SI9111245A - DERIVATIVES OF CYCLOPROPYLOCETIC ACIDS - Google Patents

Abstract

New derivatives of 2-(2,2-difluorocyclopropyl)-acetic acid with formula I Sl 9111245 A where A represents oxygen or -NRi-, B C2-C6-alkylene, D oxygen, sulfur or -O-CH2-, E phenyl, with one to three substituents from the group of halogen, C1-C4-alkyl, C1-C3-haloalkyl or C1-C4-alkoxy substituted phenyl; a five-membered aromatic heterocycle with 1 to 3 hetero atoms from the group of nitrogen, oxygen or sulfur; a five-membered aromatic heterocycle substituted with 1 or 2 substituents from the group of halogen, C1-C4-alkyl or C1-C3-haloalkyl with 1 to 3 hetero atoms from the group of nitrogen, oxygen or sulfur; a six-membered aromatic heterocycle with 1 to 3 nitrogen atoms; or a six-membered aromatic heterocycle with 1 to 3 nitrogen atoms substituted with 1 or 2 substituents from the group of halogen, C1-C4-alkyl or C1-C3-haloalkyl; L is halogen or methyl, n is 0, 1 or 2, and R1 is hydrogen, C1-C4-alkyl, phenylthio or tolylthio, can be used as pest control agents. Insects and arachnids can be controlled preferably.

Description

Cyclopropylacetic acid derivatives

The present invention relates to novel derivatives of 2-(2,2-difluorocyclopropyl)-acetic acid, to processes and intermediates for their preparation, to pest control agents containing these compounds, as well as to their use in pest control.

The 2-(2,2-difluorocyclopropyl)-acetic acid derivatives according to the invention correspond to the formula I ₍ p^ ^iLi n

CH ₂ -CH— CH ₂ — CABO—(/ V \/ n \=Ae or _{2 0} (D where they mean

A oxygen or -NRj-,

BC ₂ -C ₆ -alkylene,

D oxygen, sulfur or -O-CH ₂ -,

E is phenyl, phenyl substituted with one to three substituents from the group of halogen, C ₁ -C ₄ -alkyl, C j -C ^ haloalkyl or C ₁ -C ₄ -alkoxy; a five-membered aromatic heterocycle with 1 to 3 hetero atoms from the group of nitrogen, oxygen or sulfur; a five-membered aromatic heterocycle substituted with 1 or 2 substituents from the group of halogen, C j -C ₄ -alkyl or C ^ C ^ haloalkyl with 1 to 3 hetero atoms from the group of nitrogen, oxygen or sulfur; a six-membered aromatic heterocycle with 1 to 3 nitrogen atoms; or a six-membered aromatic heterocycle substituted with 1 or 2 substituents from the group of halogen, C j -C ₄ -alkyl or CC ₃ - haloalkyl with 1 to 3 nitrogen atoms;

L is halogen or methyl, n is the number 0, 1 or 2, and

R is hydrogen, C1- _C4 alkyl, phenylthio or tolylthio.

Derivatives of 2,2-difluorocyclopropylethane are known from the literature as pest control agents from EP-A-318425. However, these compounds cannot always be completely satisfactory as pest control agents. Therefore, there is still a need for effective pest control agents with improved properties.

In the definition of formula I within the meaning of the invention, the following general terms should be understood:

Halogen atoms which are suitable as substituents include fluorine and chlorine as well as bromine and iodine, with fluorine and chlorine being preferred. Halogen is intended as an independent substituent or as part of a haloalkyl substituent.

Alkyl and alkoxy radicals which are suitable as substituents may be straight or branched. Examples of such alkyls include methyl, ethyl, propyl, isopropyl, butyl, i-butyl, sec-butyl or tert-butyl. Suitable alkoxy radicals include, inter alia: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers.

If the alkyl or fertile groups that are considered as substituents or the aromatic heterocycles are substituted by halogen, they may only be partially halogenated or perhalogenated. The definitions given above for halogen, alkyl and alkoxy apply. Examples of alkyl elements of these groups are methyl substituted one to three times with fluorine, chlorine and/or bromine, such as CHF ₂ or CF ₃ ; ethyl substituted one to five times with fluorine, chlorine and/or bromine, such as CH ₂ CF ₃ , CF ₂ CF ₃ , CF ₂ CC1 ₃ , CF 2 CHC1 2 , CF ₂ CHF ₂ , CF ₂ CFC1 ₂ , CF ₂ CHBr _{2 ,} CF ₂ CHC1F, CF ₂ CHBrF or CC1FCHC1F, propyl or isopropyl _substituted one to seven times with fluorine, chlorine and/or bromine, such as CH ₂ CHBrCH ₂ Br, CF ₂ CHFCF ₃ , CH ₂ CF ₂ CF ₃ or CH(CF ₃ ) ₂ ; butyl substituted one to nine times with fluorine, chlorine and/or bromine or one of its isomers, such as CF(CF ₃ )CHFCF ₃ or CH ₂ (CF ₂ ) ₂ CF ₃ . Aromatic heterocycles carry the substituents that are considered, preferably on one of the carbon atoms which together with the hetero atoms form the ring skeleton. These rings are generally also bonded via a ring carbon atom to the bridge member D. Five-membered aromatic heterocycles of the definition of the residue E within the meaning of the invention preferably represent the following basic structures: pyrrole, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, oxazole, isoxazole, thiazole, isothiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole or 1,3,4-oxadiazole. As six-membered aromatic heterocycles, pyridine, pyrimidine, pyrazine, pyridazine, 1,2,4-triazine or 1,3,5-triazine are suitable for E within the meaning of the invention. If these aromatic radicals defined under E, as well as phenyl, are further substituted, they can be substituted one to three times with the same or different substituents from those listed. Preferably, one to two substituents are present in the substituted aromatic substituents. Preferably, the aromatic radicals of the definition -DE are also given the following individual meanings:

phenoxy, phenylthio,

3.5- dichloropyrid-2-yloxy,

2- pyridyloxy, benzyloxy,

3-chlorophenoxy,

3-methyl-1,2,4-thiadiazol-5-yloxy,

4-fluorophenoxy,

3-fluorophenoxy,

2-fluorophenoxy,

3- chloro-5-trifluoromethyl-pyridi-2-yloxy,

3-chloro-5-(2,2-dichloro-1,1,2-trifluoroethyl)-pyrid-2-yloxy,

3.5- difluorophenoxy,

2-ethoxymethyl-1,3,4-thiadiazol-5-ylmethoxy,

3- isopropyl-1,2,4-thiadiazol-5-yloxy,

4-chlorophenoxy,

2-chloro-4-trifluoromethyl-phenoxy,

4.5-dichloro-imidazol-1-ylmethoxy,

5-bromo-thien-2-ylmethoxy,

4-trifluoromethyl-phenoxy,

1-imidazolylmethoxy,

1,2,4-triazol-1-ylmethoxy,

4-ethylphenoxy,

4-methoxyphenoxy,

4-chlorophenylthio and

3-chloropyridazin-4-yloxy.

The residues -D-E may occupy the ortho, meta or para position of the phenyl residue. The para position is preferred.

Among the compounds of formula I, we should highlight such subgroups in which either

a) A stands for oxygen, or

b) B for ethylene bridge or

c) A for the bridge -NH- or

d) n for the number zero or

e) D for oxygen or

f) E is phenyl, pyridyl, pyridazinyl or thiadiazolyl or phenyl, pyridyl, pyridazinyl or thiadiazolyl substituted in each case with one or two substituents from the group of fluorine, chlorine, C1-C4 haloalkyl or methyl.

Among the compounds of subgroup f), those in which E stands for phenyl, chlorophenyl, fluorophenyl, methylthiadiazolyl, pyridyl, dichloropyridyl, chlorotrifluoromethylpyridyl, chlorotrifluorodichloroethylpyridyl or chloropyridazine are preferred.

Among these preferred compounds of formula I, those in which either A represents oxygen, B represents an ethylene bridge, D represents oxygen or sulfur and n represents zero are particularly distinguished due to their good efficacy; or in which A represents an -NH- bridge, B represents an ethylene bridge, D represents oxygen or sulfur and n represents zero.

As preferred individual compounds of formula I within the meaning of the invention, the following may be mentioned:

2-(2,2-difluorocyclopropyl)-acetic acid 2-(4-phenoxy-phenoxy)-ethyl ester,

2-(2,2-difluorocyclopropyl)-acetic acid 2-(4-phenylthiophenoxy)-ethyl ester,

2-(2,2-difluorocyclopropyl)-acetic acid 2-(4-phenylthiophenoxy)-propyl ester,

2-(2,2-difluorocyclopropyl)-acetic acid 2-(4-phenoxyphenoxy)-propyl ester,

2-(2,2-difluorocyclopropyl)-acetic acid 2-[4-(3-chlorophenoxy)-phenoxy]ethyl ester, 2-(2,2-difluorocyclopropyl)-acetic acid 2-[4-(4-fluorophenoxy)-phenoxy]ethyl ester, 2-(2,2-difluorocyclopropyl)-acetic acid 2-[4-(4-fluorophenoxy)-phenoxy]ethyl ester, 2-(2,2-difluorocyclopropyl)-acetic acid 2-[4-(2-fluorophenoxy)-phenoxy]ethyl ester, 2-(2,2-difluorocyclopropyl)-acetic acid 2-[4-(3-methyl-1,2-thiadiazol-5-yloxy))-phenoxy]ethyl ester and

2-(2,2-difluorocyclopropyl)-acetic acid 2-(4-(benzyloxy-phenoxy)ethyl ester.

The 2-(2,2-difluorocyclopropyl)-acetic acid derivatives of formula I according to the invention can be prepared by either

a) 2-(2,2-difluorocyclopropyl)-acetic acid halide of formula II

CH ₂ — CH- CH _? - C - Hal (τη \ / || ^{k 7}

CF ₂ where Hal stands for chlorine or bromine, optionally in an inert solvent and in the presence of an acid-binding agent, is reacted with an alcohol or amine of formula III

(ΠΙ) where A, B, L, D, E and n have the meanings given in formula I, or

b) a 3-butenoic acid derivative of formula IV

O (IV) where A, B, L, D, E and n have the meanings given in formula I, are reacted in an inert solvent with difluorocarbene, or

c) free 2-(2,2-difluorocyclopropyl)-acetic acid of formula V

CH ₂ — CH-CH ₂ -C-OH \ / II tv) cf ₂ is reacted with an alcohol or amine of formula III, optionally in the presence of an inert solvent and a catalyst or a dehydrating agent.

The reaction of process a) (II + III ->) preferably takes place in an inert solvent free of hydroxyl groups in the presence of an organic base, such as pyridine, 4-dimethylaminopyridine, lutidine, collidine, trialkylamine, Ν,Ν-dialkylaniline or a bicyclic, non-nucleophilic base, such as 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (1,5,5) (DBU). The reaction is generally carried out at temperatures from -30°C to +70°C, preferably from -10°C to +50°C. It is expedient to carry out this in the presence of a solvent or solvent mixture inert to the reaction. Suitable for this are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ether compounds, such as dialkyl ether (diethyl ether, diisopropyl ether, tert.-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; esters, such as ethyl acetate (ethyl ester of acetic acid), propyl acetate or butyl acetate; ketones, such as acetone, diethyl ketone, methyl ethyl ketone; compounds, such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and mixtures of such solvents. The reaction can also be carried out in an excess of one of the above-mentioned bases, and in the case where the compound of formula III represents an amine (A = NR1), another equivalent or a larger excess of the compound of formula III can be used instead of the base. The reaction is carried out at ambient pressure, although it could also be carried out at elevated or reduced pressure.

