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WO1997019051A1 - Fluorobutenoyloxyacetamides - Google Patents

Fluorobutenoyloxyacetamides Download PDF

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Publication number
WO1997019051A1
WO1997019051A1 PCT/EP1996/004824 EP9604824W WO9719051A1 WO 1997019051 A1 WO1997019051 A1 WO 1997019051A1 EP 9604824 W EP9604824 W EP 9604824W WO 9719051 A1 WO9719051 A1 WO 9719051A1
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WO
WIPO (PCT)
Prior art keywords
spp
formula
compounds
alkyl
preparation
Prior art date
Application number
PCT/EP1996/004824
Other languages
German (de)
French (fr)
Inventor
Udo Kraatz
Wolfram Andersch
Christoph Erdelen
Andreas Turberg
Norbert Mencke
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU75653/96A priority Critical patent/AU7565396A/en
Priority to JP9519331A priority patent/JP2000500473A/en
Priority to EP96938093A priority patent/EP0861227A1/en
Priority to BR9611733A priority patent/BR9611733A/en
Publication of WO1997019051A1 publication Critical patent/WO1997019051A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/16—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms

Definitions

  • the present invention relates to new fluorobutenoyloxyacetic acid amides, processes for their preparation and their use for combating animal
  • Pests especially insects, arachnids and nematodes, which protect in agriculture, in the forest, in the supply and material and in the hygiene sector
  • R 1 represents hydrogen or halogen
  • R 2 represents hydrogen, alkyl or optionally substituted aryl
  • R 3 and R 4 independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, alkoxy or in each case optionally substituted aryi or hetaryl,
  • R J and R 4 together represent alkanediyl or -CH 2 -CH 7 -X-CH 9 -CH 0 -,
  • X represents oxygen, sulfur or NR 5 and
  • R s represents hydrogen, alkyl or optionally substituted aryl
  • the compounds of the formula (I) can exist as geometric and / or optical isomers or isomer mixtures of different compositions.
  • the invention relates to both the pure isomers and the isomer mixtures
  • R 2 , R and R 4 have the meaning given above,
  • R preferably represents hydrogen, fluorine or chlorine
  • R 2 preferably represents hydrogen, C r C 6 alkyl or optionally single to triple, identical or different by halogen, C j -C 6 alkyl! or C ] -C 6 alkoxy substituted phenyl.
  • R 3 and R 4 independently of one another preferably represent hydrogen, C, -C 6 alkyl, C 2 -C ] 0 alkenyl, C 4 -C 8 cycloalkyl, CT-Q-alkoxy, optionally by fluorine, chlorine, bromine , Nitro, cyano, C, -C 6 alkyl, C, -C 6 haloalkyl, C, - C 6 alkoxy, C j -C ⁇ haloalkoxy, C r C 6 alkylthio or C, -C 6 halo alkylthio-substituted phenyl, optionally substituted by fluorine, chlorine or C 1 -C 4 -alkyl, hetaryl with 5 or 6 ring atoms and one or two heteroatoms from the series nitrogen, oxygen and sulfur,
  • R 3 and R 4 stand together for C 4 - C g - AI kandiy 1 or for
  • X represents oxygen, sulfur or NR 5 ,
  • R is preferably hydrogen, C j -C 8 alkyl or optionally substituted by fluorine, chlorine, bromine or C, -C 6 alkyl substituted phenyl
  • R 1 particularly preferably represents hydrogen or fluorine
  • R ⁇ particularly preferably represents hydrogen or C ] -C 4 -alkyl
  • R 'and R 4 independently of one another particularly preferably represent hydrogen, C, -C 4 alkyl, C 3 -C 8 alkenyl, C 3 -C 6 cycloalkyl, C, -C 2 alkoxy, optionally by fluorine , Chlorine, C, -C 4 alkyl or C r C 4 alkoxy substituted phenyl or for pyridyl, furanyl or thienyl,
  • R 3 and R 4 stand together for or for -CH 2 -CH 2 -X-CH 2 -CH 2 -,
  • X represents oxygen, sulfur or NR 5
  • R 5 particularly preferably represents hydrogen, C, -C 4 -alkyl or phenyl which is optionally substituted by fluorine, chlorine, bromine or C r C 4 -alkyl
  • R 1 particularly stands for hydrogen or fluorine
  • R 3 and R 4 independently of one another are particularly emphasized for hydrogen, methyl, ethyl !, propyl, i-propyl, methoxy, ethoxy, allyl, optionally phenyl or substituted by fluorine or chlorine
  • R 3 and R 4 together represent C 5 - or C 6 -alkanedyl
  • CF 2 CF-CH 2 -COCl + HO-CH 2 -CO-N (C 4 H 9 ) 2
  • (I) is characterized in that hydroxy acetic amides of the formula (II) are reacted with acid chlorides of the formula (III), if appropriate in the presence of a diluent and if appropriate in the presence of a base
  • the process according to the invention is preferably carried out in the presence of a diluent
  • Suitable diluents are, in particular, organic solvents, for example optionally chlorinated aliphatic or aromatic hydrocarbons such as cyelohexane, toluene, xylene, dichloromethane, dichloroethane, chloroform or chlorobenzene, ethers such as diethyl ether, dioxane or tetrahydrofuran or nitriles such as acetonitrile
  • Amines are preferably used, in particular tertiary amines such as triethylamine, diazabicycloundecene (DBU), diazabicyclonones (DBN), diazabicycloctane (DABCO) or pyridine or alkali metal or alkaline earth metal carbonates, hydrogen carbonates or hydroxides.
  • tertiary amines such as triethylamine, diazabicycloundecene (DBU), diazabicyclonones (DBN), diazabicycloctane (DABCO) or pyridine or alkali metal or alkaline earth metal carbonates, hydrogen carbonates or hydroxides.
  • Examples include sodium carbonate, potassium carbonate, Sodium bicarbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide are called
  • the reaction temperature can be varied within a wide range. In general, temperatures between -20 ° C and 180 ° C, preferably between 0 ° C and 120 ° C
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is generally 3 1 to 1 3, preferably 1.5 1 to 1 1, 5
  • the reaction is generally carried out under normal pressure
  • reaction mixture is hydrolyzed and the product is extracted with an organic solvent such as ethyl acetate, dichloromethane or toluene
  • hydroxyacetic acid amides of the formula (II) required as starting materials are known and / or can be prepared in a simple manner by known methods
  • 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 products and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are sensitive to normal and resistant species and effective against all or individual development cities
  • the pests mentioned above include
  • Orthoptera e.g. Blatta orientalis, Pe ⁇ planeta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp, Locusta migrato ⁇ a migrato ⁇ oides, Melanoplus differentialis, Schistocerca grega ⁇ a
  • Thysanoptera for example Hercinothrips femorahs, Thrips tabaci
  • Heteroptera e.g. Eurygaster spp, Dysdercus intermedius, Piesma quadrata, Cimex lectulanus, Rhodmus prohxus, Tnatoma spp
  • Hymenoptera From the order of the Hymenoptera, for example Diprion spp, Hoplocampa spp, Lasius spp, Monomo ⁇ um 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, Tanniaulppia sppanppella hppiappella, Bibio , Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa
  • the plant parasitic nematodes include, for example, Pratylenchus spp, Radopholus similis, D ⁇ t ⁇ lenchus dipsaci, Tylenchulus semipenetrans Heterodera spp, Globodera spp, Meloidogyne spp, Aphelenchoides spp, Longidorus spp, Xiphinema spp, T ⁇ chodorus spp
  • the compounds of the formula (1) according to the invention are notable in particular for an excellent nematicidal action, for example against Meloidogyne incognita
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, powdered powders, suspensions, powders, dusting agents, pastes, loose powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances as well as very fine encapsulation in polymeric substances
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents
  • Aromatic compounds such as xylene, toluene or are essentially suitable as liquid solvents
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyelohexane or paraffins, eg 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 cyelohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water
  • Solid carrier materials that come into question are, for example, ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmole lumps or diatomaceous earth and synthetic rock powders, such as highly disperse silica and alumina Silicates, as solid carriers for granulates are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; come in as emulsifying and / or foaming agents
  • nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural 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, e.g. iron oxide, titanium oxide,
  • Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used
  • the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active ingredient 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 ingredients, such as insecticides, attractants, stanlants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • active ingredients such as insecticides, attractants, stanlants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • the insecticides include, for example, Phos - phosphoric esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • Fungicides 2-aminobutane, 2-anilino-4-methyl-6-cyclopropyl-py ⁇ mid ⁇ n, 2 ', 6'-dibromo-2-methyl-4'-t ⁇ fluoromethoxy-4'-trifluoro-methyl-l, 3- th ⁇ azol-5-carboxanilide, 2, 6-di- chloroN- (4-t ⁇ fluoromethylbenzyl) -benzam ⁇ d, (E) -2-methoxy ⁇ m ⁇ no-N-methyl-2- (2-phenoxyphenyl) -acetam ⁇ d, 8-Hydroxyqu ⁇ nohnsulfat, methyl- (E) -2- ⁇ 2- [6- (2-cyano-phenoxy) -py ⁇ m ⁇ d ⁇ n-4-yloxy] -phenyl ⁇ -3-methoxyacrylate, methyl- (E) -methox ⁇ m ⁇ no- [alpha- (o-tolyloxy) -o-to
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb Fenothiocarb, Fenoxycarb, Fenpropath ⁇ n, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate,
  • Fipronil Fluazinam, Flucycloxuron, Flucyth ⁇ nat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox,
  • Imidacloprid Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhaloth ⁇ n, Lufenuron,
  • Tebufenozid Tebufenpyrad, Tebupi ⁇ mphos, Teflubenzuron, Tefluth ⁇ n, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thtofanox, Thio-methon, Thionazin, Thu ⁇ ngiensin, Talomethathonon, Talomethathonon, Talomethathonon XMC, Xylylcarb, YI 5301/5302, Zetameth ⁇ n
  • 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 by which the action of the active compounds 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 and storage damage, the active ingredient is characterized by an excellent residual effect on wood and clay as well as a good alkali stability on limed substrates
  • the active compounds according to the invention act not only against plant, hygiene and supply damage, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks and mites Running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas
  • animal parasites ectoparasites
  • ectoparasites such as tick ticks, leather ticks and mites
  • Anoplu ⁇ da for example Haematopinus spp, Lmognathus spp, Pediculus spp, Phtirus spp, Solenopotes spp
  • Hyalomma spp Hyalomma spp, Rhipicephalus spp, Dermanyssus spp, Railhetia spp, Pneu- monyssus spp, Sternostoma spp, Varroa spp
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are agricultural livestock, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese , Bees, other domestic animals such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice.
