SI9111245A - Cyclopropylacetic acid derivatives - Google Patents

Abstract

New 2- (2,2-difluorocyclopropyl) -acetate derivatives acids of formula I Sl 9111245 A where A is oxygen or -NR-, B is C2-C6-alkylene, D oxygen, sulfur or -O-CH2-, E phenyls, with one to three substituents from the group of halogens, C1-C4-alkyl, C1-C3- halogenalkyl or C1-C4-alkoxy substituted phenyl; five-member an aromatic heterocycle having 1 to 3 hetero atoms from types of nitrogen, oxygen or sulfur; with 1 or 2 substituents from the group halogen, C1-C4-alkyl or C1-C3-halogenalkyl a five-membered aromatic heterocycle substituted with 1 to 3 hetero atoms of the nitrogen, oxygen or sulfur species; a six-membered aromatic heterocycle of 1 to 3 atoms nitrogen; or with 1 or 2 substituents from the group halogen, C1-C4-alkyl or C1-C3-halogenalkyl substituted a six-membered aromatic heterocycle of 1 to 3 nitrogen atoms; L is halogen or methyl, n is 0,1 or 2, and R 1 hydrogen, C 1 -C 4 alkyl, phenylthio or tolylthio can be used as pest control agents. Preferably we can suppress insects and arachnids.

Description

Cyclopropylacetic acid derivatives

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

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

CH ₂ -CH— CH ₂ - CABO - (/ V \ / n \ = Ae or _{2 0} (D 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 of the halogen group, C ₁ -C ₄ -alkyl, C ₁ -C ₄ halogenalkyl or C ₁ -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 C ^ C ^ 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 haloalkyl substituted six-membered aromatic heterocycle containing 1 to 3 nitrogen atoms;

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

R is hydrogen, Cl-C ₄ alkyl, phenylthio or toliltio.

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

In the definition of formula I of the invention, it is necessary to understand the individual general concepts as follows:

The halogen atoms that are considered substituents are fluorine and chlorine as well as bromine and iodine, with fluorine and chlorine being preferred. Halogen is intended to be a stand alone substituent or part of a halogenalkyl substituent.

The alkyl and alkoxy residues which may be considered substituents may be straight or branched. Examples of such alkyls are methyl, ethyl, propyl, isopropyl, butyl, i-butyl, sec-butyl or tert-butyl. Suitable alkoxy residues include, but are not limited to: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers.

If the alkyl or tertiary groups that are suitable as substituents or aromatic heterocycles are substituted by halogen, they may be only partially halogenated or perhalogenated. Halogen, alkyl and alkoxy are as defined above. Examples of the alkyl elements of these groups are one to three times fluorine, chlorine and / or bromine substituted methyl, such as e.g. CHF ₂ or CF ₃ ; once or five times with fluorine, chlorine and / or bromine substituted ethyl, e.g. 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, once to seven times with fluorine , chlorine and / or bromine substituted propyl or isopropyl, such as e.g. CH ₂ CHBrCH ₂ Br, CF ₂ CHFCF ₃ , CH ₂ CF ₂ CF ₃ or CH (CF ₃ ) ₂ ; one to nine times fluorine, chlorine and / or bromine substituted butyl or one of its isomers, such as e.g. CF (CF ₃ ) CHFCF ₃ or CH ₂ (CF ₂ ) ₂ CF ₃ . Aromatic heterocycles carry substituents which are suitable, preferably on one of the carbon atoms, which together with the hetero atoms form a ring framework. These rings are generally also bonded via the ring carbon atom to the bridge member D. The five-membered aromatic heterocycles of the definition of residue E 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 1,3,4oxadiazole. As the six-membered aromatic heterocycles, the E of the invention are pyridine, pyrimidine, pyrazine, pyridazine, 1,2,4-triazine or 1,3,5-triazine. If these aromatic residues defined at E, as well as phenyl, are further substituted, they can be substituted one to three times with the same or different substituents listed. Preferably, one to two substituents are present in the substituted aromatic substituents. Preferably, the aromatic residues of the -DE definition are also given by the following individual meanings:

phenoxy, phenylthio,

3.5-dichlorpyrid-2-yloxy,

2- pyridyloxy, benzyloxy,

3- kiorphenoxy,

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

4- fluorophenoxy,

3-fluorophenoxy,

2- fluorophenoxy,

3- chloro-5-trifluoromethyl-pyrid-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 -D-E residues may occupy the position of the ortho, meth, or vapor of the phenyl residue. The position of the pair is preferred.

