EP0000345B1 - Substituted phenoxybenzyloxycarbonyl derivatives, their preparation and their use as insecticides and acaricides - Google Patents

Substituted phenoxybenzyloxycarbonyl derivatives, their preparation and their use as insecticides and acaricides Download PDF

Info

Publication number
EP0000345B1
EP0000345B1 EP78100252A EP78100252A EP0000345B1 EP 0000345 B1 EP0000345 B1 EP 0000345B1 EP 78100252 A EP78100252 A EP 78100252A EP 78100252 A EP78100252 A EP 78100252A EP 0000345 B1 EP0000345 B1 EP 0000345B1
Authority
EP
European Patent Office
Prior art keywords
formula
vinyl
spp
derivatives
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100252A
Other languages
German (de)
French (fr)
Other versions
EP0000345A1 (en
Inventor
Rainer Dr. Fuchs
Ingeborg Dr. Hammann
Wilhelm Dr. Stendel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000345A1 publication Critical patent/EP0000345A1/en
Application granted granted Critical
Publication of EP0000345B1 publication Critical patent/EP0000345B1/en
Expired legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • the present invention relates to new substituted phenoxybenzyloxycarbonyl derivatives, several processes for their preparation and their use as insecticides and acaricides.
  • phenoxybenzyl acetates or carboxylates e.g. 3'-phenoxybenzyl- ⁇ -isopropyl- (3,4-dimethoxy-phenyl) -acetate, (6-chloro-piperonyl) -2,2-dimethyl-3- (2,2-dimethyl-vinyl) -cyclopropanecarboxylate and 3 '-Phenoxy-benryl-2,2-dimethyl-3-indenyl-cyclopropane-carboxylate have insecticidal and acaricidal properties (see German Offenlegungsschriften2335347 and 2605828 and US patent 2,857,309).
  • the general formula (1) includes the various possible steroisomers, the optical isomers and mixtures of these components.
  • the substituted phenoxybenzyloxycarbonyl derivatives according to the invention show a better insecticidal and acaricidal action than the corresponding previously known products of analogous constitution and the same direction of action.
  • the products according to the present invention thus represent a real enrichment of the technology.
  • process variant a) 3- (4-fluorophenoxy) benzyl alcohol and 2,2-dimethyl-3- (2-phenylvinyl) cyclopropanecarboxylic acid chloride are used and process variant b) the sodium salt of 2,2-dimethyl-3- (2-phenylthiovinyl) cyclopropanecarboxylic acid and 3-phenoxy-a-cyano-benzylbromide as starting materials, the course of the reaction can be represented by the following formula schemes:
  • the cyclopropanecarboxylic acid derivatives (V) which are also to be used as starting compounds can be prepared by acidic or alkaline saponification using processes known from the literature from the partially known ethyl cyclopropanecarboxylates (cf. Tetrahedron Letters 1976, 48, pp. 4359-4362).
  • the free acids are converted into the corresponding salts or acid halides (111) and (V) by known processes.
  • the partially known ethyl esters can in turn be prepared by processes known from the literature, for example from ethyl 2,2-dimethyl-3-formylcyclopropanecarboxylate and diester derivatives of 0,0-diethylmethanephosphonic acid, using the following formula:
  • Examples of the cyclopropanecarboxylic acid derivatives (111) and (V) are: 3- [2-phenylvinyl] -, 3- [2- (2-chlorophenyl) vinyl] -, 3- [2- (4 -Chlorphenyl) vinyl] -, 3- [2- (3,4-dichlorophenyl) vinyl] -, 3- [2- (4-fluorophenyl) vinyl] -, 3- [2-pentachlorophenyl vinyl] - , 3- [2-pentafluorophenyl vinyl] -, 3- [2-phenylthio-vinyl] -, 3- [2- (2-chlorophenylthio) vinyl] -, 3-
  • All customary acid binders can be used as acid acceptors.
  • Alkali carbonates and alcoholates such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.
  • the reaction temperature can be varied within a wide range. In general, the process is carried out between 0 and 150 ° C., preferably in process variant a) at 10 to 40 ° C. and in process variant b) at 100 to 130 ° C.
  • the reaction is generally allowed to proceed at normal pressure.
  • the processes for the preparation of the compounds according to the invention are preferably carried out using suitable solvents or diluents.
  • suitable solvents or diluents Practically all inert organic solvents can be considered as such. These include in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ether, e.g.
  • ketones for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone
  • nitriles such as aceto- and propionitrile
  • formamides e.g. Dimethylformamide.
  • the starting materials are preferably used in an equimolar ratio.
  • An excess of one or the other reaction component has no significant advantages.
  • the reaction components are usually combined in one of the specified solvents and, in the presence of an acid acceptor, are usually stirred for one to several hours at elevated temperature.
  • the reaction mixture is then worked up in such a way that it is poured into water, the organic phase is separated off and then worked up as usual by washing, drying and distilling off the solvent.
  • the procedure is customary in such a way that the methyl or ethyl ester of cyclopropanecarboxylic acid is optionally introduced in a suitable solvent together with a 10-30% excess of the alcohol of the formula (11) and with the addition of alkali metal methylate or ethylate heated.
  • the resulting lower boiling alcohol is continuously distilled off.
  • the cyclopropanecarboxylic acid derivative is preferably used in the form of an alkali metal salt. This is heated together with the benzyl halide derivative to 80 ° -140 ° C in one of the specified solvents. An excess of one or the other reaction component has no advantages. When the reaction has ended, the solvent is distilled off, the residue is taken up in methylene chloride and the organic phase is worked up as described above.
  • the new compounds are obtained in the form of oils, which can usually not be distilled without decomposing, but through so-called «distillation», i.e. can be freed from the last volatile constituents by prolonged heating under reduced pressure to moderately elevated temperatures and can be cleaned in this way.
  • «distillation i.e. can be freed from the last volatile constituents by prolonged heating under reduced pressure to moderately elevated temperatures and can be cleaned in this way.
  • the refractive index or the boiling point is used to characterize them.
  • the substituted phenoxybenzyloxycarbonyl derivatives according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medical sector against animal parasites (ectoparasites) such as parasitic fly larvae and ticks.
  • animal parasites ectoparasites
  • the active ingredients are suitable for controlling animal pests, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include:
  • Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Thysanura e.g. Lepisma saccharina.
  • Orthoptera for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesti cus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Homptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis, pad.
  • Homptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis,
  • Nephotettix cincticeps Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp.
  • the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc. as well as ULV cold and warm fog formulations.
  • customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc. as well as
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water;
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers: natural rock flour, such as kaolin, clay,
  • Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo 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 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention are used in the form of their commercially available formulations and / or the use forms prepared from these formulations.
  • 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 100% by weight of active substance, preferably between 0.01 and 10% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active ingredients When used against hygiene pests and pests of stored products, the active ingredients are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
  • the active compounds according to the invention are used in the veterinary sector in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, diving (dipping), spraying (spraying), pouring-on and spot-on) and powdering and by parenteral use in the form of, for example, injection.
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • cabbage leaves (Brassica oleracea) are sprayed to runoff point and populated with horseradish leaf beetle larvae (Phaedon Cochleariae).
  • the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Cabbage plants (Brassica oleracea) which are heavily infested with peach aphids (Myzus persicae) are sprayed to runoff point with the preparation of active compound.
  • the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Bean plants Phaseolus vulgaris
  • Triticae Bean plants (Phaseolus vulgaris), which are heavily infested with all stages of development of the common spider mite or bean spider mite (Tetranychus urticae), are sprayed to runoff point with the preparation of active compound.
  • the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
  • the active compound in question is mixed with the stated solvent in a ratio of 1: 2 and the concentrate thus obtained is diluted with water to the desired concentration.
  • Emulsifier 80 parts by weight of alkylaryl glycol ether
  • the toluene phase is then dried over sodium sulfate and the solvent is distilled off in a water jet vacuum.
  • the last solvent residues are removed by briefly distilling at 60 ° C / 1 Torr bath temperature.
  • 12.0 g (84% of theory) of 3 '- (4-fluorophenoxy) a-cyanobenzyl-2,2-dimethyl- (2-phenyl-2-chlorovinyl) cyclopropanecarboxylate are obtained as a yellow oil with the refractive index .
  • cyclopropanecarboxylic acids (V) or their salts and acid chlorides (111) required as starting compounds can be prepared as described below: 26.3 g (0.1 mol) of ethyl 4-chlorobenzylphosphonate are dissolved in 400 ml of absolute tetrahydrofuran and cooled to -70.degree. 0.11 mol of n-butyllithium (15% solution in hexane) are added dropwise in a countercurrent of nitrogen and with thorough stirring, and the reaction mixture is then stirred at -70 ° C. for a further 15 minutes.
  • the cyclopropanecarboxylic acid ethyl esters depicted according to example a) or b) are saponified acid or alkaline to the corresponding acids by known methods. These are also converted into the corresponding salts (for example alkali or ammonium salts) or acid chlorides by processes which are also known.

Landscapes

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

Description

Die vorliegende Erfindung betrifft neue substituierte Phenoxybenzyloxycarbonylderivate, mehrere Verfahren zu ihrer Herstellung und ihre Verwendung als Insetkizide und Akarizide.The present invention relates to new substituted phenoxybenzyloxycarbonyl derivatives, several processes for their preparation and their use as insecticides and acaricides.

Es ist bereits bekannt, dass Phenoxybenzylacetate oder -carboxylate, wie z.B. 3'-Phenoxybenzyl-α-isopropyl-(3,4-dimethoxy-phenyl)-acetat, (6-Chlor-piperonyl)-2,2-dimethyl-3-(2,2-dimethyl-vinyl)-cyclopropancarboxylat und 3'-Phenoxy-benryl-2,2-dimethyl-3-indenyl-cyclo- propancarboxylat insektizide und akarizide Eigenschaften haben (vergleiche Deutsche Offenlegungsschriften2335347und2605828undUSA-Patent2 857 309).It is already known that phenoxybenzyl acetates or carboxylates, e.g. 3'-phenoxybenzyl-α-isopropyl- (3,4-dimethoxy-phenyl) -acetate, (6-chloro-piperonyl) -2,2-dimethyl-3- (2,2-dimethyl-vinyl) -cyclopropanecarboxylate and 3 '-Phenoxy-benryl-2,2-dimethyl-3-indenyl-cyclopropane-carboxylate have insecticidal and acaricidal properties (see German Offenlegungsschriften2335347 and 2605828 and US patent 2,857,309).