  • arthropods are agricultural livestock, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese , Bees, other domestic animals such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice.
  • 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, drinks, drenches, granules, pastes, Boh, the feed-through method, suppositories, by parenteral administration, for example by Injections (intramuscular, subcutaneous, intravenous, intraperitonal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering and with the aid of shaped bodies containing active ingredients, such as collars, ear tags, tail tags, ghedma tapes, holsters, marking devices, etc
  • the active compounds of the formula (I) can be formulated (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or after 100 Apply up to 10,000-fold dilution or use it as a chemical bath
  • CF 2 CF-CH 2 -CO-0-CH 2 -CO-N (nC 4 H 9 ) 2
  • the active ingredient preparation is intimately mixed with soil that is heavily contaminated with the test nematodes.
  • the concentration of the active ingredient in the preparation is practically irrelevant.
  • the treated soil is filled into pots, sat lettuce and the pots are kept at a greenhouse temperature of 25 ° C
  • the lettuce roots are examined for nematode infestation (root galls) and the degree of effectiveness of the active ingredient is determined in%.
  • the degree of effectiveness is 100% if the infestation is avoided completely, it is 0% if the infestation is exactly as high as that of the Control plants in untreated but easily contaminated soil
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cockroach (Plutella macuhpennis) while the leaves are still moist
  • Rice seedlings (Oryzae sativa) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the green rice leafhopper (Nephotettix cincticeps) while the seedlings are still moist
  • Test animals adult sucked 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 Preparation Examples 1, 2, 3, 4, 5 and 6 had an activity of 100% at an exemplary active ingredient concentration of 20 ⁇ g / animal.
  • 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 concentration desired in each case.
  • the criterion for the effect is the occurrence of death in the treated larvae after 48 h (larvicidal effect), or the inhibition of Aduit hatching from the pupa or the inhibition of pupa formation.
  • the criterion for the m-vitro effect of a substance is the inhibition of Flea development, or a development standstill before the adult stage. 100% larvicidal activity means that after 48 hours all larvae have died. 100% development-inhibitory effect means that no adult flies have hatched

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention concerns fluorobutenoyloxyacetamides of formula (I), in which R?1, R2, R3 and R4¿ are as defined in the description, methods of preparing them and their use in the control of animal pests.

Description

FluorbutenoyloxyessiesäureamideFluorobutenoyloxyessamic acid amides
Die vorliegende Erfindung betrifft neue Fluorbutenoyloxyessigsäureamide, Ver- fahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung von tierischenThe present invention relates to new fluorobutenoyloxyacetic acid amides, processes for their preparation and their use for combating animal
Schädlingen, insbesondere von Insekten, Spinnentieren und Nematoden, die in der Landwirtschaft, in den Forsten, im Vorrats- und Material schütz sowie auf dem Hygienesektor vorkommenPests, especially insects, arachnids and nematodes, which protect in agriculture, in the forest, in the supply and material and in the hygiene sector
Es ist bereits bekannt geworden, daß bestimmte Fluoralkenylverbindungen als Insektizide, Akarizide und Nematizide wirksam sind (vgl. z.B WO 92/15 555,It has already become known that certain fluoroalkenyl compounds are effective as insecticides, acaricides and nematicides (cf. e.g. WO 92/15 555,
US-4 952 590, US-4 950 666, US-3 914 251). Die Wirksamkeit und Wirkungs¬ breite dieser Verbindungen ist jedoch insbesondere bei niedrigen Aufwandmengen und Konzentrationen nicht immer völlig zufriedenstellendU.S. 4,952,590, U.S. 4,950,666, U.S. 3,914,251). However, the effectiveness and range of action of these compounds is not always completely satisfactory, especially at low application rates and concentrations
Es wurden nun neue Verbindungen der Formel (I) gefunden,New compounds of the formula (I) have now been found
Figure imgf000003_0001
in welcher
Figure imgf000003_0001
in which
R1 für Wasserstoff oder Halogen steht,R 1 represents hydrogen or halogen,
R2 für Wasserstoff, Alkyl oder gegebenenfalls substituiertes Aryl steht,R 2 represents hydrogen, alkyl or optionally substituted aryl,
R3 und R4 unabhängig voneinander für Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Alkoxy oder jeweils gegebenenfalls substituiertes Aryi oder Hetaryl stehen,R 3 and R 4 independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, alkoxy or in each case optionally substituted aryi or hetaryl,
oderor
RJ und R4 gemeinsam für Alkandiyl oder für -CH2-CH7-X-CH9-CH0- stehen,R J and R 4 together represent alkanediyl or -CH 2 -CH 7 -X-CH 9 -CH 0 -,
worinwherein
X für Sauerstoff, Schwefel oder NR5 steht undX represents oxygen, sulfur or NR 5 and
Rs für Wasserstoff, Alkyl oder gegebenenfalls substituiertes Aryl steht Die Verbindungen der Formel (I) können in Abhängigkeit von der Art der Substi¬ tuenten als geometrische und/oder optische Isomere oder Isomerengemische unter¬ schiedlicher Zusammensetzung vorliegen Die Erfindung betrifft sowohl die reinen Isomeren als auch die IsomerengemischeR s represents hydrogen, alkyl or optionally substituted aryl Depending on the nature of the substituents, the compounds of the formula (I) can exist as geometric and / or optical isomers or isomer mixtures of different compositions. The invention relates to both the pure isomers and the isomer mixtures
Weiter wurde gefunden, daß man die Verbindungen der Formel (I) erhalt, wenn manIt has also been found that the compounds of the formula (I) are obtained when
Hydroxyessigsaureamide der Formel (II)Hydroxyacetic acid amides of the formula (II)
HO-CHR2-CO-NR3R4 (II)HO-CHR 2 -CO-NR 3 R 4 (II)
in welcherin which
R2, R und R4 die oben angegebene Bedeutung haben,R 2 , R and R 4 have the meaning given above,
mit Saurechloπden der Forme! (III)with acid lozenges of shapes! (III)
Figure imgf000004_0001
in welcher
Figure imgf000004_0001
in which
R die oben angegebene Bedeutung hat,R has the meaning given above,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls inoptionally in the presence of a diluent and optionally in
Gegenwart einer Base umsetztIn the presence of a base
Schließlich wurde gefunden, daß die neuen Verbindungen der Formel (I) stark ausgeprägte biologische Eigenschaften besitzen und vor allem zur Bekämpfung von tierischen Schädlingen, insbesondere von Insekten, Spinnentieren und Nematoden, die in der Landwirtschaft, in Forsten, im Vorrats- und Material schütz sowie auf dem Hygienesektor vorkommen, geeignet sindFinally, it was found that the new compounds of the formula (I) have highly pronounced biological properties and above all to control animal pests, in particular insects, arachnids and nematodes, which protect in agriculture, in forests, in the stock and material, and also occur in the hygiene sector, are suitable
Die erfindungsgemaßen Verbindungen sind durch die Formel (I) allgemein definiert Bevorzugte Substituenten bzw Bereiche der in den oben und nachstehend erwähn¬ ten Formeln aufgeführten Reste werden im folgenden erläutertThe compounds according to the invention are generally defined by the formula (I) Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below
R steht bevorzugt für Wasserstoff, Fluor oder ChlorR preferably represents hydrogen, fluorine or chlorine
R2 steht bevorzugt für Wasserstoff, CrC6-Alkyl oder für gegebenenfalls einfach bis dreifach, gleich oder verschieden durch Halogen, Cj-C6-Alky! oder C]-C6-Alkoxy substituiertes Phenyl.R 2 preferably represents hydrogen, C r C 6 alkyl or optionally single to triple, identical or different by halogen, C j -C 6 alkyl! or C ] -C 6 alkoxy substituted phenyl.
