AP284A

AP284A - Carboxymethlcyclopropane derivatives.

Info

Publication number: AP284A
Application number: APAP/P/1991/000308A
Authority: AP
Inventors: Manfred Boger; Peter Maienfisch
Original assignee: Ciba Geigy Ag
Priority date: 1990-07-27
Filing date: 1991-07-26
Publication date: 1993-09-10
Also published as: TW211561B; BR9103219A; IE912646A1; YU128891A; AU8138991A; MX9100388A; JPH0625073A; AP9100308A0; EP0468927A3; EP0468927A2; ZA915878B; CA2047901A1; IL98897A0

Abstract

Novel 2-(2-chloro-2-fluorocyclopropyl)-acetic acid derivatives of formula i wherein x is oxygen or -nr-, y is hydrogen, or is c1-c20alkyl, c-c7cycloalkyl, c3-c20alkenyl, c3-c20alkynyl, benzyl or aryl, each of which is unsubstituted or substituted, and r is hydrogen or c1-c6alkyl, can be used as pesticides. Especially insects and arachnids can be controlled.

Description

Carboxvmethylcyclopropane derivatives

The present invention relates to novel derivatives of 2-(2-chloro-2-fluorocyclopropyl)acetic acid, to processes and intermediates for the preparation thereof, to pesticides comprising those compounds, and to their use in pest control.

The 2-(2-chloro-2-fluorocyclopropyl)-acetic acid derivatives according to the invention comespond to formula I

CH, —o \ / Cl-C-F

CH- CH₂- C - X - Y

II (D wherein

X is oxygen or -NR-,

Y is hydrogen, or is C_rC₂₀alkyl, C₃-C₇cycloalkyl, C₃-C₂₀alkenyI, C₃-C₂₀alkynyl, benzyl or aryl, each of which is unsubstituted or substituted, and

R is hydrogen or C[-C₆alkyl.

Within the scope of the present invention, Y is preferably hydrogen, CpC^alkyl, C₃-C₇cycloalkyl, C₃-C₂₀alkenyl, C₃-C₂₀alkynyl, aryl, C₃-C₂ohaloalkenyl, C₃-C₂₀haloalkynyl; C₃-C7cycloalkyl substituted by halogen or by C_rC₄alkyl; aryl substituted by halogen, C_rC₄alkyl, Ci-C₄haloalkyl, C_rC₁₂alkoxy, Cj-Qhaloalkoxy, C₁-C₄alkylthio, nitro, cyano, benzoyl, halobenzoyl, phenoxy, halophenoxy, Cj-C₄alkylphenoxy, C₁-C₄haloalkylphenoxy, tri-CpQalkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, Ci-C₄alkylamino, di-CpQalkylamino, anilino, N-Ci-C₄alkylanilino, N-formylanilino, phenylthio or by halophenylthio; or C^C^alkyl substituted by hydroxy, halogen, di-C_rC₄alkylamino, Cj-C₄alkoxy, C_rC₄haloalkoxy, cyano, C₂-C₆alkoxyalkoxy, CpQhaloaikylthio, Cj-C₄alkylthio, Ci-C₄alkylsulfinyl, Ci*C₄alkylsulfonyl, Ci-C₄alkylsulfonyloxy, Cj-Qalkylcarbonyl, C_rC₄alkoxycarbonyl, C_rC₆alkylcarbonyloxy, C_rC₆alkoxycarbonyloxy, C₃-C₇cycloalkyl, aryl, aryloxy, anilinocarbonyloxy, benzyloxy, arylcarbonyloxy, arylthio, arylsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or by pyridyl; it being possible for the aryl and pyridyl

- 2 groups each to be substituted by halogen, Cj-C₄alkyl, Cj-Qhaloalkyl, C_rC₄alkoxy, Ci-C₄haloalk.oxy, Cj-C₄alkylthio, nitro, benzyloxy, cyano, phenoxy, halophenoxy, pyridyloxy, halopvridyloxy, C^Qhaloalkylpyridyloxy, C_l-C₄alkylthiadiazolvloxy, phenylthio or by halophenylthio.

In the definition of formula I according to the invention, the individual generic terms are to be understood as having the following meanings:

Halogen atoms that come into consideration as substituents are fluorine and chlorine and also bromine and iodine, with fluorine, chlorine and bromine being preferred. Halogen is here to be understood as being an independent substituent or part of a substituent, such as in haioalkyl, haloalkylthio, haloalkoxy, halophenylthio or halophenoxy.

Alkyl, alkvlthio, alkoxyalkoxy and alkoxy radicals that come into consideration as substituents may be straight-chained or branched. There may be mentioned as examples of such alkyl radicals methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl or pentyl, hexyl, octyl, decyl, dodecyl and their isomers. There may be mentioned as suitable alkoxy radicals inter alia: methoxy, ethoxy, propoxy, isopropoxy or butoxy and its isomers. Alkvlthio is, for example, methylthio, ethylthio, isopropykhio, propylthio or the isomers of butylthio.

If the alkyl, alkoxy, alkenyl, alkynyl or aryl groups that come into consideration as substituents are substituted by halogen, they may be only partially halogenated or also perhalogenated. The definitions given above apply here to halogen, alkyl and alkoxy. Examples of the alkyl elements of those groups are methyl substituted from one to three times by fluorine, chlorine and/or by bromine, for example CHF₂ or CF₃; ethyl substituted from one to five times by fluorine, chlorine and/or by bromine, for example CH2CF3, CF₂CF₃, CF₂CC1₃, CF₂CHC1₂, CF₂CHF₂, CF₂CFC1₂, CF₂CHBr₂, CF₂CHC1F, CF₂CHBrF or CCIFCHC1F; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or by bromine, for example CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃ or CH(CF₃)₂; butyl or one of its isomers substituted from one to nine times by fluorine, chlorine and/or by bromine, for example CF(CF₃)CHFCF₃ or CH₂(CF₂)₂CF₃.

If the alkyl, cycloalkyl or aryl groups defined under Y are substituted by other substituents, they may be mono- or poly-substituted by identical or different substituents selected from those listed. Preferably, the substituted groups contain one or two further

AP Ο Ο Ο 2 8 4

-3substituents.

The cycloalkyl radicals that come into consideration as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkenyl and alkynyl groups contain one or more, preferably not more than three, unsaturated carbon-carbon bonds. The double or triple bonds are separated from the site of linkage to the bridge X by at least one saturated carbon atom. Typical examples are allyl, methallyl, 2-butenyl, 3-butenyl, propargyl, 2-butynyl or 3-butynyl.

Aryl is an aromatic hydrocarbon radical. Aryl is preferably to be understood as being phenyl or naphthyl.

Examples of alkoxyalkoxy radicals are methoxymethoxy, methoxyethoxy, ethoxyethoxy, ethoxymethoxy, propoxymethoxy, propoxyethoxy, methoxvpropoxy, butoxymethoxy or propoxyethoxy.

Examples of alkoxycarbonyl radicals are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl or butoxycarbonyl. Alkylcarbonyl is, for example, acetyl, propionyl, butyryl or valeryl, and isomers thereof. Alkylcarbonyloxy is, for example, acetoxy, propionyloxy or butyryloxy.

In the literature, 2,2-difluorocyclopropylethane derivatives are known as pesticides from EP-A-318 425. However, these compounds are not always completely satisfactory as pesticides. There is therefore a continued need for pest control compounds having improved properties.