For carrying out reaction variant b) (IV + difluorocarbene -> I), ethers, such as diglyme, triglyme or tetraglyme, are preferably suitable solvents. Difluorocarbene is prepared according to methods known from the professional literature (Burton and Hahnfeld, Fluorine Chem. Rev. 8 (1977), 199 et seq.). Suitable donors of difluorocarbene are, for example, alkali chlorodifluoroacetates, such as sodium chlorodifluoroacetate; halogenodifluorocarbons, such as chloro6 difluoromethane; organotin compounds, such as trimethyl(trifluoromethyl)-tin; organomercury compounds, such as phenyl(trifluoromethyl)mercury; organophosphorus compounds, such as tris(trifluoromethyl)-difluorophosphorane and triphenyl(bromodifluoromethyl)-phosphonium bromide.

In process variant c) (V + III -*I), the reaction is advantageously carried out in the presence of reagents which are customary for esterifications and which eliminate water, such as, for example, in the presence of carbodiimide [dicyclohexylcarbodiimide (DCC)] or a 1-alkyl-2-halopyridinium salt, such as 1-methyl-2-chloropyridinium iodide. The reaction is expediently carried out in the presence of a reaction-inert solvent or solvent mixture at temperatures from -30°C to +70°C, preferably -10°C to +50°C. The reaction is preferably carried out in the presence of a base, such as, for example, in the presence of an organic amine, such as a trialkylamine (trimethylamine, triethylamine, tripropylamine or diisopropylethylamine), pyridine (pyridine itself, 4-dimethylaminopyridine or

4-pyrrolidinopyridine), morpholine, (N-methylmorpholine) or Ν,Ν-dialkylaniline (N,N-dimethylaniline or N-methyl-N-ethylaniline). Suitable solvents are therefore, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ether compounds, such as dialkyl ether (diethyl ether, diisopropyl ether), tert.-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; esters, such as ethyl acetate (ethyl acetate), propyl acetate or butyl acetate; and mixtures of such solvents with one another.

If the compound of formula III represents an alcohol (A = 0), the variant of process c) can also be carried out in the presence of an acid catalyst, such as, for example, H ₂ SO ₄ , HCl or sulfonic acids, such as methanesulfonic or p-toluenesulfonic acids. In this case, it is advantageous to work with an excess of the alcohol of formula III. In this process, the water that is released can be continuously removed from the reaction mixture. A common method for this is to remove the reaction product water by distilling off the azeotrope of the solvent with water. Suitable solvents for this are benzene, toluene, xylene, methylene chloride or chloroform.

In principle, various derivatives of formula I can also be obtained from transesterification or amidation of readily available lower alkyl esters of 2-(2,2-difluorocyclopropyl)-acetic acid.

For example, ester-type derivatives of formula I (A = O) can be obtained by base- or acid-catalyzed transesterification of lower alkyl esters of formula Va

CH ₂ —CH-CH ₂ -COC ₁ -C ₄ -Alkyl \ / cf ₂

II (Va) with alcohols of formula lilac

H—O—B—O

DE (nia) where B, D, E, L and n have the meanings given in formula I. Particularly suitable acid catalysts are HCl, H ₂ SO ₄ or sulfonic acid. In the base-catalyzed transesterification, sodium or potassium alcoholate of the alcohol of formula IIIa is preferably used as the base, which is obtainable from IIIa, e.g. by addition of sodium or potassium hydride. The transesterification reaction is preferably carried out at temperatures between -20°C and + 120°C, in particular between 0°C and +100°C. The alcohol component IIIa is advantageously used in excess. Suitable solvents are ethers, such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran, halogenated hydrocarbons or aliphatic or aromatic hydrocarbons.

Amide-type derivatives of formula I (A = NRj) are obtained from lower alkyl esters of formula Va by reacting them with amines of formula Hib

H—n—B—O

DE (Hib) where R _p B, D, e, L and n have the meanings given in formula I. The amidation reactions are carried out at temperatures between 0°C and +120°C. The reactants are advantageously reacted in an inert solvent or solvent mixture. Suitable solvents for this are, for example, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ether compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert.-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; alcohols such as methanol, ethanol, propanol, isopropanol; or water. The amine component Hib is advantageously used in excess.

Compounds of formulae II, III, IIIa, Hib, V and Va and their preparation are known from the literature. Compounds II and V are obtained by conventional hydrolysis and halogenation reactions from the basic benzyl ester of 2-(2,2-difluorocyclopropyl)-acetic acid. This can again be easily prepared by the addition of difluorocarbene to benzyl ester of 3-butenoic acid. The reaction conditions correspond to the conditions of reaction variant b) for the addition of difluorocarbene. The reaction conditions for the synthesis of the free acid from the benzyl ester and the subsequent optional conversion of this acid V into the acid halide of formula II correspond to the conventional conditions for acid- or base-catalyzed hydrolysis or for the halogenation of carboxylic acids. Compounds of formulae III, IIIa and IHb, which have not yet been described in the literature, can be obtained analogously to known processes by conventional synthesis methods. Compounds of formula IV are new. They were developed specifically for the synthesis of active ingredients of formula I. The compounds of formula IV therefore form a component of the present invention.

Compounds of formula IV can be obtained from known products by reacting 3-butenoic acid of formula VI

CH ₂ =CH-CH ₂ -COOH (VI) is reacted with an alcohol or amine of the formula III, optionally in the presence of an inert solvent and a catalyst or a dehydrating agent. The reaction conditions for this esterification or amidation correspond to those of process variant c) of the process according to the invention for the preparation of compounds of the formula I.