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

a) A stands for oxygen, but

b) B for ethylene bridge or

c) A for bridge -NH- or

d) n for zero or

e) D for oxygen or

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

Among the compounds of subgroup f), preferred are those wherein E stands for phenyl, chlorophenyl, fluorophenyl, methylthiadiazolyl, pyridyl, dichloropyridyl, chloro-trifluoromethylpyridyl, chlorofluorocycloretyl-pyridyl or chlorpyridazine.

Among these preferred compounds of Formula I, for their good performance, they are particularly distinguished where either A is oxygen, B is the ethylene bridge, D is oxygen or sulfur and n is zero; or where A is a bridge -NH-, B is an ethylene bridge, D is oxygen or sulfur and n is zero.

The preferred individual compounds of formula I of the invention 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- (2,2-Difluorocyclopropyl) -acetic acid 2- (4-phenylthiophenoxy) -propyl ester,

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

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

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

2- (2 ^ 2-Difluorocyclopropyl) -acetic acid derivatives of formula I according to the invention can be prepared in such a way that 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-butenic acid derivative of formula IV

O (IV) where A, B, L, D, E, and n have the meanings given in formula I, in the inert solvent are mixed 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 optionally, in the presence of an inert solvent and catalyst or water-withdrawing agent, is reacted with an alcohol or amine of formula III.

The reaction of process a) (II + III ->) preferably takes place in an inert solvent without hydroxyl groups in the presence of an organic base, such as e.g. pyridine, 4-dimethylaminopyridine, lutidine, colidine, trialkylamine, Ν, dial-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. In doing so, it is advantageous in the presence of the reaction of an inert solvent or solvent mixture. For example, they are suitable for example. aliphatic and aromatic hydrocarbons such as benzene, toluene, xylols, petroleum ether, hexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, tetrachlorocarbon, tetrachlorethylene; ethers and ethereal 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 (acetic acid ethyl ester), propyl acetate or butyl acetate; ketones such as acetone, diethyl ketone, methylethyl ketone; compounds such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and mixtures of such solvents. Alternatively, the reaction can be carried out in excess of one of the above bases, and if the compound of formula III is an amine (A = NRJ, then another equivalent or a larger excess of the compound of formula III may be used instead of the base. environment, although it could also be performed at elevated ah reduced pressure.

Suitable solvents are preferably ethers such as diglyme, triglyme or tetraglyme, for the implementation of reaction variant b) (IV + difluorocarbene -> I). Difluorkarben is prepared according to methods known from the literature (Burton and Hahnfeld, Fluorine Chem. Rev. 8 (1977), 199 ff. Suitable donors are, for example, alkali chlorodifluoroacetates, such as sodium chlorodifluoroacetate; , such as trimethyl (trifluoromethyl) -tin; organosilver compounds such as phenyl (trifluoromethyl) mercury; organophosphorus compounds such as tris (trifluoromethyl) -difluorophosphorane and triphenyl (bromdifluoromethyl) -phosphonium bromide.

