EP0000345A1 - 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

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Publication number
EP0000345A1
EP0000345A1 EP78100252A EP78100252A EP0000345A1 EP 0000345 A1 EP0000345 A1 EP 0000345A1 EP 78100252 A EP78100252 A EP 78100252A EP 78100252 A EP78100252 A EP 78100252A EP 0000345 A1 EP0000345 A1 EP 0000345A1
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vinyl
formula
halogen
derivatives
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French (fr)
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EP0000345B1 (en
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Rainer Dr. Fuchs
Ingeborg Dr. Hammann
Wilhelm Dr. Stendel
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Bayer AG
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Bayer AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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 acetate or carboxylates e.g. 3'-phenoxy-benzyl- ⁇ -isopropyl (3,4-dimethoxy-phenyl) acetate.
  • (6-Chloro-piperonyl) -2,2-dimethyl-3- (2,2-dimethyl'-vinyl) -cyclopropanecarboxyate and 3'-phenoxybenzyl-2,2-dimethyl-3-indenyl-cyclopropanecarboxylate have insecticidal and acaricidal properties (See German Laid-Open Patent Nos. 2,335,347 and 2,605,828 and U.S. Patent 2,857,329).
  • the general formula (I) includes the various possible stereoisomers, 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 technology.
  • process variant a) uses 3- (4-fluorophenoxy) benzyl alcohol and 2,2-dimethyl-3- (2-phenylvinyl) cyclopropanecarboxylic acid chloride and process variant b) uses the sodium salt of 2,2-dimethyl-3- (2 -phenylthio-vinyl) -cyclopropanecarboxylic acid and 3-phenoxy- ⁇ -cyano-benzyl bromide 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, 43, 5. 435? -4362). The free acids are converted into the corresponding salts or acid halides (III) 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:
  • 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, have proven particularly useful Triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.
  • 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 4 ° 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 in the usual way 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, if appropriate in a suitable solvent, is initially introduced together with a 10-30% excess of the alcohol of the formula (II) 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 by so-called “distillation”. can be freed from the last volatile components 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 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 paraf fine, 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 ka
  • 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, for example 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 death rate is ventilated 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 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 substance 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.
  • reaction mixture is poured into 150 ml of water, the organic phase is separated off and washed again with 100 ml of water.
  • the toluene phase is then dried over sodium sulfate and the solvent is distilled off in a water jet vacuum.
  • Last solvent residues are removed by briefly distilling at 60 ° C./1 torr bath temperature.
  • 12-, og (34% of theory) 3 '- (4-fluorophenoxy) - ⁇ -cyanobenzyl-2,2-dimethyl- (2-phenyl-2-chlorovinyl) -cyclopropanecarboxylate are obtained as a yellow oil with the refractive index : 1.5670.
  • cyclopropanecarboxylic acids (V) or their salts and acid chlorides (III) required as starting compounds can be prepared as described below: 26.3 g (0.1 mol) of 4-chlorobenzylphosphonate diethyl ester are dissolved in 400 ml of absolute tetrahydrofuran and cooled to -70.degree. 0.11 mol of n-butyllithium (15% solution in hexane) is 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.
  • cyclopropanecarboxylic acid ethyl esters shown in Example a) or b) are saponified by known or acidic or alkaline means to give the corresponding acids. These are also converted into the corresponding salts (e.g. alkali or ammonium salts) or acid chlorides by known processes.

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  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (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)

Abstract

Substituierte Phenoxybenzyloxycarbonylderivate der Formel <IMAGE> in welcher R1 R¹ 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. Diese Verbindungen zeichnen sich durch starke insektizide und akarizide Eigenschaften aus. Sie werden erhalten, indem man die entsprechenden Phenoxybenzylalkohole mit Cyclopropancarbonsäurederivaten umsetzt oder die entsprechenden Phenoxybenzylhalogenide mit Cyclopropancarbonsäurederivaten umsetzt. Substituierte Cyclopropancarbonsäurederivate der Formel <IMAGE> in welcher R² und R³ die oben ausgegebene Bedeutung haben, und R<4> für OH, Halogen oder C1-C4-Alkoxy steht, wobei R<4> für den Fall, dass R³ für Phenyl steht, für OH, Halogen oder Methoxy steht.Substituted phenoxybenzyloxycarbonyl derivatives of the formula <IMAGE> in which R1 R¹ and R² may be the same or different and stand for hydrogen or halogen, R³ stands for phenyl or phenylthio, the phenyl rings optionally being substituted one or more times, identically or differently, by alkyl or halogen , Y is hydrogen or nitrile, n is an integer from 1 to 5 and m is an integer from 1 to 4. These compounds are characterized by strong insecticidal and acaricidal properties. They are obtained by reacting the corresponding phenoxybenzyl alcohols with cyclopropanecarboxylic acid derivatives or by reacting the corresponding phenoxybenzyl halides with cyclopropanecarboxylic acid derivatives. Substituted cyclopropanecarboxylic acid derivatives of the formula <IMAGE> in which R² and R³ have the meaning given above and R <4> represents OH, halogen or C1-C4-alkoxy, where R <4> in the event that R³ represents phenyl, represents OH, halogen or methoxy.