Unless otherwise stated, the compounds of formula I are mixtures of optical isomers. Alternatively, optically pure isomers can be obtained by starting from optically pure starting materials, such as R- or S-2-(2,2-difluorocyclopropyl)acetic acid or its halides, or by resolving optically pure isomers from racemates by known methods.

This can be done, for example, by reacting compounds of the general formula II or V with a chiral auxiliary reagent, such as an optically active amine or an optically active alcohol, and then separating the diastereomers thus obtained by means of physical methods (Tetrahedron 33, 2725 (1977)), such as crystallization, distillation or solid-liquid chromatography. The subsequent hydrolytic cleavage, which can be carried out either under acid or base catalysis, gives optical isomers of the free acids of the general formula V, which can be converted into compounds according to the invention according to process variant c).

Furthermore, in the synthesis of the resulting mixture of optical isomers of the general formula I, it is possible to separate the enantiomers by chromatography on chiral stationary phases, such as optically active amino acid derivatives bound to cyclodextrins, starch or polymers (Angev. Chem. 92, 14 (1980)).

We have now found that the compounds according to the invention of formula I, while being well tolerated by warm-blooded creatures, fish and plants, are valuable active ingredients in pest control. The use of the active ingredients according to the invention particularly affects insects and arachnids that occur in useful and ornamental plants in agriculture, especially in cotton, vegetable and fruit plantations, in the forest, in the protection of stocks and materials as well as in the hygiene sector, especially on domestic and useful animals. They are effective against all or individual development stages of normally sensitive as well as resistant species. Their effect can be manifested in the immediate destruction of the pests or only after some time, e.g. during molting or in a reduction in egg laying and/or hatching frequency. The above-mentioned pests include:

from the order Lepidoptera, for example

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;

from the order Coleoptera, for example

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp.,

Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.; from the order Orthoptera, for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp., and Schistocerca spp·;

from the order Isoptera, for example

Reticulitermes spp.; from the Psocoptera order, for example Liposcelis spp.; from the order Anoplura, for example Haematopinus spp., Linognathus spp. Pediculus spp., Pemphigus spp. and Phylloxera spp.; from the order Mallophaga, for example Damalinea spp. and Trichodectes spp.; from the order Thysanoptera for example

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantii; from the order Heteroptera for example

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;

from the order Homoptera, for example

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;

from the order Hymenoptera, for example

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp., and Vespa spp.;

from the order Diptera, for example

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Cu!ex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp. Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; from the order Siphonaptera e.g.

Ceratophyllus spp., Xenopsylla cheopis, from the order Acarina for example

Acarus siro, Aceria shelodoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Lxodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polvphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; and from the Thysanura order for example

Lepisma saccharina.

In particular, the compounds of formula I are particularly suitable for controlling pests in fruit and rice crops, such as spider mites, aphids and rice cicadas. Furthermore, the active ingredients of formula I can advantageously control parasites of warm-blooded creatures, such as mites and ticks.

The good pesticidal effect of the compounds of formula I according to the invention corresponds to at least a 50 to 60% degree of destruction (mortality) of the said pests.

The effect of the compounds according to the invention and the agents containing them can be significantly expanded and adapted to the given circumstances by the addition of other insecticides and/or acaricides. As additives, for example, representatives of the following classes of active ingredients are considered: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and preparations of Bacillus thuringiensis.

The compounds of formula I are used in their unmodified form, preferably together with auxiliaries which are customary in formulation technology, and therefore, for example, can be processed in a known manner into emulsifiable concentrates, into solutions which can be directly sprayed or diluted, into dilute emulsions, wettable powders, soluble powders, dusting agents, granulates, and also encapsulation in polymer materials. The application methods, such as spraying, misting, dusting, sprinkling or pouring, are selected in the same way as the agents according to the intended objectives and the given circumstances.

The formulation, i.e. agents, preparations or compositions containing the active ingredient of formula I or combinations of these active ingredients with other insecticides or acaricides and, if applicable, a solid or liquid additional substance, is prepared in a known manner, e.g. by thoroughly mixing and/or grinding the active ingredients with diluents, such as e.g. solvents, solid carriers and, if applicable, surface-active compounds (surfactants).

Suitable solvents include aromatic hydrocarbons, preferably fractions of _C8 to _C12 alkylbenzenes, such as mixtures of xylenes or alkylated naphthalenes, aliphatic or cycloaliphatic hydrocarbons, such as cyclohexane, paraffins or tetrahydronaphthalene, alcohols, such as ethanol, propanol or butanol and glycols, as well as their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones, such as cyclohexanone, isophorone or diacetanol alcohol, highly volatile solvents, such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, or water, vegetable oils, such as rapeseed, castor, coconut or soybean oil; optionally also silicone oils.

As solid carriers, e.g. for dusting agents and dispersible powders, we generally use natural rock flours, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, highly dispersed silica or highly dispersed absorbent polymers can also be added. Porous types such as pumice, brick chips, sepiolite or bentonite are suitable as granular, adsorptive granulate carriers, and calcite or sand as non-absorbent carrier materials. In addition, many granular materials of inorganic or organic nature can be used, such as dolomite or crushed plant residues in particular.

Suitable surface-active compounds, depending on the type of active ingredient of the formula I or the combination of these active ingredients with other insecticides or acaricides to be formulated, are nonionic, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants also include surfactant mixtures.

Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids ( _C10 - _C22 ), such as sodium or potassium salts of oleic or stearic acid, or mixtures of natural fatty acids, which can be obtained, for example, from coconut oil or tall oil. Furthermore, methyltaurine salts of fatty acids should also be mentioned as surfactants.

More commonly, we use so-called synthetic surfactants, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives, or alkylarylsulfonates.