R3 und R4 stehen unabhängig voneinander bevorzugt für Wasserstoff, C,-C6-Alkyl, C2-C] 0-Alkenyl, C4-C8-Cycloalkyl, CT-Q-Alkoxy, gegebenenfalls durch Fluor, Chlor, Brom, Nitro, Cyano, C,-C6-Alkyl, C,-C6-Halogenalkyl, C,- C6-Alkoxy, Cj-C^Halogenalkoxy, CrC6-Alkylthio oder C, -C6-Halogen- alkylthio substituiertes Phenyl, gegebenenfalls durch Fluor, Chlor oder C, - C4-Alkyl substituiertes Hetaryl mit 5 oder 6 Ringatomen und ein oder zwei Heteroatomen aus der Reihe Stickstoff, Sauerstoff und Schwefel,R 3 and R 4 independently of one another preferably represent hydrogen, C, -C 6 alkyl, C 2 -C ] 0 alkenyl, C 4 -C 8 cycloalkyl, CT-Q-alkoxy, optionally by fluorine, chlorine, bromine , Nitro, cyano, C, -C 6 alkyl, C, -C 6 haloalkyl, C, - C 6 alkoxy, C j -C ^ haloalkoxy, C r C 6 alkylthio or C, -C 6 halo alkylthio-substituted phenyl, optionally substituted by fluorine, chlorine or C 1 -C 4 -alkyl, hetaryl with 5 or 6 ring atoms and one or two heteroatoms from the series nitrogen, oxygen and sulfur,
oderor
R 3 u n d R 4 s t e h e n g e m e i n s a m fü r C 4 - C g - A I k a n d i y 1 o d e r fü rR 3 and R 4 stand together for C 4 - C g - AI kandiy 1 or for
-CH2-CHrX-CH2-CH2-, worin-CH 2 -CH r X-CH 2 -CH 2 -, wherein
X für Sauerstoff, Schwefel oder NR5 steht,X represents oxygen, sulfur or NR 5 ,
R steht bevorzugt für Wasserstoff, Cj-C8-Alkyl oder gegebenenfalls durch Fluor, Chlor, Brom oder C,-C6-Alkyl substituiertes PhenylR is preferably hydrogen, C j -C 8 alkyl or optionally substituted by fluorine, chlorine, bromine or C, -C 6 alkyl substituted phenyl
R1 steht besonders bevorzugt für Wasserstoff oder FluorR 1 particularly preferably represents hydrogen or fluorine
R~ steht besonders bevorzugt für Wasserstoff oder C]-C4-AlkylR ~ particularly preferably represents hydrogen or C ] -C 4 -alkyl
R' und R4 stehen unabhängig voneinander besonders bevorzugt für Wasserstoff, C,-C4 -Alkyl, C3-C8-Alkenyl, C3-C6-Cycloalkyl, C,-C2-Alkoxy, gegebenen¬ falls durch Fluor, Chlor, C,-C4-Alkyl oder CrC4-Alkoxy substituiertes Phenyl oder für Pyridyl, Furanyl oder Thienyl,R 'and R 4 independently of one another particularly preferably represent hydrogen, C, -C 4 alkyl, C 3 -C 8 alkenyl, C 3 -C 6 cycloalkyl, C, -C 2 alkoxy, optionally by fluorine , Chlorine, C, -C 4 alkyl or C r C 4 alkoxy substituted phenyl or for pyridyl, furanyl or thienyl,
oder R 3 u n d R 4 s t e h e n g e m e i n s a m fü r
Figure imgf000006_0001
o d e r fü r -CH2-CH2-X-CH2-CH2-,or R 3 and R 4 stand together for
Figure imgf000006_0001
or for -CH 2 -CH 2 -X-CH 2 -CH 2 -,
worinwherein
X für Sauerstoff, Schwefel oder NR5 stehtX represents oxygen, sulfur or NR 5
R5 steht besonders bevorzugt für Wasserstoff, C,-C4-Aikyl oder gege¬ benenfalls durch Fluor, Chlor, Brom oder CrC4-Alkyl substituiertes PhenylR 5 particularly preferably represents hydrogen, C, -C 4 -alkyl or phenyl which is optionally substituted by fluorine, chlorine, bromine or C r C 4 -alkyl
R1 steht besonders hervorgehoben für Wasserstoff oder FluorR 1 particularly stands for hydrogen or fluorine
R" steht besonders hevorgehoben für Wasserstoff oder MethylR "stands for hydrogen or methyl
R3 und R4 stehen unabhängig voneinader besonders hervorgehoben für Wasser¬ stoff, Methyl, Ethy!, Propyl, i-Propyl, Methoxy, Ethoxy, Allyl, gegebenen¬ falls durch Fluor oder Chlor substituiertes Phenyl oderR 3 and R 4 independently of one another are particularly emphasized for hydrogen, methyl, ethyl !, propyl, i-propyl, methoxy, ethoxy, allyl, optionally phenyl or substituted by fluorine or chlorine
R3 und R4 stehen gemeinsam für C5- oder C6-AlkandιylR 3 and R 4 together represent C 5 - or C 6 -alkanedyl
Die oben aufgeführten allgemeinen oder in Vorzugsbereichen aufgeführten Reste- definitionen bzw Erläuterungen gelten für die Endprodukte und für die Ausgangs¬ und Zwischenprodukte entsprechend Diese Restedefintionen können untereinander, also auch zwischen den jeweiligen Vorzugsbereichen, beliebig kombiniert werdenThe general definitions or explanations of residues or explanations given above or in preferred areas apply accordingly to the end products and to the starting and intermediate products. These residual definitions can be combined with one another as desired, that is to say also between the respective preferred areas
Erfindungsgemaß bevorzugt werden die Verbindungen der Formel (I), in welchen eine Kombination der vorstehend als bevorzugt (vorzugsweise) aufgeführten Be- deutungen vorliegtAccording to the invention, preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as preferred (preferred)
Erfindungsgemaß besonders bevorzugt werden die Verbindungen der Formel (I), in welchen eine Kombination der vorstehend als besonders bevorzugt aufgeführten Bedeutungen vorliegtAccording to the invention, particular preference is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as being particularly preferred
Erfindungsgemaß besonders hevorgehoben werden die Verbindungen der Formel (I), in welchen eine Kombination der vorstehend als besonders hervorgehoben aufgeführten Bedeutungen vorliegt In den oben und nachstehend aufgeführten Restedefinitionen sind Kohlenwasser¬ stoffreste, wie Alkyl oder Alkenyl, - auch in Verbindung mit Heteroatomen wie Alkoxy oder Alkylthio - soweit möglich, geradkettig oder verzweigtAccording to the invention, particular emphasis is given to the compounds of the formula (I) in which there is a combination of the meanings listed above as particularly emphasized In the radical definitions listed above and below, hydrocarbon radicals, such as alkyl or alkenyl, are straight-chain or branched as far as possible, even in conjunction with heteroatoms such as alkoxy or alkylthio
Verwendet man bei der Herstellung von Verbindungen der Formel (I), z.B 3,4,4- Trifluorbut-3-en-saurechlorid und Hydroxyessigsäure-N,N-dibutylamid als Aus- gangsstoffe, so kann der Reaktionsverlauf durch folgendes Reaktionsschema wiedergegeben werden:If, in the preparation of compounds of the formula (I), for example 3,4,4-trifluorobut-3-ene acid chloride and hydroxyacetic acid-N, N-dibutylamide, are used as starting materials, the course of the reaction can be represented by the following reaction scheme:
CF2=CF-CH2-COCl + HO-CH2-CO-N(C4H9)2 CF 2 = CF-CH 2 -COCl + HO-CH 2 -CO-N (C 4 H 9 ) 2
— > CF2=CF-CH2-CO-0-CH2-CO-N(C4H9)2 -> CF 2 = CF-CH 2 -CO-0-CH 2 -CO-N (C 4 H 9 ) 2
Das oben beschriebene Verfahren zur Herstellung von Verbindungen der FormelThe method described above for the preparation of compounds of the formula
(I) ist dadurch gekennzeichnet, daß man Hydroxy essigsaureamide der Formel (II) mit Saurechloriden der Formel (III) gegebenenfalls in Gegenwart eines Ver¬ dünnungsmittels und gegebenenfalls in Gegenwart einer Base umsetzt(I) is characterized in that hydroxy acetic amides of the formula (II) are reacted with acid chlorides of the formula (III), if appropriate in the presence of a diluent and if appropriate in the presence of a base
Das erfindungsgemäße Verfahren wird vorzugsweise in Gegenwart eines Verdun- nungsmittels durchgeführtThe process according to the invention is preferably carried out in the presence of a diluent
Als Verdünnungsmittel kommen insbesondere organische Losungsmittel in Frage, beispielsweise gegebenenfalls chlorierte aliphatische oder aromatische Kohlenwas¬ serstoffe wie Cyelohexan, Toluol, Xylol, Dichlormethan, Dichlorethan, Chloroform oder Chlorbenzol, Ether wie Diethylether, Dioxan oder Tetrahydrofuran oder Nitrile wie AcetonitrilSuitable diluents are, in particular, organic solvents, for example optionally chlorinated aliphatic or aromatic hydrocarbons such as cyelohexane, toluene, xylene, dichloromethane, dichloroethane, chloroform or chlorobenzene, ethers such as diethyl ether, dioxane or tetrahydrofuran or nitriles such as acetonitrile
Als Base können prinzipiell alle für derartige Acylierungsreaktionen geeigneten or¬ ganischen oder anorganischen Basen verwendet werdenIn principle, all organic or inorganic bases suitable for such acylation reactions can be used as the base
Bevorzugt verwendet werden Amine, insbesondere tertiäre Amine wie Tri¬ ethylamin, Diazabicycloundecen (DBU), Diazabicyclononen (DBN), Diazabicyclo- octan (DABCO) oder Pyridin oder Alkali- oder Erdalkalicarbonate, -hydrogen¬ carbonate oder -hydroxide Beispielhaft seien Natriumcarbonat, Kaliumcarbonat, Natriumhydrogencarbonat, Natriumhydroxid, Kaliumhydroxid und Calciumhy¬ droxid sienannt Die Reaktionstemperatur kann in einem größeren Bereich variiert werden Im allgemeinen arbeitet man bei Temperaturen zwischen -20°C und 180°C, bevorzugt zwischen 0°C und 120°CAmines are preferably used, in particular tertiary amines such as triethylamine, diazabicycloundecene (DBU), diazabicyclonones (DBN), diazabicycloctane (DABCO) or pyridine or alkali metal or alkaline earth metal carbonates, hydrogen carbonates or hydroxides. Examples include sodium carbonate, potassium carbonate, Sodium bicarbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide are called The reaction temperature can be varied within a wide range. In general, temperatures between -20 ° C and 180 ° C, preferably between 0 ° C and 120 ° C.