Description

Die vorliegende Erfindung betrifft neue substituierte Phenoxybenzyloxycarbonylderivate, mehrere Verfahren zu ihrer Herstellung und ihre Verwendung als Insektizide 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 Phenoxybenzyl-acetate oder -carboxylate, wie z.B. 3'-Phenoxy-benzyl-α-isopropyl-(3,4-dimethoxy-phenyl)-acetat. (6-Chlor-piperonyl)-2,2-dimethyl-3-(2,2-dimethy'-vinyl)-cyclopropancarboxyat und 3'-Phenoxybenzyl-2,2-dimethyl-3-indenyl-cyclopropancarboxylat insektizide und akarizide Eigenschaften haben (vergleiche Deutsche Offenlegungsschriften 2 335 347 und 2 605 828 und USA-Patent 2 857 3o9).It is already known that phenoxybenzyl acetate or carboxylates, e.g. 3'-phenoxy-benzyl-α-isopropyl (3,4-dimethoxy-phenyl) acetate. (6-Chloro-piperonyl) -2,2-dimethyl-3- (2,2-dimethyl'-vinyl) -cyclopropanecarboxyate and 3'-phenoxybenzyl-2,2-dimethyl-3-indenyl-cyclopropanecarboxylate have insecticidal and acaricidal properties (See German Laid-Open Patent Nos. 2,335,347 and 2,605,828 and U.S. Patent 2,857,329).

Es wurden nun die neuen substituierten Phenoxybenzyloxycarbonylderivate der Fomel (I)

Figure imgb0001
gefunden, In welcher

  • R, R1 und R2 gleich oder verschieden sein können und für Wasserstof 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 derivatives of 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 can 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 (I) schließt dabei die verschiedenen möglichen Stereoisomeren, die optischen Isomeren und Mischungen dieser Komponenten ein.The general formula (I) includes the various possible stereoisomers, the optical isomers and mixtures of these components.

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

  • a) Phenoxybenzylalkohole der Formel (II)
    Figure imgb0002
     in welcher
    • R, R1. 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 C1-4-Alkoxy, vorzugsweise Methoxy oder Äthoxy 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, R , 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
    • R 2 und R 3 die oben angegebene Bedeutung haben,

gegebenfalls 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 (I I )
    Figure imgb0002
     in which
    • R, R 1 . 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 C 1-4 alkoxy, preferably methoxy or ethoxy,
    • 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 imgb0004
     in which
    • R, R, 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 optionally in the presence of an acid acceptor and optionally 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 vorlegender 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 technology.

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

Figure imgb0006
Figure imgb0007
 For example, process variant a) uses 3- (4-fluorophenoxy) benzyl alcohol and 2,2-dimethyl-3- (2-phenylvinyl) cyclopropanecarboxylic acid chloride and process variant b) uses the sodium salt of 2,2-dimethyl-3- (2 -phenylthio-vinyl) -cyclopropanecarboxylic acid and 3-phenoxy-α-cyano-benzyl bromide as starting materials, the course of the reaction can be represented by the following formula schemes:
Figure imgb0006
Figure imgb0007

Die zu verwendenden Ausgangsstoffe sind durch die Formeln (II) bis (V) eindeutig allgemein definiert. Vorzugsweise stehen darin jedoch

  • R und R1 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, insbesonderel bis 4, Kohlenstoffatome hat,
  • R 4 für Chlor oder Methoxy,
  • Y für Wasserstoff oder Nitril,
  • 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 (II) to (V). Preferably, however, are in it
  • R and R 1 are hydrogen or fluorine,
  • R2 for 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 e 1 to 4, carbon atoms,
  • R 4 for chlorine or methoxy,
  • Y for hydrogen or nitrile,
  • for an integer from 1 to 5 and
  • m for an integer from 1 to 4.

Die als Ausgangsverbindungen zu verwendenden Phenoxybenzylalkohole (II) sind größtenteils bekannt oder nach allgemein üblichen, in der Literatur beschriebenen Verfahren herstellbar (vergleiche Deutsche Offenlegungsschrift 2 547 534).Most of the phenoxybenzyl alcohols (II) to be used as starting compounds are known or can be prepared by generally customary processes described in the literature (cf. German Offenlegungsschrift 2,547,534).

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-Fluorophenoxy)-4-fluor- α-cyan-benzylalkohol
  • 3-(3-Fluorphenoxy)-4-fluor-α-cyan-berzylalkohol
  • 3-(2-Fluorphenoxy)-4-fluor-α-cyan-benzylalkohol
  • 3-Phenoxy-6-fluor-α -cyan-benzylalkohol
  • 3-(4-Fluorphenoxy)-6-fluor- α-cyan-benzylalkohol
  • 3-(3-Fluorphenoxy)-6-fluor-α -cyan-benzylalkohol
  • 3-(2-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-cyanobenzyl alcohol
  • 3- (4-fluorophenoxy) -α-cyanobenzyl alcohol
  • 3- (3-fluorophenoxy) -α-cyanobenzyl 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-cyanobenzyl alcohol
  • 3- (2-fluorophenoxy) -4-fluoro-α-cyano-benzyl alcohol
  • 3-phenoxy-6-fluoro-α-cyanobenzyl alcohol
  • 3- (4-fluorophenoxy) -6-fluoro-α-cyano-benzyl alcohol
  • 3- (3-fluorophenoxy) -6-fluoro-α-cyanobenzyl alcohol
  • 3- (2-fluorophenoxy) -6-fluoro-α-cyanobenzyl alcohol.

