2,3-p-Dιoxanedιthiol-S,S-bis(0,0-dιethylphosphorodithιonat,2,3-p-Dιoxanedιthiol-S, S-bis (0,0-dιethylphosphorodithιonat,
2-Chlor-l-(2,4-dichlorphenyl)-vinyldiethylphosphat (Chlorfenvinphos),2-chloro-l- (2,4-dichlorophenyl) vinyl diethyl phosphate (chlorfenvinphos),
0,0-Dimethyl-0-(3 -methyl-4-methylthiophenyl)-thionophosphorsaureester0.0-dimethyl-0- (3-methyl-4-methylthiophenyl) thionophosphoric acid ester
(Fenthion)(Fenthion)
Zu den Carbamaten gehörenThe carbamates include
2-Isopropoxyphenylmethylcarbamat (Propoxur),2-isopropoxyphenylmethyl carbamate (propoxur),
1 -Naphthyl-N-methylcarbamat (Carbaryl)1-naphthyl-N-methyl carbamate (carbaryl)
Zu den synthetischen Pyrethroiden zahlen Verbindungen der Formel VCompounds of the formula V include the synthetic pyrethroids
Figure imgf000012_0001
Figure imgf000012_0001
in welcherin which
R1 und R2 für Halogen, gegebenenfalls halogensubstituiertes Alkyl, gegebenen¬ falls halogensubstituiertes Phenyl stehen,R 1 and R 2 represent halogen, optionally halogen-substituted alkyl, optionally halogen-substituted phenyl,
R' für Wasserstoff oder CN steht,R 'represents hydrogen or CN,
R" für Wasserstoff oder Halogen steht,R "represents hydrogen or halogen,
R1 für Wasserstoff oder Halogen steht,R 1 represents hydrogen or halogen,
Bevorzugt sind synthetische Pyrethroide der Formel V in welcher R1 für Halogen, insbesondere Fluor, Chlor, Brom steht,Synthetic pyrethroids of the formula V in which are preferred R 1 represents halogen, in particular fluorine, chlorine, bromine,
R2 für Halogen, insbesondere Fluor, Chlor, Brom, Tπhalogenmethyl,R 2 for halogen, in particular fluorine, chlorine, bromine, tπhalomethyl,
Phenyl, Chlorphenyl steht,Phenyl, chlorophenyl,
R^ für Wasserstoff oder CN steht,R ^ represents hydrogen or CN,
R4 für Wasserstoff oder Fluor steht,R 4 represents hydrogen or fluorine,
R"1 für Wasserstoff stehtR "1 represents hydrogen
Besonders bevorzugt sind synthetische Pyrethroide der Formel V in welcherSynthetic pyrethroids of the formula V in which are particularly preferred
R1 für Chlor steht,R 1 represents chlorine,
R2 für Chlor, Trifluormethyl, p-Chlorphenyl steht,R 2 represents chlorine, trifluoromethyl, p-chlorophenyl,
R* für CN steht,R * stands for CN,
R4 für Wasserstoff oder Fluor steht,R 4 represents hydrogen or fluorine,
R- für Wasserstoff stehtR- stands for hydrogen
Insbesondere seien Verbindungen der Formel V genannt in welcherCompounds of the formula V may be mentioned in particular
R1 für Chlor steht,R 1 represents chlorine,
R2 für Chlor oder p-Chlorphenyl steht,R 2 represents chlorine or p-chlorophenyl,
R' für CN steht,R 'stands for CN,
R4 für Fluor in 4-Stellung steht,R 4 represents fluorine in the 4-position,
R5 für Wasserstoff steht Im Einzelnen seien genannt:R 5 represents hydrogen The following may be mentioned in detail:
3-[2-(4-Chlorphenyl)-2-chlorvinyl]-2,2-dimethyl-cyclo-propancarbonsäure[(α- cyano-4-fluor-3-phenoxy)-benzyl]-ester (Flumethrin),3- [2- (4-chlorophenyl) -2-chlorovinyl] -2,2-dimethyl-cyclo-propanecarboxylic acid [(α-cyano-4-fluoro-3-phenoxy) benzyl] ester (flumethrin),
2,2-Dimethyl-3-(2,2-dichlorvinyl)-cyclopropancarbonsäure-α-cyano(4-fluor-3- phenoxy)-benzyl-ester (Cyfluthrin) und seine Enantiomere und Stereoisomere,2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid-α-cyano (4-fluoro-3-phenoxy) -benzyl ester (cyfluthrin) and its enantiomers and stereoisomers,
α-Cyano-3-phenoxybenzyl(+)-cis, trans-3-(2,2-dibromvinyl)-2,2-dimethylcyclopro- pancarboxylat (Deltamethrin),α-cyano-3-phenoxybenzyl (+) - cis, trans-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate (deltamethrin),
2,2-Dimethyl-3-(2,2-dichlorvinyl)-cyclopropancarbonsäure-α-cyano-3-phenoxyben- zylester (Cypermethrin),2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid-α-cyano-3-phenoxybenzyl ester (cypermethrin),
3-Phenoxybenzyl(±)-cis, trans-3-(2,2-dichlorvinyl)-2,2-dimethylcyclopropan- carboxylat (Permethrin),3-phenoxybenzyl (±) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane carboxylate (permethrin),
α-(p-Cl-phenyl)-isovaleriansäure-α-cyano-3-phenoxy-benzylester (Fenvalerate),α- (p-Cl-phenyl) -isovaleric acid-α-cyano-3-phenoxy-benzyl ester (fenvalerate),
2-Cyano-3-phenoxybenzyl-2-(2-chlor-α,α,α-trifluor-p-toluidino)-3-methylbutyrat (Fluvalinate).2-Cyano-3-phenoxybenzyl-2- (2-chloro-α, α, α-trifluoro-p-toluidino) -3-methylbutyrate (fluvalinate).
Zu den Amidinen gehören:The amidines include:
3-Methyl-2-[2,4-dimethyl-phenylimino]-thiazolin3-methyl-2- [2,4-dimethylphenylimino] thiazoline
2-(4-Chlor-2-methylphenylimino)-3-methylthiazolidin2- (4-chloro-2-methylphenylimino) -3-methylthiazolidine
2-(4-Chlor-2-methylphenylimino)-3-(isobutyl-l-enyl)-thiazolidin2- (4-chloro-2-methylphenylimino) -3- (isobutyl-l-enyl) thiazolidine
l,5-Bis-(2,4-dimethylphenyl)-3-methyl-l,3,5-triazapenta-l ,4-dien (Amitraz).1,5-bis (2,4-dimethylphenyl) -3-methyl-1,3,5-triazapenta-1,4-diene (Amitraz).