Das Molverhaitnis der Verbindung der Formel (II) zur Verbindung der Formel (III) betragt im allgemeinen 3 1 bis 1 3, vorzugsweise 1,5 1 bis 1 1 ,5The molar ratio of the compound of formula (II) to the compound of formula (III) is generally 3 1 to 1 3, preferably 1.5 1 to 1 1, 5
Die Umsetzung wird im allgemeinen unter Normaldruck durchgeführtThe reaction is generally carried out under normal pressure
Zur Aufarbeitung wird beispielsweise das Reaktionsgemisch hydrolysiert und das Produkt mit einem organischen Losungsmittel wie Ethylacetat, Dichlormethan oder Toluol extrahiertFor working up, for example, the reaction mixture is hydrolyzed and the product is extracted with an organic solvent such as ethyl acetate, dichloromethane or toluene
Die als Ausgangsstoffe benotigten Hydroxyessigsaureamide der Formel (II) sind bekannt und/oder lassen sich nach bekannten Methoden in einfacher Weise her¬ stellenThe hydroxyacetic acid amides of the formula (II) required as starting materials are known and / or can be prepared in a simple manner by known methods
Die als Ausgangsstoffe benotigten Saurechloπde der Formel (III) sind bekannt (s z B US-5 389 680 sowie EP-432 861)The acid chlorides of the formula (III) required as starting materials are known (see, for example, US Pat. No. 5,389,680 and EP-432,861)
Die Wirkstoffe eignen sich zur Bekämpfung von tierischen Schädlingen, insbeson¬ dere Insekten, Spinnentieren und Nematoden, die in der Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen Sie können vorzugsweise als Pflanzenschutzmittel eingesetzt werden Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwick- lungsstadten wirksam Zu den oben erwähnten Schädlingen gehörenThe 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 products and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are sensitive to normal and resistant species and effective against all or individual development cities The pests mentioned above include
Aus der Ordnung der Isopoda z B Oniscus asellus, Armadillidium vulgäre, Por¬ cellio scaberFrom the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Por¬ cellio scaber
Aus der Ordnung der Diplopoda z B Blaniulus guttulatusFrom the order of the Diplopoda, for example, Blaniulus guttulatus
Aus der Ordnung der Chilopoda z B Geophilus carpophagus, Scutigera specFrom the order of the Chilopoda, for example Geophilus carpophagus, Scutigera spec
Aus der Ordnung der Symphyla z B Scutigerella ImmaculataFrom the order of the Symphyla eg Scutigerella Immaculata
Aus der Ordnung der lhysanura z B Lepisma sacchaπna Aus der Ordnung der Collembola z B Onychiurus armatusFrom the order of the lhysanura, for example Lepisma sacchaπna From the order of the Collembola, for example Onychiurus armatus
Aus der Ordnung der Orthoptera z B Blatta orientalis, Peπplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp , Locusta migratoπa migratoπoides, Melanoplus differentialis, Schistocerca gregaπaFrom the order of the Orthoptera, e.g. Blatta orientalis, Peπplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp, Locusta migratoπa migratoπoides, Melanoplus differentialis, Schistocerca gregaπa
Aus der Ordnung der Dermaptera z B Forficula auπculaπaFrom the order of the Dermaptera eg Forficula auπculaπa
Aus der Ordnung der Isoptera z B Reüculitermes sppFrom the order of the Isoptera, for example Reüculitermes spp
Aus der Ordnung der Anoplura z B Pediculus humanus corpoπs, Haematopinus spp , Linognathus sppFrom the order of the Anoplura, for example Pediculus humanus corpoπs, Haematopinus spp, Linognathus spp
Aus der Ordnung der Mallophaga z B Tnchodectes spp , Damalinea sppFrom the order of the Mallophaga, for example Tnchodectes spp, Damalinea spp
Aus der Ordnung der Thysanoptera z B Hercinothrips femorahs, Thrips tabaciFrom the order of the Thysanoptera, for example Hercinothrips femorahs, Thrips tabaci
Aus der Ordnung der Heteroptera z B Eurygaster spp , Dysdercus intermedius, Piesma quadrata, Cimex lectulanus, Rhodmus prohxus, Tnatoma sppFrom the order of Heteroptera, e.g. Eurygaster spp, Dysdercus intermedius, Piesma quadrata, Cimex lectulanus, Rhodmus prohxus, Tnatoma spp
Aus der Ordnung der Homoptera z B Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus πbis, Aphis fabae, Aphis pomi, Eπosoma lanigerum, Hyalopterus arundmis,From the order of Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus πbis, Aphis fabae, Aphis pomi, Eπosoma lanigerum, Hyalopterus arundmis,
Phylloxera vastatπx, Pemphigus spp , Macrosiphum avenae, Myzus spp , Phorodon humuh, Rhopalosiphum padi, Empoasca spp , Euscehs bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax stnatellus, Nilaparvata lugens, Aonidiella aurantn, Aspidiotus hederae, Pseudococcus spp , Psylla sppPhylloxera vastatπx, Pemphigus spp, Macrosiphum avenae, Myzus spp, Phorodon humuh, Rhopalosiphum padi, Empoasca spp, Euscehs bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax stnatataonidus, aphatobella sapatella sylatyluga, Python aphatophyllus aphid, spp
Aus der Ordnung der Lepidoptera z B Pectinophora gossypiella, Bupalus piniaπus,From 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 , Bucculatπx thurbeπella, Phyllocnistis citrella, Agrotis spp , Euxoa spp , Feltia spp , Earias insulana, Heliothis spp , Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp , Tπchoplusia ni Carpocapsa pomonella, Pieπs spp , Chilo spp , Pyrausta nubilahs, Ephestia kuehniella Galleπa mellonella, Tineola bisselhella, Tinea pelhonella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortπx viπdanaCheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustπa, Euproctis chrysorrhoea, Lymantria spp, Bucculatπx thurbeπella, Phyllocnistis citrella, Agrotis spp, Euxoa spp, Eppiasiappa, Heliothia sppea, Spi , Spodoptera litura, Spodoptera spp, Tπchoplusia ni Carpocapsa pomonella, Pieπs spp, Chilo spp, Pyrausta nubilahs, Ephestia kuehniella Galleπa mellonella, Tineola bisselhella, Tinea pelhonella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortπx viπdana
Aus der Ordnung der Coleoptera z B Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemiineata, Phaedon cochleaπae, Diabrotica spp , Psylliodes chrysocephala, Epilachna vaπvestis, Atomana spp , Oryzaephilus surinamensis, Anthonomus spp , Sitophilus spp , Otiorrhynchus sulcatus, Cosmopohtes sordidus, Ceuthorrhynchus assimihs, Hypera postica, Dermestes spp , Trogoderma spp , Anthrenus spp , Attagenus spp , Lyctus spp , Meligethes aeneus, Ptinus spp , Niptus hololeucus, Gibbium psylloides, Tribolium spp , Tenebno molitor, Agriotes spp , Conoderus spp , Melolontha melolontha, Amphimallon solstitiahs, Costelytra zealandicaFrom the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemiineata, Phaedon cochleaπae, Diabrotica spp, Psylliodes Chrysachisphomususomomusususomomusis, Manalpha spp, Otiorrhynchus sulcatus, Cosmopohtes sordidus, Ceuthorrhynchus assimihs, Hypera postica, Dermestes spp, Trogoderma spp, Anthrenus spp, Attagenus spp, Lyctus spp, Meligethes aeneus, Ptinus spp, Niptus hololeucylides, Agribole sppole, sppolebol sppolides, Agribole sppole, sppolium sppolides, Agribole sppole Conoderus spp, Melolontha melolontha, Amphimallon solstitiahs, Costelytra zealandica
Aus der Ordnung der Hymenoptera z B Diprion spp , Hoplocampa spp , Lasius spp , Monomoπum pharaonis, Vespa sppFrom the order of the Hymenoptera, for example Diprion spp, Hoplocampa spp, Lasius spp, Monomoπum pharaonis, Vespa spp
Aus der Ordnung der Diptera z B Aedes spp , Anopheles spp , Culex spp ,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 , Stomoxys spp , Oestrus spp , Hypoderma spp , Tabanus spp , Tannia spp , Bibio hortulanus, Oscinella fπt, Phorbia spp , Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosaDrosophila 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, Tanniaulppia sppanppella hppiappella, Bibio , Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa
Aus der Ordnung der Siphonaptera z B Xenopsylla cheopis, Ceratophyllus sppFrom the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp
Aus der Ordnung der Arachnida z B Scorpio maurus, Latrodectus mactansFrom the order of the Arachnida, for example Scorpio maurus, Latrodectus mactans
Aus der Ordnung der Acaπna z B Acarus siro, Argas spp , Ornithodoros spp , Dermanyssus galhnae, Eπophyes πbis, Phyllocoptruta oleivora, Boophilus spp , Rhipicephalus spp , Amblyomma spp , Hyalomma spp , Ixodes spp , Psoroptes spp , Chonoptes spp , Sarcoptes spp , Tarsonemus spp , Bryobia praetiosa, Panonychus spp , Tetranychus sppFrom the order of the Acaπna, for example Acarus siro, Argas spp, Ornithodoros spp, Dermanyssus galhnae, Eπophyes πbis, Phyllocoptruta oleivora, Boophilus spp, Rhipicephalus spp, Amblyomma spp, Hyalomma spp, Ixodes spp, Choroptes spp, Choroptes spp, Choroptes spp spp, Bryobia praetiosa, Panonychus spp, Tetranychus spp
Zu den pflanzenparasitaren Nematoden gehören z B Pratylenchus spp , Radopho¬ lus similis, Dιtγlenchus dipsaci, Tylenchulus semipenetrans Heterodera spp , Globodera spp , Meloidogyne spp , Aphelenchoides spp , Longidorus spp , Xiphinema spp , Tπchodorus sppThe plant parasitic nematodes include, for example, Pratylenchus spp, Radopholus similis, Dιtγlenchus dipsaci, Tylenchulus semipenetrans Heterodera spp, Globodera spp, Meloidogyne spp, Aphelenchoides spp, Longidorus spp, Xiphinema spp, Tπchodorus spp
Die erfindungsgemaßen Verbindungen der Formel (1) zeichnen sich insbesondere durch eine hervorragende nematizide Wirkung aus, beispielsweise gegen Meloido- gyne incognitaThe compounds of the formula (1) according to the invention are notable in particular for an excellent nematicidal action, for example against Meloidogyne incognita
Sie zeigen systemische Wirkung und können auch über das Blatt angewendet werdenThey have a systemic effect and can also be used over the leaf
Die Wirkstoffe können in die üblichen Formulierungen überfuhrt werden, wie Lo¬ sungen, Emulsionen, Spπtzpulver, Suspensionen, Pulver, Staubemittel, Pasten, los- liehe Pulver, Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-imprag- nierte Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymeren StoffenThe active ingredients can be converted into the customary formulations, such as solutions, emulsions, powdered powders, suspensions, powders, dusting agents, pastes, loose powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances as well as very fine encapsulation in polymeric substances
Diese Formulierungen werden in bekannter Weise hergestellt, z B durch Vermischen der Wirkstoffe mit Streckmitteln, also flussigen Losungsmitteln und/oder festen Tragerstoffen, gegebenenfalls unter Verwendung von oberflächen¬ aktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaum¬ erzeugenden MittelnThese formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents
Im Falle der Benutzung von Wasser als Streckmittel können z B auch organische Losungsmittel als Hilfslosungsmittei verwendet werden Als flüssige Losungsmittel kommen im wesentlichen in Frage Aromaten, wie Xylol, Toluol, oderIf water is used as an extender, it is also possible, for example, to use organic solvents as auxiliary solvents. Aromatic compounds such as xylene, toluene or are essentially suitable as liquid solvents