According to the present invention, therefore, the compounds of formula I are proposed for pest control, especially for the control of insects and representatives of the class of the Acarina.

On account of their advantageous biological activity, special mention is to be made of those sub-groups of the compounds of formula I wherein either

a) X is oxygen, -NH-, -NCH₃- or -NC₂H₅-, or

b) Y is hydrogen, C_rC₂₀alkyl, C3-C₇cycloalkyl, C₃-C₂₀alkenyl, C₃-C₂oalkynyl, phenyl,

- 4 naphthyl, C₃-C₂₀haloalkenvl. C₃-C₂₀haloalkynyl; Cj-Cjcycloalkyl substituted by fluorine, chlorine, bromine or by Cj-C',alkyl; phenyl or naphthyl each substituted by fluorine, chlorine, bromine, Cj-Cjalkyl, C^^haloalkyl, Cj-Qalkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio; or C^-C^alkyl substituted by hydroxy, fluorine, chlorine, bromine, di-Ci-C4alkvlamino, Cj^alkoxy, C₁-C₄haloalkoxy, C₂-C₆alkoxyalkoxy, C1-C4haloalkylthio, Ci-C₄alkylthio, Q^alkylsulfinyl, C₁-C₄alkylsulfonyl, C_rC₄alkylsulfonyloxy, Cj^alkylcarbonyl, Q^alkoxycarbonyl, C^Qalkylcarbonyloxy, C₃-C7cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfonyloxy or by pyridyl, it being possible for the phenyl and pyridyl groups to be substituted by fluorine, chlorine, bromine, C_rC₃alkyl, Ci-C₃haloalkyl, Ci-C₃alkoxy, Ci-C₃haloalkoxy, Ci-Qalkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio.

Of the compounds of sub-group a), preference is given to those wherein X is oxygen or -ΝΉ-.

Of sub-group b) of compounds of formula I, prominence is to be given on the one hand to those compounds wherein Y is phenyl, benzyl, naphthyl or 3-pyridylmethyl, or phenyl, benzyl, naphthyl or

3-pyridylmethyl each substituted by fluorine, chlorine, bromine, Ci-C₃alkyl, Cj-C₃haloalkyl, Ci-C₃alkoxv, Cj-Qhaloalkoxy, Cj-C^alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio. Of these compounds, preference is in turn given to those wherein X is oxygen or -NR- and R is hydrogen, methyl or ethyl.

Of sub-group b) of compounds of formula I, special mention is also to be made, on the other hand, of those compounds wherein Y is Cj-C^alkyl or Cj-C^alkyl substituted by hydroxy, fluorine, chlorine, bromine, dimethylamino, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or by phenoxy, it being possible for the phenyl or phenoxy radical to be substituted by fluorine, chlorine, bromine, phenoxy, halophenoxy or by phenylthio. Of this group of compounds, preference is given to those wherein X is oxygen or -NR- and R is hydrogen or Ci-C₄alkyl.

A very interesting group of compounds of sub-group b) of formula I comprises those compounds wherein Y is C₃-C₁₂alkenyl or C₃-Cj₂alkynyl, or is C₃-C₁₂alkenyl or C₃-C₃₂alkynvl each substituted by fluorine, chlorine or by bromine. Of this group, preference is

AP Ο Ο Ο 2 8 4 •5given to those compounds wherein X is oxygen or -NR- and R is hydrogen or C[-C₄alkyl.

Special mention is to be made also of the group of compounds of formula I wherein the radical Y has the following formula:

n (L) wherein

B is a C₂-C₆alkylene bridge,

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

E is benzyloxy, phenyl, halophenoxy, naphthoxy, pyridyloxy, halopyridyloxy,

Ci-C₄haloalkylpyridyloxy, C₁-C₄alkykhiadiazolyloxy, phenylthio or halophenylthio.

The radical E may have, for example, the following meanings: phenoxy, phenylthio,

3.5- dichloropyrid-2-yloxy, 2-pyridyloxy, benzyloxy, 3-chlorophenoxy, 3-methyl-1,2,4thiadiazol-5-yloxy, 4-fluorophenoxy, 3-fluorophenoxy, 2-fluorophenoxy,

3.5- difluorophenoxy, 3-isopropyl-1,2,4-thiadiazol-5-yloxy, 4-chlorophenoxy,

2-chlorophenoxy, 5-trifluoromethylpyrid-2-yloxy, 5-(2,2-dichloro-1,1,2-trifluoroethyl)pyrid-2-yloxy, 4-chlorophenylthio, 3,4-dichlorophenylthio and 2-naphthoxy.

Special preference is given also to those compounds of formula I wherein X is oxygen and the radical Y has the formula

wherein

B is a bridge -CH₂-CH₂-, -CH-CH₂-, CH₃

E is phenoxy, phenylthio or halophenoxy.

There may be mentioned as preferred individual compounds of formula I according to the

- 6invention:

2-(2-chloro-2-fluorocyclopropvl)-acetic acid,

2-(2-chloro-2-fluorocyclopropyl)-acetic acid benzyl ester,

2-(2-chloro-2-fluorocyclopropyl)-acetic acid 2-(4-chlorophenoxy)-ethyl ester,

2-(2-chloro-2-fluorocyclopropyl)-acetic acid 2-(4-phenoxyphenoxy)-ethyl ester and

2-(2-chloro-2-fluorocvclopropyl)-acetic acid 2-(4-phenylthiophenoxy)-ethyl ester.

The 2-(2-chloro-2-fluorocyclopropyl)-acetic acid derivatives of formula I according to the invention can be prepared by

a) reacting a 2-(2-chloro-2-fluorocyclopropyl)-acetic acid halide of formula Π

CH₂ —CH—CH₂—C-Hal

(U).

wherein Hal is chlorine or bromine, optionally in an inert solvent and in the presence of an acid-binding agent, with an alcohol or amine of formula III

H-X-Y (ΠΙ) wherein X and Y are as defined under formula I, or

b) reacting a 3-butenoic acid derivative of formula IV

H₂C == CH- CH₂- C - X - Y

II o

wherein X and Y are as defined under formula I, in an inert solvent with chlorofluorocarbene, or

c) reacting the free 2-(2-chloro-2-fluorocyclopropyl)-acetic acid of formula la

CH₂ —CH-CH₂-C-OH

II da),

AP Ο Ο Ο 2 8 4

-7in the absence or presence of an inert solvent and of a catalyst or of a water-removing agent, with an alcohol or amine of formula III.

The reaction of process a) (H + III —* I) is preferably carried out in an inert solvent that is free of hydroxy groups, in the presence of an organic base, for example pyridine,

4-dimethylaminopyridine, lutidine, collidine, trialkylamine or Ν,Ν-dialkyIaniline, or of a bicyclic, non-nucleophilic base, such as l,4-diazabicyclo[2.2.2]octane (DABCO), l,5-diazabicyclo[4.3.0]non-5-ene (DBN) or l,8-diazabicyclo[5.4.0]undec-7-ene (1.5-5) (DBU). The reaction is generally carried out at temperatures of from -30°C to +70°C, preferably from -10°C to +50°C. The reaction is advantageously carried out in the presence of a solvent or solvent mixture that is inert towards the reaction. Examples of suitable solvents are 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 ethereal compounds, such as dialkyl ethers (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, methyl ethyl ketone; compounds such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF); and mixtures of such solvents with one another. However, the reaction may also be carried out in an excess of one of the above-mentioned bases or, when the compound of formula ΙΠ is an amine (X = NR), there may be used instead of the base a second equivalent or a greater excess of the compound of formula III. The reaction is carried out under atmospheric pressure, although it could also be carried out under elevated or reduced pressure.