Zu den Juvenilhormonen oder juvenilhormonartigen Substanzen gehören substitu¬ ierte Diarylether, Benzoylharnstoffe und Triazinderivate. Zu den Juvenilhormonen und juvenilhormonartigen Substanzen gehören insbesondere Verbindungen der folgenden Formeln: Juvenile hormones or juvenile hormone-like substances include substituted diaryl ethers, benzoyl ureas and triazine derivatives. Juvenile hormones and juvenile hormone-like substances include in particular compounds of the following formulas:
Figure imgf000015_0001
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000015_0002
Figure imgf000015_0003
Figure imgf000015_0003
Figure imgf000015_0004
Figure imgf000015_0004
Figure imgf000015_0005
Figure imgf000015_0005
Figure imgf000015_0006
Figure imgf000015_0006
Figure imgf000015_0007
Figure imgf000015_0007
Zu den substituierten Diarylethern gehören insbesondere substituierte Alkoxydiphenylether oder -diphenylmethane der allgemeinen Formel VI
Figure imgf000016_0001
The substituted diaryl ethers include, in particular, substituted alkoxydiphenyl ethers or diphenyl methanes of the general formula VI
Figure imgf000016_0001
wobeiin which
R1 für Wasserstoff, Halogen, Alkyl, Alkoxy, Alkylthio, Halogenalkyl, Halogenalkoxy, Halogenalkylthio, Dioxyalkylen, Dioxyhalogenalkylen, CN, NO2, Alkenyl, Alkinyl, Alkoxyalkyl, Alkoxyalkoxy, Hydroxyalkoxy steht,R 1 represents hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, dioxyalkylene, dioxyhalogenalkylene, CN, NO 2 , alkenyl, alkynyl, alkoxyalkyl, alkoxyalkoxy, hydroxyalkoxy,
R2 für die bei R1 angegebenen Reste steht,R 2 represents the radicals specified for R 1 ,
R3 für die bei R1 angegebenen Reste steht,R 3 represents the radicals specified for R 1 ,
R4 für Wasserstoff, Alkyl, Halogenalkyl oder Halogen steht,R 4 represents hydrogen, alkyl, haloalkyl or halogen,
R-1 für die bei R4 angegebenen Reste steht,R -1 represents the radicals specified for R 4 ,
Het für gegebenenfalls substituiertes Heteroaryl steht, das nicht über dasHet stands for optionally substituted heteroaryl, which does not have the
Heteroatom an den übrigen Rest gebunden ist,Hetero atom is bound to the rest of the rest,
X, Y unabhängig voneinander für -O-, -S- stehenX, Y independently of one another represent -O-, -S-
Z für -O-, -S-, -CH2-, -CHCH3-, -C(CH3)2- steht,Z represents -O-, -S-, -CH 2 -, -CHCH 3 -, -C (CH 3 ) 2 -,
m und n unabhängig voneinander für 0, 1 , 2, 3 stehen ihre Summe aber gleich oder größer 2 ist.m and n independently of one another represent 0, 1, 2, 3 but their sum is equal to or greater than 2.
Besonders bevorzugt sind Verbindungen der Formel VICompounds of the formula VI are particularly preferred
in welcherin which
R1 Wasserstoff, Methyl, Trifluorm ethyl, Methoxy, Trifluormethoxy, Chlor, Fluor steht R~ für Wasserstoff steht,R 1 is hydrogen, methyl, trifluoromethyl, methoxy, trifluoromethoxy, chlorine, fluorine R ~ stands for hydrogen,
R1 für Wasserstoff, Fluor, Chlor, Methyl steht,R 1 represents hydrogen, fluorine, chlorine, methyl,
R4 für Wasserstoff oder Methyl steht,R 4 represents hydrogen or methyl,
R5 für Methyl, Ethyl, Trifluormethyl oder Wasserstoff steht,R 5 represents methyl, ethyl, trifluoromethyl or hydrogen,
Het für Pyridyl oder Pyridazinyl steht die gegebenenfalls substituiert sind durchHet is pyridyl or pyridazinyl which are optionally substituted by
Fluor, Chlor, Methyl, NO2, Methoxy, Methylmercapto,Fluorine, chlorine, methyl, NO 2 , methoxy, methylmercapto,
X für O steht,X stands for O,
Y für O steht,Y stands for O,
Z für O, CH2 oder -C(CH3)2- steht,Z represents O, CH 2 or -C (CH 3 ) 2 -,
m für 1 steht,m represents 1,
n für 1 stehtn stands for 1
Im einzelnen seien folgende Verbindungen genannt The following compounds may be mentioned in detail
Figure imgf000018_0001
Figure imgf000018_0001
Figure imgf000018_0003
Figure imgf000018_0003
Figure imgf000018_0002
Figure imgf000018_0002
Figure imgf000018_0004
Figure imgf000018_0004
Figure imgf000019_0001
Figure imgf000019_0001
Figure imgf000019_0003
Figure imgf000019_0003
Zu den Benzoylharnstoffen gehören Verbindungen der Formel VIIBenzoylureas include compounds of the formula VII
Figure imgf000019_0002
Figure imgf000019_0002
wobeiin which
R für Halogen steht,R represents halogen,
R1 für Wasserstoff oder Halogen steht, R3 für Wasserstoff, Halogen oder C,_4-Alkyl steht,R 1 represents hydrogen or halogen, R 3 represents hydrogen, halogen or C 1 -C 4 -alkyl,
R4 für Halogen, l -5-Halogen-C1.4-alkyl, C] .4-Alkoxy, l -S-Halogen-C,^- alkoxy, C 1.4-Alkylthio, l -5-Halogen-C ,.4-alkylthιo, Phenoxy oderR 4 for halogen, l -5-halogen-C 1.4 -alkyl, C ] .4 -alkoxy, l -S-halogen-C, ^ - alkoxy, C 1 . 4 alkylthio, l -5-halogeno-C, .4- alkylthio, phenoxy or
Pyπdyloxy die gegebenenfalls substituiert sein können durch Halogen,Pyπdyloxy which may optionally be substituted by halogen,