Fatty sulfonates or sulfates are generally present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and generally have an alkyl radical with 8 to 22 carbon atoms, alkyl also including the alkyl part of acyl radicals, e.g. sodium or calcium salt of ligninsulfonic acid, dodecyl sulfuric acid ester or fatty alcohol sulfate mixtures prepared from natural fatty acids. These also include salts of sulfuric acid esters and sulfonic acids of fatty alcohol and ethylene oxide adducts. Sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical with e.g. 8 to 22 carbon atoms. Alkylaryl sulfonates are e.g. sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or the condensation product of naphthalenesulfonic acid and formaldehyde. Suitable phosphates, such as e.g. salts of the phosphoric acid ester of the adduct of p-nonylphenol and (4-14)-ethylene oxide, or phospholipids.

Nonionic surfactants that are particularly suitable are polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms in the alkyl residue of alkylphenols. Furthermore, suitable nonionic surfactants are water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

Cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical with 8 to 22 carbon atoms as N-substituent and which have lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyl-di-(2-chloroethyl)-ethylammonium bromide.

Surfactants used in formulation technology are described, for example, in the following publications:

Mc Cutcheon's Detergents and Emulsifiers Annual, Mc Publishing Corp., Glen Rock, N J, USA, 1988,

H. Stache, Tensid-Taschenbuch, 2.Aufl., C.Hanser Verlag Munchen, Wien 1981.

M. and J. Asch. Encyclopedia of Surfactants, Vol.I-III, Chemical Publishing Co., New York, 1980-1981.

Pesticide preparations generally contain 0.1 to 99%, in particular 0.1 to 95% of the active ingredient of the formula I or combinations of this active ingredient with other insecticides or acaricides, 1 to 99.9% of solid or liquid additional substances and 0 to 25%, in particular 0.1 to 25% of surfactant. While concentrated preparations are preferred as commercial products, the end user generally uses diluted preparations which have significantly lower concentrations of active ingredient. Typical use concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The amounts used per hectare are generally 1 to 1000 g of active ingredient per hectare, preferably 25 to 500 g/ha.

Preferred formulations are composed in particular as follows:

(% = mass percent)

Emulsifying concentrates:

Active ingredient surfactant liquid carrier

Powders:

Active ingredient solid carrier

Suspension concentrates:

Active ingredient water surfactant

Wettable powders:

Active ingredient surfactant carrier solid material

Granules:

Active ingredient solid carrier up to 90%, preferably 5 to 20% up to 30%, preferably 10 to 20% 5 to 94%, preferably 70 to 85%

0.1 to 10%, preferably 0.1 to 1% 99.9 to 90%, preferably 99.9 to 99% up to 75%, preferably 10 to 50% 94 to 24%, preferably 88 to 30% 1 to 40%, preferably 2 to 30%

0.5 to 90%, preferably 1 to 80% 0.5 to 20%, preferably 1 to 15% 5 to 95%, preferably 15 to 90%

0.5 to 30%, preferably 3 to 15% 99.5 to 70%, preferably 97 to 85%

The agents may also contain further additives such as stabilizers, e.g. where applicable epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), antifoaming agents, e.g. silicone oil, preservatives, viscosity regulators, binders, adhesives as well as fertilizers or other active ingredients to achieve special effects.

The following examples serve to illustrate the invention. They do not limit the invention.

Preparation examples

Example HI: 2-(2,2-difluorocyclopropyl)-acetic acid 2-(4-phenoxy-phenoxy)-ethyl ester

CH ₂ — CH- ch ₂ -co-o-ch ₂ -ch ₂ -o \ /

CF ₂

To a solution of 1.5 g of 2-(2,2-difluorocyclopropyl)-acetic acid in 20 ml of methylene chloride, 0.1 g of 4-pyrrolidino-pyridine and 2.53 g of 2-(4-phenoxy-phenoxy)-ethanol are added and cooled to 0°C. At a temperature between 0°C and +5°C, a total of 2.5 g of N,Ν'-dicyclohexylcarbodiimide are added in portions, the ice cooling is removed and the reaction mixture is allowed to warm to room temperature for 5 hours with stirring. The Ν,Ν'-dicyclohexylurea separated as a precipitate is separated and discarded. The supernatant solution is washed twice with 10 ml of water each time, dried over magnesium sulfate and evaporated. The residue is purified by column chromatography on silica gel (eluent: hexane/ethyl acetate, 85:15). Thus, 2-(4-phenoxy-phenoxy)-ethyl ester of 2-(2,2-difluorocyclopropyl)-acetic acid is obtained in pure form as a yellow-tinged oil with a refractive index n _D ²² :1.5309.

Example H2: 2-(4-phenoxy-phenoxy)-ethyl ester of 2-(2,2-difluorocyclopropyl)-acetic acid

CH ₂ — CH- CH ₂ -CO-O-CH ₂ -CH ₂ -O·

a) 3-Butenoic acid 2-(4-phenoxy-phenoxy)-ethyl ester

To a solution of 6.45 g of 3-butenoic acid in 100 ml of dichloromethane, 0.05 g of 4-pyrrolidino-pyridine and 17.25 g of 2-(4-phenoxy-phenoxy)ethanol are added with stirring at room temperature. At a temperature of 0°C, 17.0 g (82.5 mmol) of N,N-dicyclohexylcarbodiimide are then added in portions and the reaction mixture is stirred for 3 hours at room temperature. The reaction mixture is filtered. The precipitate that separates is discarded, the filtrate is washed with water and dried over sodium sulfate. After evaporation, the oily residue is purified by column chromatography on silica gel with hexane/acetic acid (9:1). This gives 20.0 g of 2-(4-phenoxy-phenoxy)-ethyl ester of 3-butenoic acid with the formula

CH ₂ =CH-CH ₂ -CO-CH ₂ CH ₂ -a

as a colorless oil with a refractive index n _D ²³ :1.5538.

b) 14.8 g of 2-(4-phenoxy-phenoxy)-ethyl ester of 3-butenoic acid are dissolved in 30 ml of diethylene glycol dimethyl ether (diglyme) and heated with stirring to +165°C. At this temperature, a solution of 15.25 g of sodium salt of chlorodifluoroacetic acid in 30 ml of diglyme is added dropwise for 8 hours. The mixture is stirred for another 1 hour at +165°C and then cooled to room temperature.