Suitable solvents for carrying out reaction variant b) (IV + chlorofluorocarbene —> I) are preferably ethers, such as diglvme, triglyme or tetraglyme. Chlorofluorocarbene is produced in accordance with methods known per se in the specialist literature (Burton and Hahnfeld, Fluorine Chem. Rev. 8 (1977), 119ff.). Suitable chlororiuorocarbene donors are, for example, alkali metal dichlorofluoroacetates, such as sodium dichlorofluoroacetate, or halochlorofluorohydrocarbons, such as dichlorofluoromethane.

In process variant c) (Ia + ΙΠ —»I), the reaction is advantageously carried out in the presence of water-removing reagents customary for esterification reactions, for example in the presence of a carbodiimide [dicyclohexylcarbodiimide (DCC)J or of a l-alkyl-2-halopyridinium salt, such as l-methyl-2-chloropyridinium iodide.

-8Advantageously, the reaction is then carried out in the presence of a solvent or solvent mixture that is inert towards the reaction, at temperatures of from -30°C to +70³C, preferably from -10°C to +50°C. The reaction is preferably carried out in the presence of a base, for example in the presence of an organic amine, such as a trialkylamine (trimethylamine, triethylamine, tripropylamine or diisopropylethylamine), a pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidinopyridine), a morpholine (N-methylmorpholine) or an N,N-dialkylaniline (Ν,Ν-dimethylaniline or N-methyl-N-ethylaniline). Examples of suitable solvents for this reaction are 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 ethereal compounds, such as dialkyl ethers (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; and mixtures of such solvents with one another.

When the compound of formula III is an alcohol (X = O), process variant c) may also be carried out in the presence of an acid catalyst, for example H₂SO₄, HCl or a sulfonic acid, such as methanesulfonic acid or p-toluenesulfonic acid. The reaction is advantageously carried out using an excess of the alcohol of formula III. In this process, water that is liberated can be removed from the reaction mixture continuously. A customary method for that purpose is removal of the water reaction product by distilling off an azeotrope of the solvent with water. Suitable solvents for that purpose are benzene, toluene, xylene, methylene chloride or chloroform.

In principle, the various derivatives of formula I are also obtainable by transesterification or amidation from the readily obtainable lower alkyl esters of 2-(2-chloro-2-fluorocyclopropyl)-acetic acid.

For example, the ester-type derivatives of formula I (X = 0) can be obtained by base- or acid-catalysed transesterification of the lower alkyl esters of formula lb

CH₂ — CH- CH₂- C - 0 - C,-C₄alkyl \ / ||

Cl- C - F A (lb) with the alcohols of formula Ilia

AP Ο Ο Ο 2 8 4

-9Η-Ο-Χ-Υ (Dla) wherein X and Υ are as defined under formula I. Especially suitable acid catalysts are HCl, H2SO4 or a sulfonic acid. The base used in the base-catalysed transesterification is preferably the sodium or potassium alcoholate of the alcohol of formula Ilia, which is obtainable from Dla, for example, by the addition of sodium or potassium hydride. The transesterification reaction is preferably carried out at temperatures of from -20°C to +120°C, especially from 0°C to +100°C. The alcohol component Ilia 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 (X = NR) are obtained from the lower alkyl esters of formula lb by reacting those esters with amines of formula Illb

R

I

H-N-X-Y (Hlb) wherein R, X and Y are as defined under formula I. The amidation reactions are carried out at temperatures of from 0°C to +120°C. The reactants are advantageously reacted in an inert solvent or solvent mixture. Examples of suitable solvents are 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 ethereal 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 Illb is advantageously used in excess.

Various compounds of formulae ΙΠ, Ilia and Illb and IV and their preparation are known in the literature, and some of them are available commercially. The compounds of formulae ΙΠ, Ilia, Illb and IV which have not yet been described in the literature can be obtained analogously to the known processes by customary methods of synthesis.

- 10The compounds of formula IV can be obtained from known products, by reacting

3-butenoic acid of formula V

CH₂=CH-CH₂-COOH (V), in the absence or presence of an inert solvent and of a catalyst or of a water-removing agent, with an alcohol or amine of formula ΠΙ. 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 the compounds of formula I.

The compound of formula II is novel. It was developed specifically for the synthesis of the compounds of formula I. The present invention therefore relates also to the compound of formula II.

The compounds of formulae Ia and Π are obtained in simple manner from the readily obtainable esters of formula Ib, by hydrolysing and halogenating the latter in customary manner. Similarly, the compounds of formulae Ia and Π can also be obtained from other simple esters, for example 2-(2-chloro-2-fluorocyclopropyl)-acetic acid benzyl ester. The conditions for the synthesis of the free acid of formula Ia from the basic benzyl ester or an ester of formula Ib, and the subsequent optional conversion of that acid Ia into the acid halide of formula Π, correspond to the customary conditions for an acid- or base-catalysed hydrolysis, or for the halogenation of a carboxylic acid.

The esters of formula Ib and the corresponding benzyl ester can readily be prepared by the addition of chlorofluorocarbene to 3-butenoic acid lower alkyl ester (Cj-C₄) or 3-butenoic acid benzyl ester. The reaction conditions correspond to those of reaction variant b) for the chloro fluorocarbene addition.

Unless expressly mentioned, the compounds of formula I are in the form of a mixture of two diastereoisomeric enantiomer pairs. The pure enantiomer pairs are obtained by means Of customary physical separation methods. The optically pure isomers can be obtained by using optically pure starting materials, such as RR-, RS-, SR- or SS-2-(2-chloro-2-fluorocyclopropyl)-acetic acid, or their halides, or by separating the optically pure isomers from the enantiomer pairs (racemates) by methods known per se.

For example, the optical isomers of the free acids of the general formula Ia are obtained by

AP Ο Ο Ο 2 8 4

- 11 reacting compounds of the general formula II or Ia with a chiral auxiliary reagent, for example an optically active amine or an optically active alcohol, and then separating the resulting diastereoisomers by means of physical methods (Tetrahedron 33, 2725 (1977)), such as crystallisation, distillation or solid/liquid chromatography, and subsequent hydrolytic cleavage of the resulting pure diastereoisomers, which may be carried out with either acid or base catalysis. The compounds of formula I according to the invention can be obtained in optically pure form according to process variant c) from the optical isomers of the free acid.

The mixtures of optical isomers of the general formula I that are formed during the synthesis can also be separated into the enantiomers by chromatography on chiral stationary phases, for example optically active amino acid derivatives bound to cyclodextrins, starches or to polymers (Angew. Chem. 92, 14 (1980)).