Die weiterhin als Ausgangsverbindungen zu verwendenden Cyclopropancarborisäurederivate (V) können nach literaturbekannten Verfahren aus den teilweise bekannten Cyclopropancarbonsäure- äthylestern (vergleiche Tetrahedron Letters 1976, 43, 5. 435?-4362) durch saure oder alkalische Verseifung hergestellt werden. Die freien Säuren werden nach bekannten Verfahren in die entsprechenden Salze oder Säurehalogenide (III) und (V) übergeführt. Die teilweise bekannten Äthylester können wiederum nach literaturbekannten Verfahren z.B. aus 2,2-Dimethyl-3-formylcyclo- propancarbonsäureäthylester und 0,0-Diäthylmethanphosphonsäurediesterderivaten nach folgendem Formelschema hergestellt werden:

Figure imgb0008
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, 43, 5. 435? -4362). The free acids are converted into the corresponding salts or acid halides (III) 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

Als Beispiele für die Cyclopropancarbonsäurederivate (III) und (V) seien im einzelnen genannt:

  • 3-[2-Phenyl-vinyl]-, 3-[2-(2-Chlorphenyl)-vinyl]-, 3-[2-(4-Ghlorahenyl)-vinyl]-, 3-[2-(3,4-Dichlorphenyl)-vinyl]-,
  • 3-[2-(4-Fluorphenyl)-vinyl]-, 3-[2-Pentachlorphenyl-vinyl]-,
  • 3-[2-Pentafluorphenyl-vinyl]-, 3-[2-Pherylthio-vinyl]-,
  • 3-[2-(2-Chlorphenylthio)-vinyl]-, 3-[2-(4-Chlorphenylthio)-vinyl]-, 3-[2-(3,4-Dichlorphenylthio)-vinyl]-, 3-E2-(4-Fluor- phenylthio)-vinyl]-,3-[2-Pentachlorphenyl], 3-C2-Pentafluorphenyl]-thio-vinyl]-, 3-[2-{4-tert.-Butylphenyl)-vinyl]-2,2-dimethylcyclopropancarbonsäure bzw. -2,2-dimethylcyclo- aropancarbonsäurechlorid, ferner
  • 3-[2-Phenyl-2-chlor-vinyl]-, 3-[2-(2-Chlorphenyl)2-chlor- vinyl]-, 3-[2-{4-Chlorphenyl)-2-chlor-vinyl]-, 3-C2-(3,4-Dichlorphenyl)-2-chlor-vinyl]-, 3[2-(4-Fluorphenyl)-2-chlor- vinyl]-, 3-(2-Pentachlorphenyl)-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-Chlor- phenylthio)-2-chlor-vinyl]-, 3-[2-(3,4-Dichlorphenylthio)2-chlor-vinyl]-, 3-[2-(4-Fluorphenylthio)-2-chlor-vinyl]-,
  • 3- [2-Pentachlorphenyl-thio-2-chlor-vinyl]-. 3-[2-Pentafluor- pheny]-thio-2-chkir-vinyl]-, 3-[2-(4-tert.-Butylphenyl)-2-chlor- vinyl]-2,2-dimethylcyclopropancarbonsäure bzw. -2,2-dimethyl- cyclopropancarbonsäurechlorid, ferner
  • 3-[2-Phenyl-2-brom-vinyl]-, 3-[2-(2-Chlorphenyl)-2-brom- vinyl]-, 3-[2-(4-Chlorpheny])-2-brom-vinyl]-, 3-[2-(3,4-Dichlorphenyl)-2-brom―vinyl]-, 3-[2-(4-Fluorphenyl)-2-brom― vinyl]-, 3-[2-Pentachlorphenyl-2-brom-vinyl]-, 3-(2-Pentafluorphenyl-2-brom-vinyl)-, 3-[2-Phenylthio-2-brom-vinyl]-,
  • 3-[2-(2-Chlorphenylthio)-2-brom―vinyl]-, 3-C2-(4-Chlorphenyl- thio)-2-brom―vinyl]-, 3-[2-(3,4-Dichlorphenylthio)-2-brom- vinyl]-, 3-[2-(4-Fluorphenylthio)2-brom-vinyl]-, 3-[2-Penta- chlorpheny-thio-2-brom―vinyl]-, 3-[2-Pentafluorphenyl-thio-2-brom- vinyl]-, 3-[2-(4-tert.-Butylphenyl)-2-brom ―vinyl]-2,2-dimethyl-

cyclopropancarbonsäure bzw -2,2-dimethylcyclopropancarbon- säurechlorid.Examples of the cyclopropanecarboxylic acid derivatives (III) and (V) are:
  • 3- [2-phenyl-vinyl] -, 3- [2- (2-chlorophenyl) vinyl] -, 3- [2- (4-ghlorahenyl) vinyl] -, 3- [2- (3,4 -Dichlorophenyl) -vinyl] -,
  • 3- [2- (4-fluorophenyl) vinyl] -, 3- [2-pentachlorophenyl vinyl] -,
  • 3- [2-pentafluorophenyl vinyl] -, 3- [2-pherylthio-vinyl] -,
  • 3- [2- (2-chlorophenylthio) vinyl] -, 3- [2- (4-chlorophenylthio) vinyl] -, 3- [2- (3,4-dichlorophenylthio) vinyl] -, 3-E2 - (4-fluorophenylthio) vinyl] -, 3- [2-pentachlorophenyl], 3-C2-pentafluorophenyl] thio-vinyl] -, 3- [2- {4-tert-butylphenyl) vinyl] -2,2-dimethylcyclopropane carboxylic acid or -2,2-dimethylcyclo aropane carboxylic acid chloride, furthermore
  • 3- [2-phenyl-2-chloro-vinyl] -, 3- [2- (2-chlorophenyl) 2-chloro-vinyl] -, 3- [2- {4-chlorophenyl) -2-chloro-vinyl] -, 3-C2- (3,4-dichlorophenyl) -2-chloro-vinyl] -, 3 [2- (4-fluorophenyl) -2-chloro-vinyl] -, 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-pentachlorophenyl-thio-2-chloro-vinyl] -. 3- [2-Pentafluoropheny] thio-2-chkir-vinyl] -, 3- [2- (4-tert-butylphenyl) -2-chloro-vinyl] -2,2-dimethylcyclopropanecarboxylic acid or -2 , 2-dimethyl-cyclopropanecarboxylic acid chloride, further
  • 3- [2-phenyl-2-bromo-vinyl] -, 3- [2- (2-chlorophenyl) -2-bromo-vinyl] -, 3- [2- (4-chloropheny]) - 2-bromo- vinyl] -, 3- [2- (3,4-dichlorophenyl) -2-bromo ― vinyl] -, 3- [2- (4-fluorophenyl) -2-bromo― vinyl] -, 3- [2-pentachlorophenyl -2-bromo-vinyl] -, 3- (2-pentafluorophenyl-2-bromo-vinyl) -, 3- [2-phenylthio-2-bromo-vinyl] -,
  • 3- [2- (2-Chlorophenylthio) -2-bromo ― vinyl] -, 3-C2- (4-chlorophenylthio) -2-bromo ― vinyl] -, 3- [2- (3,4-dichlorophenylthio ) -2-bromo-vinyl] -, 3- [2- (4-fluorophenylthio) 2-bromo-vinyl] -, 3- [2-pentachlorophenythio-2-bromo ― vinyl] -, 3- [ 2-pentafluorophenyl-thio-2-bromo-vinyl] -, 3- [2- (4-tert-butylphenyl) -2-bromo-vinyl] -2,2-dimethyl-

cyclopropanecarboxylic 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-Fhenoxy-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-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(4-Fluorphenoxy)-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(3-Fluorphenoxy)-α-cyan-benzylchlorid bzw. -benzylbromid
  • 3-(2-Fluorphenoxy)-α-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-Fluornhenoxy)-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-Fluornhenoxy)-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-Fhenoxy-benzyl chloride or benzyl bromide
  • 3- (4-fluorophenoxy) benzyl chloride or benzyl bromide
  • 3- (3-fluorophenoxy) -benzyl C hlorid 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-α-cyanobenzyl chloride or benzyl bromide
  • 3- (4-fluorophenoxy) -α-cyanobenzyl chloride or benzyl bromide
  • 3- (3-fluorophenoxy) -α-cyanobenzyl chloride or benzyl bromide
  • 3- (2-fluorophenoxy) -α-cyanobenzyl 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-fluoronhenoxy) -4-fluoro-α-cyanobenzyl chloride or benzyl bromide
  • 3- (2-fluorophenoxy) -4-fluoro-α-cyanobenzyl chloride or benzyl bromide
  • 3-phenoxy-6-fluoro-α-cyanobenzyl chloride or benzyl bromide
  • 3- (4-fluoronhenoxy) -6-fluoro-α-cyanobenzyl chloride or benzyl bromide
  • 3- (3-fluorophenoxy) -6-fluoro-α-cyanobenzyl 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, have proven particularly useful Triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

Die Reaktionstemperatur kann innerhalb eines größeren Bereichs variiert werden. Im allgemeinen arbeitet man zwischen o und 15o°C, vorzugsweise bei der Verfahrensvariante a) bei lo bis 4C°C und bei der Verfahrensvariante b) bei loo bis 13o°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 4 ° 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 in the usual way 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 ÄthylEster der Cyclopropancarbonsäure gegebenenfalls in einem geeigneten Lösungsmittel zusammen mit 10-30 % Überschuß des Alkohols der Formel (II) 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, if appropriate in a suitable solvent, is initially introduced together with a 10-30% excess of the alcohol of the formula (II) 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 anderen Reaktionskomponente 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 Tmperaturen 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 by so-called "distillation". can be freed from the last volatile components 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:

  • Aus der Ordnung der Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Aus der Ordnung der Diplopoda z. B. Blaniulus guttulatus.
  • Aus der Ordnung der Chilopoda z. B. Geophilus carpophagus, Scutigera spec.
  • Aus der Ordnung der Symphyla z. B. Scutigerella immaculata. Aus der Ordnung der Thysanura z. B. Lepisma saccharina.
  • Aus der Ordnung der Collembola z. B. 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.
  • Aus der Ordnung der Dermaptera z. B. Forficula auricularia. Aus der Ordnung der Isoptera z. B. 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.
  • Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci.
  • Aus der Ordnung der Heteroptera z.B. Eurygaster spp., Dyadercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • Aus der Ordnung der Homoptera z.B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypli, srevicoryne 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..
  • Aus der Ordnung der Lepidoptera z. B. Pectinophora soasypiella, Hupalus piniariua, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neuatria, Euproctis chrysorrhoea, Lymantria app., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotia spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flaamea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pofonslla, Pieria spp., Chilo spp., Pyrausta nubilalis, Ephestia kushniella, Calleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia asbiguella, Homona magnanimm, Tortrix viridana. Aus der Ordnug der Coleoptera z. B. Anobium punctatum, Rhizopertha doainica, Bruchidius obtectus, Acanthoacelides obtectus, Hylotrupes bajulus, Agalastica alni, Leptinotarsa deceslineata, Phaedon cochleariae, Diabrotica spp., Paylliodes chrysocephala, Epilachna variveatis, Atomaria spp., Oryzaephilus surinaaansis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Couthorrhynchus asaiailis, Hypera postica, Dersestes spp., Trosoderma spp., Anthrenua app., Attagenus spp., Lyctus spp., Meligathes aeneus, Ptinus app., Niptus hololeucus, Gibbium paylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Aaphimallon solstitialis, Coatelytra zeslandica.
  • Aus der Ordnung der Hymenoptera z. B. Diprion app., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. Aus der Ordnung der Diptera z.B. Aëdes epp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Pannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastroghilus spp., Hyppobosca spp., Stamoxys spp., Oestrus spp., Hypoderma spp., Tabanua 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..
  • Aus der Ordnung der Arachnida z.B. 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..
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:
  • From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • From the order of the Diplopoda z. B. Blaniulus guttulatus.
  • From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.
  • From the order of the Symphyla z. B. Scutigerella immaculata. From the order of the Thysanura z. B. Lepisma saccharina.
  • From the order of the Collembola z. B. Onychiurus armatus.
  • From the order of the 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 Dermaptera z. B. Auricular Forficula. From the order of the Isoptera z. B. Reticulitermes spp ..
  • From the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
  • From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.
  • From the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci.
  • From the order of the Heteroptera, for example Eurygaster spp., Dyadercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • From the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypli, srevicoryne 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 oleaarvitella, Laataelellaidia Pseudococcus spp., Psylla spp ..
  • From the order of the Lepidoptera z. B. Pectinophora soasypiella, Hupalus piniariua, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neuatria, Euproctis chrysorrhoea, Lymantria app., Bucculatrix thurberiuxia spp., Epp , Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flaamea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pofonslla, Pieria spp., Chilo spp., Pyrausta nubilalis, Ephestia kushniella, Callaco mellella, Calleria mella Choristoneura fumiferana, Clysia asbiguella, Homona magnanimm, Tortrix viridana. From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha doainica, Bruchidius obtectus, Acanthoacelides obtectus, Hylotrupes bajulus, Agalastica alni, Leptinotarsa deceslineata, Phaedon cochleariae, Diabrotica spp., Paylliodes chrysoceppusivus, suril. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Couthorrhynchus asaiailis, Hypera postica, Dersestes spp., Trosoderma spp., Anthrenua app., Attagenus spp., Lyctus spp., Meligathes aeneus, Ptinus app., Niptus hololeucuso. Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Aaphimallon solstitialis, Coatelytra zeslandica.
  • From the order of the Hymenoptera z. B. Diprion app., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of the Diptera, for example Aëdes epp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Pannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastroghilus spp., Hyppobosca ., Stamoxys spp., Oestrus spp., Hypoderma spp., Tabanua spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, D acus oleae, Tipula paludosa. From the order of the Siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp ..
  • From the order of the Arachnida, for example Scorpio maurus, Latrodectus mactans.
  • Spp From the order of the Acarina, for example Acarus siro, Argas., Spp Ornithodoros., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Spp Rhipicephalus., Amblyomma spp., Spp Hyalomma., Ixodes spp., Psoroptes s p p ., Chorioptes spp., Sarcoptes spp., 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, Kethylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckcitteln 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 Gesteins- .mehle, 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, Kokosnußschalen, 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 paraf fine, 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 kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flours, such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifiers and / or foam-generating agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, 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. Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.Dyes such as inorganic pigments, for example 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%.

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 A Example A

Phaedon-Larven-Test

  • Lösungsmittel: 3 Gewichtsteile Dimethylformamid
  • Emulgator: 1 Gewichtsteil Alkylarylpolyglykoläther
Phaedon larval test
  • Solvent: 3 parts by weight of dimethylformamide
  • Emulsifier: 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
Active substances, active substance concentrations, times of evaluation and results are shown in the table below:
Figure imgb0009

Beispiel BExample B

Myzus-Test (Kontakt-Wirkung)

  • Lösungsmittel: 3 Gewichtsteile Dimethylformamid
  • Emulgator : 1 Gewichtsteil Alkylarylpolyglykoläther
Myzus test (contact effect)
  • Solvent: 3 parts by weight of dimethylformamide
  • Emulsifier: 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 % beatimmt. Dabei bedeutet 100 %, daß alle Blattläuse abgetötet wurden; 0 % bedeutet, daß keine Blattlause abgetötet wurden.After the specified times, the death rate is ventilated in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

Wirkstoffe, wirkstoffkonzentrationen, Auswertungazeiten und Reaultate gehen aus der nachlolgenden Tabelle hervor:

Figure imgb0010
Figure imgb0011
 Active substances, active substance concentrations, evaluation times and results are shown in the table below:
Figure imgb0010
Figure imgb0011

Beispiel CExample C

Tetranychus-Test (resistent)

  • Lösungsmittel: 3 Gewichtsteile Dimethylformamid
  • Emulgator: 1 Gewichtsteil Alkylarylpolyglykoläther
Tetranychus test (resistant)
  • Solvent: 3 parts by weight of dimethylformamide
  • Emulsifier: 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 imgb0012
Figure imgb0013
 Active substances, active substance concentrations, evaluation times and results are shown in the table below:
Figure imgb0012
Figure imgb0013

Beispiel DExample D

Test mit parasitierenden adulten Rinderzecken (Boophilus microplus res.)

  • Lösungsmittel: Alkylarylpolyglykoläther
Parasitic adult tick test (Boophilus microplus res.)
  • Solvent: 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 substance 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 imgb0014
10 adult beef ticks (b. Microplus res.) Are immersed in the active ingredient preparation to be tested for 1 min. After being placed in 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 imgb0014

Beispiel EExample E

Test mit parasitierenden Fliegenlarven (Lucilia cuprina)

  • Emulgator: 80 Gewichtsteile Alkylarylglykoläther
Test with parasitic fly larvae (Lucilia cuprina)
  • Emulsifier: 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 imgb0015
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 imgb0015

Herstellungsbeispiele

Figure imgb0016
7,3 g (o,o3 Mol) 3-(4-Fluorphenoxy)-α-cyanbenzylalkohol und 8,1 g (0,03 Mol) 2,2-Dimethyl-3-(2-phenyl-2-chlorvinyl)-cyclopropancarbonsäurechlorid werden in 15o ml wasserfreiem Toluol gelöst und bei 25 - 3o°C 2,4 g (0,03 Mol) Pyridin, gelöst in 5o ml Toluol, unter Rühren zugetropft. Anschließend wird weitere 3 Stunden bei 25°C gerührt. Das Reaktionsgemisch wird in 15o ml Wasser gegossen, die organische Phase abgetrennt und nochmals mit loo ml Wasser gewaschen. Anschließend wird die Toluolphase über Natriumsulfat getrocknet und das Lösungsmittel im Wasserstrahlvakuum abdestilliert Letzte Lösungsmittelreste werden durch kurzes Andestillieren bei 60°C/l Torr Badtemperatur entfernt. Man erhält 12-,o g (34 % der Theorie) 3'-(4-Fluorphenoxy)-α-cyanbenzyl-2,2-dimethyl-(2-phenyl-2-chlorvinyl)-cyclopropancarboxylat als gelbes Öl mit dem Brechungsindex
Figure imgb0017
: 1,5670.
Figure imgb0018
24,3 g (0,05 Mol) 2,2-Dimethyl-3-(2-phenylthio-2-chlorvinyl)-cyclopropancarbonsäure-natriumsalz werden in 15o 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 2oo ml Methylenchlorid aufgenommen. Anschließend wird zweimal mit je 15o ml Wasser ausgeschüttelt, die organische Phase über Natriumsulfat getrocknet und das Lösungsmittel im Vakuum abgezogen. Letzte Lösungsmittelreste werden durch kurzes Andestillieren bei 60°C/l Torr Badtemperatur entfernt. Man erhält 15 g (53,8 % der Theorie) 3'-Phenoxy-benzyl-2,2-dimethyl-(2-phenylthio-2-chlorvinyl)-cyclopropancarboxylat als gelbes Öl mit dem Brechungsindex
Figure imgb0019
:1,5948.Manufacturing examples
Figure imgb0016
 7.3 g (o, o3 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 is 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 25-3 ° 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. The toluene phase is then dried over sodium sulfate and the solvent is distilled off in a water jet vacuum. Last solvent residues are removed by briefly distilling at 60 ° C./1 torr bath temperature. 12-, og (34% of theory) 3 '- (4-fluorophenoxy) -α-cyanobenzyl-2,2-dimethyl- (2-phenyl-2-chlorovinyl) -cyclopropanecarboxylate are obtained as a yellow oil with the refractive index
Figure imgb0017
 : 1.5670.
Figure imgb0018
 24.3 g (0 05 mole) of 2,2-dimethyl-3- (2-phenylthio-2-chloro vinyl) -cyclopropanecarboxylic acid sodium salt are dissolved in 15o ml of dimethylformamide and, together with 15.8 g (0.06 mol) 3-Phenoxybenzylbromid heated at 120 ° C for 4 hours. After finished Reaction, the dimethylformamide is distilled off in vacuo and the remaining residue is taken up in 2oo ml of methylene chloride. The mixture is then extracted twice with 150 ml of water, 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 / l 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
Figure imgb0019
 : 1.5948.

In analoger Weise können die folgenden Verbindungen hergestellt werden:

Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
 The following connections can be made in an analogous manner:
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026

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

Figure imgb0027
26,3, g (o,l Mol) 4-Chlorbenzyl-phosphonslurediäthylester werden in 4oo 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 (o,l Mol) Tetrachlorkohlenstoff bei -70°C zugetropft, die Reaktionsmischung färbt sich dabei rotbraun. Nach weiterem 15-minütigem Rühren gibt man bei -65°C 18.6 g (o,l Mol) 2,2-Dimethyl-3-formyl-cyclopropancarbon- säureäthylester zu. Man läßt dann die Reaktionsmischung auf Raumtemperatur kommen und rührt noch 3 Stunden bei 25°C nach. Der Reaktionsansatz wird dann in 2 1 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-ghenyl-vinyl)-cyclopropancarbonsäureäthylester.The cyclopropanecarboxylic acids (V) or their salts and acid chlorides (III) required as starting compounds can be prepared as described below:
Figure imgb0027
 26.3 g (0.1 mol) of 4-chlorobenzylphosphonate diethyl ester are dissolved in 400 ml of absolute tetrahydrofuran and cooled to -70.degree. 0.11 mol of n-butyllithium (15% solution in hexane) is 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-formylcyclopropanecarboxylic 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 l of water and extracted with 6 00 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-chloro-ghenyl-vinyl) -cyclopropanecarboxylic acid ethyl ester is obtained in 54.3% yield.

Analog können dargestellt werden:

Figure imgb0028
Figure imgb0029
22.8 g (o,1 Mol) Benzyl-phosphonsäurediäthylester werden in 4oo ml absolutem Tetrahydrofuran gelöst und auf -7o°C abgekühlt. Im Stickstoffgegenstrom und unter gutem Rühren werden o,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 (o,1 Mol) 2,2-Dimethyl-3-formyl-cyclopropancarbonsäureäthyl- ester zugetropft. Man läßt dann die Reaktionsmischung auf Raumtemperatur kommen und rührt noch 3 Stunden bei 25°C. Der Reaktionsansatz wird dann in 2 1 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)-cyclopropancarbonsäureäthylester mit dem Brechungsindex
Figure imgb0030
: 1,5022.The following can be represented analogously:
Figure imgb0028
Figure imgb0029
 22.8 g (0.1 mol) of ethyl benzylphosphonate are dissolved in 4oo ml of absolute tetrahydrofuran and cooled to -7 ° C. 0.11 mol of n-butyllithium (15% solution in hexane) are added dropwise in a countercurrent of nitrogen and with thorough stirring, then the mixture is stirred for a further 15 minutes at -70.degree. C. and then at -65.degree 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. The reaction mixture is then poured into 2 l of water and extracted with 6 00 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) -cyclopropanecarboxylic acid ethyl ester with the refractive index is obtained in 69.6% yield
Figure imgb0030
 : 1.5 0 22.

Analog können dargestellt werden:

Figure imgb0031
Figure imgb0032
 The following can be represented analogously:
Figure imgb0031
Figure imgb0032

Die nach Beispiel a) oder b) dargestellten 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 cyclopropanecarboxylic acid ethyl esters shown in Example a) or b) are saponified by known or acidic or alkaline means to give the corresponding acids. These are also converted into the corresponding salts (e.g. alkali or ammonium salts) or acid chlorides by known processes.

Claims (6)

1. Substituierte Phenoxybenzyloxycarbonylderivate der Formel (I)
Figure imgb0033
in welcher R. R1 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. 1. Substituted phenoxybenzyloxycarbonyl derivatives of the formula (I)
Figure imgb0033
 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 can 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. 2. Verfahren zur Herstellung der substituierten Phenoxybenzyloxycarbonylderivate der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß man a) Phenoxybenzylalkohole der Formel (II)
Figure imgb0034
in welcher R, R1, Y, n und m die oben angegebene Bedeutung haben, mit Cyclopropancarbonsäurederivaten der Formel
Figure imgb0035
in welcher R2 und R3 die oben angegebene Bedeutung haben, und R4 für Halogen oder C1-4-Alkoxy, vorzugsweise Methoxy oder Äthoxy 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 imgb0036
in welcher R, R1, Y, n und m die oben angegebene Bedeutung haben und Hal für Halogen, vorzugsweise Chlor oder Brom, steht, mit Cyclopropancarbonsäurederivaten der Formel
Figure imgb0037
in welcher R 2 und R 3 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.
, Insektizide und akarizide Mittel, gekennzeichnet durch einen Gehalt an substituierte Phenoxybenzyloxycarbonylderivate der Formel (I), gemäß Anspruch 1.2. A process for the preparation of the substituted phenoxybenzyloxycarbonyl derivatives of the formula (I) according to claim 1, characterized in that a) phenoxybenzyl alcohols of the formula (II)
Figure imgb0034
 in which R, R 1 , Y, n and m have the meaning given above, with cyclopropanecarboxylic acid derivatives of the formula
Figure imgb0035
 in which R 2 and R 3 have the meaning given above, and R4 represents halogen or C 1-4 alkoxy, preferably methoxy or ethoxy, 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 imgb0036
 in which R, R 1 , 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 imgb0037
 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.
, Insecticides and acaricidal agents, characterized by a content of substituted phenoxybenzyloxycarbonyl derivatives of the formula (I) according to claim 1. 4. Verwendung von substituierten Phenoxybenzyloxycarbonylderivate der Formel (I) gemäß Anspruch 1 zur Bekämpfung von Insekten und Acarina.4. Use of substituted phenoxybenzyloxycarbonyl derivatives of the formula (I) according to Claim 1 for controlling insects and acarina. 5. Verfahren zur Bekämpfung von Insekten und Acarina, dadurch gekennzeichnet, daß man substituierte Phenoxybenzyloxycarbonylderivate der Formel (I) gemäß Anspruch 1 auf Insekten, Acarina und/oder ihren Lebensraum einwirken läßt.5. A method for controlling insects and acarina, characterized in that substituted phenoxybenzyloxycarbonyl derivatives of the formula (I) according to claim 1 are allowed to act on insects, acarina and / or their habitat. 6. Verfahren zur Herstellung von insektiziden und akariziden Mittel, dadurch gekennzeichnet, daß man substituierte Phenoxybenzyloxycarbonylderivate der Formel (I) gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Stoffen vermischt.6. A process for the preparation of insecticidal and acaricidal agents, characterized in that substituted phenoxybenzyloxycarbonyl derivatives of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active substances. 7. Cyclopropancarbonsäurederivate der Formel (III)
Figure imgb0038
in welcher R2 und R 3 die oben angegebene Bedeutung haben, und R 4 für OH, Halogen oder C1-4-Alkoxy, vorzugsweise Methoxy oder Äthoxy steht, wobei R für den Fall, daß R3 für Phenyl steht, für OH, Halogen oder Methoxy steht. 7. Cyclopropanecarboxylic acid derivatives of the formula (III)
Figure imgb0038
 in which R 2 and R 3 have the meaning given above, and R 4 stands for OH, halogen or C 1-4 alkoxy, preferably methoxy or ethoxy, where R stands for OH, halogen or methoxy if R 3 stands for phenyl.
EP78100252A 1977-07-06 1978-06-28 Substituted phenoxybenzyloxycarbonyl derivatives, their preparation and their use as insecticides and acaricides Expired EP0000345B1 (en)

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EP0009792A1 (en) * 1978-10-11 1980-04-16 Bayer Ag (4-Fluoro-3-phenoxy-alpha-cyanobenzyl)esters of 3-chlorostyryl-2,2-dimethyl-cyclopropanoic acid, method of preparation and use as ectoparasiticides
FR2453140A1 (en) * 1979-04-03 1980-10-31 American Cyanamid Co Insecticide and acaricide-phenoxy-benzyl pyrethroid ester prodn. - by reaction of acid chloride with 3-phenoxy-benzaldehyde and alkali cyanide in two=phase system in presence of a phase-transfer catalyst
EP0022971A1 (en) * 1979-07-21 1981-01-28 Bayer Ag Process for the preparation of 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid derivatives
EP0023598A1 (en) * 1979-07-21 1981-02-11 Bayer Ag Process for the preparation of 1,1-dichloro alkenes
EP0025542A2 (en) * 1979-09-12 1981-03-25 Bayer Ag (+/-)-(alpha-cyano-3-phenoxy-4-fluoro-benzylic)esters of (+/-)-trans-3-(E,Z-2-chloro-2-(4-chloro-phenyl)-vinyl)-2,2-dimethyl-cyclopropane carboxylic acid, their E and Z isomers, a process for their preparation and their application as ectoparasiticides
EP0025542A3 (en) * 1979-09-12 1981-05-20 Bayer Ag (+/-)-(alpha-cyano-3-phenoxy-4-fluoro-benzylic)esters of (+/-)-trans-3-(e,z-2-chloro-2-(4-chloro-phenyl)-vinyl)-2,2-dimethyl-cyclopropane carboxylic acid, their e and z isomers, a process for their preparation and their application as ectoparasiticides
EP0043492A2 (en) * 1980-07-03 1982-01-13 Bayer Ag 1-Aryl-cyclopropane-1-carboxylic-acid esters, their preparation and their use as insecticides
EP0043492B1 (en) * 1980-07-03 1983-10-05 Bayer Ag 1-aryl-cyclopropane-1-carboxylic-acid esters, their preparation and their use as insecticides
EP0045424A1 (en) * 1980-08-02 1982-02-10 Bayer Ag Pour-on formulations active against ticks
EP0046950A1 (en) * 1980-09-03 1982-03-10 Bayer Ag Optically active isomers of trans-3(2-(4-chlorophenyl)-vinyl)-2,2-dimethyl-cyclopropion-1-ic acid-(alpha-cyano-4-fluoro-3-phenoxy-benzyl)-esters, process for their preparation and their use as ectoparasiticides
US5286749A (en) * 1980-11-21 1994-02-15 Pitman-Moore Inc. Control of sheep ectoparasites
EP0088919B1 (en) * 1982-03-09 1987-01-14 Bayer Ag Pesticidal pour-on formulations
EP0135853A2 (en) * 1983-09-17 1985-04-03 Bayer Ag Shaped bodies containing pyrethroids for the control of ectoparasites
EP0135853A3 (en) * 1983-09-17 1987-05-20 Bayer Ag Shaped bodies containing pyrethroids for the control of ectoparasites
EP0224697A1 (en) * 1985-10-31 1987-06-10 Bayer Ag Use of synthetic pyrethroids for the manufacture of a medicament for the control of parasitosis in bees

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