Alkylnaphthahne, chlorierte Aromaten und chlorierte aliphatische Kohlenwasser¬ stoffe, wie Chlorbenzole, Chlorethylene oder Methylenchloπd, aliphatische Koh¬ lenwasserstoffe, wie Cyelohexan oder Paraffine, z B Erdolfraktionen, mineralische und pflanzliche Ole, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Methyl isobutylketon oder Cyelo¬ hexanon, stark polare Losungsmittel, wie Dimethylformamid und Dimethyl¬ sulfoxid, sowie WasserAlkylnaphthahne, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyelohexane or paraffins, eg 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 cyelohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water
Als feste Tragerstoffe kommen in Frage z B Ammoniumsalze und naturliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmoπllomt oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsaure Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z B gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengeln; als Emulgier- und/oder schaumerzeugende Mittel kommen inSolid carrier materials that come into question are, for example, ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmole lumps or diatomaceous earth and synthetic rock powders, such as highly disperse silica and alumina Silicates, as solid carriers for granulates are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; come in as emulsifying and / or foaming agents
Frage. z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fett- saure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkylaryl-polyglykolether, Al- kylsulfonate, Alkylsulfate, Arylsulfonate sowie Einweißhydrolysate; als Dispergier¬ mittel kommen in Frage: z.B. Lignin-Sulfitablaugen und MethylcelluloseQuestion. e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natur¬ liche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholipide Weitere Additive können mineralische und vegetabile Ole seinAdhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils
Es können Farbstoffe wie anorganische Pigmente, z.B Eisenoxid, Titanoxid,Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide,
Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalo- cyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werdenFerrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used
Die Formulierungen enthalten im allgemeinen zwischen 0, 1 und 95 Gew -% Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
Der erfindungsgemäße Wirkstoff kann in seinen handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit anderen Wirkstoffen, wie Insektiziden, Lockstoffen, Steπlantien, Bakteriziden, Akariziden, Nematiziden, Fungiziden, wachstumsregulierenden Stof- fen oder Herbiziden vorliegen Zu den Insektiziden zahlen beispielsweise Phos- phorsaureester, Carbamate, Carbonsaureester, chlorierte Kohlenwasserstoffe, Phe- nylharnstoffe, durch Mikroorganismen hergestellte Stoffe u aThe active ingredient 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 ingredients, such as insecticides, attractants, stanlants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, Phos - phosphoric esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
Besonders gunstige Mischpartner sind z B die folgendenThe following are particularly advantageous mixed partners
Fungizide: 2-Amιnobutan, 2-Anilino-4-methyl-6-cyclopropyl-pyπmidιn, 2',6'-Dibromo-2-me- thyl-4'-tπfluoromethoxy-4'-trifluoro-methyl- l ,3-thιazol-5-carboxanilid, 2, 6-Di- chloroN-(4-tπfluoromethylbenzyl)-benzamιd, (E)-2-Methoxyιmιno-N-methyl-2-(2- phenoxyphenyl)-acetamιd, 8-Hydroxyquιnohnsulfat, Methyl-(E)-2-{2-[6-(2-cyano- phenoxy)-pyπmιdιn-4-yloxy]-phenyl }-3-methoxyacrylat, Methyl-(E)-methoxιmιno- [alpha-(o-tolyloxy)-o-tolyl]acetat, 2-Phenylphenol (OPP), Aldimorph, Ampropylfos, Anilazin, Azaconazol,Fungicides: 2-aminobutane, 2-anilino-4-methyl-6-cyclopropyl-pyπmidιn, 2 ', 6'-dibromo-2-methyl-4'-tπfluoromethoxy-4'-trifluoro-methyl-l, 3- thιazol-5-carboxanilide, 2, 6-di- chloroN- (4-tπfluoromethylbenzyl) -benzamιd, (E) -2-methoxyιmιno-N-methyl-2- (2-phenoxyphenyl) -acetamιd, 8-Hydroxyquιnohnsulfat, methyl- (E) -2- {2- [6- (2-cyano-phenoxy) -pyπmιdιn-4-yloxy] -phenyl} -3-methoxyacrylate, methyl- (E) -methoxιmιno- [alpha- (o-tolyloxy) -o-tolyl] acetate, 2-phenylphenol (OPP ), Aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupiπmate, Buthiobate,Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupiπmate, Buthiobate,
Calciumpolysulfid, Captafol, Captan, Carbendazim, Carboxin, Chinomethionat (Quinomethionat), Chloroneb, Chloropicπn, Chlorothalonil, Chlozolinat, Cufraneb, Cymoxanil, Cyproconazole, Cyprofuram,Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicπn, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, Diclobutrazol, Diclofluanid, Diclomezin, Dicloran, Diethofencarb, Difenoconazol, Dimethiπmol, Dimethomorph, Diniconazol, Dinocap, Diphenyl- amin, Dipyπthion, Ditahmfos, Dithianon, Dodine, Drazoxolon, Edifenphos, Epoxyconazole, Ethiπmol, Etπdiazol, Fenaπmol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidm, Fen- propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Feπmzone, Fluazinam, Flu- dioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flu¬ triafol, Folpet, Fosetyl-Aiuminium, Fthahde, Fubeπdazol, Furalaxyl, Furmecyclox, Guazatine, Hexachlorobenzol, Hexaconazol, Hymexazol,Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethiπmol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyπthione, ditahmfos, dithianon, dodine, draifenololazolone, epidonololololone, epidonololololone, epidonololololone, epidonololololone, epidonolololone, epidonolole Fenitropan, Fenpiclonil, Fenpropidm, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Feπmzone, Fluazinam, Fluioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flu¬ triafol, Folpet, Fosetylfaxylolahium, Fosetylfaxyl-Aaholium Furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazole,
Imazahl, Imibenconazol, Iminoctadin, Iprobenfos (IBP), Iprodion Isoprothiolan Kasugamycin, Kupfer-Zubereitungen, wie Kupferhydroxid Kupfernaphthenat, Kupferoxychloπd, Kupfersulfat, Kupferoxid, Oxin-Kupfer und Bordeaux-Mi ¬ schung, Mancopper, Mancozeb, Maneb, Mepanipyπm, Meproni! Metalaxyl, MetconazolImazahl, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion Isoprothiolan Kasugamycin, copper preparations, such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture, Mancopper, Mancozeb, Manπ, Meπ, Mepan, Mepan Metalaxyl, metconazole
Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel-dimethyldithiocarbamat, Nitrothal -isopropyl, Nuaπmol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Phthahd, Pimaπcin, Piperahn Polycarbamate, Polyoxin, Probenazol, Prochloraz, Procymidon, Propamocarb,Methasulfocarb, methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel-dimethyldithiocarbamat, Nitrothal-isopropyl, Nuaπmol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phypahdaminophenol, Phosahdiphenphen, Phosahidiphenphen, Phosahipidoxin, Phosahipidoxin, Phosahipidoxin, Phosahidiphenol Propamocarb
Propiconazole, Propineb, Pyrazophos, Pyπfenox, Pyπmethanil, Pyroquilon, Quintozen (PCNB), Schwefel und Schwefel-Zubereitungen, l ebuconazol, Tecloftalam, Tecnazen, Tetraconazol, Thiabendazol, Thicyofen, Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Tπadimefon Tπadi- menol, Tπazoxid Tπchlamid, Tπcyclazol, Tπdemorph, Tπflumizol Tπfoπn, Tπ- ticonazol. Validamycin A, Vinclozolin, Zineb, ZiramPropiconazole, Propineb, Pyrazophos, Pyπfenox, Pyπmethanil, Pyroquilon, Quintozen (PCNB), sulfur and sulfur preparations, l ebuconazol, Tecloftalam, Tecnazen, Tetraconazol, Thiabendazol, Thicyofen, Thiophanat-methyl, Thiramethyl, Toliradimid, Toliradimid, Toliradimid, Toliradimid, Toliradimid, Toliradimid, Toliradimid, Toliradimid, Toliradimid, Tol - Menol, Tπazoxid Tπchlamid, Tπcyclazol, Tπdemorph, Tπflumizol Tπfoπn, Tπ- ticonazol. Validamycin A, vinclozolin, zineb, ziram
Bakterizide:Bactericides:
Bronopol, Dichlorophen, Nitrapyπn, Nickel-Dimethyldithiocarbamat, Kasugamy- ein, Octhilinon, Furancarbonsaure, Oxytetracyclin, Probenazol, Streptomycin,Bronopol, dichlorophene, nitrapyne, nickel dimethyldithiocarbamate, kasugamyan, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin,
Tecloftalam, Kupfersulfat und andere Kupfer-ZubereitungenTecloftalam, copper sulfate and other copper preparations
Insektizide / Akarizide / Nematizide:Insecticides / acaricides / nematicides:
Abamectin, AC 303 630, Acephat, Acπnathπn, Alanycarb, Aldicarb, Alpha- methπn, Amitraz, Avermectin, AZ 60541 , Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,Abamectin, AC 303 630, Acephat, Acπnathπn, Alanycarb, Aldicarb, Alpha-methπn, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuπngiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthπn, Bifen- thπn, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyπdaben,Bacillus thunngiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthπn, Bifen-thπn, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyπdaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor- fluazuron, Chlormephos, Chlorpyπfos, Chlorpyπfos M, Cis-Resmethπn, Clocy- thπn, Clofentezin, Cyanophos, Cycloprothπn, Cyfluthπn, Cyhalothπn Cyhexatin, Cypermethπn, Cyromazin,Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorofluazuron, Chlormephos, Chlorpyπfos, Chlorpyπfos M, Cis-Resmethπn, Clothiopentosin, Cyfluthπn, Cyhalothπn Cyhexatin, Cypermethπn, Cyromazin,
Deltamethπn, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Di- azinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu- benzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho- prophos, Etπmphos,Deltamethπn, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinone, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu- benzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphi, Emifenphonofen, Emifenphonofen, Emifenphosofen, Emifenphosofen Ethion, ethofenprox, ethoprophos, etπmphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb Fenothiocarb, Fenoxycarb, Fenpropathπn, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate,Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb Fenothiocarb, Fenoxycarb, Fenpropathπn, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate,
Fipronil, Fluazinam, Flucycloxuron, Flucythπnat, Flufenoxuron, Flufenprox, Fluva- linate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox,Fipronil, Fluazinam, Flucycloxuron, Flucythπnat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox,
Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Iver- mectin, Lambda-cyhalothπn, Lufenuron,Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothπn, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyd, Methacπfos, Methamidophob, Methidathion, Methiocarb, Methomyl Metolcarb Milbemectm Monocrotophos, Moxidectin, Naled, NC 184 NI 25, Nitenpyram, Omethoat Oxamyl, Oxydemethon M, Oxydeprofos, Parathion A, Parathion M, Permethnn, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Piπmicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophos, Pyradaphenthion, Pyresmethπn, Pyrethrum, Pyπdaben, Pyπmidifen, Pyπproxifen, Quinalphos,Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyd, Methacπfos, Methamidophob, Methidathion, Methiocarb, Methomyl Metolcarb Milbemectm Monocrotophos, Moxidectin, Naled, NC 184 NI 25, Nitenpyram, Omethoat Oxamyl, Oxydemofos M Parathion A, Parathion M, Permethnn, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Piπmicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophion, Pyrachlophionos Pyπdaben, Pyπmidifen, Pyπproxifen, Quinalphos,
RH 5992,RH 5992,
Sahthion, Sebufos, Silafluofen, Sulfotep, Sulprofos,Sahthion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupiπmphos, Teflubenzuron, Tefluthπn, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thtofanox, Thio- methon, Thionazin, Thuπngiensin, Tralomethπn, Tπarathen, Tπazophos, Tπ- azuron, Tπchlorfon, Tπflumuron, Tπmethacarb, Vamidothion, XMC, Xylylcarb, YI 5301 / 5302, ZetamethπnTebufenozid, Tebufenpyrad, Tebupiπmphos, Teflubenzuron, Tefluthπn, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thtofanox, Thio-methon, Thionazin, Thuπngiensin, Talomethathonon, Talomethathonon, Talomethathonon XMC, Xylylcarb, YI 5301/5302, Zetamethπn
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Herbiziden oder mit Düngemitteln und Wachstumsregulatoren ist möglichA mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible
Die erfindungsgemaßen Wirkstoffe können ferner in ihren handelsüblichen Formu¬ lierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit Synergisten vorliegen Synergisten sind Verbindungen, durch die die Wirkung der Wirkstoffe gesteigert wird, ohne daß der zugesetzte Synergist selbst aktiv wirksam sein mußThe 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 by which the action of the active compounds is increased without the added synergist itself having to be active
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten An¬ wendungsformen kann in weiten Bereichen variieren Die Wirkstoffkonzentration der Anwendungsformen kann von 0,0000001 bis zu 95 Gew -% Wirkstoff, vorzugsweise zwischen 0,0001 und 1 Gew -% liegenThe active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight
Die Anwendung geschieht in einer den Anwendungsformen angepaßten üblichen WeiseThe application takes place in a customary manner adapted to the application forms
Bei der Anwendung gegen Hygiene- und Vorratsschadhnge zeichnet sich der Wirkstoff durch eine hervorragende Residualwirkung auf Holz und Ton sowie durch eine gute Alkali Stabilität auf gekalkten Unterlagen ausWhen used against hygiene and storage damage, the active ingredient is characterized by an excellent residual effect on wood and clay as well as a good alkali stability on limed substrates
Die erfindungsgemaßen Wirkstoffe wirken nicht nur gegen Pflanzen-, Hygiene- und Vorratsschadhnge, sondern auch auf dem veterinärmedizinischen Sektor gegen tierische Parasiten (Ektoparasiten) wie Schildzecken Lederzecken Raudemilben Laufmilben, Fliegen (stechend und leckend), parasitierende Fliegenlarven, Lause, Haarlinge, Federlinge und Flohe Zu diesen Parasiten gehörenThe active compounds according to the invention act not only against plant, hygiene and supply damage, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks and mites Running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas These parasites include
Aus der Ordnung der Anopluπda z B Haematopinus spp , Lmognathus spp , Pediculus spp , Phtirus spp , Solenopotes sppFrom the order of the Anopluπda, for example Haematopinus spp, Lmognathus spp, Pediculus spp, Phtirus spp, Solenopotes spp
Aus der Ordnung der Mallophagida und den Unterordnungen Amblyceπna sowie Ischnoceπna z B Tπmenopon spp , Menopon spp , Tπnoton spp , Bovicola spp , Werneckiella spp , Lepikentron spp , Damalina spp , Tnchodectes spp , Felicola sppFrom the order of the Mallophagida and the subordinates Amblyceπna and Ischnoceπna eg Tπmenopon spp, Menopon spp, Tπnoton spp, Bovicola spp, Werneckiella spp, Lepikentron spp, Damalina spp, Tnchodectes spp, Felicola spp
Aus der Ordnung Diptera und den Unterordnungen Nematocerina sowie Brachyceπna z B Aedes spp , Anopheles spp , Culex spp , Simuhum spp , Eusimuhum spp , Phlebotomus spp , Lutzomyia spp , Cuhcoides spp , Chrysops spp , Hybomitra spp , Atylotus spp , Tabanus spp , Haematopota spp , Phihpomyia spp , Braula spp , Musca spp , Hydrotaea spp , Stomoxys spp , Haematobia spp , Morellia spp , Fannia spp , Glossina spp , Calhphora spp , Lucilia spp , Chrysomyia spp , Wohlfahrtia spp , Sarcophaga spp , Oestrus spp , Hypoderma spp , Gasterophilus spp , Hippobosca spp , Lipoptena spp , Melophagus sppFrom the order Diptera and the subordinates Nematocerina and Brachyceπna eg Aedes spp, Anopheles spp, Culex spp, Simuhum spp, Eusimuhum spp, Phlebotomus spp, Lutzomyia spp, Cuhcoides spp, Chrysops spp, Hybomitra spp, Tabylopus spp, Atylotusota, , Phihpomyia spp, Braula spp, Musca spp, Hydrotaea spp, Stomoxys spp, Haematobia spp, Morellia spp, Fannia spp, Glossina spp, Calhphora spp, Lucilia spp, Chrysomyia spp, Wohlfahrtia spp, Sarcophaga spp, Oestrus spp, Gasterophil spp, Hypoderma spp, Hypoderma spp spp, Hippobosca spp, Lipoptena spp, Melophagus spp
Aus der Ordnung der Siphonapteπda z B Pulex spp , Ctenocephahdes spp , Xenopsylla spp , Ceratophyllus sppFrom the order of the Siphonapteπda eg Pulex spp, Ctenocephahdes spp, Xenopsylla spp, Ceratophyllus spp
Aus der Ordnung der Heteropteπda z B Cimex spp , Tπatoma spp , Rhodmus spp , Panstrongylus sppFrom the order of the heteropteπda, for example Cimex spp, Tπatoma spp, Rhodmus spp, Panstrongylus spp
Aus der Ordnung der Blattaπda z B Blatta orientalis, Peπplaneta americana, Blattela germanica, Supella sppFrom the order of the Blattaπda, for example Blatta orientalis, Peπplaneta americana, Blattela germanica, Supella spp
Aus der Unterklasse der Acaπa (Acaπda) und den Ordnungen der Meta- sowie Mesostigmata z B Argas spp , Ornithodorus spp , Otobius spp , Ixodes spp , Amblyomma spp , Boophilus spp , Dermacentor spp , Haemophysahs spp ,From the subclass of the Acaπa (Acaπda) and the orders of the Meta and Mesostigmata e.g. Argas spp, Ornithodorus spp, Otobius spp, Ixodes spp, Amblyomma spp, Boophilus spp, Dermacentor spp, Haemophysahs spp,
Hyalomma spp , Rhipicephalus spp , Dermanyssus spp , Railhetia spp , Pneu- monyssus spp , Sternostoma spp , Varroa sppHyalomma spp, Rhipicephalus spp, Dermanyssus spp, Railhetia spp, Pneu- monyssus spp, Sternostoma spp, Varroa spp
Aus der Ordnung der Actinedida (Prostigmata) und Acaπdida (Astigmata) z B Acarapis spp , Cheyletiella spp , Ornithocheyletia spp , Myobia spp , Psorergates spp , Demodex spp , Trombicula spp , Listrophorus spp , Acarus spp , Tyrophagus spp , Caloglyphus spp , Hypodectes spp , Pterohchus spp , Psoroptes spp , Chonoptes spp , Otodectes spp , Sarcoptes spp , Notoedres spp , Knemidocoptes spp , Cytodites spp , Laminosioptes sppFrom the order of the Actinedida (Prostigmata) and Acaπdida (Astigmata) z. B. Acarapis spp, Cheyletiella spp, Ornithocheyletia spp, Myobia spp, Psorergates spp, Demodex spp, Trombicula spp, Listrophorus spp, Acarus spp, Tyrophagus spp, Caloglyphus spp, Hypodectes spp, Pterohchus spp, Psoroptes spp, Chonoptes spp, Otodectes spp, Sarcoptes spp, Notoedres spp, Knemidocodtes spp, Knemidocodtes
Die erfindungsgemaßen Wirkstoffe der Formel (I) eignen sich auch zur Be¬ kämpfung von Arthropoden, die landwirtschaftliche Nutztiere, wie z B Rinder, Schafe, Ziegen, Pferde, Schweine, Esel, Kamele, Büffel, Kaninchen, Huhner, Puten, Enten, Gänse, Bienen, sonstige Haustiere wie z B Hunde, Katzen, Stuben¬ vogel, Aquarienfische sowie sogenannte Versuchstiere, wie z B Hamster, Meer- schweinchen, Ratten und Mause befallen Durch die Bekämpfung dieser Arthro¬ poden sollen Todesfalle und Leistungsminderungen (bei Fleisch, Milch, Wolle, Hauten, Eiern, Honig usw ) vermindert werden, so daß durch den Einsatz der er¬ findungsgemaßen Wirkstoffe eine wirtschaftlichere und einfachere Tierhaltung möglich istThe active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are agricultural livestock, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese , Bees, other domestic animals such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice. By fighting these arthropods death cases and reduced performance (with meat, milk , Wool, skin, eggs, honey, etc.) can be reduced, so that the use of the active compounds according to the invention enables more economical and simple animal husbandry
Die Anwendung der erfindungsgemaßen Wirkstoffe geschieht im Veteπnarsektor in bekannter Weise durch enterale Verabreichung in Form von beispielsweise Tabletten, Kapseln, Tranken, Drenchen, Granulaten, Pasten, Boh, des feed- through- Verfahrens, von Zäpfchen, durch parenterale Verabreichung, wie zum Beispiel durch Injektionen (intramuskulär, subcutan, intravenös, intraperitonal u a ), Implantate, durch nasale Applikation, durch dermale Anwendung in Form bei¬ spielsweise des Tauchens oder Badens (Dippen), Sprühens (Spray), Aufgießens (Pour-on und Spot-on), des Waschens, des Einpuderns sowie mit Hilfe von wirkstoffhaltigen Formkorpern, wie Halsbandern, Ohrmarken, Schwanzmarken, Ghedmaßenbandern, Halftern, Markierungsvorrichtungen uswThe 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, drinks, drenches, granules, pastes, Boh, the feed-through method, suppositories, by parenteral administration, for example by Injections (intramuscular, subcutaneous, intravenous, intraperitonal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering and with the aid of shaped bodies containing active ingredients, such as collars, ear tags, tail tags, ghedma tapes, holsters, marking devices, etc
Bei der Anwendung für Vieh, Geflügel, Haustiere etc kann man die Wirkstoffe der Formel (I) als Formulierungen (beispielsweise Pulver, Emulsionen, fließfahige Mittel), die die Wirkstoffe in einer Menge von 1 bis 80 Gew -% enthalten, direkt oder nach 100 bis 10 000-facher Verdünnung anwenden oder sie als chemisches Bad verwendenWhen used for cattle, poultry, pets, etc., the active compounds of the formula (I) can be formulated (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or after 100 Apply up to 10,000-fold dilution or use it as a chemical bath
Die Herstellung und die Verwendung der erfindungsgemaßen Wirkstoffe gehen aus den folgenden Beispielen hervor - l o -The preparation and use of the active compounds according to the invention can be seen from the following examples - lo -
HerstellungsbeispieleManufacturing examples
Beispiel 1example 1
CF2=CF-CH2-CO-0-CH2-CO-N(n-C4H9)2 CF 2 = CF-CH 2 -CO-0-CH 2 -CO-N (nC 4 H 9 ) 2
Zu einer Losung von 9,35 g (50 mmol) Hydroxyessigsaure-N,N-dibutylamid in 30 ml Acetonitril und 7,3 g (53 mmol) Kaliumcarbonat tropft man bei 20°C unterA solution of 9.35 g (50 mmol) of hydroxyacetic acid-N, N-dibutylamide in 30 ml of acetonitrile and 7.3 g (53 mmol) of potassium carbonate is added dropwise at 20 ° C.