C -Alkyl, l -5-Halogen-C1.4-alkyl, C1.4-Alkoxy, l-5-Halogen-C,.4-alkoxy,C-alkyl, l -5-halogen-C 1 . 4- alkyl, C 1.4 -alkoxy, l-5-halo-C, .4 -alkoxy,
C] .4-Alkylthιo, 1-5-Halogen- C] .4-alkylthιo Insbesondere seien genanntC ] .4 -Alkylthιo, 1-5-halo-C ] .4 -alkylthιo May be mentioned in particular
Figure imgf000020_0001
Figure imgf000020_0001
Figure imgf000020_0002
46101
Figure imgf000020_0002
46101
1919
Zu den Triazinen gehören Verbindungen der Formel (VIII)The triazines include compounds of the formula (VIII)
NH R,NH R,
N^ (VIII)N ^ (VIII)
R — HN 'N' "NH — R,R - HN ' N ' " NH - R,
worinwherein
R, für Cyclopropyl oder Isopropyl steht;R represents cyclopropyl or isopropyl;
R-, Wasserstoff, Halogen, C]-C12-Alkylcarbonyl; Cyclopropylcarbonyl, C,-Cp- Alkylcarbamoyl, C,-Cp-Alkylthiocarbamoyl oder C2-C6-Alkenyl carbamoyl bedeutet, undR-, hydrogen, halogen, C ] -C 12 alkylcarbonyl ; Cyclopropylcarbonyl, C, -C p - alkyl carbamoyl, C, -C p alkylthiocarbamoyl or C 2 -C 6 alkenyl carbamoyl means, and
R3 für Wasserstoff, CrC12-Alkyl, Cyclopropyl, C2-C6-Alkenyl, C,-C] 2-Alkyl- carbonyl, Cyclopropylcarbonyl, Cj-Cp-Alkylcarbamoyl, CrCp-Alkylthio- carbamoyl oder C2-C -Alkenylcarbamoyl steht und deren Saureadditions- salze, die für Warmblüter untoxisch sind.R 3 for hydrogen, C r C 12 alkyl, cyclopropyl, C 2 -C 6 alkenyl, C, -C ] 2 alkylcarbonyl, cyclopropylcarbonyl, C j -Cp alkylcarbamoyl, C r C p alkylthio carbamoyl or C 2 -C -alkenylcarbamoyl and their acid addition salts, which are non-toxic to warm-blooded animals.
Insbesondere seien genannt'In particular,
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Besonders hervorgehoben seien die arthropodiziden Wirkstoffe mit den comnon names Propoxur, Cyfluthπn, Flumethπn, Pyπproxyfen, Methoprene, Diazinon, Amitraz, Fenthion, Imidaclopπd, Ti 435, AKD 1022, Ti 304, Tπflumuron, Ivermectin, AvermectinParticularly noteworthy are the arthropodicidal active ingredients with the comnon names Propoxur, Cyfluthπn, Flumethπn, Pyπproxyfen, Methoprene, Diazinon, Amitraz, Fenthion, Imidaclopπd, Ti 435, AKD 1022, Ti 304, Tπflumuron, Ivermectin, Avermectin
Die Wirkstoffe liegen in den Mitteln m Konzentrationen von 0,1 bis 20 Gew -% vor, bevorzugt zwischen 1 bis 10 Gew -%The active substances are present in the compositions in m concentrations of 0.1 to 20% by weight, preferably between 1 to 10% by weight.
Die erfindungsgemaßen Mittel haben erhebliche Vorteile für die Praxis Ihre Wirkung auf Schädlinge ist sofort einsetzend, d h der Verbraucher sieht denThe agents according to the invention have considerable practical advantages. Their action on pests is immediate, that is, the consumer sees them
Erfolgt der Bekampfungsmaßnahme direktThe control measure is carried out directly
Die erfindungsgemaßen Mittel zeigen zum Teil erheblich bessere Verträglichkeit im Vergleich zur Anwendung der Einzel Wirkstoffe Die erfindungsgemäßen Mittel eignen sich zur Bekämpfung von tierischen Schädlingen, vorzugsweise Arthropoden, insbesondere Insekten und Spinnentieren, die in der Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam Zu den oben erwähnten Schädlingen gehörenThe agents according to the invention sometimes show considerably better tolerability compared to the use of the individual active ingredients The compositions according to the invention are suitable for controlling animal pests, preferably arthropods, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are resistant to normally sensitive and resistant species and to all or some of them Developmental stages effective The pests mentioned above include
Aus der Ordnung der Isopoda z B Oniscus asellus, Armadillidium vulgäre,From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare,
Porcelli o scaberPorcelli o scaber
Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus Aus der Ordnung der Chilopoda z B Geophilus carpophagus, Scutigera specFrom the order of the Diplopoda e.g. Blaniulus guttulatus From the order of the Chilopoda eg Geophilus carpophagus, Scutigera spec
Aus der Ordnung der Symphyla z.B Scutigerella immaculataFrom the order of the Symphyla e.g. Scutigerella immaculata
Aus der Ordnung der Thysanura z B Lepisma saccharinaFrom the order of the Thysanura, for example Lepisma saccharina
Aus der Ordnung der Collembola z B Onychiurus armatusFrom the order of the Collembola, for example Onychiurus armatus
Aus der Ordnung der Orthoptera z.B Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp ,From the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp,
Locusta migratoria migratorioides, Melanoplus differentiahs, Schistocerca gregariaLocusta migratoria migratorioides, Melanoplus differentiahs, Schistocerca gregaria
Aus der Ordnung der Dermaptera z B. Forficula auπculaπaFrom the order of the Dermaptera e.g. Forficula auπculaπa
Aus der Ordnung der Isoptera z.B Reticulitermes spp.From the order of the Isoptera e.g. Reticulitermes spp.