It has now been found that the compounds of formula I according to the invention are valuable active ingredients in pest control while being well tolerated by warm-blooded animals, fish and plants. The compounds according to the invention can be used especially against insects and arachnids which occur on useful plants and ornamentals in agriculture, especially in cotton, vegetable and fruit crops, in forestry, in the protection of stored goods and material stocks, and also in the hygiene sector, especially on domestic animals and productive livestock. They are effective against all or individual development stages of normally sensitive and also resistant species. Their action may manifest itself in the death of the pests immediately or only at a later date, for example at moulting, or in reduced oviposition and/or a reduced hatching rate. The above-mentioned pests include:

of 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,

- 12 Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xvlostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;

of 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.; of the order Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.;

of the order Isoptera, for example,

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

of the order Thysanoptera, for example,

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and

Scinothrips aurantii;

of 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.;

of the order Homoptera, for example,

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiorus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium comi, 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;

of the order Hymenoptera, for example,

AP ο ο η 2 8 4

Acromyrmex, Atta spp., f'ephus spp , Diprion spp., Diprioniduc, Ciipmia pol\tom;t, lupiucampa spp., I.asius pp., Moauiiiuinun pliaraonis, Ncudipiion spp., Siilcih>p'is spp. and Vespa spp.; tof the order Diptera, tor example,

Aedes spp., Antherigoiia soecata, Bibio Iionulanus, Callipbora erylhrocepliala, Ceiatilis * spp., Chrysoinyia spp., Culex spp., Cutercbra spp., Daeus spp., Drosophila nielanogaster,

Fannia spp., Gastrophilus spp., Glossina spp., Ilypodenna spp., Ilyppobosca spp.,

Liriomyza spp., Lueilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Oiseolia spp., Oseinella frit, Pcgotuyia hyoseyami, Phorbia spp., Rhagoletis pomonella, Seiara spp.,

7'

F . Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

of the order Siphon.iplera, for example,

Ceralophyltus spp., Xcnopsylla eheopis, of the order Aearina, for example,

Aearus siro, /\cena sheldoni, Aculus schlechiendali, .Amblyomma spp., Argas spp.,

Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonenius latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp.,

Sarcoptes spp., Tarsonemus spp. and Tciranyehus spp.; and of the order Thysanura, for example,

Lepisma saccharina.

In particular I He compounds of formula I are suitable especially for controlling pests in fruit and vegetable crops, such as spider miles and aphids, furthermore the compounds of fuimula I can also be used in advantageous manner for controlling parasites of warm-blooded animals, such as mites and ticks. -»'

The good pesticidal activity of the compounds of formula 1 according to the invention corresponds lo a mortality of at least 50-60 % of the mentioned pests.

The activity of the compounds of the invention and of the compositions comprising them can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaricides. Examples of suitable additives include representatives of the following classes of compounds: organophosphorus compounds, nitropbcnols and derivatives thereof, fonnamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations. ORIGINAL

- 14 The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and can therefore be formulated in know n manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymer substances. As with the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or combinations of those compounds with other insecticides or acaricides, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surfaceactive compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the Cg to C₁₂ fractions of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes, aliphatic or cycloaliphatic hydrocarbons such as cyclohexane, paraffins or tetrahydronaphthalene, alcohols such as ethanol, propanol or butanol, and glycols and their ethers and esters, such as propylene glycol, dipropylene givcol ether, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, or water, vegetable oils such as rape oil, castor oil, coconut oil or soybean oil; and, where appropriate, silicone oils.

The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acids or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of granulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of formula I to be formulated, or of the

AP Ο Ο Ο 2 8 4

- 15 · combinations of those compounds with other insecticides or acaricides, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term surfactants will also be understood as comprising mixtures of surfactants.

Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil. Mention may also be made of fatty acid methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a C₈-C₂2alkyl radical, which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and

- 16 alkylpolvpropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropvlene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C₈-C₂2alkvl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in formulation technology are described, for example, in the following publications:

McCutcheon’s Detergents and Emulsifiers Annual, MC Publishing Corp., Glen Rock, NJ, USA, 1988,

H. Stache, Tensid-Taschenbuch, 2nd edition, C. Hanser Verlag, Munich, Vienna, 1981,

M. and J. Ash, Encyclopedia of Surfactants, Vol. Ι-ΙΠ, Chemical Publishing Co., New York, 1980-1981.

The pesticidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or combinations of that compound with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations comprising considerably lower active ingredient concentrations. Typical application concentrations are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm. The rates of application per hectare are generally from 1 to 1000 g of active ingredient per hectare, preferably from 25 to _Αρ ο ο Ο 2 8 4

500 g/ha.

- 17 -

Preferred formulations have especially the following compositions (throughout, percentages are by weight):

Emulsifiable concentrates: active ingredient: surface-active agent: liquid carrier:	1 to 90 %, preferably 5 to 20 % 1 to 30 %, preferably 10 to 20 % 5 to 94 %, preferably 70 to 85 %
Dusts: active ingredient: solid carrier:	0.1 to 10 %, preferably 0.1 to 1 % 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concenffates: active ingredient: water: surface-active agent:	5 to 75 %, preferably 10 to 50 % 94 to 24 %, preferably 88 to 30 % I to 40 %, preferably 2 to 30 %

Wettable powders: active ingredient: surface-active agent: solid carrier:	0.5 to 90 %, preferably 1 to 80 % 0.5 to 20 %, preferably 1 to 15 % 5 to 95 %, preferably 15 to 90 %
Granules: active ingredient: solid carrier:	0.5 to 30 %, preferably 3 to 15 % 99.5 to 70 %, preferably 97 to 85 %

The compositions may also comprise further auxiliaries such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.

The following Examples serve to illustrate the invention, but do not limit the invention.

- 18 Preparation Examples

Example Pl: 2-(2-Chloro-2-fluorocvclopropvl)-acetic acid benzvl ester

CH, — CH- CH,- COOCH, \ / *

Cl-C- F

10.6 g of 3-butenoic acid benzyl ester are dissolved in 40 ml of diethylene glycol dimethyl ether (diglyme), and a solution of 20.3 g of sodium dichlorofluoroacetate in 40 ml of diglyme is added over a period of 4 hours at +165°C. The mixture is stirred for a further 4 hours at +165°C and then cooled. The resulting sodium chloride is separated off and then washed with a small amount of diglyme. The solvent is evaporated off under a high vacuum at +40°C and the residue is taken up in 80 ml of diethyl ether, washed twice with 20 ml of water each time, dried over sodium sulfate and concentrated by evaporation. The oily residue is then fractionated under a high vacuum, yielding

2-(2-chloro-2-fluorocycloprcpyi)-acetic acid benzyl ester in the form of a colourless liquid, b.p. 110°C/0.25 mbar, n_D ²⁰: 1.5031.

Example P2: 2-(2-Chloro-2-fluorocvclopropvl)-acetic acid

8.0 g of 2-(2-chloro-2-fluorocyclopropyl)-acetic acid benzyl ester are added dropwise, while cooling with ice, to a solution of 1.85 g of potassium hydroxide in 25 ml of methanol, and the mixture is stirred for 4 hours at room temperature. The solvent is then evaporated off, 30 ml of ether are added to the residue, and the resulting potassium salt is separated off. The salt is dissolved in 20 ml of water, acidified with 3.5 ml of concentrated HCI and extracted three times with 20 ml of ethyl acetate each time. The combined ethyl acetate phase is washed twice with 10 ml of brine each time, dried over sodium sulfate and concentrated by evaporation, yielding 2-(2-chloro-2-fluorocyclopropyl)-acetic acid in the form of a yellowish oil having a refractive index of n_D ²⁰: 1.4442.