Rühren 7,9 g (50 mmol) 3,4,4-Trifluorbut-3-ensaurechlorid Nach 1 Stunde Nach- ruhrzeit gießt man auf Wasser und extrahiert das Produkt mit Methylenchlorid Die organische Phase wird abgetrennt, im Vakuum eingedampft und der Rück¬ stand am Kieselgel im System Chloroform/Essigester (9 1) gereinigt Man erhalt 5,6 g (36 % der Theorie) 3,4,4-Trifluor-but-3-ensaure-N,N-dibutylaminocarbonyl- methylester vom Kp 130°/0,3 mm und einem log p* = 3,43Stirring 7.9 g (50 mmol) of 3,4,4-trifluorobut-3-ene acid chloride After 1 hour of stirring, the mixture is poured onto water and the product is extracted with methylene chloride. The organic phase is separated off, evaporated in vacuo and the residue purified on silica gel in the chloroform / ethyl acetate (9 l) system. 5.6 g (36% of theory) of 3,4,4-trifluorobut-3-eneate N, N-dibutylaminocarbonyl methyl ester of bp 130 ° / 0.3 mm and a log p * = 3.43
Analog bzw gemäß den allgemeinen Angaben zur Herstellung erhalt man die folgenden Verbindungen der Formel (I)The following compounds of the formula (I) are obtained analogously or according to the general information on the preparation
* log p = Dekadischer Logarithmus des n-Ocanol/Wasser-Verteilerkoeffizien- ten, bestimmt durch HPLC-Analytik an reversed phase mit* log p = decimal logarithm of the n-ocanol / water distribution coefficient, determined by HPLC analysis on reversed phase with
H.O/CH^CN
Figure imgf000019_0001
HO / CH ^ CN
Figure imgf000019_0001
- 1 ö -- 1 ö -
AnwendungsbeisnieleApplication examples
Beispiel AExample A
Grenzkonzentrations-Test / NematodenLimit concentration test / nematodes
Testnematode Meloidogyne incognitaTest nematode Meloidogyne incognita
Losungsmittel 4 Gewichtstelle AcetonSolvent 4 weight acetone
Emulgator 1 Gewichtstell AlkylarylpolyglykoletherEmulsifier 1 part by weight alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge- wichtsteil Wirkstoff mit der angegebenen Menge Losungsmittel, gibt die angege¬ bene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die ge¬ wünschte KonzentrationTo produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration
Die Wirkstoffzubereitung wird innig mit Boden vermischt, der mit den Test- nematoden stark verseucht ist Dabei spielt die Konzentration des Wirkstoffs in der Zubereitung praktisch keine Rolle, entscheidend ist allein die Wirkstoffmenge pro Volumeneinheit Boden, welche in ppm (= mg/l) angegeben wird Man füllt den behandelten Boden in Topfe, sat Salat em und halt die Topfe bei einer Gewachs¬ haus-Temperatur von 25°CThe active ingredient preparation is intimately mixed with soil that is heavily contaminated with the test nematodes. The concentration of the active ingredient in the preparation is practically irrelevant. The decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (= mg / l) The treated soil is filled into pots, sat lettuce and the pots are kept at a greenhouse temperature of 25 ° C
Nach vier Wochen werden die Salatwurzeln auf Nematodenbefall (Wurzelgallen) untersucht und der Wirkungsgrad des Wirkstoffs in % bestimmt Der Wirkungs¬ grad ist 100 %, wenn der Befall vollständig vermieden wird, er ist 0 %, wenn der Befall genau so hoch ist wie bei den Kontroll pflanzen in unbehandeltem aber in o »leicher Weise verseuchtem BodenAfter four weeks, the lettuce roots are examined for nematode infestation (root galls) and the degree of effectiveness of the active ingredient is determined in%. The degree of effectiveness is 100% if the infestation is avoided completely, it is 0% if the infestation is exactly as high as that of the Control plants in untreated but easily contaminated soil
Bei diesem Test besaßen z B die Verbindungen gemäß den Herstellungsbeispielen 2 und 8 bei einer beispielhaften Wirkstoffkonzentration von 20 ppm einen Wirkungsgrad von 100 % Beispiel BIn this test, for example, the compounds according to Preparation Examples 2 and 8 had an efficiency of 100% at an exemplary active ingredient concentration of 20 ppm. Example B
Phaedon-Larven-TestPhaedon larval test
Losungsmittel 7 Gewichtsteile DimethylformamidSolvent 7 parts by weight of dimethylformamide
Emulgator. 1 Gewichtsteil AlkylarylpolyglykoletherEmulsifier. 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge¬ wichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und der angegebe¬ ne Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte KonzentrationTo produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the given amount of emulsifier, and the concentrate is diluted with water to the desired concentration
Kohlblatter (Brassica oleracea) werden durch Tauchen in die Wirkstoffzubereitung der gewünschten Konzentration behandelt und mit Meerrettichblattkafer-Larven (Phaedon cochleariae) besetzt, solange die Blatter noch feucht sindCabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with horseradish leaf beetle larvae (Phaedon cochleariae) while the leaves are still moist
Nach der gewünschten Zeit die die Abtötung in % bestimmt Dabei bedeutet 100 %, daß alle Kafer-Larven abgetötet wurden, 0 % bedeutet, daß keine Kafer- Larven abgetötet wurdenAfter the desired time, which determines the destruction in%. 100% means that all the beetle larvae have been killed, 0% means that no beetle larvae have been killed
In diesem Test bewirkte z B die Verbindung gemäß Herstellungsbeispiel 5 bei einer beispielhaften Wirkstoffkonzentration von 0,1 % eine Abtötung von 100 % nach 7 Tagen In this test, for example, the compound according to Preparation Example 5, with an exemplary active ingredient concentration of 0.1%, caused 100% killing after 7 days
Beispiel CExample C
Plutella-TestPlutella test
Losungsmittel 7 Gewichtstelle DimethylformamidSolvent 7 weight unit dimethylformamide
Emulgator 1 Gewichtstell AlkylarylpolyglykoletherEmulsifier 1 part by weight alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge¬ wichtsteil Wirkstoff mit der angegebenen Menge Losungsmittel und der angegebe¬ ne Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte KonzentrationTo produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the given amount of emulsifier, and the concentrate is diluted with water to the desired concentration
Kohlblatter (Brassica oleracea) werden durch Tauchen in die Wirkstoffzubereitung der gewünschten Konzentration behandelt und mit Raupen der Kohlschabe (Plutella macuhpennis) besetzt, solange die Blatter noch feucht sindCabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the cockroach (Plutella macuhpennis) while the leaves are still moist
Nach der gewünschten Zeit die die Abtötung in % bestimmt Dabei bedeutet 100 %, daß alle Raupen abgetötet wurden, 0 % bedeutet, daß keine Raupen abgetötet wurdenAfter the desired time, which determines the kill in%. 100% means that all the caterpillars have been killed, 0% means that no caterpillars have been killed
In diesem Test bewirkten z B die Verbindungen gemäß den Herstellungsbeispielen 2, 3, 4, 5, 6 und 7 bei einer beispielhaften Wirkstoffkonzentration von 0, 1 % eine Abtötung von 100 % nach 7 Tagen In this test, for example, the compounds according to Preparation Examples 2, 3, 4, 5, 6 and 7, with an exemplary active compound concentration of 0.1%, caused 100% killing after 7 days
Beispiel DExample D
Nephotettix-TestNephotettix test
Losungsmittel 7 Gewichtstelle DimethylformamidSolvent 7 weight unit dimethylformamide
Emulgator 1 Gewichtstell AlkylarylpolyglykoletherEmulsifier 1 part by weight alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge- wichtsteil Wirkstoff mit der angegebenen Menge Losungsmittel und der angegebe¬ ne Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte KonzentrationTo produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration
Reiskeimlinge (Oryzae sativa) werden durch Tauchen in die Wirkstoffzubereitung der gewünschten Konzentration behandelt und mit Larven der grünen Reiszikade (Nephotettix cincticeps) besetzt, solange die Keimlinge noch feucht sindRice seedlings (Oryzae sativa) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the green rice leafhopper (Nephotettix cincticeps) while the seedlings are still moist
Nach der gewünschten Zeit die die Abtötung in % bestimmt Dabei bedeutet 100 %, daß alle Zikaden abgetötet wurden, 0 % bedeutet, daß keine Zikaden abgetötet wurdenAfter the desired time, which determines the kill in%. 100% means that all cicadas have been killed, 0% means that no cicadas have been killed
In diesem Test zeigte z B die Verbindung gemäß Herstellungsbeispiel 6 bei einer beispielhaften Wirkstoffkonzentration von 0,1 % nach 6 Tagen einen Abtotungs- grad von 100 % In this test, for example, the compound according to Preparation Example 6, with an exemplary active ingredient concentration of 0.1%, showed a degree of death of 100% after 6 days.