Aus der Ordnung der Anoplura z.B Pediculus humanus corporis, Haematopinus spp , Linognathus sppFrom the order of the Anoplura e.g. Pediculus humanus corporis, Haematopinus spp, Linognathus spp
Aus der Ordnung der Mallophaga z B Tπchodectes spp , Damalinea sppFrom the order of the Mallophaga, for example Tπchodectes spp, Damalinea spp
Aus der Ordnung der Thysanoptera z.B Hercinothrips femoralis, Thrips tabaciFrom 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, for example Eurygaster spp, Dysdercus intermedius,
Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp Aus der Ordnung der Homoptera z.B Aleurodes brassicae, Bemisia tabaci,Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma 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 lamgerum, Hyalopterus arundinis,Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lamgerum, Hyalopterus arundinis,
Phylloxera vastatrix, Pemphigus spp , Macrosiphum avenae, Myzus spp , Phorodon humuli, Rhopalosiphu padi, Empoasca spp , Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp Psylla sppPhylloxera vastatrix, Pemphigus spp, Macrosiphum avenae, Myzus spp, Phorodon humuli, Rhopalosiphu padi, Empoasca spp, Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellidium, Aspelocidium syllabus, Nilaparocidium lp
Aus der Ordnung der Lepidoptera z B Pectinophora gossypiella, Bupalus piniaπus, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustπa, Euproctis chrysorrhoea, Lymantria spp Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp , Euxoa spp , Feltia spp., Earias insulana, Heliothis spp , Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia 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 viridanaFrom the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniaπus, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustπa, Euproctis chrysorrhoea, Lymantria spp Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp, Euxoa spp, Feltia spp., Earias insulana, Heliothis spp, Laphygma exica, Prodisiaiappeaia, Spodiaia triappaia, Spodiaia triappia, Spodiaia triappaia, Spodiaia triappaia Carpocapsa pomonella, Pieris spp, Chilo spp, Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferanuell, viralia, triaxialia, Clysia
Aus der Ordnung der Coleoptera z.B Anobiu punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,From the order of the Coleoptera e.g. Anobiu 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 Sulcatushidpphidpphidispphppisidpphidisidpphidispphidispphidispphcpphc, spp spp, Lyctus spp., Meligethes aeneus, Ptinus spp,
Niptus hololeucus, Gibbium psylloides, Tribolium spp , Tenebno mohtor, Agriotes spp , Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandicaNiptus hololeucus, Gibbium psylloides, Tribolium spp, Tenebno mohtor, Agriotes spp, Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica
Aus der Ordnung der Hymenoptera z.B Diprion spp , Hoplocampa spp , Lasius spp , Monomorium pharaonis, Vespa sppFrom 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 , 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,From the order of Diptera, for example Aedes spp, Anopheles spp, Culex spp, Drosophila melanogaster, Musca spp, Fannia spp, Calliphora erythrocephala, Lucilia spp, Chrysomyia spp., Cuterebra spp, Gastrophilus spp., Hyppobosca spp., Stomoxyspp ., Hypoderma spp, Tabanus spp, Tannia spp, Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata,
Dacus oleae, Tipula paludosa.Dacus oleae, Tipula paludosa.
Aus der Ordnung der Siphonaptera z.B Xenopsylla cheopis, Ceratophyllus spp Aus der Ordnung der Arachnida z.B Scorpio maurus, Latrodectus mactans Aus der Ordnung der Acaπna z B Acarus siro, Argas spp , Ornithodoros spp , Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp ,From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans From the order of the Acaπna z B Acarus siro, Argas spp, Ornithodoros spp, Dermanyssus gallinae, Eriophyes ribis, Phyllivoraopilil, Phyllivoraopil
Rhipicephalus spp , Amblyomma spp , Hyalomma spp , Ixodes spp , Psoroptes sp , Chorioptes spp., Sarcoptes spp , Tarsonemus spp , Bryobia praetiosa, Panonychus spp , Tetranychus spp Die Mittel eignen sich bei günstiger Warmblütertoxizität zur Bekämpfung von tierischen Schädlingen wie Arthropoden, vorzugsweise Insekten, Spinnentieren, die in der Tierhaltung und Tierzucht bei Nutz-, Zucht-, Zoo-, Labor-, Versuchs- und Hobbytieren vorkommen. Sie sind dabei gegen alle oder einzelne Entwick- lungsstadien der Schädlinge sowie gegen resistente und normal sensible Arten derRhipicephalus spp, Amblyomma spp, Hyalomma spp, Ixodes spp, Psoroptes sp, Chorioptes spp., Sarcoptes spp, Tarsonemus spp, Bryobia praetiosa, Panonychus spp, Tetranychus spp With favorable warm-blood toxicity, the agents are suitable for controlling animal pests, such as arthropods, preferably insects, arachnids, which occur in livestock farming and animal breeding in farm animals, breeding, zoo, laboratory, experimental and hobby animals. They are against all or individual stages of development of the pests and against resistant and normally sensitive types of
Schädlinge wirksam.Pests effective.
Zu den Schädlingen gehören:The pests include:
Aus der Ordnung der Anoplura z.B. Haematopinus spp., Linognathus spp., Soleno- potes spp., Pediculus spp., Pthirus spp.; aus der Ordnung der Mallophaga z.B. Trimenopon spp., Menopon spp.,From the order of the anoplura e.g. Haematopinus spp., Linognathus spp., Solenopotes spp., Pediculus spp., Pthirus spp .; from the order of the Mallophaga e.g. Trimenopon spp., Menopon spp.,
Eomenacanthus spp., Menacanthus spp., Trichodectes spp., Felicola spp.,Eomenacanthus spp., Menacanthus spp., Trichodectes spp., Felicola spp.,
Damalinea spp., Bobiola spp.; aus der Ordnung der Diptera z.B. Chrysops spp., Tabanus spp., Musca spp.,Damalinea spp., Bobiola spp .; from the order of the Diptera e.g. Chrysops spp., Tabanus spp., Musca spp.,
Hydrotaea spp., Muscina spp., Haematobosca spp., Haematobia spp., Stomoxys spp., Fannia spp., Glossina spp., Lucilia spp., Calliphora spp., Auchmeromyia spp.,Hydrotaea spp., Muscina spp., Haematobosca spp., Haematobia spp., Stomoxys spp., Fannia spp., Glossina spp., Lucilia spp., Calliphora spp., Auchmeromyia spp.,
Cardylobia spp., Cochiomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia spp., Gaserophilus spp., Oesteromyia spp., Oedemagena sp., Hypoderma spp.,Cardylobia spp., Cochiomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia spp., Gaserophilus spp., Oesteromyia spp., Oedemagena sp., Hypoderma spp.,
Oestrus spp., Rhinoestrus spp., Melophagus spp., Hippobosca spp.Oestrus spp., Rhinoestrus spp., Melophagus spp., Hippobosca spp.