^>00028*

- 19Example P3: 2-(2-Chloro-2-fIuorocvclopropvl)-acetic acid 2-(4-phenoxvphenoxv)-ethyl ester

CH,— CH—CH,-C00-CH,-CH,-0

Cl

mg of 4-pyrrolidinopyridine and 1.51 g of 2-(4-phenoxyphenoxy)-ethanol are added to a solution of 1.0 g of 2-(2-chloro-2-fluorocyclopropyl)-acetic acid in 20 ml of dichloromethane, and the mixture is cooled to 0°C. At a temperature of from 0°C to +5°C, 1.50 g of N.N-dicyclohexylcarbodiimide are added in portions, and the reaction mixture is then stirred at room temperature for 5 hours. The resulting Ν,Ν-dicyclohexylurea is filtered off and the filtrate is washed twice with 10 ml of water each time, dried and concentrated by evaporation. The residue is purified by column chromatography on silica gel (eluant: hexane/ethyl acetate, 9:1), yielding 2-(2-chloro-2-fluorocyclopropyl)-acetic acid 2-(4phenoxyphenoxy)-ethyl ester in the form of a slightly yellowish oil having a refractive index of n_D ²⁰: 1.5461.

Example P4: 2-(2-Chloro-2-fluorocvclopropyl)-acetic acid chloride

1.42 g of oxalyl chloride are added to a solution of 1.53 g of

2-(2-chloro-2-fluorocyclopropyl)-acetic acid in 25 ml of tetrahydrofuran and one drop of dimethylformamide, and the mixture is then stirred for one hour at room temperature. The reaction mixture is then concentrated by evaporation using a rotary evaporator at 80 mbar and at a bath temperature of +50°C.

2-(2-Chloro-2-fluorocyclopropyl)-acetic acid chloride is thus obtained in the form of a yellowish liquid.

- 20Example P5: 2-(2-Chloro-2-fluorocvclopropyl)-acetic acid 4-chloroanilide

Cl

Without further purification, the 2-(2-chloro-2-fluorocyclopropyl)-acetic acid chloride obtained in Example P4 is taken up in 40 ml of toluene, and a solution of 1.02 g of

4-chloroaniline and 0.95 ml of pyridine in 10 ml of toluene is slowly added dropwise at from 0°C to +5°C. The reaction mixture is then stirred at room temperature for 2 hours and is then washed three times with 10 ml of brine each time, dried over sodium sulfate and concentrated by evaporation. The residue is recrystallised from an ethyl acetate/hexane mixture.

2-(2-Chloro-2-fluorocyclopropyl)-acetic acid 4-chloroanilide is thus obtained in the form of a light-beige powder having a melting point of 126-128°C.

Example P6: 2-(2-Chloro-2-fluorocyclopropvl)-acetic acid 2-(4-phenoxyphenoxv)-ethyl ester

Cl .

a) 3-butenoic acid 2-(4-phenoxyphenoxy)-ethyl ester

0.05 g of 4-pyrrolidinopyridine and 17.25 g of 2-(4-phenoxyphenoxy)-ethanol are added at room temperature, with stirring, to a solution of 6.45 g of 3-butenoic acid in 100 ml of dichloromethane. At a temperature of 0°C, 17.0 g of Ν,Ν-dicyclohexylcarbodiimide are then added in portions, and the reaction mixture is stirred at room temperature for 3 hours. The reaction mixture is filtered. The precipitate which has been separated off is discarded, and the filtrate is washed with water and dried over sodium sulfate. After concentration by evaporation, the oily residue is purified by column chromatography on silica gel with hexane/ethyl acetate (9:1), yielding 20.0 g of 3-butenoic acid 2-(4-phenoxyphenoxy)-ethyl

AP Ο Ο Ο 2 8 4

- 21 ester of the formula

II

CH₂=CH—CH,—C— O—CH₂—CH;—' in the form of a colourless oil having a refractive index of Πβ²³: 1.5538.

b) 14.8 g of 3-butenoic acid 2-(4-phenoxyphenoxy)-ethyl ester are dissolved in 30 ml of diethylene glycol dimethyl ether (diglyme), and the solution is heated to +165°C with stirring. A solution of 16.9 g of sodium dichlorofluoroacetate in 30 ml of diglyme is then added dropwise at that temperature over a period of 8 hours. The mixture is stirred for a further one 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 concentrated completely by evaporation and then taken up in 40 ml of diethyl ether, washed twice with 20 ml of water each time and dried over sodium sulfate. The solvent is concentrated by evaporation and the oily residue is then purified by column chromatography on silica gel with hexane/ethyl acetate (9.T), yielding 12.5 g of 2-(2-chloro-2-fluorocyclopropyl)-acetic acid 2-(4-phenoxyphenoxy)-ethyl ester in the form of a slightly yellowish oil having a refractive index of n_D ²⁰: 1.5461.

The compounds of formula I listed in the following Tables can be prepared analogously.

- 22 Table 1:

CHCH— CH,— C — 0 — \/ Cl—C — F

Comp. No.	Y	Physical data
1.01	C-.-0	n_D ²⁰: 1.5031
1.02	H	n_D ²⁰: 1.4442
1.03	-ch₂-ch₂-o 0	n_D ²⁰: 1.5461
1.04	-CH₂— ch₂— 0 —— Cl	n_D ²⁰: 1.5168
1.05	ch₃
1.06	C₂H₅
1.07	C₃H₇-n
1.08	C₃H₇-i
1.09
1.10	C₄H₉-n
1.11	C₆H₁₃-n
1.12	CioH₂i-n
1.13	C₂oH₄i-n
1.14	CH₂C(CH₃)₃	n_D ²³: 1.4 3 3 0
1.15	ch₂ch₂oh
1.16	ch₂ch₂o-coch₃
1.17	ch₂ch₂o-cooch₃
1.18	ch₂ch₂oconhc₆h₅
1.19	ch₂ch₂oc₂h₅
1.20	ch₂ch₂och₂ch₂och₃
1.21	ch₂cci₃
1.22	CH₂CBr₃
1.23	ch₂ch₂sch₃

AP Ο Ο Ο 2 8 4

Comp. No.	Y
1.24	CH₂CH₂OCH₂C₆H₅
1.25	ch₂ch₂ci
1.26	ch₂-c₆h₅
1.27	CH(CH₃)C₆H₅
1.28	CH(CH₃)C₆H₅ (R)
1.29	CH(CH₃)C₆H₅ (S)
1.30	CH₂-C₆H₄-NO₂-(4)
1.31	CH₂-C₆H₄-NO₂-(2)
1.32	CH₂-C₆H₄-Cl-(2)
1.33	CH₂-C₆H₅-F-(4)
1.34	CH₂-C₆H₄-O-C₆H₅-(3)
1.35	-c₆h₅
1.36	-C₆H₄-O-C₆H_s-(4)
1.37	-C₆H₄-NO₂-(4)
1.38	-C₆H₄-F-(4)
1.39	“O'⁰¹ o₂n

Physical data no²³: 1.5478

1.41

1.42

1.40 -CH₂CH₂O

- 24 Comp.

No.

Physical data

1.43

1.44

1.45

1.46

1.47

-CH₂CH₂O

C^n-cycl

CjH^-cycl.

C₃H5-cycl.

F

-Γ/ο/Λ

-ch₂ -( >

1.48

1.49

1.50

1.51

1.52

1.53

1.54

1.55

1.56

1.57 -

-CH₂ -<^

-ch₂-ch=ch₂

-CH₂CH=C(CH₃)CH_;CH_;CH=C(CH₃)₂

-CH₂CH=C(CH₃)CH₂CH₂CH=C(CH₃)-CH₂CH₂CH=C(CH₃)₂

-CH₂-CHhCH ^ΐόΗ₃₃-η

-CH(CH₂CH₂CH₂CH₃)₂

-CH₂-(CH₂)₄CH₂C1

-CH₂-C(CH₃)₂CH₂

OC₂H₅

1.58

1.59

1.60

-CH₂C(CH₃)₂-O

Cl

-ch₂ch₂ch₂ch₂-c₆h₅

-ch₂ch₂o

1.61

AP Ο Ο Ο 2 8 4

-25 Comp.

No.

1.62

1.63

1.64

1.65

1.66

1.67

1.68

1.69 .

1.70

Physical data

-CH₂-CH₂-O —/ Yoch₂-/

n_D ²²: 1.5744 n_D ²²: 1.5449

m.p. 57-59°C

1.71

- 26Comp. Y Physical data

No.

1.72

1.73

1.74

1.75

1.76

1.77

1.78

1.79

1.80

1.81

AP Ο Ο Ο 2 8 4

-27Comp. Υ Physical data

No.

1.82

1.83

1.84

1.85

1.86

1.87

1.88

1.89

-(CH₂)₂-OC-(CH₂)₄CH₃

n_D ²²: 1.5472

-28Table 2:

CH₂-CH— CH₂— CO-

Comp. No.	R	Y
2.01	H	-ch₃
2.02	ch₃	-ch₃
2.03	0^13’°	*Q^H13’ⁿ
2.04	H	-C₆H₄-F-(4)
2.05	H	-C₂H₅
2.06	H	-C₃H₇-n
2.07	H	-C₃H₇-i
2.08	H	-C₄H₉-n
2.09	H	-C₄H₉-t
2.10	H	-C₆H_l3-n
2.11	H	CioFLi-n
2.12	H	-C₂oH₄₁-n
2.13	H	-CH₂C(CH₃)₃
2.14	H	-ch₂ch₂oh
2.15	H	-ch₂ch₂o-coc₆h₅
2.16	H	-ch₂ch₂o-cooch₃
2.17	H	-CH₂CH₂O-CONHC₆H;
2.18 .	H	-ch₂ch₂oc₂h₅
2.19	H	-ch₂cf₃
2.20	H	-ch₂cci₃
2.21	H	-CH(CH₃)C₆H₅
2.22	H	-CH(CH₃)C₆H₅ (R)
2.23	H	-CH(CH₃)C₆H₅ (S)
2.24	H	-ch₂-c₆h₅
2.25	H	-CH₂-C₆H₄-NO₂-(4)
2.26	H	-CH₂-C₆H₄-F-(4)
2.27	H	-CH₂-C₆H₄-Cl-(2)

Physical data

m.p. 50-52°C

AP Ο Ο Ο 2 8 4

-29Comp. R Υ

No.

Physical data

2.28

2.29

2.30

2.31

2.32

2.33

2.34

2.35

2.36

2.37

2.38

2.39

2.40

2.41

2.42

H

CH₃ ch₃

H

-c₆h₅

-C₆H₄-NO₂-(4)

-ch₂

Cl / %

-_CH₂y >

\=N

-C₆H₄-CN-(4)

-C₆H₄-CF₃-(2)

-C₆H₄-C₆H₅-(4)

-C₆H₄-CF₃-(3)

Comp. No.	R	Y
2.43	H	-C₆H₄-Cl-(4)
2.44	H	-C₆H₄-Cl-(3)
2.45	H	-C₆H₄-OCH₃-(4)
2.46	H	-C₆H₄-CH₃-(4)
2.47	H	-C₆H₄-SCH₃-(3)
2.48	H	H
2.49	H	Ci6^H3₃-n
2.50	H	*Ci₈H₃₇-n
2.51	H	-C^H^-n
2.52	H	-C^Hj^-n
2.53	H	-C₈H_l7-n
2.54	H	-CH₂(CH₃)-CH₂CH₂CH₃
2.55	H	-ch₂ch₂ch₂ch₂oh
2.56	H	-ch₂ch₂ch₂ch₂och₃ Λ-\
2.57	H	-CH₂CH₂CH₂CH₂O-SO₂ —F V-i
2.58	H	-ch₂ch₂ch₂ch₂o-so₂ch₃ Z-λ.
2.59	H	-CH₂CH₂O-CO—/ \—CI
2.60	H	\ ,/ -CH₂CH₂O-CH₂CF₃
2.61	H	-CH₂CH₂N(CH₃)₂
2.62	H	-CH₂(CH₃)-CH₂CH₂CH₂-N(CH₂CH₃)_:
2.63	H	-CH₂CH₂ J OCH₃
2.64	H	-ch₂ch₂ J \ och₃
2.65	H	-CH₂(CH₃)-C(CH₃)₃
2.66	H	-CH₂CH(OCH₂CH₃)₂
2.67	H	-ch₂-co-c₆h₅

Physical data

m.p. 126-128°C

Comp. R Υ

No.

2.68

2.69

2.70

2.71

2.72

2.73

2.74

2.75

2.76

2.77

2.78

2.79

2.80 2.81 2.82

2.83

2.84

2.85

2.86

Η

CH₃ ch₃ ch₃

Η

-CH.

2.87

2.88 ftp ο Ο Ο 2 8 4

-31 Ο

-CH₂(CH₃)-CH₂OCH₃

-CH₂CH₂-CH(CH₃)₂

-CH₂(CH₂)₇-CH=CH-(CH₂)₇CH₃ ^I8^37'ⁿ

-C₃H₇-n

-ch₂ch₂-c₆h₅

-CH₂-C₆H₄-OCH₃-(4)

-CH₂-C₆H₄-F-(2)

-CH₂-C₆H₃-F₂-(2,6)

-CH₂-C₆H₃-F₂-(2,4)

-CH₂-C₆H₃-F₂-(3,4)

-CHi-C₆H₄-C1-(4)

-CH₂-C₆H₃-Cl₂-(3,4)

-CH₂-C₆H₄-CF₃-(4)

-CH₂-C₆H₄-NO₂-(3)

-CH(C₆H₅)₂

-CH,

Physical data

-32Comp. R Y Physical data

No.

2.89

2.90

2.91

2.92

2.93

2.94

2.95

2.96

2.97

2.98

H

CH₃

H

n_D ²³: 1.5 2 97

m.p. 49-51 °C

m.p. 40-43°C

AP Ο Ο Ο 2 8 4

-33Comp. R Υ

No.

Physical data

2.99 H

2.100 H

2.101 H

2.102 H

2.103 H •CH₂CH₂CH₂-O

-CH₂CH₂CH₂CH₂-O

O —m._p. 58-6O°C

-ch₂ch₂-o —Z y~ o —Z \

C₆H₄-OCF₃-(4)

C₆H₄-Si(CH₃)₃-(4)

Cl n_D ²²: 1.4904 m.p. 94-96°C

Formulation Examples (throughout, percentages are by weight)

Example FI: Emulsifiable concentrates compound no. 1.04 calcium dodecylbenzenesulfonate castor oil polyethylene glycol ether (36 mol of ethylene oxide) tributylphenol polyethylene glycol ether (30 mol of ethylene oxide) cyclohexanone xylene mixture

a) b) c) % 40 % 50 % % 8 % 6 % %

% 4 % % 20 % % 25 % 20 %

Emulsions of any desired concentration can be produced from such concentrates by dilution with water.