In the process variant c) (V + III - * I), the reaction is advantageously carried out in the presence of reagents which are conventional for esterification and water separation, such as e.g. in the presence of carbodiimide [dicyclohexylcarbodiimide (DCC) j or 1-alkyl-2-halogen-pyridinium salts, such as 1-methyl-2-chloropyridinium iodide. The reaction is then conveniently carried out in the presence of a reaction of an inert solvent or solvent mixture at temperatures from -30 ° C to + 70 ° C, preferably -10 ° C to + 50 ° C. We work preferably in the presence of a base, such as. in the presence of an organic amine such as trialkylamine (trimethylamine, triethylamine, tripropylamine or diisopropylethylamine), pyridine (pyridine alone, 4-dimethylaminopyridine or

4-pyrrolidinopyridine), morpholine, (N-methylmorpholine) or Ν, dial-dialkylaniline (N, N-dimethylaniline or N-methyl-N-ethylaniline). They are therefore suitable as solvents e.g. aliphatic and aromatic hydrocarbons such as benzene, toluene, xylols, petroleum ether, hexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, tetrachlorocarbon, tetrachlorethylene; ethers and ethereal compounds such as dialkyl ether (diethyl ether, diisopropylether), tert-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate (acetic acid ethyl ester), propyl acetate or butyl acetate; and mixtures of such solvents.

If the compound of formula III is an alcohol (A = 0), a variant of process c) may also be carried out in the presence of an acid catalyst, such as e.g. H ₂ SO ₄ , HC1 or sulfonic acids, such as methanesulfonic or p-toluenesulfonic acids. In doing so, we work with the benefit of excess alcohol of formula III. In this process, the released water can be continuously removed from the reaction mixture. The usual method for this is to remove the reaction product of water by distilling the solvent azeotrope with water. Suitable solvents include benzene, toluene, xylene, methylene chloride or chloroform.

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

E.g. ester type derivatives of formula I (A = O) can be obtained by base or acid catalyzed esterification of lower alkyl esters of formula Va

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

II (Va) with alcohols of the formula lilac

H-O-B-O

DE (nia) wherein B, D, E, L and n have the meanings given by formula I. HC1, H ₂ SO ₄ or sulfonic acid are particularly suitable as acid catalysts. In base-catalyzed diversion, it is preferable to use as a base sodium or potassium alcoholate an alcohol of the formula lilac, accessible from lilac e.g. with the addition of sodium or potassium hydride. The diversion reaction is preferably carried out at temperatures between -20 ° C and + 120 ° C, especially between 0 ° C and + 100 ° C. Use the alcoholic component of lilac with the excess. Ethers such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran, halogenated hydrocarbons or aliphatic or aromatic hydrocarbons are suitable solvents.

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) wherein 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. With the benefit of the reactant, it is reacted in an inert solvent or solvent mixture. For example, they are suitable for example. aliphatic and aromatic hydrocarbons such as benzene, toluene, xylols, petroleum ether, hexane; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, tetrachlorocarbon, tetrachlorethylene; ethers and ethereal compounds such as dialkyl ether (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 Hib amine component is advantageously used in excess.

The compounds of formulas II, III, lilac, Hib, V and Va and their preparation are known from the literature. Compounds II and V are obtained by conventional hydrolysis and halogenation reactions of 2- (2,2-difluorocyclopropyl) -acetic acid basic benzyl ester. It can again be readily prepared by the addition of difluorocarbene to benzyl ester of 3-butenic 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 benzyl ester and the subsequent optional conversion of this acid V to an acid halide of formula II correspond to the usual conditions for acid or base catalyzed hydrolysis or. for carboxylic acid halogenation. Compounds of formulas III, lilac and IHb that have not yet been described in the literature can be prepared analogously to known methods by conventional synthesis methods. The compounds of formula IV are novel. They have been specifically developed for the synthesis of the active ingredients of formula I. The compounds of formula IV therefore form an ingredient of the present invention.

Compounds of formula IV can be obtained from known products such that 3-butene acid of formula VI

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

Unless specifically mentioned, the compounds of formula I are a mixture of optical isomers. Alternatively, optically pure isomers may be obtained by starting from optically pure starting materials, such as R- or S-2- (2,2-difluorocyclopropyl) acetic acid or. halides, or optically pure isomers to be derived from racemates by known methods.