Aus der Ordnung der Siphonaptera z.B. Ctenocephalides spp., Echidnophaga spp., Ceratophyllus spp.From the order of the Siphonaptera e.g. Ctenocephalides spp., Echidnophaga spp., Ceratophyllus spp.
Aus der Ordnung der Metastigmata z.B. Hyalomma spp., Rhipicephalus spp., Boophilus spp., Ambyomma spp., Haemophysalis spp., Dermacentor spp., Ixodes spp., Argas spp., Ornithodorus spp., Otobius spp.; aus der Ordnung der Mesastigmata z.B. Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp.From the order of the metastigmata e.g. Hyalomma spp., Rhipicephalus spp., Boophilus spp., Ambyomma spp., Haemophysalis spp., Dermacentor spp., Ixodes spp., Argas spp., Ornithodorus spp., Otobius spp .; from the order of the mesastigmata e.g. Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp.
Aus der Ordnung der Prostigmata z.B. Cheyletiella spp., Psorergates spp., Myobia spp., Demdex spp., Neotrombicula spp.;From the order of the prostigmata e.g. Cheyletiella spp., Psorergates spp., Myobia spp., Demdex spp., Neotrombicula spp .;
Zu den Haus- und Nutztieren gehören Säugetiere wie z.B. Rinder, Schafe, Ziegen, " Pferde,- Schweine, Hunde, Katzen, Kamele, Wasserbüffel, Esel, Kaninchen, Damwild, Rentiere, Pelztiere wie z.B. Nerze, Chinchilla, Waschbär, Vögel wie z.B. Hühner, Puten, Fasanen, Gänse, Enten.Domestic and farm animals include mammals such as cattle, sheep, goats, "horses, pigs, dogs, cats, camels, water buffalo, donkeys, rabbits, Fallow deer, reindeer, fur animals such as mink, chinchilla, raccoon, birds such as chickens, turkeys, pheasants, geese, ducks.
Zu Labor- und Versuchstieren gehören z.B. Mäuse, Ratten, Meerschweinchen, Goldhamster, Hunde und Katzen.Laboratory and experimental animals include e.g. Mice, rats, guinea pigs, golden hamsters, dogs and cats.
Zu den Hobbytieren gehören z.B. Hunde und Katzen.Hobby animals include e.g. Dogs and cats.
Die erfindungsgemäßen Mittel lassen sich auch in geschlossenen Räumen wie Wohnungen, Hallen o.a. einsetzen. Sie eignen sich besonders zur Bekämpfung tierischer Schädlinge und Lästlinge, die im Haushalt vorkommen.The agents according to the invention can also be used in closed rooms such as apartments, halls or the like. deploy. They are particularly suitable for controlling animal pests and nuisances that occur in the household.
Dazu seien besonders genannt Fliegen, Mücken, Wespen, Ameisen, Schaben, Silberfischchen.These include flies, mosquitoes, wasps, ants, cockroaches, and silverfish.
Die Anwendung der erfindungsgemäßen Mittel am Tier erfolgt direkt oder in Form von geeigneten Zubereitungen dermal oder durch Behandlung ihrer Umgebung.The agents according to the invention are used directly or in the form of suitable preparations dermally or by treating their environment.
Die dermale Anwendung geschieht z.B. in Form des Badens, Tauchens (Dippen), Sprühens (Sprayen), Aufgießens (pour-on oder spot-on), Waschens, Schamponie- rens, Begießens, Einpuderns.The dermal application happens e.g. in the form of bathing, diving (dipping), spraying (spraying), pouring on (pour-on or spot-on), washing, shampooing, watering, powdering.
Geeignete Zubereitungen sind:Suitable preparations are:
Lösungen oder Konzentrate zur Verabreichung nach Verdünnung, Lösungen zumSolutions or concentrates for administration after dilution, solutions for
Gebrauch auf der Haut, Aufgußformulierungen, Gele;Skin use, infusion formulations, gels;
Emulsionen und Suspensionen zur dermalen Anwendung sowie halbfeste Zubereitungen;Emulsions and suspensions for dermal use and semi-solid preparations;
Formulierungen, bei denen die Wirkstoffe in einer Salbengrundlage oder in einer Öl in Wasser oder Wasser in Öl Emulsionsgrundlage verarbeitet ist;Formulations in which the active ingredients are processed in an ointment base or in an oil in water or water in oil emulsion base;
Feste Zubereitungen wie Pulver oder Stäube, auch durch Mikroverkapselung der flüssigen Inhaltsstoffe. Diese Zubereitungen lassen sich außer zur Anwendung am Tier auch im Haushalt, in der Hygiene oder in der Landwirtschaft einsetzenSolid preparations such as powder or dusts, also through microencapsulation of the liquid ingredients. In addition to use on animals, these preparations can also be used in the home, in hygiene or in agriculture
Losungen zum Gebrauch auf der Haut werden aufgeträufelt, aufgestrichen, eingerieben, aufgespritzt, aufgesprüht oder durch Tauchen (Dippen), Baden oder Waschen aufgebrachtSolutions for use on the skin are dripped on, spread on, rubbed in, sprayed on, sprayed on or applied by dipping (dipping), bathing or washing
Die Losungen werden hergestellt, indem die Wirkstoffe in den cycl Silikonen und/oder geeigneten Losungsmitteln gelost werden und evtl Zusätze wie Losungs¬ vermittler, Sauren, Basen, Puffersalze, Antioxidantien, Konservierungsmittel zuge¬ fugt werdenThe solutions are prepared by dissolving the active ingredients in the cyclic silicones and / or suitable solvents and possibly adding additives such as solubilizers, acids, bases, buffer salts, antioxidants and preservatives
Als Losungsmittel seien genannt Physiologisch vertragliche Losungsmittel wiePhysiologically contractual solvents such as
Wasser, Alkohole wie Ethanol, Butanol, Benzylakohol, Glyceπn, Kohlenwasser¬ stoffe, Propylenglykol, Polyethylenglykole, N-Methyl-pyrrohdon, sowie Gemische derselbenWater, alcohols such as ethanol, butanol, benzyl alcohol, glycols, hydrocarbons, propylene glycol, polyethylene glycols, N-methyl-pyrrohdon, and mixtures thereof
Die Wirkstoffe lassen sich gegebenenfalls auch in physiologisch vertraglichen pflanzlichen oder synthetischen Ölen losenThe active ingredients can optionally also be dissolved in physiologically acceptable vegetable or synthetic oils
Als Losungsvermittler seien genannt Losungsmittel, die die Losung des Wirkstoffs im Hauptlosungsmittel fordern oder sein Ausfallen verhindern Beispiele sind Polyvinylpyrrohdon, polyoxyethyliertes Rhizinusol, polyoxy- ethylierte SorbitanesterSolvents which may be mentioned are solvents which require the active ingredient to be dissolved in the main solvent or prevent it from precipitating out. Examples are polyvinylpyrrohdon, polyoxyethylated castor oil, polyoxyethylated sorbitan esters
Konservierungsmittel sind Benzylalkohol, Tπchlorbutanol, p-Hydroxybenzoe- saureester, n-ButanolPreservatives are benzyl alcohol, chlorobutanol, p-hydroxybenzoic acid ester, n-butanol
Es kann vorteilhaft sein, bei der Herstellung der Losungen Verdickungsmittel zuzufügen Verdickungsmittel sind Anorganische Verdickungsmittel wie Bentonite, kolloidale Kieselsaure, Aluminiummonostearat, organische Verdik- kungsmittel wie Cellulosedeπvate, Polyvinylalkohole und deren Copolymere,It may be advantageous to add thickeners in the preparation of the solutions. Thickeners are inorganic thickeners such as bentonites, colloidal silica, aluminum monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers.