Es wurden nun die neuen substituierten Pheno- xybenzyloxycarbonylderivatederFormel(I)

Figure imgb0001
gefunden,
in welcher

  • R, Rl und R2 gleich oder verschieden sein können und für Wasserstoff oder Halogen stehen,
  • R3 für Phenyl oder Phenylthio steht, wobei die Phenylringe gegebenenfalls ein- oder mehrfach, gleich oder verschieden durch Alkyl oder Halogen substituiert sein können,
  • Y für Wasserstoff oder Nitril steht,
  • n für eine ganze Zahl von 1 bis 5 steht und
  • m für eine ganze Zahl von 1 bis 4 steht.
The new substituted phenoxybenzyloxycarbonyl-derivatized formula (I)
Figure imgb0001
 found,
in which
  • R, R 1 and R 2 may be the same or different and represent hydrogen or halogen,
  • R 3 represents phenyl or phenylthio, where the phenyl rings may optionally be substituted one or more times, identically or differently, by alkyl or halogen,
  • Y represents hydrogen or nitrile,
  • n stands for an integer from 1 to 5 and
  • m represents an integer from 1 to 4.

Diese neuen Verbindungen zeichnen sich durch starke insektizide und akarizide Eigenschaften aus.These new compounds are characterized by strong insecticidal and acaricidal properties.

Die allgemeine Formel (1) schliesst dabei die verschiedenen möglichen Steroisomeren, die optischen Isomeren und Mischungen dieser Komponenten ein.The general formula (1) includes the various possible steroisomers, the optical isomers and mixtures of these components.

Weiterhin wurde gefunden, dass die substituierten Phenoxybenzyloxycarbonylderivate (I) erhalten werden, wenn man

  • a) Phenoxybenzylalkohole der Formel (11)
    Figure imgb0002
    in welcher
    • R, Rl, Y, n und m die oben angegebene Bedeutung haben,
    • mit Cyclopropancarbonsäurederivaten der Formel
      Figure imgb0003
      in welcher
    • R2 und R3 die oben angegebene Bedeutung haben, und
    • R4 für Halogen oder C1-4Alkoxy, vorzugsweise Methoxy oder Äthyoxy steht,
      Hal für Halogen, vorzugsweise Chlor, steht, gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Lösungsmittels umsetzt oder
  • b) Phenoxybenzylhalogenide der Formel
    Figure imgb0004
    in welcher
    • R, Rl, Y, n und m die oben angegebene Bedeutung haben und
    • Hal für Halogen, vorzugsweise Chlor oder Brom, steht, mit Cyclopropancarbonsäurederivaten der Formel
      Figure imgb0005
      in welcher
    • R2 und R3 die oben angegebene Bedeutung haben,
      gegebenenfalls in Form der Alkali-, Erdalkali-oder Ammoniumsalze oder gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Lösungsmittels umsetzt.
Furthermore, it has been found that the substituted phenoxybenzyloxycarbonyl derivatives (I) are obtained when
  • a) phenoxybenzyl alcohols of the formula (11)
    Figure imgb0002
     in which
    • R, R l , Y, n and m have the meaning given above,
    • with cyclopropanecarboxylic acid derivatives of the formula
      Figure imgb0003
       in which
    • R 2 and R 3 have the meaning given above, and
    • R 4 represents halogen or C1-4alkoxy, preferably methoxy or ethoxy,
      Hal represents halogen, preferably chlorine, optionally in the presence of an acid acceptor and optionally in the presence of a solvent
  • b) phenoxybenzyl halides of the formula
    Figure imgb0004
     in which
    • R, R l , Y, n and m have the meaning given above and
    • Hal represents halogen, preferably chlorine or bromine, with cyclopropanecarboxylic acid derivatives of the formula
      Figure imgb0005
       in which
    • R 2 and R 3 have the meaning given above,
      if appropriate in the form of the alkali metal, alkaline earth metal or ammonium salts or if appropriate in the presence of an acid acceptor and if appropriate in the presence of a solvent.

Überraschenderweise zeigen die erfindungsgemässen substituierten Phenoxybenzyloxycarbonylderivate eine bessere insektizide und akarizide Wirkung als die entsprechenden vorbekannten Produkte analoger Konstitution und gleicher Wirkungsrichtung. Die Produkte gemäss vorliegender Erfindung stellen somit eine echte Bereicherung der Technik dar.Surprisingly, the substituted phenoxybenzyloxycarbonyl derivatives according to the invention show a better insecticidal and acaricidal action than the corresponding previously known products of analogous constitution and the same direction of action. The products according to the present invention thus represent a real enrichment of the technology.

Verwendet man beispielsweise bei Verfahrensvariante a) 3-(4-Fluorphenoxy)-benzylalkohol und 2,2-Dimethyl-3-(2-phenylvinyl)-cyclopropancar- bonsäurechlorid und bei Verfahrensvariante b) das Natriumsalz der 2,2-Dimethyl-3-(2-phenyl- thiovinyl)-cyclopropancarbonsäure und 3-Phenoxy-a-cyan-benzylbromid als Ausgangsmaterialien, so kann der Reaktionsverlauf durch die folgenden Formelschemata wiedergegeben werden:

Figure imgb0006
Figure imgb0007
 If, for example, process variant a) is used, 3- (4-fluorophenoxy) benzyl alcohol and 2,2-dimethyl-3- (2-phenylvinyl) cyclopropanecarboxylic acid chloride are used and process variant b) the sodium salt of 2,2-dimethyl-3- (2-phenylthiovinyl) cyclopropanecarboxylic acid and 3-phenoxy-a-cyano-benzylbromide as starting materials, the course of the reaction can be represented by the following formula schemes:
Figure imgb0006
Figure imgb0007

Die zuverwendenden Ausgangsstoffe sind durch die Formeln (I) bis (V) eindeutig allgemein definiert. Vorzugsweise stehen darin jedoch

  • Rund Rl für Wasserstoff oder Fluor,
  • R2 für Wasserstoff, Chlor oder Brom,
  • R3 für Phenyl, Phenylthio, Halogenphenyl, wobei Halogen insbesondere Chlor oder Fluor ist, oder Alkylphenyl, wobei der Alkylrest 1 bis 6, insbesondere 1 bis 4, Kohlenstoffatome hat,
  • R4für Chlor oder Methoxy,
  • YfürWasserstoff oder Nitril,
  • n für eine ganze Zahl von 1 bis 5 und
  • m für eine ganze Zahl von 1 bis 4.
The starting materials to be used are clearly defined in general terms by formulas (I) to (V). Preferably, however, are in it
  • R 1 for hydrogen or fluorine,
  • R 2 represents hydrogen, chlorine or bromine,
  • R 3 is phenyl, phenylthio, halophenyl, where halogen is in particular chlorine or fluorine, or alkylphenyl, where the alkyl radical has 1 to 6, in particular 1 to 4, carbon atoms,
  • R 4 for chlorine or methoxy,
  • Yfor hydrogen or nitrile,
  • n for an integer from 1 to 5 and
  • m for an integer from 1 to 4.

Die als Ausgangsverbindungen zu verwendenden Phenoxybenzylalkohole (11) sind grösstenteils bekannt oder nach allgemein üblichen, in der Literatur beschriebenen Verfahren herstellbar (vergleiche Deutsche Offenlegungsschrift 2547534).Most of the phenoxybenzyl alcohols (11) to be used as starting compounds are known or can be prepared by the generally customary processes described in the literature (see German Offenlegungsschrift 2547534).

Als Beispiele dafür seien im einzelnen genannt:

  • 3-Phenoxy-benzylalkohol
  • 3-(4-Fluorphenoxy)-benzylalkohol
  • 3-(3-Fluorphenoxy)-benzylalkohol
  • 3-(2-Fluorphenoxy)-benzylalkohol
  • 3-Phenoxy-4-fluor-benzylalkohol
  • 3-(4-Fluorphenoxy)-4-fluor-benzylalkohol
  • 3-(3-Fluorphenoxy)-4-fluor-benzylalkohol
  • 3-(2-Fluorphenoxy)-4-fluor-benzylalkohol
  • 3-Phenoxy-α-cyan-benzylalkohol
  • 3-(4-Fluorphenoxy)-α-cyan-benzylalkohol
  • 3-(3-Fluorphenoxy)-α-cyan-benzylalkohol
  • 3-(2-Fluorphenoxy)-α-cyan-benzylalkohol
  • 3-Phenoxy-4-fluor-α-cyan-benzylalkohol
  • 3-(4-Fluorphenoxy)-4-fluor-α-cyan-benzylalkohol
  • 3-(3-Fluorphenoxy)-4-fluor-α-cyan-benzylalkohol
  • 3-(2-Fluorphenoxy)-4-fluor-α-cyan-benzylalkohol
  • 3-Phenoxy-6-fluor-a-cyan-benzylalkohol
  • 3-(4-Fiuorphenoxy)-6-fluor-α-cyan-benzylalkohol
  • 3-(4-Fluorphenoxy)-6-fluor-α-cyan-benzylalkohol
  • 3-(3-Fluorphenoxy)-6-fluor-α-cyan-benzylalkohol
The following are examples of this:
  • 3-phenoxy-benzyl alcohol
  • 3- (4-fluorophenoxy) benzyl alcohol
  • 3- (3-fluorophenoxy) benzyl alcohol
  • 3- (2-fluorophenoxy) benzyl alcohol
  • 3-phenoxy-4-fluoro-benzyl alcohol
  • 3- (4-fluorophenoxy) -4-fluoro-benzyl alcohol
  • 3- (3-fluorophenoxy) -4-fluoro-benzyl alcohol
  • 3- (2-fluorophenoxy) -4-fluoro-benzyl alcohol
  • 3-phenoxy-α-cyano-benzyl alcohol
  • 3- (4-fluorophenoxy) -α-cyanobenzyl alcohol
  • 3- (3-fluorophenoxy) -α-cyano-benzyl alcohol
  • 3- (2-fluorophenoxy) -α-cyano-benzyl alcohol
  • 3-phenoxy-4-fluoro-α-cyano-benzyl alcohol
  • 3- (4-fluorophenoxy) -4-fluoro-α-cyano-benzyl alcohol
  • 3- (3-fluorophenoxy) -4-fluoro-α-cyano-benzyl alcohol
  • 3- (2-fluorophenoxy) -4-fluoro-α-cyano-benzyl alcohol
  • 3-phenoxy-6-fluoro-a-cyano-benzyl alcohol
  • 3- (4-Fiorphenoxy) -6-fluoro-α-cyano-benzyl alcohol
  • 3- (4-fluorophenoxy) -6-fluoro-α-cyano-benzyl alcohol
  • 3- (3-fluorophenoxy) -6-fluoro-α-cyano-benzyl alcohol