The reaction mixture is filtered, the residue is washed with 20 ml of diglyme and the filtrate is completely evaporated, then taken up in 40 ml of diethyl ether and washed twice with 20 ml of water and dried over sodium sulfate. After evaporation of the solvent, the oily residue is purified by column chromatography on silica gel with hexane/acetic acid (9:1). This gives 12.1 g of 2-(4-phenoxy-phenoxy)-ethyl ester of 2-(2,2-difluorocyclopropyl)-acetic acid as a colorless oil with a refractive index n _D ²² :1.5309.

In an analogous manner, the compounds of formula I listed in the following tables can be prepared.

Table 1:

CH ₂ CH—CH ₂ —C —O —R \/ II cf ₂ II

Compound R no.

Physical data

n _D ²² : 1.53 09 n _D ²⁰ : 1.5619 n _D ²⁰ : 1.5483

n _D ²⁰ : 1.5544 n _D ²⁰ : 1.5248

-20(continued)

1.13 n _D ²⁰ : 1.5307

'Oh

-Ό mol.: 53-54°C n _D ²¹ : 1.5356 n _D ²¹ : 1.5256 n _D ²¹ : 1.5192 n _D ²¹ ; 1.5195 n _D ²¹ : 1.5195 (continued)

-21 1.14

1.15

CF ₃ cf ₂ cfci ₂ n _D ²³ : 1.5049

1.16 -CH ₂ -CH ₂ -O · •Cl

1.17

1.18

1.19

1.20

F

1.21

-ch ₂ -ch ₂ -o

1.22

1.23

1.24

1.25

1.26

1.27

1.28 (continued)

-CH ₂ -CH ₂ -O

-ch ₂ -ch ₂ -o

-ch ₂ -ch ₂ -o

S-N

1.29

-23(continued)

-24Table 2:

CH ₂ -CH- CH ₂ — C — N — R '\/ cf ₂

Connection.

no.

Rj Physical data

2.01

-ch ₂ -ch ₂ -o

Melting point: 87-89°C

2.02

-ch ₂ -ch ₂ -o

chapter ₃

2.03

-ch ₂ -ch ₂ -o

2.04

-ch ₂ -ch ₂ -o

Melting point: 69-71°C

2.05

-ch ₂ -ch ₂ -o

Melting point: 64-66°C

2.06

2.07

-25(continued)

2.08 -CH ₂ -CH ₂ -O—<7 ^-OCHg-1^^ JJ—CH ₂ QC ₂ H ₅ H

CF

H

CH,

2.13

-CH ₂ -CH ₂ -CH ₂ -O

2.14

-(CH ₂ ) ₄ -O

Temperature: 86-88°C

2.15

-(CH ₂ ) ₅ -O

Melting point: 66-68°C

2.16

-26(continued)

2.19

^CF3H

CF ₂ CFCI ₂ pj

2.21 -CH ₂ -CH ₂ -O—7—O——C ₂ H ₅ h

2.22 -CH ₂ -CH ₂ -O ch ₃

2.23 -CH ₂ -CH ₂ -O —& \—O—fl \— OCH ₃ H

2.24 -CH ₂ -CH ₂ -O

Table 2 (continued)

CF _q melting point: 64-66°C

2.TJ -CH-CH ₂ CH,

melting point: 90-92°C

Formulation examples (% = weight percent)

Example Fl: Emulsion concentrates a)

b) active ingredient No. 1.01 25%

Ca dodecylbenzenesulfonate 5% castor oil polyethylene glycol ether (36 moles EO) 5% tributylphenol polyethylene glycol ether (30 moles EO) cyclohexanone mixed xylenes 65%

40%

8%

c)

50%

6%

12% 15% 25%

4%

20%

20%

From such concentrates, emulsions of any desired concentration can be prepared by diluting with water.

Example F2: Solutions a) active ingredient No. 1.05 80%

b) c) d) % 5 % 95 % ethylene glycol monomethyl ether 20 % polyethylene glycol m.m. 400 - 70 % N-methyl-2-pyrrolidone - 20 % epoxidized coconut oil - - 1 % 5 % gasoline (boiling range 160-190 °C) - - 94 % Solutions are suitable for use in the form of the smallest droplets.

Example F3: Granules ^a ) b) c) d) active ingredient no. 1.02 5% 10% 8% 21% kaolin 94% - 79% 54% highly dispersed silica 1% 13% 7% attapulgite - 90% - 18%

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier, and the solvent is then evaporated in vacuo.

Example F4: Dust a) b)

active ingredient no. 1.03 2% 5% highly dispersed quartz 1% 5% talcum powder 97% - kaolin - 90%

By thoroughly mixing the carrier substances with the active ingredient, ready-to-use powders are obtained.

^c )

Example F5: Sprayable powders a)

b)

active ingredient no. 1.07 25% 50% On lignin sulfonate 5% 5% On lauryl sulfate 3% - On diisobutylnaphthalene- sulfonate 6% octylphenolpolyethyleneglycolether (7-8 moles EO) 2% highly dispersed silica 5% 10% kaolin 62% 27%

%

10%

10%

The active ingredient or combination of active ingredients is mixed with additional substances and ground well in a suitable mill. This produces sprayable powders that can be diluted with water into a suspension of any desired concentration.

Example F6: Emulsion concentrate active ingredient No. 1.07 10% octylphenol polyethylene glycol ether (4-5 moles EO) 3%

Ca dodecylbenzenesulfonate 3% castor oil polyglycol ether (36 moles EO) 4% cyclohexanone 30% mixed xylenes 50%

From this concentrate, emulsions of any desired concentration can be prepared by diluting with water.

