DE2837524A1 - Phenylacetic acid ester derivs. from pyrethroid alcohol(s) - useful as insecticides and acaricides, and new intermediates - Google Patents

Abstract

Phenylacetate esters of formula (I) are new: (R = residue of an alcohol usual for pyrethroids; R1 = 2-4C alkyl or alkenyl, or cyclopropyl; X = H, halo, alkyl, alkoxy, OCHF2, SCHFi, SCClF2 or SCF3; when r is 4-fluoro-3-phenoxybenzyl alcohol residue (opt. alpha-CN or alpha-ethynjyl substd.) X1 is haloalkoxy or haloalkylthio, or together with X is fluoro-substd. OCH2O or OCH2CH2O; also provided R1 is cyclopropyl, X1 can be H, halo, alkyl, haloalkyl, alkoxy, alkylthio or with X is opt. fluoro-substd. OCH2O or OCH2CH2O; when r has any other significance, X1 is H, OCHF2, SCHF2, SCClF2, SCF3, or together with X is OCH2CF2O or OCHFCFiO, but X must be OCH F2, SCHF2, SCClF2 or SCF3 if X1 = H). (I) are insecticides and acaricides more effective than known similar cpds. and with a wider range of activity.

Description

Substituted α-phenyl-carboxylic acid (4-fluoro-3-phenoxy

benzyl) esters, process for their preparation and their use as insecticides and acaricides The invention relates to new substituted t-phenylcarboxylic acid (4-fluoro-3-phenoxy-benzyl) esters, a process for their production and their use as insecticides and acaricides.

It is known that certain α-phenyl-carboxylic acid (3-phenoxy-benzyl) esters, such as 3. £ - (3,4-Dimethoxyphenyl) -α-iso-propyl-acetic acid (3-phenoxy-benzyl) ester, α- (4-Fluoro-phenyl) -α-iso-propyl-acetic acid (3-phenoxy-benzyl) ester, - (4-Trifluoromethoxy-phenyl) -α-iso-propyl-acetic acid (3-phenoxy-α-cyano-benzyl) ester, 1- (4-chloro-phenyl) -4-cyclopropyl-acetic acid- (3-phenoxy-benzyl) -ester and α- (4-chloro-phenyl) -α cyclopropyl-acetic acid (3-phenoxy-t-cyano-benzyl) ester, are insecticidal (Compare DE-OS '2 335 347, 2 743 416 and 2 717 414).

The effect of these compounds is, however, especially at low levels Active ingredient concentrations and application rates, not always satisfactory.

There were now new substituted t-phenyl-carboxylic acid (4-fluoro-3-phenoxy-benzyl) esters of the formula I. found, in which R represents hydrogen, halogen, alkyl or alkoxy, R1 represents haloalkoxy or haloalkylthio and - in the event that R2 - is cyclopropyl - additionally represents hydrogen, halogen, alkyl, haloalkyl, alkoxy, alkythio or together with the radical R stands for a methylenedioxy radical.

R2 stands for ethyl, n-propyl, iso-propyl, iso-propenyl or cyclopropyl and R3 is hydrogen, cyano or ethynyl The general Formula (I) includes the various possible stemoisomers and their mixtures with a.

The new α-phenyl-carboxylic acid (4-fluoro-3-phenoxy-benzyl) esters of the formula (I) are obtained if α-phenyl-carboxylic acids of the formula (II) in which R, R1 and R2 have the meaning given above, or reactive derivatives thereof, with 4-fluoro-3-phenoxybenzyl alcohols of the formula (III) in which R3 has the meaning given above, or reacts with a reactive derivative thereof, if appropriate in the presence of an acid acceptor and if appropriate using a diluent.

The new α-phenyl-carboxylic acid (4-fluoro-3-phenoxybenzyl) esters of formula (I) are characterized by high insecticidal and acaricidal effectiveness.

Surprisingly, the k -phenyl-carboxylic acid according to the invention (4-fluoro-3-phenoxy-benzyl) ester (I) a considerably higher level of insecticidal and acaricidal properties Effect than the compounds of analogous constitution known from the prior art and the same direction of action.

The invention preferably relates to ε-phenylcarboxylic acid (4-fluoro-3-phenoxy-benzyl) esters of the formula (I) in which R represents hydrogen, fluorine, chlorine or bromine and also represents alkyl or alkoxy, the latter each having 1 or 2 carbon atoms, R1 is fluorine or chlorofluoroalkoxy and fluoro or chlorofluoroalkylthio, each with 1 or 2 carbon atoms, and - in the event that R2 is cyclopropyl. Additionally for hydrogen, fluorine, chlorine or bromine as well as for alkyl, fluoro- or chlorofluoroalkyl, Alkoxy or alkylthio - the latter each having 1 or 2 carbon atoms - or in which - likewise in the event that R² is cyclopropyl -R and R1 together represent methylenedioxy, R2 represents isopropyl or cyclopropyl and R3 represents hydrogen, cyano or ethynyl.

The invention relates in particular to compounds of the formula (I) in which R represents hydrogen, chlorine, methyl or methoxy, R1 represents trifluoromethoxy or trifluoromethylthio and - in the event that R2 is cyclopropyl - additionally for hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or methylthio, or in which - likewise in the event that R2 is cyclopropyl - R and R1 together stand for methylenedioxy, R2 for iso-propyl or cyclopropyl and R3 is hydrogen, cyano or ethynyl.

A preferred process for the preparation of the new compounds of the formula (I) consists in that, as reactive derivatives of the t-phenylcarboxylic acids of the formula (II), 4-phenylcarboxylic acid chlorides of the formula (IV) in which R, R¹ and R² have the meaning given above, with 4-pluoro-3-phenoxy-benzyl alcohols of the formula III (above) in the presence of an acid acceptor and using a diluent.

A particularly preferred process for the preparation of compounds of the formula (I) in which R3 is cyano is characterized in that carboxylic acid chlorides of the formula IV (above) are mixed with 4-fluoro-3-phenoxybenzaldehyde of the formula V. in the presence of at least the equimolar amount of a cyanide (preferably sodium cyanide or potassium cyanide), if appropriate in the presence of a catalyst and if appropriate using one or more diluents.

If the starting materials used are, for example, α- (4-methoxyphenyl) -α-cyclopropyl-acetic acid chloride and 4-fluoro-3-phenoxy-benzyl alcohol or k - (4-trifluoromethylthio-phenyl) - ~ -iso-propyl-acetic acid chloride, 4 -Fluoro-3-phenoxy-benzaldehyde and sodium cyanide, the reactions of these compounds can be outlined by the following formula schemes: The α-phenylcarboxylic acids to be used as starting materials are defined by the formula (II), the corresponding acid chlorides by the formula (IV). In these formulas, R is preferably hydrogen, chlorine or bromine, fluorine, and also alkyl or alkoxy, the latter each having 1 or 2 carbon atoms, R1 being fluorine- or chlorofluoroalkoxy and fluorine- or chlorofluoroalkylthio, each with 1 or 2 carbon atoms, and - in the event that R2 stands for cyclopropyl - additionally - i for hydrogen fluorine, chlorine or bromine and for alkyl, fluorine or chlorofluoro-alkyl, alkoxy or alkylthio -latter each with 1 or 2 carbon atoms or - likewise for in the event that R2 stands for cyclopropyl - R and R1 together for methylenedioxy and R² for iso-propyl or cyclopropyl.

In particular, starting compounds of the formulas (11) or (IV) preferred, in which R represents hydrogen, chlorine, methyl or methoxy, R1 represents Trifluoromethoxy or trifluoromethylthio and - in the event that R2 is cyclo- propyl stands - also for hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or methylthio or in which - also in the event that R2 is cyclopropyl -R and R1 together represent methylenedioxy and R2 represents isopropyl or cyclopropyl stands.

The inventively usable; -Phenyl-carboxylic acids of the formula (11) or the corresponding acid chlorides of the formula (IV) are known or can can be prepared analogously to known processes (compare DE-OS 2,335,347, 2,717 414 and 2 743 416). Examples include: α-phenyl-α-cyclopropyl-acetic acid, α- (4-Fluoro-phenyl) -α-cyclopropyl-acetic acid, α- (4-chlorophenyl) -α-cyclopropyl-acetic acid, α- (4-bromo-phenyl) -α-cyclopropyl-acetic acid, α- (4-methyl-phenyl) -α-cyclopropyl-acetic acid, .k- (4-trifluoromethyl-pheny44> -cyclopropyl-acetic acid, α- (4-methoxyphenyl) -α-cyclopropyl-acetic acid, t- (4-Methylthio-phenyl) - k -cyclopropyl-acetic acid, α- (4-trifluoromethoxyphenyl) -α-cyclopropyl-acetic acid, α- (4-trifluoromethylthio-phenyl) -α-cyclopropyl-acetic acid, α- (3,4-methylenedioxy-phenyl) -α-cyclopropyl-acetic acid, α- (4-trifluoromethoxyphenyl) -α-iso-propyl-acetic acid, and a - (4-trifluoromethylthio-phenyl i Ä-iso-propyl-acetic acid and the corresponding acid chlorides.

The 4-fluoro- 3-phenoxy-benzyl alcohols of the formula (III) and 4-fluoro-3-phenoxy-benzaldehyde of the formula (V) are the subject matter an older, not previously published patent application by the applicant (cf. DE-OS 2 709 264).

The starting compounds of the formulas (III) and (V) are obtained starting from the 3-bromo-4-fluoro-toluene known from the literature, for example according to the following reaction scheme: 4-Fluoro-3-phenoxy-toluene is advantageously produced from 3-bromo-4-fluorotoluene by reaction with excess potassium phenolate in the presence of a catalytic amount of copper oxide and using dimethylformamide as a diluent at reaction temperatures between 120 and 100 OC. The reaction of the intermediate product thus obtained with N-bromosuccinimide in the presence of a free radical initiator such as azodiisobutyronitrile, optionally using a diluent such as carbon tetrachloride, at temperatures between 50 and 100 oC leads to 4-fluoro-3-phenoxy-benzyl bromide.

This can be obtained in a Sommelet reaction, i.e. by reaction with hexamethylenetetramine in the presence of a diluent such as methylene chloride at temperatures between 0 and 50C, then with aqueous acetic acid and afterwards. with hydrochloric acid at temperatures between 80 and 120C 4-fluoro-3-phenoxybenzaldehyde (V) can be produced.

The corresponding alcohols of the formula are obtained from the aldehyde (V) (III) depending on the meaning of R2 by different methods: a) for the case, that R2 is hydrogen, by reaction with a complex metal hydride such as e.g.

Lithium aluminum hydride in an inert diluent such as e.g. Diethyl ether at temperatures between 0 and So0C, b) in the event that R2 stands for cyano, through reaction with an alkali cyanide such as sodium cyanide in the presence of an acid such as acetic acid, which may be diluted with water is at temperatures between 0 and 50 ° C and -c) in the event that R2 is ethynyl by reaction with an ethynyl compound such as ethynyl magnesium bromide, optionally using an inert diluent such as diethyl ether at temperatures between 0 and 5o0C.

Examples of the alcohols of the formula (III) are: 4-fluoro-3-phenoxy-benzyl alcohol, 4-fluoro-3-phenoxy-ε-cyano-benzyl alcohol and 4-F; uoro-3-phenoxy-tL-ethinylbenzyl alcohol.

The process for the preparation of the compounds according to the invention of Formula (I) are generally carried out using diluents. Practically all inert organic solvents can be used as such, and if appropriate - when working in a two-phase medium - also water as a second solvent component. as Organic solvents for the process according to the invention may be mentioned: aliphatic and aromatic, optionally chlorinated hydrocarbons such as pentane, hexane, Heptane, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, Chlorobenzene and dichlorobenzene, Ethers such as diethyl ether, tetrahydrofuran and dioxane and nitriles such as acetonitrile and propionitrile.

In the process mentioned as preferred, starting from acid chlorides of the formula (IV) and alcohols of the formula (III) can all be used as acid acceptors common acid binders can be used. The following may be mentioned in particular: alkali metal carbonates such as sodium and potassium carbonate, alkali alcoholates such as sodium and potassium methylate as well as sodium and potassium ethylate, also aliphatic, aromatic or heterocyclic Amines such as trimethylamine and triethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

In the method mentioned as particularly preferred, starting from Acid chlorides of the formula (IV) and 4-fluoro-3-phenoxybenzaldehyde (V) are used as Catalysts generally used compounds which are usually used in reactions serve as an aid for phase transfer of reactants in multiphase media. In particular, there are tetraalkyl and trialkyl aralkyl ammonium salts such as tetrabutyl ammonium bromide and called trimethylbenzylammonium chloride. Usable alkali cyanides are e.g. Sodium cyanide and potassium cyanide.

The reaction temperature can vary within a relatively wide range will. In general, the reactions are carried out at temperatures between 0 and 100 ° C, preferably carried out at 10 to 50C. The reactions are left in general run at normal pressure.

The starting components are used to carry out the process according to the invention generally in equimolar amounts. An excess of one or the other Component does not have any significant advantages.

The reaction components are generally in one or more of the specified diluents and to complete the list. the Reaction stirred for several hours. Then the reaction mixture, if appropriate after neutralization, shaken with toluene / water, the organic phase separated, washed with water and dried. After distilling off the solvent in vacuo the new compounds are generally obtained in the form of oils, some of which do not allow to distill without decomposition. You can, however, by so-called "distillation", i.e. by prolonged heating under reduced pressure to moderately elevated temperatures, freed from the last volatile components and cleaned in this way. The refractive index is used to characterize them.

The active ingredients are suitable if they are well tolerated by plants and are less expensive Warm-blooded toxicity for the control of animal pests, in particular insects and arachnids, which are used in agriculture, in forests, in storage and material protection as well as in the hygiene sector. They are sensitive and resistant to normal Species as well as effective against all or individual stages of development. To the above mentioned Pests include: From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda, e.g. Blaniulus guttulatus.

From the order of the Chilopoda, e.g. Geophilus carpophagus and Scutigera spec.

From the order of the Symphyla, e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola, e.g. Onychiurus armatus.

From the order of the Orthoptera, e.g. 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, e.g. Forficula auricularia.

From the order of the Isoptera, e.g. Reticulitermes 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, for example Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera, e.g. Hercinothrips femoralis, Thrips tabaci.

From the order of the Heteroptera, e.g. -Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectulariu.s, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera, 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., 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 Lepidoptera, e.g. 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 kuehn.iella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

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 chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes sps., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus s, p., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Glbbium psylloides, Tribolium spp., Tenebrio molitor, AcTriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanooaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Crsomyia 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 Siphonaptera, e.g. Xenopsylla cheopis, Ceratophyllus spp ..

From the order of the Arachnida, e.g. Scorpio maurus, Latrodectus mactans.

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., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..

nit: active ingredients can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, Active ingredient-impregnated natural and synthetic materials, b'elnst encapsulation in polymeric substances and in coating compounds for seeds, also in formulations with fuel charges, such as smoking cartridges, cans, coils and the like, as well as UDi cold and warm mist formulations.

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, alo liquid solvents, under Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as an extender For example, organic solvents can also be used as auxiliary solvents. The following liquid solvents are essentially: 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, e.g. petroleum fractions, alcohols, such as butanol or glycol and their Xther and esters, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers are meant liquids which are at normal temperature and are gaseous under normal pressure, e.g. aerosol turbulence gases such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: e.g. natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; as solid carriers for granulates are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well as granules made of organic material such as sawdust, coconut shells, Corn on the cob and tobacco stalks; come as emulsifying and / or foam-producing agents in question: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azole-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 Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention are used in the form of them commercial formulations and / or those prepared from these formulations Application forms.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary within wide ranges. The active ingredient concentration the application forms can range from 0.0000001 up to. 100% by weight active ingredient, preferably between 0.01 and 10 wt .-%.

They are used in a customary manner adapted to the use forms Way.

When used against hygiene and storage pests stand out the active ingredients -by having an excellent residual effect on wood and clay as well due to good alkali stability 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, potions, granules, through dermal application in the form of, for example, the Dipping (dipping), spraying (spraying), pour-on and spot-on and des Powder and parenteral use in the form of, for example, the rnjeltLon.

Example Phaedon larvae test solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ethers 1 part by weight of active compound preparation is mixed with the specified one Amount of solvent and the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped into the preparation of active compound the desired. Concentration treated and treated with mustard beetle larvae (Phaedon cochleariae) occupied as long as the leaves are still moist.

After the desired time, the destruction is determined in%.

100% means that all beetle larvae have been killed; 0 z means that none of the beetle larvae have been killed.

In this test, for example, the following compounds of the preparation examples show superior effectiveness compared to the prior art: 1, 2, 5, 4, 8, 9 example B Tetranychus test (resistant) Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether for the preparation of an appropriate active ingredient preparation, 1 part by weight of active ingredient is mixed with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water on the desired concentration.

Bean plants (Phaseolus szlgaris), which differ greatly from all stages of development the common spider mite or bean spider mite (Tetranychus urticae) are infested, are treated by being dipped into the preparation of active compound of the desired concentration.

After the desired time, the destruction is determined in%.

100% means that all spider mites have been killed; O% means that no spider mites have been killed.

In this test, for example, the following compounds of the preparation examples show superior effectiveness compared to the state of the art: 1, 2, 3, 4, 8, 9 example C Limit concentration test / soil insect test insect: Phorbia antiqua maggots (im Soil) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether 1 part by weight is mixed to produce a suitable preparation of active compound Active ingredient with the specified amount of solvent, gives the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil, thereby the concentration of the active ingredient in the preparation is practically irrelevant, The only decisive factor is the amount of active substance by weight per unit volume of soil, which is given in ppm (= mg / l). You fill the bottom in pots and leave them at Stand room temperature.

After 24 hours, the test animals are placed in the treated soil and after a further 2 to 7 days the effectiveness of the active ingredient will count through Off of the dead and living test insects determined in%. The efficiency is 109% when all test insects have been killed; it is O% if there are just as many test insects live like in the untreated control.

In this test, for example, the following compounds of the preparation examples show superior effect compared to the state of the art: 1,2, =, 4, b, 9 example D Limit concentration test / soil insects Test insect: Tenebrio molitor larvae (im Soil) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight is mixed Active ingredient with the specified amount of solvent, gives the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil.

The concentration of the active ingredient in the preparation plays a practical role Doesn't matter, the only decisive factor is the amount of active ingredient by weight per unit volume Soil, which is given in ppm (= mg / l). The bottom is filled into pots and left these stand at room temperature.

After 24 hours, the test animals are placed in the treated soil and after another 2 to 7 days, the effectiveness of the active ingredient is determined by counting of the dead and living test insects determined in%. The efficiency is 100% when all test insects have been killed; it is O% if there are just as many test insects live like in the untreated control.

In this test, for example, the following compounds of the preparation examples show superior effect over the prior art: 1.8 example E Led test test animals: leaf orientalis Number of test animals: 10 -Solvent: acetone 2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The solution obtained in this way is adjusted to the desired concentrations with further solvent diluted.

2.5 ml of the active ingredient solution are pipetted into a Petri dish.

There is a filter paper with a on the bottom of the Petri dish Diameter of about 9.5 cm. The Petri dish remains open until the Solvent has completely evaporated. Depending on the concentration of the active ingredient solution the amount of active ingredient per m2 of filter paper varies. Then there put the specified number of test animals into the Petri dish and cover it with one Glass lid.

The condition of the test animals is checked 3 days after the experiments have been started. The destruction is determined in%.

100% means that all test animals were killed; 0% means that no test animals were killed.

In this test, for example, the following compounds of the preparation examples show superior effect compared to the state of the art: 1 example F LT100 test for Diptera test animals: Each aegypti number of animals: 25 Solvents: Acetone 2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The solution obtained in this way is reduced to the desired lower levels with further solvent Concentrations diluted.

2.5 ml of the active ingredient solution are pipetted into a Petri dish.

There is a filter paper with a on the bottom of the Petri dish Diameter of about 3.5 cm. The Petri dish remains open until the Solvent has completely evaporated. Depending on the concentration of the active ingredient solution the amount of active ingredient per m2 of filter paper varies. Then there put the specified number of test animals into the Petri dish and cover it with one Glass lid.

The condition of the test animals is continuously monitored. It will be the one Determines the time required for a 100% knock-down effect.

In this test, for example, the following compounds of the preparation examples show superior effect compared to the state of the art: 1 example G LT100 test for Diptera Test animals: Musca domestica Number of animals: 25 Solvents: Acetone 2 parts by weight of active ingredient are taken up in 1000 parts by volume of solvent. The solution obtained in this way is reduced to the desired lower level with further solvent Concentrations diluted.

2.5 ml of the active ingredient solution are pipetted into a Petri dish at the bottom of the petri dish is a filter paper with a diameter of about 9.5 cm. The petri dish remains open until the solvent has completely evaporated. The amount depends on the concentration of the active ingredient solution Different levels of active ingredient per m2 of filter paper. Then you give the specified Place the number of test animals in the Petri dish and cover it with a glass lid.

The condition of the test animals is continuously monitored. It will be the one Determines the time required for a 100% knock-down effect.

In this test, for example, the following compounds of the preparation examples show superior effect compared to the state of the art: 2 Example Test with parasitic adult beef ticks (Boophilus microplus res.) Solvent: Alkylaryl polyglycol ether For the production of an expedient active ingredient preparation the active substance in question is mixed with the specified solvent in a ratio of 1: 2 and dilute the concentrate obtained in this way with water to the desired Concentration.

10 adult beef ticks (b.microplus res.) Are put into the to testing active ingredient preparation immersed. After transferring to a plastic cup and storage The degree of destruction is determined in an air-conditioned room.

In this test, for example, the following compounds of the preparation examples show superior effect compared to the state of the art: 1, 2, 5, 4, 8 example I Test with parasitic fly larvae (Lucilia cuprina res.) Emulsifier: 80 parts by weight Alkylaryl polyglycol ether For the production of an expedient active ingredient preparation mix 20 parts by weight of the b-relevant active substance with the specified Amount of emulsifier and dilute the resulting mixture with water to the desired Concentration. About 20 fly larvae (Lucilia cuprina) are placed in a cotton plug Brought a test tube of the appropriate size, which contains approx. 3 ml of a 20 contains its own egg yolk powder suspension in water. On this egg yolk powder suspension 0.5 ml of the active ingredient preparation are brought.

The degree of destruction is determined after 24 hours.

In this test, for example, the following compounds of the preparation examples show a superior action compared to the prior art; 2, 4 production examples: Example 1: 94 g (0.043 moles) of 3-phenoxy-4-fluoro-benzyl alcohol and 9.9 g (0.045 moles) of C-cyclopropyl-4-chlorophenyl-acetic acid chloride are dissolved in 100 ml of anhydrous toluene and heated to 4 ° C. g of pyridine, dissolved in 50 ml of anhydrous toluene, were added dropwise 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 to which 10 ml of concentrated hydrochloric acid are added, 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. The last residues of solvent are removed by brief distillation at 60 ° C./1 Torr bath temperature. 14.9 g (84.4% of theory) ε-cyclopropyl-4-chlorophenyl-acetic acid 3-phenoxy-4-fluoro-benzyl ester are obtained as a yellow oil. The structure is confirmed by the H-NMR spectrum.

Example 2: 8.64 g (0.04 mol) of 3-phenoxy-4-fluoro-benzaldehyde and 11.22 g (0.04 mol) of α-isopropyl-4-trifluoromethoxyphenyl-acetic acid chloride are mixed together with stirring at 20-250C of 3 g of sodium cyanide, 4.7 ml of water, 200 ml of n-hexane and 1 g of tetrabutylammonium bromide and then stirred at 20-25 ° C for 4 hours.

300 ml of toluene are then added to the reaction mixture and shaken twice with 300 ml of water each time.

The organic phase is separated off, dried over magnesium sulfate and the solvent is distilled off in a water jet vacuum. The last remaining solvent residues are removed by brief distillation at 60 ° C./1 Torr bath temperature. 15.6 g (80.1% of theory) of oil-isopropyl-4-trifluoromethoxyphenylacetic acid 3-phenoxy-4-fluoro-α-cyanobenzyl ester are obtained as a yellow oil with the refractive index 29 D analogously to Example 1 or Example 2 the following connections are made: At- yield game (the game (p the calculation No. Product formula theory) index: 3 CF3- O -CH-CO-O-CH2- -F 70 27: 1.5561 nD XC \ HO n H3C CH3 0 4 CF3-O-C'H-CO-O-CH2- X83 n27: 1.5172 CH H3C CH3 5 CF3 ~ 0 ~ O ~ CH ~ C ° ~ ° ~ CH ~ X ~ F 72 n27: 1.5246 5 CF: -O - (/ \ 72 D CH CsCH -7 H3C CH3 6CH-CO-O-CH, - 7 e CH ~ CO ~ O ~ CH ~ -F CC1HNÄOD At- game yield (% of refractive No. Product formula theory) index: 8 Cl - # - CH-CO-O-CH - # - F # # # # CN O- # 79 9 CF3-S - # - CH-CO-O-CH - # - F # # # CH CN O- # # # H3C CH3 72 nD27: 1.5407 The required starting products can be produced as follows: 67.2 g (0.242 mol) of α-isopropyl-4-trifluoromethylmercapto-phenylacetic acid are dissolved in 300 ml of carbon tetrachloride. 150 g of thionyl chloride are then added dropwise and the reaction mixture is then refluxed for 6 hours. After the reaction has ended, excess thionyl chloride and carbon tetrachloride are distilled off in a water jet vacuum, and the residue that remains is distilled. 57.2 g (79.7% theoretical) of α-isopropyl-4-trifluoromethylmercapto-phenylacetic acid chloride are obtained as a slightly reddish liquid with a boiling point of 1050 ° C./2 Torr.

Analogously one obtains in a yield of 72.8% of theory with a boiling point of 88 ° C./2 Torr A mixture of 85.5 g (0.33 mol) of α-isopropyl-4-trifluoromethyl mercaptophenyl acetic acid nitrile and 37 g (0.66 mol) of solid potassium hydroxide in 300 ml of ethylene glycol is heated to 140-150 ° C. for 30 hours while stirring. After cooling, the reaction mixture is poured into 500 ml of water and the alkaline aqueous phase is extracted twice with 3 o nil methylene chloride each time. The aqueous phase is separated off, acidified with 20% sulfuric acid and extracted twice with 300 ml of methylene chloride. The methylene chloride phase is separated off, dried over magnesium sulfate and the solvent in a water jet.

distilled off in vacuo, last solvent residues are removed by briefly Incipient distillation at 70 ° C / 1 Torr bath temperature removed. You get 67,?. g (73.3 96 of theory) α-isopropyl-4-trifluoromethylmercapto-phenylacetic acid as viscous oil.

Analogously one obtains: in a yield of 75.3 of theory 17 g (o , 1 mol) of isopropyl iodide is added dropwise, then the mixture is refluxed for a further 4 hours. After cooling to room temperature, the reaction mixture is poured into 500 ml of water, the toluene phase is separated off and the aqueous phase is extracted again with 200 ml of toluene. The combined toluene phases are then dried over magnesium sulfate and the solvent is then distilled off in a water jet vacuum. The remaining residue is distilled. 15.2 g (58.7 of theory) of 2-isopropyl-4-trifluoromethylmercapto-phenylacetic acid nitrile are obtained as a yellow liquid with a boiling point of 119-120 ° C /; ' Torr.

Analogously one obtains: in a yield of 41.6% of theory with a boiling point of 105-106 ° C 5ol g of 4-trifluoromethoxytoluene are dissolved in 350 ml of carbon tetrachloride and treated with 68 g of gas under UV irradiation at 60.degree. Treated chlorine (56% of theory). Distillation then gives 150 g of 4-trifluoromethoxybenzyl chloride as a water-white liquid with a boiling point of 1850C, nD20: 1.4549 in a purity of 96.5% according to GC.

105 g of the above benzyl chloride are added dropwise at room temperature to a solution of 31.5 g of NaCN in 28 ml of H 2 O and 85 ml of ethanol. The mixture is then heated to reflux temperature in 30 'and allowed to react for 3 hours at this temperature. After filtration, most of the solvent is distilled off, water is added to the residue and the organic phase is separated off, dried and distilled. 80 g of 4-trifluoromethoxyphenyl-acetonitrile with a boiling point of 18 mm: 1150 ° C., nD20: 1.4479 are obtained. The liquid solidifies when rubbed and cooled. F: 29-30 0C.

4-Trifluoromethylmercaptotoluene is obtained in the same way 4-trifluoromethyl mercaptobenzyl chloride with a boiling point of 15 mm: 100 ° C, nD20: 1.5070 and from it 4-trifluoromethylmercapto-phenylacetonitrile, boiling point 16: 142 ° C, nD20: 1.4989.

Claims (6)

Claims: 9 i-phenyl-carboxylic acid (4-fluoro-3-phenoxy-benzyl) ester of the formula t in which R represents hydrogen, halogen, alkyl or alkoxy, R1 represents haloalkoxy or haloalkythio and - in the event that R2 is cyclopropyl - additionally represents hydrogen, halogen, alkyl, haloalkyl, alkoxy, alkylthio or together with the remainder R stands for a methylenedioxy radical. R2 for ethyl, n-propyl, iso-propyl, iso-propenyl or cyclopropyl and R3 is hydrogen, cyano or ethynyl. 2. Process for the preparation of the c6-phenyl-carboxylic acid (4-fluoro-3-phenoxy-benzyl) esters of the formula (I), characterized in that α-phenyl-carboxylic acids of the formula (II) in which R, R1 and R2 have the meaning given above, or reactive derivatives thereof1 with 4-fluoro-5'-phenoxybenzyl alcohols of the formula (III) in which has the meaning given above, or reacts with a reactive derivative thereof, optionally in the presence of an acid acceptor and optionally using a diluent. 3. Insecticidal and / or acaricidal agents, characterized by a Content of at least one o-phenyl-carboxylic acid (4-fluoro-3-phenoxy-benzyl) ester of formula (I). 4. Use of α-phenyl-carboxylic acid (4-fluoro-3-phenoxybenzyl) esters for Control of insects and / or arachnids. 5. methods of combating insects and / or arachnids, characterized in that c phenylcarboxylic acid (4-fluoro-3-phenoxybenzyl) ester of formula (I) act on insects and / or arachnids and / or their habitat l'iss. 6. Process for the production of insecticidal and / or acaricidal agents, characterized in that one ci -phenylcarboxylic acid (4-fluoro-3-phenoxy-benzyl) ester of formula (I) mixed with extenders and / or surface-active agents.