Die weiterhin als Ausgangsverbindungen zu verwendenden Cyclopropancarbonsäurederivate (V) können nach literaturbekannten Verfahren aus den teilweise bekannten Cyclopropancarbonsäureäthylestern (vergleiche Tetrahedron Letters 1976, 48, S. 4359-4362) durch saure oder alkalische Verseifung hergestellt werden. Die freien Säuren werden nach bekannten Verfahren in die entsprechenden Salze oder Säurehalogenide (111) und (V) übergeführt. Die teilweise bekannten Äthylester können wiederum nach literaturbekannten Verfahren z.B. aus 2,2-Dimethyl-3-for- mylcyclopropancarbonsäureäthylester und 0,0-Diäthylmethanphosphonsäurediesterderivaten nach folgendem Formelschema hergestellt werden:

Figure imgb0008
Als Beispiele für die Cyclopropancarbonsäurederivate (111) und (V) seien im einzelnen genannt: 3-[2-Phenyl-vinyl]-, 3-[2-(2-Chlorphenyl)-vinyl]-, 3-[2-(4-Chlorphenyl)-vinyl]-, 3-[2-(3,4-Dichlorphenyl)-vinyl]-,3-[2-(4-Fluorphenyl)-vinyl]-, 3-[2-Pentachlorphenyl-vinyl]-, 3-[2-Pentafluorphenyl- vinyl]-, 3-[2-Phenylthio-vinyl]-, 3-[2-(2-Chlorphe- nylthio)-vinyl]-, 3-[2-(4-Chlorphenylthio)-vinyl]-, 3-[2-(3,4-Dichlorphenylthio)-vinyl]-, 3-[2-(4-Fluorphenylthlo)-vinyl]-, 3-[2-Pentachlorphenyl- thio-vinyl]-, 3-[2-Pentafluorphenylthio-vinyl]-, 3-[2-(4-tert.-Butylphenyl)-vinyl]-2,2-dimethylcy- clopropancarbonsäure bzw. -2,2-dimethylcyclo- propancarbonsäurechlorid, ferner 3-[2-Phenyl-2-chlor-vinyl]-, 3-[2-(2-Chlorphenyl)-2-chlor-vinyl]-, 3-[2-(4-Chlorphenyl)-2-chlor-vinyl]-, 3-[2-(3,4-Dichlorphenyl)-2-chlor-vinyl]-, 3-[2-(4-Fluorphenyl)-2-chlorvinyl]-, 3-(2-Pentach- lorphenyl)-2-chlor-vinyl)-, 3-(2-Pentafluorphenyl-2-chlor-vinyl)-, 3-[2-Phenylthio-2-chlor-vinyl]-, 3-[2-(2-Chlorphenylthio)-2-chlor-vinyl]-, 3-[2-(4-Chlorphenylthio)-2-chlor-vinyl]-, 3-[2-(3,4-Dich- lorphenylthio)-2-chlor-vinyl]-, 3-[2-(4-Fluorphe- nylthio)-2-chlor-vinyl]-, 3-[2-Pentachlorphenyl- thio-2-chlor-vinyl]-, 3-[2-Pentafluorphenylthio-2-chlor-vinyl]-, 3-[2-(4-tert.-Butylphenyl)-2-chlor- vinyl]-2,2-dimethylcyclopropancarbonsäure bzw.The cyclopropanecarboxylic acid derivatives (V) which are also to be used as starting compounds can be prepared by acidic or alkaline saponification using processes known from the literature from the partially known ethyl cyclopropanecarboxylates (cf. Tetrahedron Letters 1976, 48, pp. 4359-4362). The free acids are converted into the corresponding salts or acid halides (111) and (V) by known processes. The partially known ethyl esters can in turn be prepared by processes known from the literature, for example from ethyl 2,2-dimethyl-3-formylcyclopropanecarboxylate and diester derivatives of 0,0-diethylmethanephosphonic acid, using the following formula:
Figure imgb0008
 Examples of the cyclopropanecarboxylic acid derivatives (111) and (V) are: 3- [2-phenylvinyl] -, 3- [2- (2-chlorophenyl) vinyl] -, 3- [2- (4 -Chlorphenyl) vinyl] -, 3- [2- (3,4-dichlorophenyl) vinyl] -, 3- [2- (4-fluorophenyl) vinyl] -, 3- [2-pentachlorophenyl vinyl] - , 3- [2-pentafluorophenyl vinyl] -, 3- [2-phenylthio-vinyl] -, 3- [2- (2-chlorophenylthio) vinyl] -, 3- [2- (4-chlorophenylthio) -vinyl] -, 3- [2- (3,4-dichlorophenylthio) vinyl] -, 3- [2- (4-fluorophenylthlo) vinyl] -, 3- [2-pentachlorophenylthio-vinyl] -, 3- [2-pentafluorophenylthio-vinyl] -, 3- [2- (4-tert-butylphenyl) vinyl] -2,2-dimethylcyclopropanecarboxylic acid or -2,2-dimethylcyclopropanecarboxylic acid chloride, furthermore 3- [ 2-phenyl-2-chloro-vinyl] -, 3- [2- (2-chlorophenyl) -2-chloro-vinyl] -, 3- [2- (4-chlorophenyl) -2-chloro-vinyl] -, 3- [2- (3,4-dichlorophenyl) -2-chloro-vinyl] -, 3- [2- (4-fluorophenyl) -2-chlorovinyl] -, 3- (2-pentachlorophenyl) -2- chloro-vinyl) -, 3- (2-pentafluorophenyl-2-chloro-vinyl) -, 3- [2-phenylthio-2-chloro-vinyl] -, 3- [2- (2-chlorophenylthio) -2-chloro -vinyl] -, 3- [2- (4-chlorophenylthio) -2-chloro-vinyl] -, 3- [2- (3,4-dichlorophenylthio) -2-chloro-vinyl] -, 3- [ 2- (4-fluorophenylthio) -2-chloro-vinyl] -, 3- [2-pentachlorophenylthio-2-chloro-vinyl] -, 3- [2-pentafluorophenylthio-2-chloro-vinyl] -, 3- [2- (4-tert-butylphenyl) -2-chloro-vinyl] -2,2-dimethylcyclopropanecarboxylic acid or

-2,2-dimethylcyclopropancarbonsäurechlorid, ferner

  • 3-[2-Phenyl-2-brom-vinyl]-, 3-[2-(2-Chlorphenyl)-2-brom-vinyl]-, 3-[2-(4-Chlorphenyl)-2-brom-vinyl]-, 3-[2-(3,4-Dichlorphenyl)-2-brom-vinyl]-, 3-[2-(4-Fluorphenyl)-2-brom-vinyl]-, 3-[2-Pen- tachlorphenyl-2-brom-vinyl]-, 3-(2-Pentafluorphenyl-2-brom-vinyl)-, 3-[2-Phenylthio-2-brom- vinyl]-, 3-[2-(2-Chlorphenylthio)-2-brom-vinyl]-, 3-[2-(4-Chlorphenylthio)-2-brom-vinyl]-, 3-[2-(3,4-Dichlorphenylthio)-2-bromvinyl]-, 3-[2-(4-Fluorphenylthio)-2-brom-vinyl]-, 3-[2-Penta- chlorphenylthio-2-brom-vinyl]-, 3-[2-Pentafluor- phenylthio-2-brom-vinyl]-,3-[2-(4-tert.-Butylphenyl)-2-brom-vinyl]-2,2-dimethylcyclopropancar- bonsäure bzw. -2,2-dimethylcyclopropancarbon- säurechlorid.
-2,2-dimethylcyclopropanecarboxylic acid chloride, further
  • 3- [2-phenyl-2-bromo-vinyl] -, 3- [2- (2-chlorophenyl) -2-bromo-vinyl] -, 3- [2- (4-chlorophenyl) -2-bromo-vinyl ] -, 3- [2- (3,4-dichlorophenyl) -2-bromo-vinyl] -, 3- [2- (4-fluorophenyl) -2-bromo-vinyl] -, 3- [2-pen- tachlorophenyl-2-bromo-vinyl] -, 3- (2-pentafluorophenyl-2-bromo-vinyl) -, 3- [2-phenylthio-2-bromo-vinyl] -, 3- [2- (2-chlorophenylthio) -2-bromo-vinyl] -, 3- [2- (4-chlorophenylthio) -2-bromo-vinyl] -, 3- [2- (3,4-dichlorophenylthio) -2-bromovinyl] -, 3- [ 2- (4-fluorophenylthio) -2-bromo-vinyl] -, 3- [2-pentachlorophenylthio-2-bromo-vinyl] -, 3- [2-pentafluorophenylthio-2-bromo-vinyl] -, 3- [2- (4-tert-butylphenyl) -2-bromo-vinyl] -2,2-dimethylcyclopropanecarboxylic acid or -2,2-dimethylcyclopropanecarboxylic acid chloride.

Ausserdem werden die Phenoxybenzylhalogenide (IV) als Ausgangsverbindungen verwendet, die ebenfalls nach literaturbekannten Verfahren herzustellen sind. Als Beispiele dafür seien im einzelnen genannt:

  • 3-Phenoxy-benzylchlorid bzw. -benzylbromid
  • 3-(4-Fluorphenoxy)-benzylchlorid bzw. -benzylbromid
  • 3-(3-Fluorphenoxy)-benzylchlorid bzw. -benzylbromid
  • 3-(2-Fluorphenoxy)-benzylchlorid bzw. -benzylbromid
  • 3-Phenoxy-4-fluor-benzylchlorid bzw. -benzylbromid
  • 3-(4-Fluorphenoxy)-4-fluor-benzylchlorid bzw. -benzylbromid
  • 3-(3-Fluorphenoxy)-4-fluor-benzylchlorid bzw. -benzylbromid
  • 3-(2-Fluorphenoxy)-4-fluor-benzylchlorid bzw. -benzylbromid
  • 3-Phenoxy-a-eyan-benzylchlorid bzw. -benzylbromid
  • 3-(4-Fluorphenoxy)-a-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(3-Fluorphenoxy)-a-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(2-Fluorphenoxy)-a-cyan-benzylchlorid bzw. -benzylbromid
  • 3-Phenoxy-4-fluor-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(4-Fluorphenoxy)-4-fluor-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(3-Fluorphenoxy)-4-fluor-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(2-Fluorphenoxy)-4-fluor-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-Phenoxy-6-fluor-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(4-Fluorphenoxy)-6-fluor-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(3-Fluorphenoxy)-6-fluor-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(2-Fluorphenoxy)-6-fluor-α-cyan-benzylchlorid bzw. -benzylbromid.
In addition, the phenoxybenzyl halides (IV) are used as starting compounds, which can also be prepared by processes known from the literature. The following are examples of this:
  • 3-phenoxy-benzyl chloride or benzyl bromide
  • 3- (4-fluorophenoxy) benzyl chloride or benzyl bromide
  • 3- (3-fluorophenoxy) benzyl chloride or benzyl bromide
  • 3- (2-fluorophenoxy) benzyl chloride or benzyl bromide
  • 3-phenoxy-4-fluoro-benzyl chloride or benzyl bromide
  • 3- (4-fluorophenoxy) -4-fluoro-benzyl chloride or benzyl bromide
  • 3- (3-fluorophenoxy) -4-fluoro-benzyl chloride or benzyl bromide
  • 3- (2-fluorophenoxy) -4-fluoro-benzyl chloride or benzyl bromide
  • 3-phenoxy-a-eyan benzyl chloride or benzyl bromide
  • 3- (4-fluorophenoxy) a-cyano-benzyl chloride or benzyl bromide
  • 3- (3-fluorophenoxy) a-cyano-benzyl chloride or benzyl bromide
  • 3- (2-fluorophenoxy) a-cyano-benzyl chloride or benzyl bromide
  • 3-phenoxy-4-fluoro-α-cyanobenzyl chloride or benzyl bromide
  • 3- (4-fluorophenoxy) -4-fluoro-α-cyano-benzyl chloride or benzyl bromide
  • 3- (3-fluorophenoxy) -4-fluoro-α-cyanobenzyl chloride or benzyl bromide
  • 3- (2-fluorophenoxy) -4-fluoro-α-cyano-benzyl chloride or benzyl bromide
  • 3-phenoxy-6-fluoro-α-cyanobenzyl chloride or benzyl bromide
  • 3- (4-fluorophenoxy) -6-fluoro-α-cyano-benzyl chloride or benzyl bromide
  • 3- (3-fluorophenoxy) -6-fluoro-α-cyano-benzyl chloride or benzyl bromide
  • 3- (2-fluorophenoxy) -6-fluoro-α-cyanobenzyl chloride or benzyl bromide.

Als Säureakzeptoren können alle üblichen Säurebindemittel Verwendung finden. Besonders bewährt haben sich Alkalicarbonate und -alkoholate, wie Natrium- und Kaliumcarbonat, Natrium-und Kaliummethylat bzw. -äthylat, ferner aliphatische, aromatische oder heterocyclische Amine, beispielsweise Triäthylamin, Trimethylamin, Dimethylanilin, Dimethylbenzylamin und Pyridin.All customary acid binders can be used as acid acceptors. Alkali carbonates and alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.

Die Reaktionstemperatur kann innerhalb eines grösseren Bereichs variiert werden. Im allgemeinen arbeitet man zwischen 0 und 150°C, vorzugsweise bei der Verfahrensvariante a) bei 10 bis 40°C und bei der Verfahrensvariante b) bei 100 bis 130°C.The reaction temperature can be varied within a wide range. In general, the process is carried out between 0 and 150 ° C., preferably in process variant a) at 10 to 40 ° C. and in process variant b) at 100 to 130 ° C.

Die Umsetzung lässt man im allgemeinen bei Normaldruck ablaufen.The reaction is generally allowed to proceed at normal pressure.

Die Verfahren zur Herstellung der erfindungsgemässen Verbindungen werden bevorzugt unter Mitverwendung geeigneter Lösungs- oder Verdünnungsmittel durchgeführt. Als solche kommen praktisch alle inerten organischen Solventien infrage. Hierzu gehören insbesondere aliphatische und aromatische, gegebenenfalls chlorierte Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Benzin, Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Chlorbenzol, oder Äther, z.B. Diäthyl- und Dibutyläther, Dioxan, ferner Ketone, beispielsweise Aceton, Methyläthyl-, Methylisopropyl- und Methylisobutylketon, ausserdem Nitrile, wie Aceto- und Propionitril, oder Formamide, z.B. Dimethylformamid.The processes for the preparation of the compounds according to the invention are preferably carried out using suitable solvents or diluents. Practically all inert organic solvents can be considered as such. These include in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ether, e.g. Diethyl and dibutyl ether, dioxane, also ketones, for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, also nitriles, such as aceto- and propionitrile, or formamides, e.g. Dimethylformamide.

Zur Durchführung der Verfahrensvariante a) setzt man die Ausgangsstoffe vorzugsweise im äquimolaren Verhältnis ein. Ein Überschuss der einen oder anderen Reaktionskomponente bringt keine wesentlichen Vorteile. Die Reaktionskomponenten werden meist in einem der angegebenen Lösungsmittel zusammengegeben und in Gegenwart eines Säureakzeptors meist bei erhöhter Temperatur ein bis mehrere Stunden gerührt. Danach arbeitet man die Reaktionsmischung in der Weise auf, dass man sie in Wasser giesst, die organische Phase abtrennt und diese dann wie üblich durch Waschen, Trocknen und Abdestillieren des Lösungsmittels aufarbeitet.To carry out process variant a), the starting materials are preferably used in an equimolar ratio. An excess of one or the other reaction component has no significant advantages. The reaction components are usually combined in one of the specified solvents and, in the presence of an acid acceptor, are usually stirred for one to several hours at elevated temperature. The reaction mixture is then worked up in such a way that it is poured into water, the organic phase is separated off and then worked up as usual by washing, drying and distilling off the solvent.

Bei der Umesterung nach Verfahrensvariante a) wird in üblicher Weise so verfahren, dass man den Methyl- oder Äthyl-Ester der Cyclopropancarbonsäure gegebenenfalls in einem geeigneten Lösungsmittel zusammen mit 10-30% Überschuss des Alkohols der Formel (11) vorlegt und unter Zugabe von Alkalimethylat oder -äthylat erhitzt. Der entstehende niedriger siedende Alkohol wird dabei laufend abdestilliert.In the transesterification according to process variant a), the procedure is customary in such a way that the methyl or ethyl ester of cyclopropanecarboxylic acid is optionally introduced in a suitable solvent together with a 10-30% excess of the alcohol of the formula (11) and with the addition of alkali metal methylate or ethylate heated. The resulting lower boiling alcohol is continuously distilled off.

Bei der Durchführung der Verfahrensvariante b) setzt man vorzugsweise das Cyclopropancarbonsäurederivat in Form eines Alkalisalzes ein. Dieses wird in einem der angegebenen Lösungsmittel zusammen mit dem Benzylhalogenidderivat auf 80°-140°C erhitzt. Ein Überschuss der einen oder anderenReaktionskomponente bringt keine Vorteile. Nach beendeter Reaktion wird das Lösungsmittel abdestilliert, der Rückstand in Methylenchlorid aufgenommen und die organische Phase wie oben beschrieben aufgearbeitet.When carrying out process variant b), the cyclopropanecarboxylic acid derivative is preferably used in the form of an alkali metal salt. This is heated together with the benzyl halide derivative to 80 ° -140 ° C in one of the specified solvents. An excess of one or the other reaction component has no advantages. When the reaction has ended, the solvent is distilled off, the residue is taken up in methylene chloride and the organic phase is worked up as described above.

Die neuen Verbindungen fallen in Form von Ölen an, die sich meist nicht unzersetzt destillieren lassen, jedoch durch sogenanntes «Andestillieren», d.h. durch längeres Erhitzen unter vermindertem Druck auf mässig erhöhte Temperaturen von den letzten flüchtigen Anteilen befreit und auf diese Weise gereinigt werden. Zu ihrer Charakterisierung dient der Brechungsindex oder der Siedepunkt.The new compounds are obtained in the form of oils, which can usually not be distilled without decomposing, but through so-called «distillation», i.e. can be freed from the last volatile constituents by prolonged heating under reduced pressure to moderately elevated temperatures and can be cleaned in this way. The refractive index or the boiling point is used to characterize them.

Die erfindungsgemässen substituierten Phenoxybenzyloxycarbonylderivate wirken nicht nur gegen Pflanzen-, Hygiene- und Vorratsschädlinge, sondern auch auf dem veterinär-medizinischen Sektor gegen tierische Parasiten (Ektoparasiten), wie parasitierende Fliegenlarven und Zecken.The substituted phenoxybenzyloxycarbonyl derivatives according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medical sector against animal parasites (ectoparasites) such as parasitic fly larvae and ticks.

Die Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit und günstiger Warmblütertoxizität zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten und Spinnentieren, die in der Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:With good plant tolerance and favorable warm-blood toxicity, the active ingredients are suitable for controlling animal pests, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:

Aus der Ordnung der Isopoda z.B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus.From the order of the Diplopoda e.g. Blaniulus guttulatus.

Aus der Ordnung der Chilopoda z.B. "Geophilus carpophagus, Seutigera spec.From the order of the Chilopoda e.g. "Geophilus carpophagus, Seutigera spec.

Aus der Ordnung der Symphyla z.B. Scutigerella immaculata.From the order of the Symphyla e.g. Scutigerella immaculata.

Aus der Ordnung der Thysanura z.B. Lepisma saccharina.From the order of the Thysanura e.g. Lepisma saccharina.

Aus der Ordnung der Collembola z.B. Onychiurus armatus.From the order of the Collembola e.g. Onychiurus armatus.

Aus der Ordnung der Orthoptera z.B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.From the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesti cus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

Aus der Ordnung der Dermaptera z.B. Forficula auricularia.From the order of the Dermaptera e.g. Forficula auricularia.

Aus der Ordnung der Isoptera z.B. Reticulitermes spp.From the order of the Isoptera e.g. Reticulitermes spp.

Aus der Ordnung der Anoplura z.B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp. Aus der Ordnung der Mallophaga z.B. Trichodectes spp., Damalinea spp.From the order of the anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp. From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.

Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci.From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.

Aus der Ordnung der Heteroptera z.B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

Aus der Ordnung der Homptera z.B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.From the order of the Homptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis, pad. Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

Aus der Ordnung der Lepidoptera z.B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisisppppi, Fpp., Phyllocnist spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonodanaanaanaanaanaanaanaanaanaa, Capa , Clysia ambiguella, Homona magnanima, Tortrix viridana.

Aus der Ordnung der Coleoptera z.B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephususpp sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psioloides , Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

Aus der Ordnung der Hymenoptera z.B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

Aus der Ordnung der Diptera z.B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

Aus der Ordnung der Siphonaptera z.B. Xenopsylla cheopis, Ceratophyllus spp.From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.

Aus der Ordnung der Arachnida z.B. Scorpio maurus, Latrodectus mactans.From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.