Example F7: Dust

a)

b) active ingredient No. 1.07 talc kaolin % 8 %

95%

92%

Ready-to-use powders are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.

Example F8: Extrusion granulate active ingredient No. 1.07 10%

Per ligninsulfonate 2% carboxymethylcellulose 1% kaolin 87%

The active ingredient is mixed with additional substances, ground and moistened with water. This mixture is extruded, granulated and then dried in an air stream.

Example F9: Coating granulate active ingredient no. 1.07 3% polyethylene glycol (m.w. 200) 3% kaolin 94%

The finely ground active ingredient is evenly applied in a mixer to kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

Example F10: Suspension concentrate active ingredient No. 1.07 40% ethylene glycol 10% nonylphenol polyethylene glycol ether (15 moles EO) 6%

On lignin sulfonate 10% carboxymethylcellulose 1% silicone oil in the form of a 75% aqueous emulsion 1% water 32%

The finely ground active ingredient is thoroughly mixed with additional substances. This results in a suspension concentrate from which suspensions of any desired concentration can be prepared by diluting with water.

Biological examples

Example BI: Effect against Boophilus microplus

Fully engorged adult female ticks are glued to a PVC plate and covered with a wad of cotton wool. For treatment, 10 ml of an aqueous test solution containing 125 ppm of the active substance to be tested is poured over the test animals. The wad of cotton wool is then removed and the ticks are incubated for 4 weeks for egg laying. The effect against Boophilus microplus is manifested either as mortality or sterility in the female or as ovicidal effect in the eggs.

The compounds according to Tables 1 and 2 show good activity against Boophilus microplus in this test. In particular, compounds 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.10, 1.11, 1.12, 1.14, 1.32, 2.01, 2.04, 2.05 and 2.14 show activity above 80%.

Example B2: Effect against Nilaparvata lugens

Rice plants are treated with an aqueous emulsion spray slurry containing 400 ppm of active ingredient. After the spray has dried, the rice plants are infested with 2nd and 3rd instar cicada larvae. Evaluation is performed after 21 days. The percentage population reduction (% effect) is determined by comparing the number of surviving cicadas on treated plants with those on untreated plants.

In this test, the compounds of Tables 1 and 2 show good activity against Nilaparvata lugens. In particular, compounds 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12 and 1.14 show activity above 80%.

Example B3: Effect against Tetranvchus urticae

Young bean plants are inoculated with a mixed population of Tetranychus urticae and sprayed after 1 day with an aqueous emulsion spray slurry containing 400 ppm active ingredient. The plants are then incubated for 6 days at 25°C and then evaluated. The percentage population reduction (% effect) is determined by comparing the number of dead eggs, larvae and adults on treated plants with those on untreated plants.

In this test, the compounds of Tables 1 and 2 show good activity against Tetranychus urticae. In particular, compounds 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.09, 1.10, 1.11, 1.14 and 2.26 show activity above 80%.

Example B4: Effect against Aphis craccivora

Pea seedlings are infested with Aphis craccivora and then sprayed with a spray solution containing 400 ppm of the active ingredient and incubated at 20°C. Evaluate after 3 and 6 days. The percentage reduction in population (% effect) is determined by comparing the number of dead aphids on treated plants with those on untreated plants.

In this test, the compounds of Tables 1 and 2 show good activity against Aphis craccivora. In particular, compounds 1.02, 1.03, 1.04, 1.05, 1.09, 1.10, 1.11, 1.12, 1.32 and 2.04 show activity above 80%.

Example B5: Systemic effect against Nilaparvata lugens

Place the pots of rice plants in an aqueous emulsion solution containing 400 ppm of the active ingredient. Then populate the rice plants with 2nd and 3rd instar larvae. Evaluate after 6 days. From a comparison of the number of cicadas on treated plants versus those on untreated plants, determine the percentage reduction in population (% effect).

In this test, the compounds of Tables 1 and 2 show good activity against Nilaparvata lugens. In particular, compound 1.04 shows an activity of over 80%.

Example B6: Effect against Dermanvssus gallinae

In a glass container with an open top, add 2 to 3 ml of a solution containing 10 ppm of the active ingredient and about 200 mites in various developmental stages. The container is then closed with a wad of cotton wool, shaken for 10 minutes until the mites are completely wetted, and then briefly inverted so that the cotton wool can absorb the remaining test solution. After 3 days, determine the mortality of the mites.

In this test, the compounds of Tables 1 and 2 show good activity against Dermanyssus gallinae. In particular, compounds 1.01, 1.02, 1.03, 1.04, 1.12 and 1.32 show activity above 80%.

Example B7: Effect against Panonvchus ulmi (OP and Carb. resistant)

Apple seedlings are infested with adult female Panonychus ulmi. After 7 days, the infested plants are sprayed with an aqueous emulsion containing 400 ppm of the compound to be tested, so that it drips from them, and cultivated in a greenhouse. Evaluate after 14 days. The percentage population reduction (% effect) is determined by comparing the number of dead spider mites on treated plants with those on untreated plants.

In this test, the compounds of Tables 1 and 2 show good activity against Panonychus ulma. In particular, compounds 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11 and 2.16 show activity above 80%.