Acrylate und Metacrylate Gele, die auf die Haut aufgetragen oder aufgestrichen werden, werden hergestellt indem Losungen, die wie oben beschrieben hergestellt worden sind, mit soviel Verdickungsmittel versetzt werden, daß eine klare Masse mit salbenartiger Konsistenz entsteht. Als Verdickungsmittel werden die weiter oben angegebenen Verdickungsmittel eingesetztAcrylates and metacrylates Gels that are applied or spread on the skin are produced by adding enough thickening agent to solutions that have been prepared as described above to produce a clear mass with an ointment-like consistency. The thickeners specified above are used as thickeners
Aufgießformulierungen werden auf begrenzte Bereiche der Haut aufgegossen oder aufgespritzt, wobei die Wirkstoffe sich auf der Korperoberflache verteilenPour-on formulations are poured or sprayed onto limited areas of the skin, the active ingredients being distributed over the surface of the body
Aufgießformulierungen werden hergestellt, indem die Wirkstoffe in geeigneten hautvertraglichen Losungsmitteln oder Losungsmittelgemischen gelost, suspendiert oder emulgiert werden Gegebenenfalls werden weitere Hilfsstoffe wie Farbstoffe,Pour-on formulations are prepared by dissolving, suspending or emulsifying the active ingredients in suitable solvents or solvent mixtures that are compatible with the skin.
Antioxidantien, Lichtschutzmittel, Haftmittel zugefugtAntioxidants, light stabilizers, adhesives added
Als Losungsmittel seien genannt Wasser, Alkanole, Glycole, Polyethylenglycole, Polypropylenglycole, Glycerin, aromatische Alkohole wie Benzylalkohol, Phenyl- ethanol, Phenoxyethanol, Ester wie Essigester, Butylacetat, Benzylbenzoat, Ether wie Alkylenglykolalkylether wie Dipropylenglykolmonomethylether, Diethylen- glykolmono-butylether, Ketone wie Aceton, Methylethylketon, aromatische und/oder aliphatische Kohlenwasserstoffe, pflanzliche oder synthetische Ole, DMF, Dimethylacetamid, N-Methylpyrrolidon, 2-Dimethyl-4-oxy-methylen- 1 ,3-dιoxolanSolvents which may be mentioned are water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol and glycol monoethyl ether , Methyl ethyl ketone, aromatic and / or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, N-methylpyrrolidone, 2-dimethyl-4-oxy-methylene-1, 3-dιoxolan
Farbstoffe sind alle zur Anwendung am Tier zugelassenen Farbstoffe, die gelost oder suspendiert sein könnenDyes are all dyes approved for use on animals, which can be dissolved or suspended
Hüfsstoffe sind auch spreitende Ole wie Isopropylmyπstat, Dipropylenglykol- pelargonat, Silikonole, Fettsaureester, Triglyceride, FettalkoholeExcipients are also spreading oils such as isopropyl mypstat, dipropylene glycol pelargonate, silicone oils, fatty acid esters, triglycerides, fatty alcohols
Antioxidantien sind Sulfite oder Metabisulfite wie Kaliummetabisulfit, Ascorbin- saure, Butylhydroxytoluol, Butylhydroxyanisol, TocopherolAntioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylated hydroxytoluene, butylated hydroxyanisole, tocopherol
Lichtschutzmittel sind z B Stoffe aus der Klasse der Benzophenone oderLight stabilizers are, for example, substances from the class of the benzophenones or
Novantisol saure Haftmittel sind z.B. Cellulosederivate, Stärkederivate, Polyacrylate, natürliche Polymere wie Alginate, Gelatine.Novantisol acidic Adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates, natural polymers such as alginates, gelatin.
Emulsionen sind entweder vom Typ Wasser in Öl oder vom Typ Öl in Wasser.Emulsions are either water in oil or oil in water.
Sie werden hergestellt, indem man die Wirkstoffe entweder in der hydrophoben oder in der hydrophilen Phase löst und diese unter Zuhilfenahme geeigneterThey are produced by dissolving the active substances either in the hydrophobic or in the hydrophilic phase and using suitable ones
Emulgatoren und gegebenenfalls weiterer Hilfsstoffe wie Farbstoffe, resorptions- fördernde Stoffe, Konservierungsstoffe, Antioxidantien, Lichtschutzmittel, viskosi- tätserhöhende Stoffe, mit dem Lösungsmittel der anderen Phase homogenisiertEmulsifiers and optionally other auxiliaries such as dyes, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-increasing substances, homogenized with the solvent of the other phase
Als hydrophobe Phase (Öle) seien genannt: Paraffinöle, Silikonöle, natürliche Pflanzenöle wie Sesamöl, Mandelöl, Rizinusöl, synthetische Triglyceride wieThe following may be mentioned as the hydrophobic phase (oils): paraffin oils, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as
Capryl/ Caprinsäure-bigylcerid, Triglyceridgemisch mit Pflanzenfettsäuren der Kettenlänge C8.,2 oder anderen speziell ausgewählten natürlichen Fettsäuren, Partialglyceridgemische gesättigter oder ungesättigter eventuell auch hydroxyl- gruppenhaltiger Fettsäuren, Mono- und Diglyceride der C8/C10-Fettsäuren.Caprylic / capric acid bigylceride, triglyceride mixture with vegetable fatty acids of chain length C 8 , 2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids, which may also contain hydroxyl groups, mono- and diglycerides of C 8 / C 10 fatty acids.