Aus der Ordnung der Acarina z.B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.From the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

Die Wirkstoffe können in die üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Schäume, Pasten, lösliche Pulver, Granulate, Aerosole, Suspensions-Emulsionskonzentrate, Saatgutpuder, Wirkstoff-imprägnierte Natur- und synthetische Stoffe, Feinstverkapselungen in polymeren Stoffen und in Hüllmassen für Saatgut, ferner in Formulierungen mit Brennsätzen, wie Räucherpatronen, -dosen, -spiralen u.ä. sowie ULV-Kalt- und Warmnebel-Formulierungen.The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc. as well as ULV cold and warm fog formulations.

Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen infrage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oderCyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid; als feste Trägerstoffe: natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als feste Trägerstoffe für Granulate: 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 Sägemehle, Kokosnusschalen, Maiskolben und Tabakstengel; als Emulgier- und/oder schaumerzeugende Mittel: nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fettsäure-Ester, Polyoxyäthylen-Fettalkohol- Äther, z.B. Alkylaryl-polyglykol-äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweisshydrolysate; als Dispergiermittel: z.B. Lignin-Sulfitablaugen und Methylcellulose.These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers: natural rock flour, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as fixed Carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersing agents: eg lignin sulfite liquor and methyl cellulose.

Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat.Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.

Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo-Metallphthalocyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo 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 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90%.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

Die Anwendung der erfindungsgemässen Wirkstoffe erfolgt in Form ihrer handelsüblichen Formulierungen und/oder den aus diesen Formulierungen bereiteten Anwendungsformen.The active compounds according to the invention are used in the form of their commercially available formulations and / or the use forms prepared from these formulations.

Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen kann von 0,0000001 bis zu 100 Gew.-% Wirkstoff, vorzugsweise zwischen 0,01 und 10 Gew.-% liegen.The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 100% by weight of active substance, preferably between 0.01 and 10% by weight.

Die Anwendung geschieht in einer den Anwendungsformen angepassten üblichen Weise.The application takes place in a customary manner adapted to the application forms.

Bei der Anwendung gegen Hygiene- und Vorratsschädlinge zeichnen sich die Wirkstoffe durch eine hervorragende Residualwirkung auf Holz und Ton sowie durch eine gute Alkalistabilität auf gekälkten Unterlagen aus.When used against hygiene pests and pests of stored products, the active ingredients are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.

Die Anwendung der erfindungsgemässen Wirkstoffe geschieht im Veterinärsektor in bekannter Weise, wie durch orale Anwendung in Form von beispielsweise Tabletten, Kapseln, Tränken, Granulaten, durch dermale Anwendung in Form beispielsweise des Tauchens (Dippen), Sprühens (Sprayen), Aufgiessens (pour-on and spot-on) und des Einpuderns sowie durch parenterale Anwendung in Form beispielsweise der Injektion.The active compounds according to the invention are used in the veterinary sector in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, diving (dipping), spraying (spraying), pouring-on and spot-on) and powdering and by parenteral use in the form of, for example, injection.

Beispiel AExample A Phaedon-Larven-TestPhaedon larval test

  • Lösungsmittel: 3 Gewichtsteile DimethylformamidSolvent: 3 parts by weight of dimethylformamide
  • Emulgator: 1 Gewichtsteil AlkylarylpolyglykolätherEmulsifier: 1 part by weight of alkylaryl polyglycol ether

Zur Herstellung einer zweckmässigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Mit der Wirkstoffzubereitung besprüht man Kohlblätter (Brassica oleracea) tropfnass und besetzt sie mit Meerrettichblattkäfer-Larven (Phaedon Cochleariae).With the preparation of active substance, cabbage leaves (Brassica oleracea) are sprayed to runoff point and populated with horseradish leaf beetle larvae (Phaedon Cochleariae).

Nach den angegebenen Zeiten wird die Abtötung in % bestimmt. Dabei bedeutet 100%, dass alle Käfer-Larven abgetötet wurden; 0% bedeutet, dass keine Käfer-Larven abgetötet wurden.After the specified times, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.

Wirkstoffe, Wirkstoffkonzentrationen, Zeiten der Auswertung und Resultate gehen aus der nachfolgenden Tabelle hervor:

Figure imgb0009
Figure imgb0010
 Active substances, active substance concentrations, times of evaluation and results are shown in the table below:
Figure imgb0009
Figure imgb0010

Beispiel BExample B Myzus-Test (Kontakt-Wirkung)Myzus test (contact effect)

  • Lösungsmittel: 3 Gewichtsteile DimethylformamidSolvent: 3 parts by weight of dimethylformamide
  • Emulgator: 1 Gewichtsteil AlkylarylpolyglykolätherEmulsifier: 1 part by weight of alkylaryl polyglycol ether

Zur Herstellung einer zweckmässigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Mit der Wirkstoffzubereitung werden Kohlpflanzen (Brassica oleracea), welche stark von der Pfirsichblattlaus (Myzus persicae) befallen sind, tropfnass besprüht.Cabbage plants (Brassica oleracea) which are heavily infested with peach aphids (Myzus persicae) are sprayed to runoff point with the preparation of active compound.

Nach den angegebenen Zeiten wird die Abtötung in % bestimmt. Dabei bedeutet 100%, dass alle Blattläuse abgetötet wurden; 0% bedeutet, dass keine Blattläuse abgetötet wurden.After the specified times, the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle hervor:

Figure imgb0011
Figure imgb0012
 Active substances, active substance concentrations, evaluation times and results are shown in the table below:
Figure imgb0011
Figure imgb0012

Beispiel CExample C Tetranychus-Test (resistent)Tetranychus test (resistant)

  • Lösungsmittel: 3 Gewichtsteile DimethylformamidSolvent: 3 parts by weight of dimethylformamide
  • Emulgator: 1 Gewichtteil AlkylarylpolyglykolätherEmulsifier: 1 part by weight of alkylaryl polyglycol ether

Zur Herstellung einer zweckmässigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und der angegebenen Menge Emulgator und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Mit der Wirkstoffzubereitung werden Bohnenpflanzen (Phaseolus vulgaris), die stark von allen Entwicklungsstadien der gemeinen Spinnmilbe oder Bohnenspinnmilbe (Tetranychus urticae) befallen sind, tropfnass besprüht.Bean plants (Phaseolus vulgaris), which are heavily infested with all stages of development of the common spider mite or bean spider mite (Tetranychus urticae), are sprayed to runoff point with the preparation of active compound.

Nach den angegebenen Zeiten wird die Abtötung in % bestimmt. Dabei bedeutet 100%, dass alle Spinnmilben abgetötet wurden; 0% bedeutet, dass keine Spinnmilben abgetötet wurden.After the specified times, the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.

Wirkstoffe, Wirkstoffkonzentrationen, Auswertungszeiten und Resultate gehen aus der nachfolgenden Tabelle hervor:

Figure imgb0013
Figure imgb0014
 Active substances, active substance concentrations, evaluation times and results are shown in the table below:
Figure imgb0013
Figure imgb0014

Beispiel DExample D Test mit parasitierenden adulten Rinderzecken (Boophilus microplus res.)Parasitic adult tick test (Boophilus microplus res.) Lösungsmittel: AlkylarylpolyglykolätherSolvent: alkylaryl polyglycol ether

Zur Herstellung einer zweckmässigen Wirkstoffzubereitung vermischt man die betreffende aktive Substanz mit dem angegebenen Lösungsmittel im Verhältnis 1:2 und verdünnt das so erhaltene Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, the active compound in question is mixed with the stated solvent in a ratio of 1: 2 and the concentrate thus obtained is diluted with water to the desired concentration.

10 adulte Rinderzecken (b. microplus res.) werden in der zu testenden Wirkstoffzubereitung 1 Min. getaucht. Nach Überführung in Plastikbecher und Aufbewahrung in einem klimatisierten Raum wird der Abtötungsgrad in Prozent bestimmt, wobei 100% bedeuten, dass alle und 0%, dass keine Zecken abgetötet worden sind.

Figure imgb0015
10 adult beef ticks (b. Microplus res.) Are immersed in the active ingredient preparation to be tested for 1 min. After being transferred to a plastic cup and stored in an air-conditioned room, the degree of kill is determined in percent, 100% meaning that all and 0% that no ticks have been killed.
Figure imgb0015

Beispiel EExample E Test mit parasitierenden Fliegenlarven (Lucilia cuprina)Test with parasitic fly larvae (Lucilia cuprina) Emulgator: 80 Gewichtsteile AlkylarylglykolätherEmulsifier: 80 parts by weight of alkylaryl glycol ether

Zur Herstellung einer zweckmässigen Wirkstoffzubereitung vermischt man 20 Gewichtsteile der betreffenden aktiven Substanz mit der angegebenen Menge des Emulgators und verdünnt das so erhaltene Gemisch mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 20 parts by weight of the active substance in question are mixed with the stated amount of the emulsifier and the mixture thus obtained is diluted with water to the desired concentration.

Etwa 20 Fliegenlarven (Lucilia cuprina) werden in ein mit Wattestopfen entsprechender Grösse beschicktes Teströhrchen gebracht, welches ca. 3 ml einer 20%igen Eigelbpulver-Suspension in Wasser enthält. Auf diese Eigelbpulver-Suspension werden 0,5 ml der Wirkstoffzubereitung gebracht. Nach 24 Stunden wird der Abtötungsgrad in % bestimmt. Dabei bedeuten 100%, dass alle und 0%, dass keine Larven abgetötet worden sind.

Figure imgb0016
About 20 fly larvae (Lucilia cuprina) are placed in a test tube filled with cotton plugs of the appropriate size, which contains approx. 3 ml of a 20% egg yolk powder suspension in water. 0.5 ml of the active ingredient preparation is added to this egg yolk powder suspension. After 24 hours, the degree of destruction is determined in%. 100% means that all and 0% that no larvae have been killed.
Figure imgb0016

HERSTELLUNGSBEISPIELEMANUFACTURING EXAMPLES Beispiel 1:Example 1:

Figure imgb0017
7,3 g (0,03 Mol) 3-(4-Fluorphenoxy)-α-cyanbenzyl- alkohol und 8,1 g (0,03 Mol) 2,2-Dimethyl-3-(2-phenyl-2-chlorvinyl)-cyclopropancarbon- säurechlorid werden in 150 ml wasserfreiem Toluol gelöst und bei 25-30°C 2,4 g (0,03 Mol) Pyridin, gelöst in 50 ml Toluol, unter Rühren zugetropft. Anschliessend wird weitere 3 Stunden bei 25°C gerührt. Das Reaktionsgemisch wird in 150 ml Wasser gegossen, die organische Phase abgetrennt und nochmals mit 100 ml Wasser gewaschen.
Figure imgb0017
 7.3 g (0.03 mol) of 3- (4-fluorophenoxy) α-cyanobenzyl alcohol and 8.1 g (0.03 mol) of 2,2-dimethyl-3- (2-phenyl-2-chlorovinyl) ) -cyclopropanecarboxylic acid chloride are dissolved in 150 ml of anhydrous toluene and 2.4 g (0.03 mol) of pyridine, dissolved in 50 ml of toluene, are added dropwise at 25-30 ° C. with stirring. The mixture is then stirred at 25 ° C for a further 3 hours. The reaction mixture is poured into 150 ml of water, the organic phase is separated off and washed again with 100 ml of water.