Example F2: Solutions compound no. 1.03 ethylene glycol monomethyl ether polyethylene glycol

a) b) 80 % 10 %

c) d) 5 % 95 %

20%

(mol. wt. 400)	70%	-	-
N-methyl-2-pyrrolidone	20%	-	-
epoxidised coconut oil	-	1 %	5 %
petroleum fraction
(boiling range 160-190°C)	-	94%	-

The solutions are suitable for application in the form of micro-drops.

Example F3: Granules	a)	b)	c)	d)
compound no. 1.03	5 %	10%	8 %	21 %
kaolin	94%	-	79%	54%
highly dispersed silicic acid	1 %	-	13 %	7 %
attapulgite	-	90%	-	18%

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

Example F4: Dusts compound no. 1.03 highly dispersed silicic acid talcum kaolin

a) b) % 5 % % 5 % %

90%

Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.

Example F5: Wettable powders compound no. 2.43 sodium lignosulfonate sodium laurylsulfate sodium diisobutylnaphthalenesulfonate octylphenol polyethylene glycol ether (7-8 mol of ethylene oxide) highly dispersed silicic acid

a) b) c)

25 %	50%	75%
5 %	5 %	-
3 %	-	5 %
	6%	10%

-	2%	-
5 %	10%	10%

AP Ο Ο Ο 2 8 4

-35 kaolin 62 % 27 %

The active ingredient is mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F6: Emulsifiable concentrate compound no. 2.43 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (36 mol of ethylene oxide) 4 % cyclohexanone 30 % xylene mixture 50 %

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

Example F7: Dusts compound no. 2.43 talcum kaolin

a) b) % 8 %

95% %

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.

Example F8: Extruder granules compound no. 2.103 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded, granulated and then dried in a stream of air.

- 36Example F9: Coated .granules compound no. 2.43 3 % polyethylene glycol (mol. wt. 200) 3 % kaolin 94 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Example F10: Suspension concentrate
compound no. 2.43	40%
ethylene glycol	10 %
nonvlphenol polyethylene glycol
ether (15 mol of ethylene oxide)	6%
sodium lignosulfonate	10%
carboxvmethyicellulose	1 %
silicone oil in the form of a 75 %
aqueous emulsion	1 %
water	32%

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

Biological Examples

Example BI: Action against Boophilus microplus

Adult female ticks which are replete with blood are affixed to a PVC plate and covered with a cotton wool swab. For treatment, 10 ml of an aqueous test solution comprising 125 ppm of the test compound are poured over the test organisms. The cotton wool swab is then removed and the ticks are incubated for 4 weeks until oviposition has taken place. The action against Boophilus microplus manifests itself either as mortality or sterility of the females or as ovicidal action in the eggs.

In this test, compounds of Tables 1 and 2 exhibit good activity against Boophilus

AP Ο Ο Ο 2 8 4 microplus. In particular, compounds 1.01, 1.02, 1.03, 1.04, 1.62, 2.43, 2.102 and 2.103 are more than 80 % effective.

Example B2: Action against Nilaparvata lugens

Rice plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Nilaparvata lugens in this test. In particular, compounds 1.02, 1.03, 1.04, 1.62, 2.102, 2.103 and 2.024 are more than 80 % effective.

Example B3: Action against Tetranychus urticae

Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed one day later with an aqueous emulsion comprising 400 ppm of the test compound. The plants are then incubated for 6 days at 25°C and then evaluated. The percentage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Tetranychus urticae in this test. In particular, compounds 1.01, 1.02, 1.03, 1.04, 1.62, 1.66, 2.24, 2.43, 2.102 and 2.103 are more than 80 % effective.

Example B4: Action against Aphis craccivora

Pea seedlings are infested with Aphis craccivora and then sprayed with a spray mixture comprising 400 ppm of the test compound, and incubated at 20°C. Evaluation is made 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Aphis craccivora in this test.

In particular, compounds 1.01, 1.02, 1.03, 1.04, 1.62, 1.66, 2.24, 2.43 and 2.103 are more than 80 % effective.

-38Example B5: Svstemic action against Nilaparvata lugens

Pots containing rice plants are placed in an aqueous emulsion solution comprising 400 ppm of the test compound. The rice plants are then populated with larvae in the 2nd and 3rd stages. Evaluation is made 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of cicadas on the treated plants with that on untreated plants.

Compounds of Tables 1 and 2 exhibit good activity against Nilaparvata lugens in this test. In particular, compounds 1.01, 2.24 and 2.103 are more than 80 % effective.

Example B6: Action against Derraanyssus gallinae to 3 ml of a solution comprising 10 ppm of test compound, and approximately 200 mites at various stages of development, are placed in a glass container that is open at the top. The container is then closed with a cotton wool plug, shaken for 10 minutes until the mites are completely wetted, and then inverted for a short time so that the remaining test solution can be absorbed by the cotton wool. The mortality of the mites is determined 3 days later.

Compounds of Tables 1 and 2 exhibit good activity against Dermanyssus gallinae in this test. In particular, compounds 1.01, 1.03 and 1.04 are more than 80 % effective.

Example B7: Ovicidal/larvicidal action against Heliothis virescens

Egg deposits of Heliothis virescens on cotton are sprayed with an aqueous emulsion comprising 400 ppm of the test compound. 8 days later, the percentage of eggs which have hatched and the survival rate of the caterpillars are evaluated in comparison with untreated controls (% reduction in the population).

Compounds of Tables 1 and 2 exhibit good activity against Heliothis virescens in this test. In particular, compounds 1.01, 1.04, 1.14 and 2.43 are more than 80 % effective.

Claims

What is claimed is:

1. A 2-(2-chloro-2-fluorocyclopropyl)-acetic acid derivative of formula I

CH₂ — CH- CH₂- C - X - Y \ / Cl-C-F

II (I) wherein

X is oxygen or-NR-,

Y is hydrogen, or is Ci-C₂₀alkyl, C₃-C₇cycloalkyl, C₃-C₂₀alkenyl, C₃-C₂₀alkynyl, benzyl or aryl, each of which is unsubstituted or substituted, and

R is hydrogen or Cj-Cgalkyl.
2. A compound according to claim 1 wherein Y is hydrogen, Cj-C^alkyl,