This can be done e.g. by reacting compounds of general formula II or V with a chiral auxiliary reagent, such as e.g. optically active amines or optically active alcohols, and the subsequent separation of the diastereomers thus obtained by physical methods (Tetrahedron 33, 2725 (1977)), such as crystallization, distillation or solid-liquid chromatography. Subsequent hydrolytic cleavage, which can be conducted either acid or base catalytic, gives optical isomers of free acids of general formula V which can be converted into the compounds of the invention according to a variant of process c).

Furthermore, the synthesis of the resulting mixture of optical isomers of general formula I by chromatography on chiral stationary phases, such as e.g. cyclodextrins, starch or polymers-bound optically active amino acid derivatives are separated into enantiomers (Angev / Chem. 92, 14 (1980)).

However, we have now found that the compounds of the invention of Formula I, with good tolerability for warm-blooded creatures, fish and plants, are valuable pest control agents. In particular, the use of the active ingredients of the invention by insects and spiders occurring in useful and ornamental plants in agriculture, particularly in cotton, vegetable and fruit plantations, in the forest, in the protection of supplies and materials as well as in the hygiene sector, in particular in the domestic and useful sectors animals. They affect all or individual stages of development of normally susceptible as well as resistant species. In doing so, their effect may be reflected in the direct destruction of the pests or only after a while, e.g. in levitating or in reducing egg deposition and / or incidence of hatching. The above-mentioned pests include:

from the order of 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. , Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparophesis castanea. spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis sppria, Lobocollethis 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., Pieris spp., Pieris spp., Pieris spp., Pieris spp. Scirpophaga spp., S esamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp .;

from the order of 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, Lissorhppilus spp., Spp. 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 of Isoptera for example

Reticulitermes spp .; from the order of Psocoptera 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 of Thysanoptera for example

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palm trees, Thrips tabaci and Scirtothrips aurantii; from the order of 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 of Homoptera for example

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum. , Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudoc, 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 of 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 Diptera order 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., 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 of Siphonapter e.g.

Ceratophyllus spp., Xenopsylla cheopis, for example Acarina

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

Lepisma saccharina.

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

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

The effect of the compounds of the invention and the agents containing them can be substantially expanded and adapted to the circumstances by the addition of other insecticides and / or acaricides. They come as extras for example. for example, representatives of the following classes of active substances: 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 unchanged form ah preferably together with auxiliary agents which are customary in the art of formulation, and therefore e.g. in a known manner it can be converted into emulsifiable concentrates, into solutions which can be directly dispersed or diluted, into dilute emulsions, sprayable powders, soluble powders, dusting agents, granulates, including capsules in polymeric substances. Use processes such as spraying, blurring, dusting, sanding or pouring are chosen in the same way as the means appropriate to the set goals and given circumstances.

Formulation, that is, agents, preparations or compositions containing an active ingredient of Formula I or. combinations of these ingredients with other insecticides or acaricides and optionally prepared solid or liquid adjuvant in a known manner, e.g. by thoroughly mixing and / or grinding the active ingredients with diluents, such as e.g. with solvents, solid carriers and optionally surfactants.

Aromatic hydrocarbons, preferably C _g to C ₁₂ alkylbenzene fractions, may be used as solvents. 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 ether, ethylene glycol ether, ethylene glycol ether , such as cyclohexanone, isophorone or diacetanol alcohol, highly flammable solvents such as N-methyl-2pyrrolidone, dimethylsulfoxide or dimethylformamide, or water, vegetable oils such as rapeseed, castor, coconut or soybean oil; in this case also silicone oils.

As solid carriers, e.g. for detergents and dispersible powders, we generally use natural rock flours such as calcite, talc, kaolin, montmorillonite or attapulgite. High-dispersion silica or high-dispersion absorbent polymerizates can also be added to improve the physical properties. As granular, adsorptive granulate carriers are considered porous species such as float, brick debris, sepiolite or bentonite, as non-sorptive carrier materials calcite or sand. In addition, many granular materials of inorganic or organic nature, such as dolomite or crushed plant residues, can be used.