Anschliessend wird die Toluolphase über Natriumsulfat getrocknet und das Lösungsmittel im Wasserstrahlvakuum abdestilliert. Letzte Lösungsmittelreste werden durch kurzes Andestillieren bei 60°C/1 Torr Badtemperatur entfernt. Man erhält 12,0 g (84% der Theorie) 3'-(4-Fluor- phenoxy)-a-cyanbenzyl-2,2-dimethyl-(2-phenyl-2-chlorvinyl)-cyclopropancarboxylat als gelbes Öl mit dem Brechungsindex

Figure imgb0018
.The toluene phase is then dried over sodium sulfate and the solvent is distilled off in a water jet vacuum. The last solvent residues are removed by briefly distilling at 60 ° C / 1 Torr bath temperature. 12.0 g (84% of theory) of 3 '- (4-fluorophenoxy) a-cyanobenzyl-2,2-dimethyl- (2-phenyl-2-chlorovinyl) cyclopropanecarboxylate are obtained as a yellow oil with the refractive index
Figure imgb0018
.

Beispiel 2:Example 2:

Figure imgb0019
24,3 g (0,05 Mol) 2,2-Dimethyl-3-(2-phenylthio-2- chlorvinyl)-cyclopropancarbonsäure-natriumsalz werden in 150 ml Dimethylformamid gelöst und zusammen mit 15,8 g (0,06 Mol) 3-Phenoxybenzylbromid 4 Stunden auf 120°C erhitzt. Nach beendeter Reaktion wird das Dimethylformamid im Vakuum abdestilliert und der verbleibende Rückstand in 200 ml Methylenchlorid aufgenommen. Anschliessend wird zweimal mit je 150 ml Wasser ausgeschüttelt, die organische Phase über Natriumsulfat getrocknet und das Lösungsmittel im Vakuum abgezogen. Letzte Lösungsmittelreste werden durch kurzes Andestillieren bei 60°C/1 Torr Badtemperatur entfernt. Man erhält 15 g (53,8% der Theorie) 3'-Phenoxy-benzyl-2,2-dimethyl-(2-phenylthio-2-chlorvinyl)-cyclopro- pancarboxylat als gelbes Öl mit dem Brechungsindex n23 D1,5948.
Figure imgb0019
 24.3 g (0.05 mol) of 2,2-dimethyl-3- (2-phenylthio-2-chlorovinyl) cyclopropanecarboxylic acid sodium salt are dissolved in 150 ml of dimethylformamide and together with 15.8 g (0.06 mol) 3-Phenoxybenzylbromid heated at 120 ° C for 4 hours. When the reaction has ended, the dimethylformamide is distilled off in vacuo and the remaining residue is taken up in 200 ml of methylene chloride. The mixture is then shaken twice with 150 ml of water each time, the organic phase is dried over sodium sulfate and the solvent is stripped off in vacuo. The last solvent residues are removed by briefly distilling at 60 ° C / 1 Torr bath temperature. 15 g (53.8% of theory) of 3'-phenoxy-benzyl-2,2-dimethyl- (2-phenylthio-2-chlorovinyl) cyclopropanecarboxylate are obtained as a yellow oil with the refractive index n 23 D 1.5948 .

In analoger Weise können die folgenden Verbindungen hergestellt werden:

Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Die Verbindungen der folgenden Seiten sind Gegenstand einer Ausscheidungsanmeldung der Nr. 79103 787.2.The following connections can be made in an analogous manner:
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
 The connections on the following pages are the subject of an application for exemption under No. 79103 787.2.

Die als Ausgangsverbindungen benötigten Cyclopropancarbonsäuren (V) bzw. deren Salze und Säurechloride (111) können wie im folgenden beschrieben hergestellt werden:

Figure imgb0026
26,3 g (0,1 Mol) 4-Chlorbenzyl-phosphonsäuredi- äthylester werden in 400 ml absolutem Tetrahydrofuran gelöst und auf -70°C abgekühlt. Im Stickstoffgegenstrom und unter gutem Rühren werden 0,11 Mol n-Butyllithium (15%ige Lösung in Hexan) zugetropft und dann die Reaktionsmischung noch 15 Minuten bei -70°C nachgerührt. Anschliessend werden weiterhin unter Stickstoff 15,4 g (0,1 Mol) Tetrachlorkohlenstoff bei -70°C zugetropft, die Reaktionsmischung färbt sich dabei rotbraun. Nach weiterem 15minütigem Rühren gibt man bei -65°C 18,6 g (0,1 Mol) 2,2-Dimethyl-3-formyl-cyclopropancarbonsäureäthylester zu. Man lässt dann die Reaktionsmischung auf Raumtemperatur kommen und rührt noch 3 Stunden bei 25°C nach. Der Reaktionsansatz wird dann in 2 Wasser gegossen und mit 600 ml Äther extrahiert. Die Ätherphase wird über Natriumsulfat getrocknet, das Lösungsmittel im Vakuum abgezogen und der ölige Rückstand bei 150-155°C/2 Torr destilliert. Man erhält in 54,3%iger Ausbeute 2,2-Dimethyl-3-(2-chlor-2-p-chlor-phenyl-vinyl)-cyclopropancarbonsäureäthylester.The cyclopropanecarboxylic acids (V) or their salts and acid chlorides (111) required as starting compounds can be prepared as described below:
Figure imgb0026
 26.3 g (0.1 mol) of ethyl 4-chlorobenzylphosphonate are dissolved in 400 ml of absolute tetrahydrofuran and cooled to -70.degree. 0.11 mol of n-butyllithium (15% solution in hexane) are added dropwise in a countercurrent of nitrogen and with thorough stirring, and the reaction mixture is then stirred at -70 ° C. for a further 15 minutes. Subsequently, 15.4 g (0.1 mol) of carbon tetrachloride are added dropwise at -70 ° C., the reaction mixture turns red-brown. After stirring for a further 15 minutes, 18.6 g (0.1 mol) of 2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid ethyl ester are added at -65 ° C. The reaction mixture is then allowed to come to room temperature and stirred at 25 ° C. for a further 3 hours. The reaction mixture is then poured into 2 water and extracted with 600 ml of ether. The ether phase is dried over sodium sulfate, the solvent is removed in vacuo and the oily residue is distilled at 150-155 ° C / 2 torr. 2,2-Dimethyl-3- (2-chloro-2-p-chlorophenyl-vinyl) -cyclopropanecarboxylic acid ethyl ester is obtained in 54.3% yield.

Analog können dargestellt werden:

Figure imgb0027
Figure imgb0028
Figure imgb0029
22,8 g (0,1 Mol) Benzyl-phosphonsäurediäthylester werden in 400 ml absolutem Tetrahydrofuran gelöst und auf -70°C abgekühlt. Im Stickstoffgegenstrom und unter gutem Rühren werden 0,11 Mol n-Butyllithium (15%ige Lösung in Hexan) zugetropft, dann wird noch 15 Minuten bei -70°C nachgerührt und anschliessend werden bei -65°C ebenfalls noch unter Stickstoff 18,6 g (0,1 Mol) 2,2-Dimethyl-3-formyl-cyclopropancar- bonsäureäthylester zugetropft. Man lässt dann die Reaktionsmischung auf Raumtemperatur kommen und rührt noch 3 Stunden bei 25°C.The following can be represented analogously:
Figure imgb0027
Figure imgb0028
Figure imgb0029
 22.8 g (0.1 mol) of diethyl benzylphosphonate are dissolved in 400 ml of absolute tetrahydrofuran and cooled to -70.degree. 0.11 mol of n-butyllithium (15% solution in hexane) are added dropwise in countercurrent nitrogen and with vigorous stirring, then the mixture is stirred for a further 15 minutes at -70.degree. C. and then at -65.degree. C. also becomes 18.6 under nitrogen g (0.1 mol) of 2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid ethyl ester was added dropwise. The reaction mixture is then allowed to come to room temperature and stirred at 25 ° C. for a further 3 hours.

Der Reaktionsansatz wird dann in 2 I Wasser gegossen und mit 600 ml Äther extrahiert. Die Ätherphase wird über Natriumsulfat getrocknet und dann das Lösungsmittel im Vakuum abgezogen. Der ölige Rückstand wird bei 145-150°C/3 Torr destilliert. Man erhält in 69,6%iger Ausbeute 2,2-Dimethyl-3-(2-phenyl-vinyl)-cyclopropancar- bonsäureäthylester mit dem Brechungsindex n23 D : 1,5022.The reaction mixture is then poured into 2 l of water and extracted with 600 ml of ether. The ether phase is dried over sodium sulfate and then the solvent is removed in vacuo. The oily residue is distilled at 145-150 ° C / 3 Torr. 2,2-Dimethyl-3- (2-phenyl-vinyl) -cyclopropanecarboxylate with the refractive index n 23 D : 1.5022 is obtained in 69.6% yield.

Analog können dargestellt werden:

Figure imgb0030
Figure imgb0031
Die nach Beispiel a) oder b) dargesellten Cyclopropancarbonsäureäthylester werden nach bekannten Methoden sauer oder alkalisch zu den entsprechenden Säuren verseift. Diese werden nach ebenfalls bekannten Verfahren in die entsprechenden Salze (z.B. Alkali- oder Ammoniumsalze) bzw. Säurechloride übergeführt.The following can be represented analogously:
Figure imgb0030
Figure imgb0031
 The cyclopropanecarboxylic acid ethyl esters depicted according to example a) or b) are saponified acid or alkaline to the corresponding acids by known methods. These are also converted into the corresponding salts (for example alkali or ammonium salts) or acid chlorides by processes which are also known.