Beispiel EExample E
Test mit Boophilus microplus resistent / SP-resistenter Parkhurst-StammTest with Boophilus microplus resistant / SP-resistant Parkhurst strain
Testtiere: adulte gesogene WeibchenTest animals: adult sucked females
Lösungsmittel: DimethylsulfoxidSolvent: dimethyl sulfoxide
20 mg Wirkstoff werden in 1 ml Dimethylsulfoxid gelöst, geringere Konzentra¬ tionen werden durch verdünnen in dem gleichen Lösungsmittel hergestellt.20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide, lower concentrations are produced by dilution in the same solvent.
Der Test wird in 5-fach-Bestimmung durchgeführt. 1 μl der Lösungen wird in das Abdomen injiziert, die Tiere in Schalen überführt und in einem klimatisierten Raum aufbewahrt. Die Wirkung wird über die Hemmung der Eiablage bestimmt. Dabei bedeutet 100 %, daß keine Zecke gelegt hat.The test is carried out in 5-fold determination. 1 μl of the solutions is injected into the abdomen, the animals are transferred to dishes and stored in an air-conditioned room. The effect is determined by the inhibition of egg laying. 100% means that no tick has laid.
In diesem Test hatten z.B. die Verbindungen gemäß den Herstellungsbeispielen 1, 2, 3, 4, 5 und 6 bei einer beispielhaften Wirkstoffkonzentration von 20 μg/Tier eine Wirkung von 100 %. In this test, for example, the compounds according to Preparation Examples 1, 2, 3, 4, 5 and 6 had an activity of 100% at an exemplary active ingredient concentration of 20 μg / animal.
Beispiel FExample F
Test mit Fliegenlarven / Entwicklungshemmende WirkungTest with fly larvae / development-inhibiting effect
Testtiere Alle larvalen Stadien von Lucilia cupπna (OP-resistent)Test animals All larval stages of Lucilia cupπna (OP-resistant)
[Puppen und Adulte (ohne Kontakt zum Wirkstoff)][Dolls and adults (without contact to the active ingredient)]
Losungsmittel 35 Gewichtsteile EthylenglykolmonomethyletherSolvent 35 parts by weight of ethylene glycol monomethyl ether
35 Gewichtsteile Nonylphenolpolyglykolether35 parts by weight of nonylphenol polyglycol ether
Zwecks Herstellung einer geeigneten Formulierung vermischt man drei Gewichts¬ teile Wirkstoff mit sieben Teilen des oben angegebenen Losungsmittel-Emulgator- Gemisches und verdünnt das so erhaltene Emulsionskonzentrat mit Wasser auf die jeweils gewünschte Konzentration.To produce a suitable formulation, three parts by weight of active ingredient are mixed with seven parts of the solvent / emulsifier mixture mentioned above, and the emulsion concentrate thus obtained is diluted with water to the concentration desired in each case.
30 bis 50 Larven je Konzentration werden auf in Glasrohrchen befindliches Pferdefleisch (1 cm3) gebracht, auf welches 500 μl der zu testenden Verdünnung pipettiert werden Die Glasröhrchen werden in Kunststoffbecher gestellt, deren Boden mit Seesand bedeckt ist, und im klimatisierten Raum (26°C ± 1 ,5°C, 70 % rei Feuchte + 10 %) aufbewahrt Die Wirkungskontrolle erfolgt nach 24 Stunden und 48 Stunden (larvizide Wirkung) Nach dem Auswandern der Larven (ca 72 h) werden die Glasrohrchen entfernt und gelochte Kunststoffdeckel auf die Becher gesetzt Nach 1 1/2-facher Entwicklungsdauer (Schlupf der Kontrollfliegen) wer¬ den die geschlupften Fliegen und die Puppen/Puppenhullen ausgezahlt30 to 50 larvae per concentration are placed on horse meat (1 cm 3 ) in glass tubes, onto which 500 μl of the dilution to be tested are pipetted. The glass tubes are placed in plastic beakers, the bottom of which is covered with sea sand, and in an air-conditioned room (26 ° C ± 1, 5 ° C, 70% pure moisture + 10%). The effectiveness is checked after 24 hours and 48 hours (larvicidal effect). After the larvae have emigrated (approx. 72 h), the glass tubes are removed and perforated plastic lids on the beakers set After 1 1/2 times the development period (hatching of the control flies), the hatched flies and the dolls / doll covers are paid out
Als Kriterium für die Wirkung gilt der Eintritt des Todes bei den behandelten Larven nach 48 h (larvizider Effekt), bzw die Hemmung des Aduitschlupfes aus den Puppen bzw die Hemmung der Puppenbildung Als Kriterium für die m-vitro-Wirkung einer Substanz gilt die Hemmung der Flohentwicklung, bzw ein Entwicklungsstillstand vor dem Adulten-Stadium Dabei bedeutet 100 % larvizide Wirkung, daß nach 48 Stunden alle Larven abgestorben sind 100 % entwicklungs- mhibitoπsche Wirkung bedeutet, daß keine adulte Fliegen geschlupft sindThe criterion for the effect is the occurrence of death in the treated larvae after 48 h (larvicidal effect), or the inhibition of Aduit hatching from the pupa or the inhibition of pupa formation. The criterion for the m-vitro effect of a substance is the inhibition of Flea development, or a development standstill before the adult stage. 100% larvicidal activity means that after 48 hours all larvae have died. 100% development-inhibitory effect means that no adult flies have hatched
In diesem Test hatten z B die Verbindungen gemäß den Herstellungsbeispielen 2, 3, 4, 5 und 6 bei einer beispielhaften Wirkstoffkonzentration von 1 000 ppm eine Wirkung von 100 % In this test, for example, the compounds according to Preparation Examples 2, 3, 4, 5 and 6 had an activity of 100% at an exemplary active ingredient concentration of 1,000 ppm

Claims

Patentansprücheclaims
1 Verbindungen der Formel (I)1 compounds of formula (I)
Figure imgf000026_0001
Figure imgf000026_0001
in welcherin which
R1 für Wasserstoff oder Halogen steht,R 1 represents hydrogen or halogen,
R~ für Wasserstoff, Alkyl oder gegebenenfalls substituiertes Aryl steht,R ~ represents hydrogen, alkyl or optionally substituted aryl,
R3 und R4 unabhängig voneinander für Wasserstoff, Alkyl, Alkenyl, Cycloalkyl, Alkoxy oder jeweils gegebenenfalls substituiertes Aryl oder Hetaryl stehen,R 3 and R 4 independently of one another represent hydrogen, alkyl, alkenyl, cycloalkyl, alkoxy or in each case optionally substituted aryl or hetaryl,
oderor
R3 und R4 gemeinsam für Alkandiyl oder für -CH2-CH2-X-CH2-CH2- stehen,R 3 and R 4 together represent alkanediyl or -CH 2 -CH 2 -X-CH 2 -CH 2 -,
worinwherein
X für Sauerstoff, Schwefel oder NR5 steht undX represents oxygen, sulfur or NR 5 and
Rs für Wasserstoff, Alkyl oder gegebenenfalls substituiertes Aryl stehtR s represents hydrogen, alkyl or optionally substituted aryl
2 Verfahren zur Herstellung von Verbindungen der Formel (I) gemäß2 Process for the preparation of compounds of formula (I) according to
Anspruch 1, dadurch gekennzeichnet, daß manClaim 1, characterized in that one
Hydroxyessigsaureamide der Formel (II)Hydroxyacetic acid amides of the formula (II)
HO-CHR2-CO-NR3R4 (II)HO-CHR 2 -CO-NR 3 R 4 (II)
in welcher R2, R3 und R4 die in Anspruch 1 angegebene Bedeutung haben,in which R 2 , R 3 and R 4 have the meaning given in claim 1,
mit Saurechloπden der Formel (III)with acid chlorides of the formula (III)
Figure imgf000027_0001
in welcher
Figure imgf000027_0001
in which
R1 die in Anspruch 1 angegebene Bedeutung hat,R 1 has the meaning given in claim 1,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart einer Base umsetztif appropriate in the presence of a diluent and if appropriate in the presence of a base
Schädlingsbekämpfungsmittel, gekennzeichnet durch einen Gehalt an mmdestens einer Verbindung der Formel (I) gemäß Anspruch 1Pesticide, characterized in that it contains at least one compound of the formula (I) according to Claim 1
Verwendung von Verbindungen der Formel (I) gemäß Anspruch 1 zur Bekämpfung von SchädlingenUse of compounds of formula (I) according to claim 1 for controlling pests
Verfahren zur Bekämpfung von Schädlingen, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) gemäß Anspruch 1 auf Schädlinge und/oder ihren Lebensraum einwirken laßtProcess for combating pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat
Verfahren zur Herstellung von Schädlingsbekämpfungsmitteln, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischtProcess for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active agents
Verwendung von Verbindungen der Formel (I) gemäß Anspruch 1 zur Herstellung von Schädlingsbekämpfungsmitteln Use of compounds of formula (I) according to claim 1 for the preparation of pesticides
PCT/EP1996/004824 1995-11-17 1996-11-05 Fluorobutenoyloxyacetamides WO1997019051A1 (en)

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Publication number Priority date Publication date Assignee Title
WO2000071500A1 (en) * 1999-05-19 2000-11-30 Bayer Aktiengesellschaft Halogen compounds

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JP2000500473A (en) 2000-01-18
EP0861227A1 (en) 1998-09-02
BR9611733A (en) 1999-02-23
AU7565396A (en) 1997-06-11
DE19542935A1 (en) 1997-05-22

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