Depending on the type of active ingredient of Formula I or the combination of these ingredients with other insecticides or acaricides to be formulated, the surfactants may be considered nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants also mean mixtures of surfactants.

Suitable anionic surfactants may be, e.g. water soluble soaps as well as water soluble synthetic surfactants.

Suitable alkaline, alkaline earth alkaline or optionally substituted higher fatty acid ammonium salts (C ₁₀ -C ₂₂ ), such as oleic or stearic acid sodium or potassium salts, or mixtures of natural fatty acids which may be obtained e.g. from coconut oil or tallow oil. The fatty acid methyltavurine salts should also be mentioned as surfactants.

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

Fatty sulphonates or sulphates generally occur as alkali, alkaline earth or optionally substituted ammonium salts and generally have an alkyl residue of 8 to 22 carbon atoms, the alkyl also including an alkyl moiety of acyl residues, e.g. sodium or calcium salt of ligninsulphonic acid, sulfuric acid dodecyl ester or a mixture of sulfates of fatty alcohols prepared from natural fatty acids. This also includes sulfuric acid and sulfonic acid esters of fatty alcohol and ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 groups of sulfonic acid and a fatty acid residue with e.g. 8 to 22 carbon atoms. Alkylarylsulfonates are e.g. sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or the condensation product of naphthalenesulfonic acid and formaldehyde. Appropriate phosphates such as e.g. phosphoric acid ester salts of the adduct p-nonylphenol and (4-14) -ethylene oxide, or phospholipids.

The non-ionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain from 3 to 30 glycol ether groups and from 8 to 20 carbon atoms in (aliphatic) hydrocarbon and 6 residues in the alkyl residue of alkylphenols. Further suitable non-ionic surfactants are water soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts per polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in alkyl. These compounds typically contain 1 to 5 units of ethylene glycol per unit of propylene glycol.

Examples of nonionic surfactants include nonylphenolpolyethoxyethanol, castor oil polyglycoleters, polypropylene polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. The fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are further preferred.

Cationic surfactants are mainly quaternary ammonium salts containing at least one alkyl residue of 8 to 22 carbon atoms as an N-substituent and exhibiting lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl residues as further substituents. The salts preferably are halides, methylsulphates or ethylsulphates, e.g. stearyltrimethylammonium chloride or benzyl di- (2-chloroethyl) ethylammonium bromide.

The surfactants used in the formulation technique are e.g. described in these 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 formula I or combinations of this active ingredient with other insecticides or acaricides, 1 to 99.9% of the solid or liquid adjuvant and 0 to 25%, in particular 0.1 to 25% surfactant. While pre-concentrated agents are preferred over commercial goods, the end-user generally uses diluted preparations having significantly lower concentrations of the active substance. Typical useful 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.

In particular, the preferred formulations are as follows:

(% = mass percentage)

Emulsifying concentrates:

Active ingredient surfactant liquid carrier

Powders:

Active substance solid carrier

Suspension concentrates:

The active substance water is the surfactant

Wetting powders:

Active ingredient surfactant carrier solid material

Granules:

Active ingredient solid carrier up to 90%, preferably 5 to 20% 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% 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. optionally 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 ingredients to achieve special effects.

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

Examples of preparation

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 was added 0.1 g of 4-pyrrolidino-pyridine and 2.53 g of 2- (4-phenoxy-phenoxy) -ethanol and cooled to 16 ° C. A total of 2.5 g of N, N'-dicyclohexylcarbodiimide is added portionwise at a temperature between 0 ° C and + 5 ° C, ice cooling is removed and the reaction mixture is allowed to warm to room temperature for 5 hours with stirring. As a precipitate of eliminated Ν, the Ν'-dicyclohexylurea is determined and discarded. The supernatant solution was washed twice with 10 ml of water each, dried over magnesium sulfate and evaporated. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate, 85:15). 2- (4-Phenoxy-phenoxy) -ethyl 2- (2,2-difluorocyclopropyl) -acetic acid is obtained in pure form as an oil which tends to yellow with a refractive index n _D ²² : 1.5309.