Claims (6)

1. Substituted phenoxybenzyloxycarbonyl derivatives of the formula (I)
Figure imgb0038
in which
R, R' and R2 may be identical or different and represent hydrogen or halogen,
R3 represents phenyl or phenylthio, and the phenyl rings may optionally be monosubstituted or polysubstituted by alkyl or halogen, the substituents in the case of polvsubstitution being identical or different,
Y represents hydrogen or nitrile,
n represents an integer from 1 to 5 and
m represents an integer from 1 to 4.
2. Substituted phenoxybenzyloxycarbonyl derivative of the formula
Figure imgb0039
3. Process for the preparation of the substituted phenoxybenzyloxycarbonyl derivatives of the formula (I) according to Claim 1, characterised in that
a) phenoxybenzyl alcohols of the formula (II)
Figure imgb0040
in which
R, R1, Y, n and m have the abovementioned
meaning, are reacted with cyclopropanecarboxylic acid derivatives of the formula
Figure imgb0041
in which
R2 and R3 have the abovementioned meaning and R4 represents halogen or CI-4-alkoxy, preferably methoxy or ethoxy and
Hal represents halogen, preferably chlorine, if appropriate in the presence of an acid acceptor and, if appropriate, in the presence of a solvent, or
b) phenoxybenzyl halides of the formula
Figure imgb0042
in which
R, RI, Y, n and m have the abovementioned meaning and
Hal represents halogen, preferably chlorine or bromine,
are reacted with cyclopropanecarboxylic acid derivatives of the formula
Figure imgb0043
in which
R2 and R3 have the abovementioned meaning, if appropriate in the form of the alkali metal salts, alkaline earth metal salts or ammonium salts or, if appropriate, in the presence of an acid acceptor and, if appropriate, in the presence of a solvent.
4. Insecticidal and acaricidal agents, characterised in that they contain substituted phenoxybenzyloxycarbonyl derivatives of the formula (I), according to Claim 1.
5. Use of substituted phenoxybenzyloxycarbonyl derivatives of the formula (I) according to Claim 1 for combating insects and acarina.
6. Process for the preparation of insecticidal and acaricidal agents, characterised in that substituted phenoxybenzyloxycarbonyl derivatives of the formula (1) according to Claim 1 are mixed with extenders and/or surface-active agents.
EP78100252A 1977-07-06 1978-06-28 Substituted phenoxybenzyloxycarbonyl derivatives, their preparation and their use as insecticides and acaricides Expired EP0000345B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2730515 1977-07-06
DE19772730515 DE2730515A1 (en) 1977-07-06 1977-07-06 SUBSTITUTED PHENOXYBENZYLOXYCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES

Publications (2)

Publication Number Publication Date
EP0000345A1 EP0000345A1 (en) 1979-01-24
EP0000345B1 true EP0000345B1 (en) 1981-04-01

Family

ID=6013281

Family Applications (2)

Application Number Title Priority Date Filing Date
EP78100252A Expired EP0000345B1 (en) 1977-07-06 1978-06-28 Substituted phenoxybenzyloxycarbonyl derivatives, their preparation and their use as insecticides and acaricides
EP79103787A Expired EP0011695B1 (en) 1977-07-06 1978-06-28 Substituted cyclopropane carboxylic acids and their derivatives; their preparation and their use for the preparation of insecticides and acaricides

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP79103787A Expired EP0011695B1 (en) 1977-07-06 1978-06-28 Substituted cyclopropane carboxylic acids and their derivatives; their preparation and their use for the preparation of insecticides and acaricides

Country Status (22)

Country Link
US (2) US4276306A (en)
EP (2) EP0000345B1 (en)
JP (2) JPS5414946A (en)
AR (1) AR227617A1 (en)
AT (1) AT361251B (en)
AU (1) AU520095B2 (en)
BR (1) BR7804334A (en)
CA (1) CA1254227C (en)
CS (1) CS199214B2 (en)
DD (2) DD146286A5 (en)
DE (3) DE2730515A1 (en)
DK (1) DK160300C (en)
EG (1) EG13788A (en)
ES (2) ES471461A1 (en)
GR (1) GR71682B (en)
HU (1) HU176473B (en)
IL (1) IL55061A (en)
IT (1) IT1097465B (en)
PH (1) PH16779A (en)
PT (1) PT68252A (en)
TR (1) TR20790A (en)
ZA (1) ZA783869B (en)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4200644A (en) * 1978-01-26 1980-04-29 Fmc Corporation Arylthiovinylcyclopropanecarboxylate insecticides
DE2844271A1 (en) * 1978-10-11 1980-04-24 Bayer Ag 3-CHLOROSTYRYL-2,2-DIMETHYL-CYCLOPROPANCARBONIC ACID (4-FLUORO-3-PHENOXY-ALPHA-CYANO-BENZYL) -ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS EECTOPARASITICIDES
DE2842542A1 (en) * 1978-09-29 1980-04-17 Bayer Ag SUBSTITUTED BROMOSTYRYL CYCLOPROPANCARBONIC ACID PHENOXYBENZYL ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES
DE2852028A1 (en) * 1978-12-01 1980-06-12 Bayer Ag AGENT AGAINST KERATIN PEDES AND METHOD FOR TREATING WOOL WITH THESE AGENTS
IT1166681B (en) * 1979-03-09 1987-05-06 Montedison Spa PYRETHROIDS
CA1142953A (en) * 1979-04-03 1983-03-15 Dale G. Brown Process for the preparation of pesticidal esters of certain carboxylic acids using phase transfer catalysts
DE2920947A1 (en) * 1979-05-23 1980-12-04 Bayer Ag 2-PHENYL-ALKEN-1-YL-CYCLOPROPANE-CARBONIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES AND INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION
DE2922481A1 (en) * 1979-06-01 1980-12-11 Bayer Ag ELECTROPARASITICIDES CONTAINING SUBSTITUTED PHENOXYBENZYLOXYCARBONYL DERIVATIVES, (IHIO) PHOSPHORIC ACID ESTERS, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS EECTOPARASICIDES
FR2471187A1 (en) * 1979-12-10 1981-06-19 Roussel Uclaf NEW COMPOSITIONS FOR THE CONTROL OF PARASITES OF HOT-BLOOD ANIMALS
FR2484256B1 (en) * 1979-06-29 1986-10-24 Roussel Uclaf METHOD FOR CONTROLLING PEST OF HOT BLOOD ANIMALS
US4296241A (en) * 1979-07-21 1981-10-20 Bayer Aktiengesellschaft Preparation of 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid derivatives
DE2929645A1 (en) * 1979-07-21 1981-02-12 Bayer Ag PROCESS FOR THE PRODUCTION OF 1,1-DICHLORALKENES
DE2936864A1 (en) * 1979-09-12 1981-04-02 Bayer Ag, 5090 Leverkusen (+ -) - TRANS-3- (E, Z-2-CHLOR-2- (4-CHLORPHENYL) -VINYL) -, 2,2-DIMETHYL-CYCLOPROPAN-CARBONIC ACID - (+ -) - (ALPHA) -CYANO -3-PHENOXY-4-FLUOR-BENZYL) -ESTERS, THE INDIVIDUAL E- AND Z-ISOMERS, METHOD FOR THE PRODUCTION OF THESE COMPOUNDS AND THEIR USE AS EECTOPARASITICIDES
DE3025218A1 (en) * 1980-07-03 1982-02-11 Bayer Ag, 5090 Leverkusen 1-ARYL-CYCLOPROPAN-1-CARBONIC ACID ESTER, METHOD FOR THE PRODUCTION AND USE THEREOF IN PEST CONTROL
DE3029426A1 (en) * 1980-08-02 1982-03-11 Bayer Ag, 5090 Leverkusen AGAINST EFFECTIVE POUR-ON FORMULATIONS
DE3033158A1 (en) * 1980-09-03 1982-04-01 Bayer Ag, 5090 Leverkusen OPTICALLY ACTIVE ISOMERS OF TRANS-3- (2-CHLOR-2- (4-CHLOR-PHENYL) -VINYL) -2,2-DIMETHYL-CYCLOPROPAN-1-CARBONIC ACID - ((ALPHA) -CYANO-4-FLUOR-3 -PHENOXY-BENZYL) -ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS EECTOPARASITICIDES
JPS5786014A (en) * 1980-11-18 1982-05-28 Ishida Scales Mfg Co Ltd Measuring or counting method by combination
US5286749A (en) * 1980-11-21 1994-02-15 Pitman-Moore Inc. Control of sheep ectoparasites
DE3048021A1 (en) * 1980-12-19 1982-07-15 Bayer Ag, 5090 Leverkusen INSECTICIDES AND ACARICIDES AND THEIR USE
JPS57169627A (en) * 1981-04-13 1982-10-19 Yamato Scale Co Ltd Combination balance
JPS57175923A (en) * 1981-04-24 1982-10-29 Yamato Scale Co Ltd Combined balance
DE3127752A1 (en) * 1981-07-14 1983-02-03 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING PERMETHRINSAEUREMENTHYLESTER
JPS5819516A (en) * 1981-07-28 1983-02-04 Ishida Scales Mfg Co Ltd Method for measuring and counting mixture and combination of plural kinds of articles
JPS5892914A (en) * 1981-11-30 1983-06-02 Ishida Scales Mfg Co Ltd Combinatorial computing device
DE3208334A1 (en) * 1982-03-09 1983-09-15 Bayer Ag, 5090 Leverkusen PESTICIDE POUR-ON FORMULATIONS
JPS59622A (en) * 1982-06-26 1984-01-05 Anritsu Corp Combinational weighing device
DE3333657A1 (en) * 1983-09-17 1985-04-25 Bayer Ag, 5090 Leverkusen MOLDED BODIES CONTAINING PYRETHROIDS FOR CONTROLLING EKTOPARASITES
DE3538688A1 (en) * 1985-10-31 1987-05-07 Bayer Ag METHOD FOR COMBATING PARASITOSIS IN BEES
AU615879B2 (en) * 1986-08-27 1991-10-17 Montedison S.P.A. Derivatives of 2,2-dimethyl-cyclopropanecarboxylic acid
DE3629387A1 (en) * 1986-08-29 1988-03-03 Bayer Ag METHOD FOR DIASTEREOMER SEPARATION OF CYCLOPROPANCARBONIC ACID ESTERS
JPH02100028U (en) * 1989-01-25 1990-08-09
DE3906556A1 (en) * 1989-03-02 1990-09-06 Desowag Materialschutz Gmbh MEDIUM OR CONCENTRATE FOR PRESERVING WOOD OR WOOD MATERIALS
DE3907069A1 (en) * 1989-03-04 1990-09-06 Basf Ag SUBSTITUTED 2-PHENYL-ALK (EN) YL-1-YL-CYCLOPROPANCARBONIC ACID LEBYL ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING Pests
CN107365252A (en) * 2016-05-11 2017-11-21 江苏优士化学有限公司 The synthetic method of 3- (the chloro- 2- of 2- (4- chlorphenyls) vinyl) -2,2- dimethyl cyclopropane carboxylic acids