C₃-C₇cycloalkyl, C₃-C₂Qalkenyl, C3-C₂₀alkynyl, aryl, C₃-C₂ohaloalkenyl, C₃-C₂₍)haloalkynyl; C₃-C7cycloalkyl substituted by halogen or by C₁-C₄alkyl; aryl substituted by halogen, C^Qalkyl, C_l-C₄haloalkyl, C_rC₁₂alkoxy, Q-Qhaloalkoxy, C₁-C₄alkylthio, nitro, cyano, benzoyl, halobenzoyl, phenoxy, halophenoxy, Ci-C₄alkylphenoxy, Cj-Qhaloalkylphenoxy, tri-Ci-C₄alkylsilyl, N-pyrrolidinyl, N-piperidinyl, N-pyrrolidin-2-onyl, N-piperidin-2-onyl, Cj-Cjalkylamino, di-C₁-C₄alkylamino, anilino, N-Cj-Qplkylanilino, N-formylanilino, phenylthio or by halophenylthio; or Cj-C^alkyl substituted by hydroxy, halogen, di-C₁-C₄alkylamino, Ci*C₄alkoxy, C[-C₄haloalkoxy, cyano, C₂-C₆alkoxyalkoxy, Ci-C₄haloalkylthio, Cj-C₄alkylthio, C_l-C₄alkylsulfinyl, Cj-C₄alkylsulfonyl, Cj-Qalkylsulfonyloxy, Ci-C₄ alkylcarbonyl, C₁-C₄alkoxycarbonyl, Cj-C₆alkylcarbonyloxy, Cj-Qalkoxycarbonyloxv, C₃-C₇cycloalkyl, aryl, aryloxy, anilinocarbonyloxy, benzyloxy, arylcarbonyloxy, arylthio, arvlsulfonyl, arylsulfinyl, arylsulfonyloxy, arylcarbonyl or by pyridyl; it being possible for the aryl and pyridyl groups to be substituted by halogen, Cj-C₄alkyl, Ci-C₄haloalkyl, C₁-C₄alkoxy, Ci-C₄haloalkoxy, Ci-C₄alkylthio, nitro, benzyloxy, cyano, phenoxy, halophenoxy, pyridyloxy, halopyridyloxy, Cj-Qhaloalkylpyridyloxy, Cj-C₄alkylthiadiazolyloxy, phenylthio or by halophenylthio.
3. A compound according to claim 1 wherein X is oxygen, -ΝΉ-, -NCH₃- or -NC₂H₅-.
4. A compound according to claim 1 wherein Y is hydrogen, CpC^alkyl,

C₃-C₇cycloalkyl, C₃-C_2Oalkenyl, C₃-C₂₀alkynyl, phenyl, naphthyl, C₃-C₂ohaloalkenyl,

-40C₃-C₂₀haloalkynyl; C₃-C₇cycloalkyl substituted by fluorine, chlorine, bromine or by Cj-C₃alkyl; phenyl or naphthyl each substituted by fluorine, chlorine, bromine, C^Cjalkyl, Ci-C₃haloalkyl, C_;-C₃alkoxy, Q-Cjhaloalkoxy, C_rC₃alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio; or CpC^alkyl substituted by hydroxy, fluorine, chlorine, bromine, di-C₁-C₄alkylamino, Ci-C₄alkoxy, Ci-C₄haloalkoxy, C₂-C₆alkoxyalkoxy, Cj-C₄haloalkylthio, C₁-C₄alkylthio, Cj-C₄alkylsulfinyl, Ci*C₄alkylsulfonyl, Cj-Qalkylsulfonyloxy, C₁-C₄alkylcarbonyl, C₁-C₄alkoxycarbonyl, Ci-C₆alkylcarbonyloxy, C₃-C₇cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfonyloxy or by pyridyl, it being possible for the phenyl and pyridyl groups to be substituted by fluorine, chlorine, bromine, Cj-C₃alkyl, Cj-^haloalkyl, C₁-C₃alkoxy, Ci-C₃haloalkoxy, Ci-C₃alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio.
5. A compound according to claim 3 wherein X is oxygen or -NH-.
6. A compound according to claim 4 wherein Y is phenyl, benzyl, naphthyl or

3-pyridylmethyl, or phenyl, benzyl, naphthyl or 3-pyridylmethyl each substituted by fluorine, chlorine, bromine, C_rC₃alkyl, Ci-C₃haloalkyl, Q-C^alkoxy, Ci-C₃haloalkoxy, Ci-C₃alkvlthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or by halophenylthio.
7. A compound according to claim 4 wherein Y is C₁-C₁₂alkyl or Cj-C^alkyl substituted by hydroxy, fluorine, chlorine, bromine, dimethylamino, methoxy, ethoxy, methoxyethoxy, ethoxyethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or by phenoxy, it being possible for the phenyl or phenoxy radical to be substituted by fluorine, chlorine, bromine, phenoxy, halophenoxy or by phenylthio.
8. A compound according to claim 4 wherein Y is C₃-C₁₂alkynyl or C₃-C_i2alkenyl, or is C₃-C₁₂alkenyl or C₃-C₁₂alkynyl each substituted by fluorine, chlorine or by bromine.
9. A compound according to claim 7 wherein X is oxygen or -NR- and R is hydrogen or Cj-C₄alkyl.
10. A compound according to claim 1 wherein the radical Y has the following formula:

AP Ο Ο Ο 2 8 4

-41 wherein

Β is a C₂-C6alkylene bridge,

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

E is benzyloxy, phenyl, halophenoxy, naphthoxy, pyridyloxy, halopyridyloxy,

C_l-C₄haloalkylpyridyloxy, Ci-C₄alkyhhiadiazolyloxy, phenylthio or halophenylthio.
11. A compound according to claim 1 wherein X is oxygen and the radical Y has the formula wherein

E is phenoxy, phenylthio or halophenoxy.
12. A compound of formula I selected from the group 2-(2chloro-2-fluorocyclopropyl)-acetic acid, 2-(2-chloro-2-fluorocyclopropyl)-acetic acid benzyl ester, 2-(2-chioro-2-fluorocyclopropyl)-acetic acid 2-(4-chlorophenoxy)-ethyl ester, 2-(2-chloro-2-fluorocyclopropyI)-acetic acid 2-(4-phenoxyphenoxy)-ethyl ester and 2-(2-chloro-2-fluorocyclopropyl)-acetic acid 2-(4-phenylthiophenoxy)-ethyl ester.
13. A process for the preparation of a compound of formula I according to claim 1, which comprises

a) reacting a 2-(2-chloro-2-fluorocyclopropyl)-acetic acid halide of formula Π

CH₂ — CH- CH₂- C - Hal (Π), wherein Hal is chlorine or bromine, optionally in an inert solvent and in the presence of an acid-binding agent, with an alcohol or amine of formula III

-42H-X-Y (III) wherein X and Y are as defined under formula I, or

b) reacting a 3-butenoic acid derivative of formula IV

H₂C = CH-CH₂-C-X-Y (IV).

O wherein X and Y are as defined under formula I, in an inert solvent with chlorofluorocarbene, or

c) reacting the free 2-(2-chloro-2-fluorocyclopropyl)-acetic acid of formula la

CH₂ — CH- CH,- C - OH \ / || ^{U λ}

Cl-C-F o in the absence or presence of an inert solvent and of a catalyst or of a water-removing agent, with an alcohol or amine of formula ΙΠ.
14. A pesticidal composition comprising as active ingredient at least one compound of formula I according to claim 1.
15. A composition according to claim 14 comprising in addition at least one carrier.
16. The use of a compound of formula I according to claim 1 for controlling pests of animals and plants.
17. Use according to claim 16 wherein the pests are plant-destructive insects and arachnids.
18. A method of controlling insects and arachnids that are harmful to animals and plants, which comprises treating the pests or their locus with an effective amount of a compound of formula I according to claim 1.
19. A 2-(2-chloro-2-fluorocyclopropyl)-acetic acid halide of formula Π

AP Ο Ο Ο 2 8 A

-43CH₂ —CH—CHj— CO Hal \ /

Cl- C - F (Π) wherein Hal is chlorine or bromine.