Fettsäureester wie Ethylstearat, Di-n-butyryl-adipat, Laurinsäurehexylester, Dipro- pylen-glykolpelargonat, Ester einer verzweigten Fettsäure mittlerer Kettenlänge mit gesättigten Fettalkoholen der Kettenlänge C16-C18, Isopropyl myristat, Isopropyl- palmitat, Capryl/Caprinsäureester von gesättigten Fettalkoholen der Kettenlänge Cp-C) 8, Isopropylstearat, Ölsäureoleylester, Ölsäuredecylester, Ethyloleat, Milch- säureethylester, wachsartige Fettsäureester wie Dibutylphthalat, Adipinsäurediiso- propylester, letzterem verwandte Estergemische u.a. Fettalkohole wie Isotri- decylalkohol, 2-Octyldodecanol, Cetylstearyl-alkohol, Oleylalkohol.Fatty acid esters such as ethyl stearate, di-n-butyryl adipate, lauric acid hexyl ester, dipropylene glycol pelargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C 16 -C 18 , isopropyl myristate, isopropyl palmitate, caprylic / capric acid esters of saturated fatty alcohol the chain length Cp-C ) 8 , isopropyl stearate, oleic acid oleyl ester, oleic acid decyl ester, ethyl oleate, lactic acid ethyl ester, waxy fatty acid esters such as dibutyl phthalate, diisopropyl adipate, the latter related ester mixtures including fatty alcohols such as isotridecyl alcohol alcohol, 2-octyl alcohol alcohol, 2-octyl alcohol alcohol, 2-octyl alcohol alcohol.
Fettsäuren wie z.B. Ölsäure und ihre Gemische.Fatty acids such as Oleic acid and its mixtures.
Als hydrophile Phase seien genannt: Wasser, Alkohole wie z.B. Propylenglycol, Glycerin, Sorbitol und ihre Gemische.The following can be mentioned as the hydrophilic phase: water, alcohols, e.g. Propylene glycol, glycerin, sorbitol and their mixtures.
Als Emulgatoren seien genannt: nichtionogene Tenside, z.B. polyoxyethyliertes ~ Rizinusöl, polyoxyethyliertes Sorbitan-monooleat, Sorbitanmonostearat, Glycerin- monostearat, Pol yoxy ethylstearat, Alkylphenolpolyglykolether; ampholytische Tenside wie Di-Na-N-lauryl-ß-iminodipropionat oder Lecithin,Be mentioned as emulsifiers: nonionic surfactants, for example polyoxyethylated ~ castor oil, polyoxyethylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, Pol yoxy ethyl stearate, alkylphenol; ampholytic surfactants such as di-Na-N-lauryl-β-iminodipropionate or lecithin,
anionaktive Tenside, wie Na-Laurylsulfat, Fettalkoholethersulfate, Mono/Dialkyl- polyglykoletherorthophosphor-saureester-monoethanolaminsalz, kationaktive Tenside wie Cetyltπmethylammoniumchloπdanionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono / dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt, cationic surfactants such as cetyl methyl methyl ammonium chloride
Als weitere Hilfsstoffe seien genannt Viskositatserhohende und die Emulsion stabilisierende Stoffe wie Carboxymethylcellulose, Methylcellulose und andere Cellulose- und Starke-Derivate, Polyacrylate, Alginate, Gelatine, Gummi-arabicum, Polyvinylpyrrohdon, Polyvinylalkohol, Copolymere aus Methylvinylether und Maleinsaureanhydrid, Polyethylenglykole, Wachse, kolloidale Kieselsaure oder Gemische der aufgeführten StoffeFurther auxiliaries which may be mentioned are substances which increase viscosity and stabilize the emulsion, such as carboxymethyl cellulose, methyl cellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrodone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, silica glycols, waxes, polyethylene glycols, waxes, polyethylene glycols, waxes, polyethylene glycols, waxes, polyethylene glycols, waxes, and ethylene glycols or mixtures of the listed substances
Suspensionen werden hergestellt, indem man die Wirkstoffe in einer Trager- flussigkeit gegebenenfalls unter Zusatz weiterer Hilfsstoffe wie Netzmittel, Farb¬ stoffe, resorptionsfordernde Stoffe, Konservierungsstoffe, Antioxidantien Lichtschutzmittel suspendiertSuspensions are produced by suspending the active ingredients in a carrier liquid, optionally with the addition of further auxiliaries such as wetting agents, dyes, absorption-promoting substances, preservatives, antioxidants, light stabilizers
Als Tragerflussigkeiten seien alle homogenen Losungsmittel und Losungs- mittelgemische genanntAll homogeneous solvents and solvent mixtures are mentioned as carrier liquids
Als Netzmittel (Dispergiermittel) seien die weiter oben angegebene Tenside genanntThe surfactants specified above may be mentioned as wetting agents (dispersants)
Als weitere Hilfsstoffe seien die weiter oben angegebenen genanntFurther additives mentioned are those mentioned above
Halbfeste Zubereitungen zur dermalen Verabreichung unterscheiden sich von den oben beschriebenen Suspensionen und Emulsionen nur durch ihre höhere ViskositätSemi-solid preparations for dermal administration differ from the suspensions and emulsions described above only in their higher viscosity
Zur Herstellung fester Zubereitungen werden die Wirkstoffe mit geeigneten Tragerstoffen gegebenenfalls unter Zusatz von Hilfsstoffen vermischt und in die gewünschte Form gebracht Als Tragerstoffe seien genannt alle physiologisch vertraglichen festen Inertstoffe Alle solche dienen anorganische und organische Stoffe Anorganische Stoffe sind z B Kochsalz, Carbonate wie Calciumcarbonat, Hydrogencarbonate, Aluminium- oxide, Kieselsauren, Tonerden, gefälltes oder kolloidales Siliciumdioxid, PhosphateTo prepare solid preparations, the active ingredients are mixed with suitable carriers, if appropriate with the addition of auxiliaries, and brought into the desired shape All physiologically compatible solid inert substances may be mentioned as carrier substances. All such serve inorganic and organic substances. Inorganic substances are, for example, table salt, carbonates such as calcium carbonate, hydrogen carbonates, aluminum oxides, silicas, clays, precipitated or colloidal silicon dioxide, phosphates