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3786052A (en) * 1966-08-26 1974-01-15 J Martel Novel cyclopropanecarboxylic acids and esters
FR1505423A (en) * 1966-08-26 1967-12-15 Roussel Uclaf New derivatives of cyclopropane and method of preparation
NL133054C (en) * 1967-11-10
SE371821B (en) * 1968-07-12 1974-12-02 Roussel Uclaf
US3666789A (en) * 1969-05-21 1972-05-30 Sumitomo Chemical Co Cyclopropanecarboxylic acid esters
FR2067854A5 (en) * 1969-11-19 1971-08-20 Roussel Uclaf Subst vinyl cyclo-propane-1-carboxylic acids insecticidal prepn
JPS5220473B1 (en) * 1970-06-29 1977-06-03
JPS515450B1 (en) * 1971-06-29 1976-02-20
US4024163A (en) * 1972-05-25 1977-05-17 National Research Development Corporation Insecticides
FR2248264B1 (en) * 1973-10-22 1977-05-27 Roussel Uclaf
IN142702B (en) * 1974-09-10 1977-08-20 Sagami Chem Res
JPS5813522B2 (en) * 1974-10-24 1983-03-14 住友化学工業株式会社 Insecticide and acaricide containing new cyclopropane carboxylic acid ester
US3966959A (en) * 1975-02-13 1976-06-29 American Cyanamid Company Insecticidal and acaricidal, pyrethroid compounds
CH602005A5 (en) 1976-02-17 1978-07-14 Ciba Geigy Ag (3)-Phenoxy-benzyl styryl-cyclopropane carboxylates
NL7701321A (en) * 1976-02-17 1977-08-19 Ciba Geigy PROCESS FOR PREPARING AN ESTER.
JPS5828264B2 (en) * 1976-03-26 1983-06-15 財団法人相模中央化学研究所 Method for producing vinyl cyclopropane carboxylic acid ester
ZA775160B (en) * 1976-08-27 1978-07-26 Fmc Corp Insecticidal styryl- and substituted-styrylcyclopropanecarboxylates
US4157397A (en) * 1976-08-27 1979-06-05 Fmc Corporation Insecticidal (β-phenylvinyl)cyclopropanecarboxylates
CA1260486A (en) * 1976-08-27 1989-09-26 John F. Engel Insecticidal styryl- and substituted- styrylcyclopropanecarboxylates
DE2848495A1 (en) * 1977-11-11 1979-05-17 Ciba Geigy Ag Cyclopropane carboxylic acid ester(s) - pesticides esp. effective against insects in cotton and vegetable cultures and house flies
DE2800922A1 (en) * 1978-01-10 1979-07-19 Bayer Ag PROCESS FOR THE SEPARATION OF STEREOISOMER VINYLCYCLOPROPANIC CARBONIC ACIDS
US4200644A (en) * 1978-01-26 1980-04-29 Fmc Corporation Arylthiovinylcyclopropanecarboxylate insecticides
DE2810634A1 (en) * 1978-03-11 1979-09-20 Bayer Ag PENTAFLUORBENZYLOXYCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES
US4358409A (en) * 1979-05-02 1982-11-09 Bayer Aktiengesellschaft Preparation of styryl cyclopropane insecticide intermediates

Also Published As

Publication number Publication date
CA1254227C (en) 1989-05-16
EP0011695B1 (en) 1982-03-24
GR71682B (en) 1983-06-21
US4276306A (en) 1981-06-30
IL55061A0 (en) 1978-09-29
EP0000345A1 (en) 1979-01-24
AU3778778A (en) 1980-01-10
DK160300B (en) 1991-02-25
JPS6248646A (en) 1987-03-03
BR7804334A (en) 1979-04-17
ES479021A1 (en) 1979-07-01
DE2861686D1 (en) 1982-04-29
TR20790A (en) 1982-08-16
AR227617A1 (en) 1982-11-30
JPS6218538B2 (en) 1987-04-23
IT7825315A0 (en) 1978-07-04
DD139991A5 (en) 1980-02-06
EG13788A (en) 1982-03-31
IT1097465B (en) 1985-08-31
IL55061A (en) 1985-04-30
DE2730515A1 (en) 1979-01-18
PT68252A (en) 1978-08-01
DD146286A5 (en) 1981-02-04
AT361251B (en) 1981-02-25
JPH0127053B2 (en) 1989-05-26
DK304178A (en) 1979-01-07
ATA484278A (en) 1980-07-15
JPS5414946A (en) 1979-02-03
PH16779A (en) 1984-02-22
EP0011695A1 (en) 1980-06-11
CS199214B2 (en) 1980-07-31
HU176473B (en) 1981-03-28
DK160300C (en) 1991-07-29
ES471461A1 (en) 1979-09-16
AU520095B2 (en) 1982-01-14
ZA783869B (en) 1979-07-25
US4611009A (en) 1986-09-09
DE2860574D1 (en) 1981-04-23

Similar Documents

Publication Publication Date Title
EP0000345B1 (en) Substituted phenoxybenzyloxycarbonyl derivatives, their preparation and their use as insecticides and acaricides
EP0019787B1 (en) 2-phenylalken-1-yl-cyclopropane-carboxylic acid esters, process for their preparation and their use as insecticides and acaricides; intermediates in their preparation
EP0001064B1 (en) Fluorosubstituted phenoxybenzyl-oxycarbonylderivatives, -alcohols and -halides, processes for their preparation and their application
EP0128350B1 (en) Pyrimidylphosphoric-acid derivatives and their use as pesticides
EP0004022B1 (en) Pentafluorobenzyloxycarbonyl derivatives, method for their preparation and their use as insecticides and acaricides
EP0033160B1 (en) Substituted 3-(1,2-dibromo-alkyl)-2,2-dimethyl-cyclopropan-1-carboxylic acid esters, their preparation and intermediates, and their application as insecticides
DE2801584A1 (en) HALOGEN-SUBSTITUTED PYRIMIDIN (2) YL-THIONO-THIOL-PHOSPHOR (PHOSPHONE) - ACID ESTERS, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS INSECTICIDES AND ACARICIDES
EP0019090B1 (en) Substituted styryl-cyclopropanecarboxylic acid derivatives, a process for their production, their use, insecticidal and acaricidal compositions, their production and process for combating insects
DE2545392A1 (en) BENZIMIDOYLTHIONOTHIOL PHOSPHORIC ACID ESTERS, METHOD FOR THEIR MANUFACTURING AND USE AS INSECTICIDES AND ACARICIDES
EP0007466B1 (en) 2-cyclopropyl-pyrimidin(4)yl-thionophosphonic acid esters, process for their production, their utilisation as insecticides and acaricides, pesticidal compositions containing these compounds and process for the production of the pesticidal compositions
EP0029515B1 (en) Fluoro-substituted 2,2,3,3-tetramethylcyclopropane-1-carboxylic acid benzyl esters, process for their preparation and their use in pesticides
EP0034731B1 (en) Trifluoromethylbenzylic esters, their intermediates, process for their preparation and their use as insecticides
EP0061114B1 (en) Phenoxypyridylmethyl esters, process for their preparation and their use in pesticidal compositions
DE2625764A1 (en) TRIFLUOROMETHYLTHIO-PHENYL (DI) -THIO -PHOSPHORIC ACID ESTER, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDE AND ACARICIDE
EP0000198A1 (en) N,N-dialkyl-0-pyrimidinyl- carbamic acid estes, process for their preparation and their use as insecticides
EP0000388B1 (en) Pyridazinon(thiono)-phosphoric acid esters, process for their preparation and their use as insecticides and acaricides
EP0076961A1 (en) Substituted vinylcyclopropanecarboxylic acid (6-phenoxy-2-pyridinyl)methyl esters, process for their preparation and their use as pesticides
EP0020954A1 (en) Fluoro-substituted oxyalkenyl-cyclopropane-carboxylic acid esters, process for their production, intermediates therefor, their production, insecticides and acaricides that contain the final products, their preparation and use
DE2455763A1 (en) O-VINYLTHIONO (THIOL) PHOSPHORUS (PHOSPHONE) ACID ESTER, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES
DE2830766A1 (en) 2-CYCLOPROPYL-PYRIMIDINE (4) YL- (THIONO) (THIOL) -PHOSPHOR- (PHOSPHON) -ACIDESTERS OR. -ESTERAMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES
WO1993024484A1 (en) Substituted 2-arylpyrroles
DE2639256A1 (en) ALKOXY- OR ALKYLTHIO-SUBSTITUTED PYRIMIDIN (THIONO) - (THIOL) -PHOSPHOR (PHOSPHON) ACID ESTERS, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS INSECTICIDES AND ACARICIDES
DE2627075A1 (en) SUBSTITUTED PYRIDAZINYL (THIONO) (THIOL) -PHOSPHORUS (PHOSPHONE) -ACID ESTER DERIVATIVES, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES AND ACARICIDES
DE2544551A1 (en) BENZISOXAZOLTHIONOTHIOL PHOSPHORIC ACID ESTER, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES AND ACARICIDES
DE2608643A1 (en) O, S-DIALKYL-O-PYRAZOLE DITHIOPHOSPHORIC ACID ESTER, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES AND ACARICIDES

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL SE

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL SE

REF Corresponds to:

Ref document number: 2860574

Country of ref document: DE

Date of ref document: 19810423

R20 Corrections of a patent specification

Effective date: 19860425

REG Reference to a national code

Ref country code: FR

Ref legal event code: CC

Free format text: FRCC 92C0409, 920609

REG Reference to a national code

Ref country code: FR

Ref legal event code: CB

Free format text: FRCB 92C0409, 780628

REG Reference to a national code

Ref country code: FR

Ref legal event code: CL

EAL Se: european patent in force in sweden

Ref document number: 78100252.2

REG Reference to a national code

Ref country code: CH

Ref legal event code: SPCF

Free format text: CHSPCFIKS 49680/910513, 951025

REG Reference to a national code

Ref country code: CH

Ref legal event code: SPCG

Free format text: IKS 49680/910513, 951025, EXPIRES:20030627

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970516

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19970522

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19970609

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970618

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970619

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19970626

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970629

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970630

Year of fee payment: 20

BE20 Be: patent expired

Free format text: 980628 *BAYER A.G.

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19980627

Ref country code: CH

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19980627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 19980628

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Effective date: 19980627

NLV7 Nl: ceased due to reaching the maximum lifetime of a patent

Effective date: 19980628

EUG Se: european patent has lapsed

Ref document number: 78100252.2

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT