CS227034B2 - Insecticide and acaricide - Google Patents

Abstract

Gegenstand der vorliegenden Erfindung sind 4-Fluor-3-halophenoxy-benzylester der Formel I in welcher

• R, R¹ und X die in der Beschreibung angegebene Bedeutung haben.

Sie werden erhalten, indem man Carbonsäuren oder deren Salze der Formel II in welcher

• R und M die in der Beschreibung angegebene Bedeutung haben oder reaktionsfähige Derivate derselben mit 4-Fluor-3-halophenoxy-benzylalkoholen oder reaktionsfähigen Derivaten derselben umsetzt.

Die neuen 4-Fluor-3-halophenoxy-benzylester der Formel (I) zeichnen sich durch hohe pestizide, insbesondere insektizide und akarizide Wirksamkeit aus.

Description

The present invention relates to insecticidal and acaricidal compositions containing novel 4-fluoro-3-halophenoxybenzyl esters as active ingredients, and to a process for the preparation thereof. The invention further provides novel intermediates for the preparation of the aforementioned active substances, and processes for their preparation.

It is already known that certain phenoxybenzyl esters such as 3- (2,2-dichlorvinyl) -2,2-dimethylcyclopropanecarboxylic acid 3-phenoxybenzyl ester (permethrin) and 3- (2,2-dichlorvinyl) α-cyano-3-phenoxybenzyl ester -2,2-dimethylcyclopropanecarboxylic acids (cypermeithrin), exhibit insecticidal and acaricidal properties (see British Patent No. 1413,491).

However, the effect of these compounds, especially when applied in lower amounts and concentrations, is not always entirely satisfactory.

The present invention provides novel 4-fluoro-3-halophenoxybenzyl esters of formula (I)

(D in which

R represents a 2,2,3,3-tetramethylcyclopropyl group or a radical of formula

where

R ⁵ represents a hydrogen, fluorine, chlorine or bromine atom or an optionally halogenated C 1 -C 4 alkyl group and

R ⁶ represents a fluorine, chlorine or bromine atom, an optionally substituted C 1 -C 4 alkyl group or a phenyl group optionally substituted by halogen, and / or an optionally halogenated radical selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 1 -C 4 alkylthio

xylic acids or their salts of the general formula II

R — СО — ОМ, (II)

and alkylenedioxy having 1 or 2 carbon atoms, or

R ⁶ and R ⁵ together form an alkanediyl group having 2 to 5 carbon atoms, or

R is a radical of formula -CH-R ^7,

R ⁸ where

R ⁷ represents a phenyl group optionally substituted by halogen and / or an optionally halogenated group selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and C 1 -C 2 alkylenedioxy carbon atoms and

R ⁸ represents an isopropyl or cyclopropyl group,

R ¹ represents hydrogen or cyano and

X is an image of chlorine or bromine.

SUMMARY OF THE INVENTION The present invention provides a process for the preparation of the novel compounds of formula (I) above. that the karbobo in which.

R is as defined above, and

M represents a hydrogen, sodium or potassium atom or reactive derivatives thereof with 4-fluoro-3-halophenoxybenzyl alcohols or ¹ reactive derivatives thereof of the general formula III

in which

X is as defined above, and

R2 represents —CHO, —CH2OH, —CH2Cl, —СНгВг, —CHCl2, —СНВГ2, —CH (OCH ₃ ) 2, -CH (or-CH-R ³ .

R ⁴ is as defined above for R ¹ except for the hydrogen atom and

R ³ represents a hydroxyl group or a halogen atom, optionally in the presence of acid acceptors, optionally in the presence of alkali metal cyanides and optionally in the presence of diluents.

The invention further provides novel 4-fluoro-3-halophenoxybenzyl alcohols and their reactive derivatives of formula III

(III) wherein

X is chlorine or bromine and

R ² is as defined above, which substances are used as starting materials in the manufacture of compounds of formula I of the invention.

The compounds of formula (III) above are prepared by the preparation of compounds of formula (IV)

in which

R ² has the abovementioned meaning, are reacted with chlorine or bromine, optionally in the presence of a catalyst and if appropriate in the presence of a diluent, at temperatures between -20 and 100 ° C and the resulting product is then optionally conventionally hydrolyzed or reduced.

The novel 4-fluoro-3-halophenoxybenzyl esters of the formula I are characterized by high insecticidal and acaricidal activity.

Surprisingly, the compounds of the formula I according to the invention exhibit considerably higher insecticidal and acaricidal activity than compounds of the analogous structure and the same mode of action known in the prior art and are, in addition, substantially less toxic to livestock animals, e.g. fish, than analogous compounds.

The invention therefore also relates to a pest control agent, characterized in that it contains at least one compound of the formula I as active substance.

In accordance with a preferred embodiment [variant a)] of the process for the preparation of the compounds of formula (I) above, the carboxylic acid chloride of formula (IIa)

R — CO — Cl, (Ha) in which ·

R is as defined above, reacted with the 4-fluoro-3-halophenoxybenzyl alcohols of formula III in the presence of acid acceptors and diluents.

· In accordance with another preferred embodiment [variant bj] .obecného process for preparing compounds of formula I in which R ¹ is cyano, a carboxylic acid chloride of the formula IIa is reacted with 4-fluoro-3-haIogenfenoxybenzaldehydy of formula V (V ) in which

X is chlorine or bromine, and at least an equimolar amount of an alkali metal cyanide (sodium cyanide or potassium ¹ ) in the presence of water and organic! a water-immiscible solvent, and optionally in the presence of a catalyst.

Other reactive carboxylic acid derivatives of formula (II) include lower alkyl esters of this carboxylic acid which can be reacted in a conventional manner with alcohols of formula (III) to form compounds of formula (I).

The alkali metal, alkaline earth metal and ammonium salts of the carboxylic acids of the formula II can also be reacted in a customary manner with the benzyl halides derived from the benzyl alcohols of the formula III to give the compounds of the formula; Formula I.

If, for example, 3-methyl-2-phenylbutanoic acid chloride and 4-fluoro-3- (4-bromophenoxy) benzyl alcohol [in the case of variant a)] or 4-fluoro-3- ( 4-chlorophenoxybenzaldehyde [in the case of variant b)], the course of both variants can be described by the following reaction schemes:

AND)

All process variants for the preparation of the compounds of formula I are preferably carried out using diluents. Suitable diluents are virtually all inert organic solvents, which include, in particular, aliphatic and aromatic or halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, petrol, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether, dibutyl ether, dimethyl ether of glycol and dimethyl ether of diglycol, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methylisopropyl ketone and methyl isobutyl ketone, esters such as methyl ester and ethyl esters such as methyl ester and ethyl esters propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, as well as dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric triamide.

Process variant a) is preferably carried out in the presence of acid acceptors. All conventional acid binding agents can be used as acid acceptors. Alkali metal carbonates and alkoxides, such as sodium carbonate, potassium carbonate, methoxide and optionally sodium and potassium ethoxide, as well as aliphatic, aromatic or heterocyclic amines, such as triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, diazabicyclooctane, diazabecyclo-cycloicone, diazabicloabicone

Process variant b) is carried out in the presence of water and one of the above organic solvents, unless it is miscible with water. The hydrocarbons mentioned above are particularly suitable in this case.

Compounds suitable for the transfer of anions from water to an organic solvent are preferably used as catalysts in the process of variant b]. Examples of such compounds include benzyltriethylammonium hydrogen sulfate, tetrabutylaimonium bromide and methyltrioctylammonium chloride.

In all variants of the process according to the invention, the reaction temperature can be varied within wide limits. Generally working at temperature between 0 ^C and 100 C, preferably at 10 to 50 ° C.

The process of the invention is generally carried out under normal pressure.

In the reaction according to the invention described above, the starting materials are usually employed in equimolar amounts. The excess of some of the reaction components does not bring any significant advantages. This is done by mixing the starting materials in a suitable diluent and mixing, optionally after addition of acid acceptors and / or catalyst, until the reaction is complete.

Working up of the reaction mixture can be carried out in a conventional manner, for example by diluting the reaction mixture with water and / or a water-immiscible organic solvent, for example toluene, for example, separating the organic phase, washing with water, filtering and drying the filtrate under reduced pressure. pressure and at moderately elevated temperatures carefully distills off the solvent.

The carboxylic acids used as starting materials are defined by the above formula (II) and the corresponding acid chlorides are defined by the formula (IIa).

In these formulas, R preferably has the same meanings as have already been mentioned as being preferred for this symbol in connection with the compounds of formula I.

Examples of starting materials of the formulas II and IIa are:

2,2,3,3-tetramethylcyclopropanecarboxylic acid and the corresponding acid chloride, 3- (2-methyl-1-propenyl) -, 3- (2,2-dichlorvinyl) -, 3- (2,2-difluorovinyl) -,

3- (2,2-dibto-vinyl) -, 3- (2-thiophenol) -, 3- (2- (4-chlorophenyl) vinyl) -, 3- [2-chloro-2- (4-chlorophenyl) vinyl ] -, 3- (2-chloro-2-phenylvinyl) -a

3- (3,3,3-fluoro-2-chloro-1-propenyl) -2,2-diinethylcyclopropanecarboxylic acid and the corresponding acid chlorides, phenyl-, 4-chlorophenyl-, 4-methylphenyl-, 4- tert-butylphenyl-, 4-trifluoromethylphenyl-, 4-methoxyphenyl-, .alpha.-trifluoromethoxyphenyl- and 3,4-methylene-4-dimethoxyphenyl-4- (4-methoxyphenyl) -acetic acid and the corresponding acid chlorides.

The carboxylic acids II and the corresponding acid chlorides IIa are known (see U.S. Patent Nos. 3,996,244, 4,157,447, 3,962,458, 3,835,176 and British Patent Nos. 1413,491 and 2,000,764). .

As starting substances used f1uor 4-3-ha1o gtnfenoxybenzyla1koho1y ^and or reactive derivatives thereof, are defined by the above general formula III ·. In this formula they are preferably

X is chlorine or bromine;

R ² radical -CHO or -CH-R ^3,

R4 where

R4 is hydrogen or cyano; and

R ³ represents a hydroxyl group.

Examples of compounds of the formula III are mentioned

4-fluoro-3- (4-chlorophenoxy) benzyl alcohol, 4-fluoro-3- (4-bromophenoxy) benzyl alcohol, 4-fluoro-3- (4-chlorophenoxy) benzaldehyde and 4-fluoro-3- ( 4-bromophenoxy] benzaldehyde.

The novel 4-fluoro-1-halo-phenoxybenzyl alcohols of formula III or their reactive derivatives are prepared as described above by reacting compounds of the above formula IV, such as 4-fluoro-1-phenoxybenzenesulfonyl, with chlorine, optionally with bromine or chlorine, optionally in the presence of a diluent such as acetic acid at a temperature between -20 and 100 ° C, optionally in the presence of a catalyst such as iodine, sulfur, sulfur trichloride, iron or ferric chloride, preferably at 10 to 60 ° C, followed by conversion to other compounds corresponding to the general formula III, if appropriate in the usual manner.

Treatment of the reaction mixture can be carried out by conventional methods, for example by diluting the reaction mixture with water and recovering the precipitated product by decantation or suction.

The crude products thus obtained can be purified by conventional methods.

The starting materials of the general formula IV are already known (see DOS No. 2 709 264).

The active compounds of the formula I have a good tolerance to plants and a favorable warm-blooded toxicity and are suitable for controlling pests, in particular insects and spider mites in agriculture, forestry, for the protection of stocks and materials, as well as for hygiene. They are effective against normally susceptible and resistant species as well as against all or only individual stages of development of pests. The above mentioned pests include:

from the order of the Isopods, for example Oniscus aselllus, Armadillidium vulgare, Porcellio scaber;

from the class of the millipedes (Diplopodaj, for example the blind millipede (Blaniulus guttulatus));

from the centipede class (Chilopodaj, for example Geophilus carpophagus], Scutiger.a spec.];

from the centipede class (Symphyla), for example

Scutigerélla immaculata;

from the order of the Thysanura, for example Lepisma saccharina;

from the order of the collembolans (Collembolaj, for example Onychiurus armatus);

from the order Orthoptera, for example, Blatta orientalis, Perlplaneta americana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotalpa spec., Locusta migratoria migratorioides],

Melanoplus differentialis, Schistocerca gregaria];

from the order of the Dermaptcra, for example, the earwig (Forficula auricularia);

from the order of the lsoptera, for example Reticulitermes spec.

from the order of the Anopluraj, for example Phylloxera vastatrix, Pemphigus spec., Pediculus humanus corporis, Haematoplnus spec., Linognathus spec .;

from the order of the Mallophaga, for example Trichodectes spec., Damalinea spec .;

from the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tabaci;

from the order of the Heteroptera, for example, Eurygaster spec., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spec .;

from the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Breviooryne brassicrae, Cryptomalis mosquito fabae), apple aphid (Doralis pomi), bloody aphid (Eriosoma lanigerum), aphid (Hyalopterus arundinis), Macrosiphum avenae, Myzus spec., aphid (Phorodon humulí), bird aphid (Rhopalosiphum speci), Emperor pidik. , Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia .oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Ps. m. (Pseudococcus spec.);

from the order of the butterflies (Lepidoptera), for example

Pectinophora gossypiella, Dark-spot Carpet (Bupalus piniarius), Cheimatobia brumata, Apple Keyhole (Lithocelletis brancardella), Apple Moth (Hyponomeuta padella), Common Forget-me-not (Plutella maculipennis); , Phyllocnistis citrella, Euproctis chrysorrhoea, Agrotis spec., Euxoa spec.

Feltia spec.,

Earias insulana, Heliothis spec.], Laphygma exigua, Cabbage moth, Panolis flammea,

Prodenia litura, Spodoptera spec., Trichoplusia ni, Carpocapsa pomonella, whitet (Pieris spec.), Chilo spec. ,

Capua reticulana,

Choristoneura fumiferana,

Clysia ambiguella, Homona magnanima Oak Tortrix (Tortrix viridana);

from the order of the beetles (Coleoptera), for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alnia, Mandelinae , leaf beetle (Phaedon cochleariae),

Diabrotica spec. (Psylliodes chrysocepha · la),

Epilachna varivestis, Atomaria spec., Oryzaephilus surinamensis, Anthonomus spec., Sitophilus spec., Otiorrhynchus sul · catus,

Cosmopolites sordidus, Ceuthorrhynchus assimilis,

Hypera postica, leather skin (Dermestes spec.),

Trogoderma spec., Anthrenus spec., Attagenus spec., Lyctus spec., Meligethes aeneus, Ptinus, Niptus hololeucus, Gibbium psylloides (Tribolium spec.), European darkling (Tenebrio molitor), Click beetle (Agriotes spec.),

Conoderus spec., Common Cockchafer (Melolontha melolontha), Common Cockchafer (Amphimallon solstitialis), Costelytra zealandica;

from the order of the Hymenoptera, for example Diprion spec., Hoplocampa spec., Lasius spec., Monomorium pharaonis, Hornet (Vespa spec.);

from the order of the diptera (Diptera), for example, the mosquito (Aedes spec.), anofeles (Anopheles spec.), mosquito (Culex spec.), Oetomella (Drosophila melanogaster), fly (Musea spec.), sunflower (Fannia spec. ), Calliphora erythrocephala, Lucilia spec.,

Chrysomyia spec., Cuterebra spec., Hamster (Gastrophilus spec.), Hyppobosca spec., Thistle (Stomoxys spec.), Hamster (Oestrus spec.), Hamster (Hypoderma spec.), Horsefly (Tabanus spec.), Tannia spec. , Garden Flycatcher (Bibio hortulanus), Barberry (Oscinella frit),

Phorbia spec., Common Beetle (Pegomyia hyoscyami), Common Propeller (Ceratitis capitata),

Dacus oleae, Tipula paludosa;

from the order of the Siphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spec.

from the order of Arachmda, for example

Scorpio maurus; Latrodectus mactans;

from the order of the Acarina, for example Acarus broad, Argas spec., Ornithodoros spec., Dermanyssus gallinae, Eriophyes ribis Phyllocoptruta oleivora, Boophilus spec. Rhipicephalus spec., Amblyomma spec., Hyalommia spec., Ixodes spec., Psoroptes spec., Chorioptes spec., Sarcoptes spec., Tarsonemus spec., Spider mite (Panonychus). spec.], spider mite (Tetranychus spec.).

The active compounds can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, natural and synthetic substances impregnated with the active compounds, small particles coated with polymeric substances and coating materials for seeds, flammable additives such as smoke cartridges, smoke jars, smoke spirals and the like, as well as compositions in the form of concentrates of the active substance for cold or hot mist dispersion.

These compositions are prepared in a known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, with liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a filler, for example, organic solvents can also be used as co-solvents. Basically suitable liquid solvents are: aromatics such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol as well as 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. By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montrnorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic flours and granules of organic material such as sawdust, shells, coconuts, corn sticks and tobacco stems. Suitable emulsifiers and / or foaming agents are non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene ethers of fatty alcohols, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as inorganic pigments, for example iron oxide, titanium dioxide and phiocyanide blue, and organic dyes such as alizarin dyes, azo dyes and metallic phthalocyanine dyes, as well as trace elements such as iron, manganese salts, boron, media, cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active ingredient.

The active compounds according to the invention can be present in mixtures with other active substances, such as insecticides, bait additives, sterility, acaricides, nematicides, fungicides, growth regulators or herbicides, in commercial preparations and in the use forms prepared from these preparations. Insecticides include, for example, phosphoric esters, carbamates, carboxylic esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.

The active compounds according to the invention can be present in mixtures with synergists in commercial preparations as well as in the use forms prepared from these preparations. Synergists are compounds that enhance the efficacy of an active ingredient without necessarily having the added synergist itself be active.

The content of active ingredient in dosage forms prepared from commercial preparations can vary within wide limits. The concentration of active ingredient in the dosage forms may range from 0.0000001 to 100% by weight, preferably from 0.0001 to 1% by weight.

The application is carried out in a conventional manner adapted to the application form used.

When used against hygiene pests and against storage pests, the active compounds according to the invention are distinguished by excellent residual properties. effect on wood and clay and good stability to alkalis on lime substrates.

The active compounds according to the invention are also suitable for combating ecto and endoparasites in the veterinary field.

In the veterinary field, the active compounds according to the invention are applied in a manner known per se, such as orally in the form of, for example, tablets, capsules, drinks or granulates, dermally in the form of, for example, dipping baths, sprays, pour-on and spot-on and powders, as well as parenterally in the form of, for example, injections.

The invention is illustrated by the following non-limiting examples.

Example 1

(1J

To a mixture of 3.9 g of sodium cyanide, 5.8 ml of water, 300 ml of cyclohexane and 0.9 g of tetrabutylammonium bromide are added dropwise a mixture of 14.75 g (0.05 mol) of 3- (4) at 20-25 ° C. -bromophenoxy) -4-fluorobenzaldehyde and 11.37 g (0.05 mol) of (±) -trans-2,2-dimethyl-3- (2,2-dichlorvinyl) cyclopropanecarboxylic acid chloride. The reaction mixture was stirred at 20-25 ° C for 4 hours, then toluene (400 mL) was added and the resulting mixture was shaken with water (2 x 300 mL). The organic phase is separated, dried over magnesium sulphate and solvent ¹ distilled off under water pump vacuum. The last residual solvent was removed by brief distillation at 1 mbar at a bath temperature of 60 ° C. 21.7 g (84.6% of theory) of (±) -d-cyano-3- (4-bromophenoxy) -4-fluorobenzyl ester (±) -trans-2,2-dimethyl-3- (2) are obtained. (2-dichlorvinyl) cyclopropanecarboxylic acid in the form of a viscous oil.

1 H-NMR spectrum (CDCl 3, δ ppm): dimethyl-H: 8.6-8.83 (multiplet, 6H), cycloproipane-H: 8.26-8.43) (multiplet, 1H) and 7.6-7.82 (multiplet, 1H), vinyl-H: 4.38 (doublet, 1H), benzyl-H: 3.64 (singlet, 1H), arom.-H: 2.4-3 2 (multiplet, 7H).

The following compounds can be prepared in an analogous manner to Example 1:

CN

Cl

n. I (2)

The product resulted (tetramethylsilane, 1 / 2H).

yield 87.3% of theory. 1 H-NMR spectrum (CDCl 3 / ppm): benzyl-H: 3.69 (singlet, 1 / 2H), and 3.73 (singlet,

(3 1

The product resulted in a yield of 85.2% of theory. Benzyl-H: 3.62 (singlet, 1H).

CN

(4)

The product resulted in a yield of 79.8% of theory. Benzyl-H: 3.69 (singlet, 1 / 2H) and 3.73 (singlet, 1 / 2H).

Yield 77.6% of theory. Benzyl-H: 3.69 (singlet, 1H), methyl-H: 8.69 to 8.85 (multiplet, 12H).

(6)

The product resulted in a yield of 67.5% of theory. Benzyl-H 3.69 (singlet, 1 / 2H) and 3.73 (singlet, 1 / 2H).

(7)

Yield 82.6% of theory. Benzyl-H; (singlet, 1 / 2H) and 3.66 (singlet, 1 / 2H); vinyl-H: 4.38 (doublet, 1 / 2H) and 4.41 (doublet, 1 / 2N).

(8)

Yield: 83%. Benzyl-H: 3.62 (singlet, 1 / 2H) and 3.64 (singlet, 1 / 2H); vinyl-H: 4.17 (doublet, 1H).

(9J

Yield: 78%. methyl H: 8.68-8.85 (multiplet, 12 N) Benzyl H: 3.67 (singlet, 1 N).

2'70 34

Example 2

(10)

5.5 g (-0.022 mol) -3- [4- (2-chlorophenyl) -4-fluorobenzyl alcohol and - 4.96 g (0.022 mol) of (±) -trans-3- (2,2-dichlorvinyl) chloride -2,2-dimethylcyclopropane acid are dissolved in 100 ml of toluene and to this bezvodého- ¹ solution. temperature used during · - - 20 - to - - 25 ° C with stirring is added dropwise 2.5 g of pyridine, dissolved in 50 ml · · anhydrous The reaction mixture is stirred for a further 3 hours at -25 DEG C., then poured into 150 ml of water containing 10 ml of concentrated hydrochloric acid, the organic phase is separated off and washed. 100 ml of water The toluene layer is dried over sodium sulphate and the solvent is distilled off in a water-jet vacuum - After the last remaining solvent is removed by brief distillation at a pressure of 133 Pa at a bath temperature of - 60 ° C. with 7.9 g (81% of theory of (±) -trans-3- (2,2-dichloro-vinyl) -2,2-dimethyl-cyclopropanecarboxylic acid 3- (4-chloro-phenoxy) -4-fluoro-benzyl ester) acid as a - yellow - - oil. Said product phase structure demonstrates - Hl-NMR - spectrum.

@ 1 H NMR Spectrum (CDCl3) .delta.

benzyl-H: - = 4.97 (singlet, 2H).

The following compounds were obtained in an analogous manner to Example 2:

The product resulted in a yield of 72.8% - theory. H-NMR (CDCl3): benzyl-H: 4.98 (singlet, 2H).

The product resulted in a yield of 85.6% of theory. Benzyl-H: 4.97 (singlet, 2H).

The following are examples of starting materials.

a) Preparation of 4-fluoro-3- (4-bromophenoxy) benzaldehyde

136.4 g (0.6 mol) of 95% 3-phenoxy-4-fluorobenzaldehyde are mixed with 130 ml of glacial acetic acid and a mixture of 96 g (0.6 mol) of bromine and 30 ml of ethyl acetate is added dropwise at 50 ° C. g of glacial acetic acid at a rate such that the temperature itself maintains the above value. The reaction mixture was then stirred for a further 30 minutes. The orange-red reaction solution was stirred with 1 liter of cold water, whereupon an oily material precipitated which soon solidified to a solid crystalline mass. The crystalline product is sucked off cold and freed from the last bromine residue by washing with water. After drying in air, 169 g of product are obtained,

The crude product is dissolved in 800 ml of hexane at 40 to 45 ° C, to which a small amount of ethanol is added, the solution is cooled to 0 ° C, the precipitated crystals are suction filtered and washed with a small amount of hexane. Yield: 124 g (70% of theory);

b) Preparation of 4-fluoro-3- (4-chlorophenoxy) benzaldehyde

To the present mixture 227.5 g (1 mol) 95%

3-Phenoxy-4-fluorobenzaldehyde and 250 g of glacial acetic acid are introduced at room temperature over 1 hour with 71 g (1 mole) of chlorine, maintaining the temperature at 35 ° C with slight external cooling. The reaction mixture was then stirred for a further 30 minutes. The yellowish reaction solution is stirred with about 1.5 liters of cold water to quickly form a white, oily matter containing crystals. This material is stirred several times with water and decanted off, then 260 g (300 ml) of toluene are taken up, the solution is shaken with dilute sodium carbonate solution, washed three times with 100 ml of sodium chloride solution each and evaporated on a rotary evaporator Bye. 275 g of a yellow oil are obtained as a residue.

For purification, 275 g of this oil are taken up at 40 ° C with 200 ml of cyclohexane / ethanol (9: 1 by volume), the solution is cooled to 0 ° C, the precipitated crystals are filtered off with suction and washed cold with about 300 ml of cyclohexane / ethanol. . The yield of white crystalline product melting at 66.5-68 ° C was 88 g (35% of theory).

A solution of 7.5 g (0.03 mol) of 3- (4-chlorophenoxy) -4-fluorobenzaldehyde in 20 ml of dioxane is added dropwise at 10 DEG C. to a mixture of 1.73 g of sodium borohydride, 25 ml of dioxane and 3 ml of water. is stirred at room temperature for 10 hours. The reaction mixture is poured into 150 ml of water and extracted twice with 100 ml of methylene chloride each time. The combined methylene chloride phases were dried over magnesium sulfate and the solvent was distilled off in vacuo. 6.2 g (82% of theory) of 3- (4-chlorophenoxy) -4-fluorobenzyl alcohol are obtained in the form of a yellowish oil which crystallizes after a short time and melts at 65-67 ° C.

The following examples illustrate the activity of the compounds of the invention.

Example A

Drosophila test solvent: 3 parts by weight acetone emulsifier: 1 part by weight alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent containing the indicated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Pipette ml of the active ingredient into 7 cm diameter round filter paper, place the wet filter paper on a glass jar containing 50 fruit flies (Drosophila melanogaster), and cover with a glass plate.

After a period of time below, the percent mortality was determined. Value 100%. means that all fruit flies have been killed, 0% means that no fruit fly has been killed.

The active substances, the active substance concentrations and the results obtained are given in the following table:

c) Preparation of 4-fluoro-3- (4-chlorophenoxy) benzylalcohol

TABLE A

Drosophila test (Dro & ophila.) Active substance concentration of the active substance in% mortality in% after 1 day

100 ALIGN!

Permethrin (known)

0.1

0.01

0.1

0.01

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

0.1

0.01

0.1

0.01

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 active substance concentration of active substance. . % mortality in% after 1 day

CN I CH

CH

CH2O-CO-CH

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

1Q0

Example B

Test for resistant spider mite (Tetranychus urticae) solvent: 3 parts by weight acetone emulsifier: 1 part by weight alkylaryl polyglycol ether

For the preparation of a suitable active agent. 1 part by weight of the respective active ingredient is mixed with said amount of solvent containing the abovementioned amount of emulsifier and the concentrate obtained is diluted with water to the desired concentration.

Ready. effective. the means up to. to. dew sprayed bean plants. (Phaseolus vulgaris). The treated plants are heavily infested with the spider mite (Tetranychus urticae). in all stages of development.

After. Percent mortality was determined over time. 100% means that all $ foxes have been killed, 0% means that none of the spider mites have been killed.

The active substances, active substance concentrations and results obtained are shown in the following table.

mortality in% after 2 days

TABLE Β active substance

Test for resistant spider mite (Tetranychus urticae) concentration of the active substance in%

t

CN

CH

0.1

0.01

, 1

0.01, 1

0.01

CH 2 O-CO-CH

I CH

0.01

0.01

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

2В

Example С

Limit test (soil-living insects) Experimental insects: Tenebrio molitor - Soil larvae Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.

The active ingredient is thoroughly mixed with the soil. The concentration of the active ingredient in the composition plays practically no role, only the amount of active ingredient per unit volume of soil, which is given in ppm (e.g. mg / liter), is decisive. The treated soil is filled with flower pots and left to stand at room temperature after filling. After 24 hours, the test insects are transferred to the treated soil and after a further 2 to 7 days the percentage of action of the active compound is determined by counting the dead and living specimens of the test insects. At killing of all specimens, the efficacy is 100%, 0% means that the number of live insect specimens is * the same as in the control.

The active compounds, the active compound concentrations and the results obtained are shown in the following table.

TABLE C

Limit test - Tenebrio molitor (larvae in soil) active substance mortality in% at active substance concentration 1.25 ppm

Permethrin (known)

100 ALIGN!

ÍQO

100 ALIGN!

100 ALIGN!

Example D

Limit concentration / soil insect test insects test Agrotis segetum (larvae in soil) solvent: 3 parts by weight acetone emulsifier: 1 part by weight alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent, the specified amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active ingredient is thoroughly mixed with the soil. The concentration of the active ingredient in the composition plays practically no role, only the amount of active ingredient per unit volume of soil, which is given in ppm (mg / liter), is decisive. The treated soil is filled with pots and left to stand at room temperature after filling.

After 24 hours, the test insects are transferred to the treated soil and after a further 2 to 7 days the percentage of action of the active compound is determined by counting the dead and living specimens of the test insects. At killing of all specimens, the efficacy is 100%, 0% means that the number of live insect specimens is the same as in the control experiment.

The active substances, active substance concentrations and results obtained are shown in the following table.

TABLE D

Limit test - Agrotis segetum (larvae in soil) mortality in% at concentration active substance active substance 1.25 ppm

Permethrin (known)

100 ALIGN!

Example E

LD 10-test test insects: cockroach (Blatta orientalis) number of test animals: 10 solvent: acetone parts by weight of active ingredient are dissolved in 1000 parts by volume of solvent and diluted with additional solvent at the desired lower concentration.

2.5 ml of the active substance solution is pipetted into a Petri-dish, at the bottom of which a circular filter paper with a diameter of about 9.5 centimeters is placed. Leave the petri dish exposed to stand until the solvent is completely evaporated. Depending on the concentration of the active substance solution, the amount of active substance, based on the rn ^{2 of the} filter paper, is of varying amounts. About 25 specimens of test insects are then transferred to the Petri dish and the dish is covered with a glass lid.

The condition of the test insects is checked at 3 days after the test, and the percent mortality is determined. 100% means that all specimens of test insects have been killed, 0% means that no specimens of test insects have been killed.

The active substances, active substance concentrations and results obtained are shown in the following table.

TABLE E

LDioo-test active substance concentration effective mortality of the substance in solution (%) in%

Permethrin (known)

0.02

100 c / - / ₃ CH3

0.2

100 ALIGN!

100 ALIGN!

Example F

TEST (Boophilus microplus) - resistant strain solvent: 35 parts by weight of ethylene glycol monomethyl ether parts by weight of nonylphenol polyglycol ether

To prepare a suitable active ingredient, 3 parts by weight of active ingredient are mixed with 7 parts by weight of the above solvent mixture and the emulsifiable concentrate obtained is diluted with water to the desired concentration.

10 adults of Boophilus microplus (resistant) ticks are immersed in the above preparation for 1 minute. The treated specimens were transferred to a plastic beaker and stored in an air-conditioned chamber, whereupon plague was detected. talita.

The active substances, active substance concentrations and results obtained are shown in the following table.

TABLE F

Tick test Boophilus microplus (resistant Biarra strain) Active substance Active substance concentration (ppm) Mortality in ° / o

3000

1000

300

100 ALIGN!

100> 50 <50

100> 50> 50

100> 50> 50 <50 <50

100 ALIGN!

100> 50

3000

1000

300

100 ALIGN!

100> 50> 50

1000

300

100 ALIGN!

100> 50

active substance concentration of the active substance (ppm) mortality in%

1000

300

100 ALIGN!

1000

300

100> 50 <50

100> 50> 50> 50

Example G

Test for resistant buccal larvae (Lucillia scum) solvent: 35 parts by weight of ethylene glycolimonomethyl ether parts by weight of nonylphenol polyglycol ether

To prepare a suitable active ingredient, 3 parts by weight of active ingredient are mixed with 7 parts by weight of the above solvent mixture, and the concentrate thus obtained is diluted with water to the desired concentration.

About 20 buzzard larvae (Lucilia lupine - a resistant strain) are placed in a test tube containing about 1 cm ^{3 of} horse muscle and 0.5 ml of active ingredient. Mortality was observed after 24 hours.

The active substances, active substance concentrations and results obtained are shown in the following table.

TABLE G

Lucilia test (resistance larvae) active substance concentration of active substance (ppm) mortality in%

1000

300

100 active ingredient concentration · active ingredient (ppm) mortality

Claims (2)

OBJECT OF THE INVENTION Insecticidal and acaricidal composition, characterized in that it contains, as an active ingredient, at least one 4-fluoro-3-halophenoxybenzyl ester of the general formula I _R -CO-O-CH-4-ro-Ox (1) in which: R is 2,2,3,3-tetramethylcyclopropyl or a radical of formula wherein R ⁵ represents a hydrogen, fluorine, chlorine or bromine atom or an optionally halogenated C 1 -C 4 alkyl group; and R ⁶ represents a fluorine, chlorine or bromine atom, an optionally substituted C 1 -C 4 alkyl group or a phenyl group optionally substituted by halogen, and / or an optionally halogenated radical selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 1 -C 4 alkylthio and C 1 -C 2 alkylenedioxy, or R ⁶ and R ⁵ together form an alkanediyl group having 2 to 5 carbon atoms, or R is a radical of formula -CH-R ^7, R ⁸ where R ⁷ represents a phenyl group optionally substituted by halogen and / or an optionally halogenated residue selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and C 1 -C 4 alkylenedioxy; 1 or 2 carbon atoms; and R ⁸ represents an isopropyl or cyclopropyl group, R ¹ represents hydrogen or cyano and X is chlorine or bromine. 2. A process for the preparation of the active compounds of the formula I as claimed in claim 1, characterized in that the carboxylic acids or their salts are of the formula II. R — СО — ОМ, (II) in which. R is as defined above and M represents a hydrogen, sodium or potassium atom, or reactive derivatives thereof with 4-fluoro-3-halophenoxybenzyl alcohols or reactive derivatives thereof of the general formula III in which: X is as defined above and R ² represents a radical -CHO, -CH 2 OH, -CH 2 Cl, -СНгВг, -CHC12, -СНВГ2, -СН (ОСНз] 2 R ⁴ has the meanings given for R ¹ with the exception of hydrogen and R ³ represents a hydroxyl group or halogen atom-, optionally in the presence- of the acid acceptor, optionally in the presence of alkali metal cyanides and if appropriate in the presence of diluents at temperatures from 0 to 150 ^Q C