Example H2: 2- (4-Phenoxy-phenoxy) -ethyl ester 2-f2,2-difluorocyclopropyl) -acetic acid

CH ₂ - CH- CH ₂ -CO-O-CH ₂ -CH ₂ -O ·

a) 2- (4-Phenoxy-phenoxy) -ethyl ester of 3-butenic acid

To a solution of 6.45 g of 3-butenoic acid in 100 ml of dichloromethane was added stirring at room temperature 0.05 g of 4-pyrrolidino-pyridine and 17.25 g of 2- (4-phenoxy-phenoxy) ethanol. At 0 ° C, 17.0 g (82.5 mmol) of N, Ndicyclohexylcarbodiimide were then added portionwise and the reaction mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered. The precipitate was discarded, the filtrate was washed with water and dried over sodium sulfate. After evaporation, the oily residue was purified by column chromatography on silica gel with hexane / ethyl acetate (9: 1). There is thus obtained 20.0 g of 3- (4-phenoxy-phenoxy) -ethyl 3-butenic acid ethyl ester of 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) Dissolve 14.8 g of 2- (4-phenoxy-phenoxy) -ethyl ester of 3-butenic acid in 30 ml of diethylene glycodimethyl ether (diglyme) and heat under stirring at + 165 ° C. At this temperature, a solution of 15.25 g of the chlorofifluoroacetic acid sodium salt in 30 ml of diglyme was added dropwise over 8 hours. The mixture was stirred at + 165 ° C for 1 hour and then cooled to room temperature.

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

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

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 melting point: 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

Compound.

no.

Rj Physical data

2.01

-ch ₂ -ch ₂ -o

H mp .: 87-89°C

2.02

-ch ₂ -ch ₂ -o

ch ₃

2.03

-ch ₂ -ch ₂ -o

2.04

-ch ₂ -ch ₂ -o

H mp .: 69-71 ° C

2.05

-ch ₂ -ch ₂ -o

H mp: 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

H mp .: 86-88 ° C

2.15

- (CH ₂ ) ₅ -O

H mp: 66-68 ° C

2.16

-26 (continued)

2.19

^CF 3 H

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,

M.p .: 90-92 ° C

Formulation Examples (% = mass percentage)

Example Fl: Emulsion concentrates a)

b) active ingredient no. 1.01 25%

Ca dodecylbenzenesulfonate 5% polyethylene glycol ether castor oil (36 moles EO) 5% tributylphenolpolyethylene glycol ether (30 moles EO) cyclohexanone mixture of xylenes 65%

40%

8%

c)

50%

6%

12%

4%

20%

20%

Emulsions of any desired concentration can be prepared from such concentrates by dilution 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% The solutions are suitable for use as a minimum drop.

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

The active substance was dissolved in methylene chloride, sprayed onto the support and the solvent was then evaporated in vacuo.

Example F4: Dusty a) b)

active ingredient no. 1.03 2% 5% highly dispersed flint 1% 5% talc 97% - kaolin - 90%

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

^c )

Example F5: Spraying powders a)

b)

active ingredient no. 1.07 25% 50% On ligninsulfonate 5% 5% On lauryl sulfate 3% - Diisobutylnaphthalene- sulfonate 6% octylphenol polyethylene glycol ether (7-8 moles EO) 2% highly dispersed flint 5% 10% kaolin 62% 27%

%

10%

10%

The active substance or combination of ingredients is mixed with additional substances and is well ground in a suitable mill. Spray powders are obtained which can be diluted with water to a suspension of any desired concentration.

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

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

Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.

Example F7: Dusty

a)

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

95%

92%

Prepared powders are prepared by mixing the active ingredient with the carrier and grinding in a suitable mill.

Example F8: Extruder granulate active ingredient no. 1.07 10%

On ligninsulfonate 2% carboxymethylcellulose 1% kaolin 87%

The substance is mixed with additional substances, ground and moistened with water. This mixture is extruded, granulated and then air-dried.

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

The finely ground ingredient is uniformly applied in a blender to a polyethylene glycol-moistened kaolin. In this way, the powderless granules are obtained.

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

Per ligninsulfonate 10% carboxymethylcellulose 1% silicone oil in the form of 75% aqueous emulsion 1% water 32%

The finely ground active ingredient is thoroughly mixed with additional substances. A suspension concentrate is thus obtained from which a suspension of any desired concentration can be prepared by diluting with water.

Biological examples

Example BI: Effect against Boophilus microplus

Whole blood-soaked adult female ticks are glued to a PVC plate and covered with cotton wool. For the treatment, pour the test animals with 10 ml of aqueous test solution containing 125 ppm of substance to be tested. Then the cotton swab is removed and the ticks incubated for 4 weeks to lay eggs. The effect against Boophilus microplus is shown either in females as mortality or sterility, or in eggs as an ovicidal effect.

The compounds of Tables 1 and 2 show a good effect in this test against Boophilus microplus. 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 an effect above 80%.

Example B2: Effect against Nilaparvata lugens

The rice plants are treated with an aqueous emulsion spray broth containing 400 ppm of active ingredient. After the spray has dried, the rice plants with the larvae of cicadas 2 and 3 are populated. stadia. We evaluate after 21 days. From the comparison of the number of surviving cycads on treated plants versus those on untreated plants, we determine the percentage decrease in population (% of effect).

In this test, the compounds of Tables 1 and 2 show a good effect 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 an effect above 80%.

Example B3: Effect against Tetranvchus urticae

Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed after 1 day with an aqueous emulsion spray broth containing 400 ppm of active substance. The plants were then incubated at 25 ° C for 6 days and then evaluated. From the comparison of the number of dead eggs, larvae and adults on treated plants versus those on untreated plants, we determine the percentage reduction in population (% effect).

In this test, the compounds of Tables 1 and 2 show a good effect 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 an effect above 80%.

Example B4: Effect against Aphis craccivora

The pea sprouts were infected with Aphis craccivora and then sprayed with a 400 ppm active substance broth and incubated at 20 ° C. We evaluate after 3 and 6 days. From the comparison of the number of dead aphids on treated plants versus those on untreated plants, we determine the percentage decrease in population (% effect).

In this test, compounds of Tables 1 and 2 show a good effect against Aphis craccivora. In particular, compounds 1.02, 1.03, 1.04, .05, 1.09, 1.10, 1.11, 1.12, 1.32, and 2.04 show an effect above 80%.

Example B5: Systemic effect against Nilaparvata lugens

Put the pots with the rice plants in an aqueous emulsion solution containing 400 ppm of the active substance. We then populate the rice plants with stage 2 and 3 larvae. We evaluate after 6 days. From the comparison of the number of cycads on treated plants versus those on untreated plants, we determine the percentage decrease in population (% of effect).

In this test, the compounds of Tables 1 and 2 show a good effect against Nilaparvata lugens. In particular, compound 1.04 has an effect above 80%.

Example B6: Effect against Dermanvssus gallinae

Place 2 to 3 ml of the solution containing 10 ppm of the active substance and about 200 mites in various stages of development into the open glass container. Then close the pan with a cotton swab, shake for 10 minutes until the mites are completely wet, and then turn briefly so that the remaining test solutions can be swollen. After 3 days mortality of mites is determined.

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

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

Apple seedlings are populated with adult Panonychus ulmi females. After 7 days, infested plants were sprayed with an aqueous emulsion containing 400 ppm of the compound to be investigated by dripping, and cultured in the greenhouse. We evaluate after 14 days. From the comparison of the number of dead dust mites on treated plants versus those on untreated plants, we determine the percentage decrease in population (% of effect).

In this test, the compounds of Tables 1 and 2 show a good effect 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 an effect 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.