Claims (17)

1. 2- (2,2-Difluorocyclopropyl) -acetic acid derivatives of formula I (L), CH ₂ CH — CH ₂ —C —A —B —O — v In II o D-E (I) where they mean A is oxygen or -NRj-, BC ₂ -C ₆ -alkylene, D oxygen, sulfur or -O-CH ₂ -, E is phenyl with one to three substituents from the group halogen, C ^ is -C alkyl, C -C ₃ haloalkyl, or Cj-C ^ alkoxy substituted phenyl; a five-membered aromatic heterocycle of 1 to 3 hetero atoms of the nitrogen, oxygen or sulfur species; with 1 or 2 substituents from the group halogen, Cj-C ^ alkyl or C-C ₃ haloalkyl substituted five-membered aromatic heterocycle containing 1 to 3 hetero atoms from the series nitrogen, oxygen or sulfur; a six-membered aromatic heterocycle with 1 to 3 nitrogen atoms; or with 1 or 2 substituents from the group halogen, C-C ₄ -alkyl or C ₃ Cp -haloalkyl substituted six-membered aromatic heterocycle containing 1 to 3 nitrogen atoms; L is halogen or methyl, n is 0,1 or 2, and R1 is hydrogen, C1-C6-alkyl, phenylthio or tolylthio. Compounds according to claim 1, characterized in that A is oxygen. Compounds according to claim 1, characterized in that B stands for the ethylene bridge. Compounds according to claim 1, characterized in that A is -NH. Compounds according to claim 1, characterized in that n is zero. Compounds according to claim 1, characterized in that D is oxygen. Ί. Compounds according to claim 1, characterized in that E is phenyl, pyridyl, pyridazine or thiadiazolyl, or in each case with one or two substituents from the group fluorine, chlorine, C 1 -C ₂ -halogenalkyl or methyl substituted phenyl, pyridyl, pyridazinyl or thiadiazolyl. Compounds according to claim 7, characterized in that E is phenyl, chlorophenyl, fluorophenyl, methylthiadiazolyl, pyridyl, dichloropyridyl, chloro-trifluoromethylpyridyl, chloro-trifluorocycloretylpyridyl or chlorpyridazinyl. Compounds according to claim 7, characterized in that A represents oxygen, B ethylene bridge, D oxygen or sulfur and n is zero. Compounds according to claim 7, characterized in that A is a bridge -NH-, B is an ethylene bridge, D is oxygen or sulfur and n is zero. 11. A compound selected from the species in which they are 2- (2,2-Difluorocyclopropyl) -acetic acid 2- (4-phenoxy-phenoxy) -ethyl ester, 2- (2,2-Difluorocyclopropyl) -acetic acid 2- (4-phenylthiophenoxy) -ethyl ester, 2- (4-Phenylthiophenoxy) -propyl 2- (2,2-difluorocyclopropyl) -acetic acid, 2- (4-phenoxyphenoxy) -propyl 2- (2,2-difluorocyclopropyl) -acetic acid, 2- [4-pyrid 2- (2,2-Difluorocyclopropyl) -acetic acid -2-yloxy) -phenoxy] ethyl ester, 2- (2,2-difluorocyclopropyl) -acetic acid 2- [4- (3-chlorophenoxy) -phenoxy] ethyl ester, 2 2- (2,2-Difluorocyclopropyl) -acetic acid - [4- (4-fluorophenoxy) -phenoxy] ethyl ester, 2- [4- (2-fluorophenoxy) -phenoxy] -ethyl ester 2- (2,2-difluorocyclopropyl) -acetic acid, 2- [4- (3-methyl-1,2-thiadiazol-5-yloxy)) -phenoxy] ethyl ester of 2- (2,2-difluorocyclopropyl) acetic acid, and 2- (2,2-Difluorocyclopropyl) -acetic acid 2-4- (benzyloxy-phenoxy] ethyl ester. A process for the preparation of compounds of the formula I according to claim 1, characterized in that a) 2- (2,2-Difluorocyclopropyl) -acetic acid halide of formula II CH ₂ —CH-CH _? -C-Hal \ / ² II (H) wherein Hal stands for chlorine or bromine, optionally in an inert solvent and in the presence of an acid-binding agent, is reacted with an alcohol or amine of formula III D-E H-A-B-O (ΠΙ) where A, B, L, D, E and n have the meanings given in formula I, or b) a 3-butenic acid derivative of formula IV H ₂ C = CH— CH ₂ - C - A - B - O n (L) (IV) D-E where A, B, L, D, E and n have the meanings given in formula I, in an inert solvent, is reacted with difluorocarbene, or c) The free 2- (2,2-difluorocyclopropyl) -acetic acid of formula V (V) is optionally reacted with an alcohol or amine of formula III in the presence of an inert solvent and a catalyst or water withdrawal agent. 13. A pest control comprising at least one compound of the formula I as claimed in claim 1 as an active component. 14. An agent according to claim 13, characterized in that it further comprises at least one carrier. The use of a compound of formula I according to claim 1 for the control of pests in animals and plants. Use according to claim 15, characterized in that the plant pests are harmful insects and arachnids. A method of controlling animals and plants of insect pests and arachnids, characterized in that the pests or their habitat are treated with an effective amount of a compound of formula I according to claim 1. 18. 3-Butene acid derivatives of formula IV O (IV) where they mean A is oxygen or -NRp, BC ₂ -C ₆ -alkylene, D oxygen, sulfur or -O-CHp, E is phenyl, with one to three substituents from the group halogen, C ₁ -C ₄ -alkyl, CpC 3 halogenalkyl or C ₃ -C ₄ alkoxy substituted phenyl; a five-membered aromatic heterocycle of 1 to 3 hetero atoms of the nitrogen, oxygen or sulfur species; with 1 or 2 substituents from the group halogen, C-C ₄ -alkyl or CpCphalogenalkila substituted five-membered aromatic heterocycle containing 1 to 3 hetero atoms from the series nitrogen, oxygen or sulfur; a six-membered aromatic heterocycle with 1 to 3 nitrogen atoms; or a six-membered aromatic heterocycle having 1 to 3 nitrogen atoms is substituted with 1 or 2 substituents from the group halogen, CpCalkyl or Cp Cphalogenalkyl; L is halogen or methyl, n is 0,1 or 2, and R 1 is hydrogen, C 1 -C 6 alkyl, phenylthio or tolylthio.