Hilfsstoffe sind Konservierungsstoffe, Antioxidantien, Farbstoffe, die bereits weiter oben aufgeführt worden sindExcipients are preservatives, antioxidants, dyes, which have already been listed above
Weitere geeignete Hilfsstoffe sind Schmier- und Gleitmittel wie z B Magnesium- stearat, Stearinsaure, Talkum, BentoniteOther suitable auxiliaries are lubricants and lubricants such as magnesium stearate, stearic acid, talc, bentonite
Anwendungsfertige Zubereitungen enthalten die Wirkstoffe in Konzentrationen vonReady-to-use preparations contain the active ingredients in concentrations of
1 ppm - 20 Gewichtsprozent, bevorzugt von 0,01 - 10 Gewichtsprozent1 ppm - 20 weight percent, preferably from 0.01 - 10 weight percent
Zubereitungen die vor Anwendung verdünnt werden, enthalten die Wirkstoffe in Konzentrationen von 0,5 - 90 Gewichtsprozent, bevorzugt von 1 bis 50 GewichtsprozentPreparations which are diluted before use contain the active compounds in concentrations of 0.5 to 90 percent by weight, preferably from 1 to 50 percent by weight
Im allgemeinen hat es sich als vorteilhaft erwiesen, Mengen von etwa 0,5 bis etwaIn general, it has been found advantageous to use amounts from about 0.5 to about
50 mg, bevorzugt 1 bis 20 mg, Wirkstoff je kg Korpergewicht pro Tag zur Erzie¬ lung wirksamer Ergebnisse zu verabreichen50 mg, preferably 1 to 20 mg, of active ingredient per kg of body weight per day to achieve effective results
Besonders bevorzugt sind erfindungsgemaße Mittel, in denen der arthropodizide Wirkstoff in dem cyclischen Polysiloxan gelost vorliegt Agents according to the invention in which the arthropodicidal active ingredient is present in solution in the cyclic polysiloxane are particularly preferred

Claims

PatentansprücheClaims
1 Schädlingsbekämpfungsmittel auf Basis cyclischer Poiysiloxane der Formel1 pesticide based on cyclic poysiloxanes of the formula
(I)(I)
(SiR2— O)-(SiR 2 - O) -
(I),(I),
in welcherin which
R für gleiche oder verschiedene Reste der Gruppe Methyl, Ethyl,R for identical or different radicals of the group methyl, ethyl,
Propyl steht,Propyl stands,
n für ganze Zahlen von 3 bis 6 steht,n stands for integers from 3 to 6,
in Mischung mit arthropodiziden Wirkstoffen.in a mixture with arthropodicidal agents.
2 Mittel gemäß Anspruch 1, dadurch gekennzeichnet, daß sie als Bestandteil der Formel (I) Verbindungen enthalten, in denen der Index n = 5 ist.2 compositions according to claim 1, characterized in that they contain as part of the formula (I) compounds in which the index n = 5.
3 Mittel gemäß Anspruch 1, dadurch gekennzeichnet, daß die Bestandteile der Formel (I) mit den Indices 4 und 5 im Gewichtsverhältnis3 Composition according to claim 1, characterized in that the components of formula (I) with the indices 4 and 5 in the weight ratio
n = 4 85 bis 50 Gew.-% n = 5 15 bis 50 Gew.-%n = 4 85 to 50% by weight n = 5 15 to 50% by weight
vorliegen available
PCT/EP1997/002622 1996-06-03 1997-05-22 Pesticides based on cyclic polysiloxanes WO1997046101A1 (en)

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DE1996122190 DE19622190A1 (en) 1996-06-03 1996-06-03 Pesticide based on cyclic polysiloxanes

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IT1393056B1 (en) * 2008-09-22 2012-04-11 Bio Lo Ga Srl USE OF VITAMIN AND OR ITS DERIVATIVES FOR THE CONTROL OF ARTHROPODS

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Publication number Priority date Publication date Assignee Title
DE2829388A1 (en) * 1977-07-27 1979-02-01 Dow Corning EMULSION BASED ON A SILOXANE-OXALKYLENE COPOLYMER AND AN ORGANIC SURFACE ACTIVE AGENT
EP0191543A1 (en) * 1985-01-15 1986-08-20 Ventec Laboratories, Inc. Silicone insect toxicants
US4654328A (en) * 1984-11-13 1987-03-31 Shin-Etsu Chemical Co., Ltd. Method for controlling sanitary and agricultural pests
EP0249409A2 (en) * 1986-06-07 1987-12-16 Coopers Animal Health Limited Liquid Formulations
JPS63316706A (en) * 1987-06-19 1988-12-26 Osaka Seiyaku:Kk Volatile solution in ambient temperature
JPH07206615A (en) * 1993-11-25 1995-08-08 Dainippon Jochugiku Co Ltd Insecticidal composition
EP0682869A1 (en) * 1994-05-20 1995-11-22 Bayer Ag Non-systemic control of parasites

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Publication number Priority date Publication date Assignee Title
DE2829388A1 (en) * 1977-07-27 1979-02-01 Dow Corning EMULSION BASED ON A SILOXANE-OXALKYLENE COPOLYMER AND AN ORGANIC SURFACE ACTIVE AGENT
US4654328A (en) * 1984-11-13 1987-03-31 Shin-Etsu Chemical Co., Ltd. Method for controlling sanitary and agricultural pests
EP0191543A1 (en) * 1985-01-15 1986-08-20 Ventec Laboratories, Inc. Silicone insect toxicants
EP0249409A2 (en) * 1986-06-07 1987-12-16 Coopers Animal Health Limited Liquid Formulations
JPS63316706A (en) * 1987-06-19 1988-12-26 Osaka Seiyaku:Kk Volatile solution in ambient temperature
JPH07206615A (en) * 1993-11-25 1995-08-08 Dainippon Jochugiku Co Ltd Insecticidal composition
EP0682869A1 (en) * 1994-05-20 1995-11-22 Bayer Ag Non-systemic control of parasites

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