WO2012150207A1

WO2012150207A1 - Use of cyclopropanecarboxylic acid ester derivatives for controlling insecticide-resistant insects

Info

Publication number: WO2012150207A1
Application number: PCT/EP2012/057888
Authority: WO
Inventors: Peter Jeschke; Ralf Nauen; Arnd Voerste; Neil Berry; Naomi DYER; Peter Gibbons; Ian HALE; Weiqian David HONG; Chinyere OKPARA; Paul O´NEILL; Chandrakala Pidathala; Stephen Ward
Original assignee: Bayer Cropscience Ag
Priority date: 2011-05-04
Filing date: 2012-04-30
Publication date: 2012-11-08

Abstract

The present application relates to the use of derivatives of cyclopropanecarboxylic acid esters for controlling insecticide-resistant insects.

Description

Use of Cyclopropanecarboxylic Ester Derivatives for Control of Insecticide-Resistant Insects

The present application relates to the use of derivatives of cyclopropanecarboxylic esters for controlling insecticide-resistant insects. Resistance can be defined as an "inheritable change in the sensitivity of a pest population that is reflected in the repeated failure of a product to achieve the expected level of control when used against the pest species, according to the manufacturer's instructions." (Insecticide Resistance Action Committee, IRAC, www Cross resistance occurs when resistance to one insecticide also leads to resistance to another insecticide, even if the insect has not come into contact with the latter due to the size and rapid generation sequence of populations of animal pests the risk of developing insecticide resistance, especially if insecticides are used incorrectly or too highly.

After introduction of synthetic organic insecticides in the 1940s, eg. For example, DDT did not take long to detect the first cases of resistance, and as early as 1947, resistance to DDT was confirmed in houseflies. Two to 20 years after the introduction of each new class of insecticides (cyclodienes, organophosphates, carbamates, formamidines, pyrethroids, spinosyns, neo-nicotinoids and even Bacillus thuringensis), resistance was found in a number of key pest species (www.irac-online.org).

There are several mechanisms of resistance development. The most common is metabolic resistance. For example, resistant insects can detoxify or destroy the insecticide faster, or they excrete it faster than normal sensitive insects. Insects use their internal enzyme systems to break down insecticides. Resistant insects have increased levels or more efficient forms of these enzymes. In addition to their higher efficiency, these enzymes can also have a broad spectrum of activity, ie reduce several different insecticides. Metabolic resistance depends on the structure of the drug. Therefore, metabolic resistance is most likely to be disrupted by drugs of different chemical structure. The second most common mechanism of resistance is a change in the target structure (protein, receptor, ion channel, etc.) of the insecticide. The insecticidal action is reduced by a change in the binding site, these are usually point mutations that are inherited to the coming generations. In addition, there is resistance through behavioral change (resistant insects recognize the danger and avoid the insecticide) and penetration resistance (the insect's outer shell develops barriers that slow the insecticide's entry into the insect's body). Frequently one finds in resistant pests also a combination of several of these resistance mechanisms. - -

Insecticide resistance management (IRM) is an important agricultural task and is recommended as a critical component of integrated pest management (IPM). The most important measure under the IRM is to reduce the selection pressure in favor of resistant pests. This is achieved by using different chemical classes of insecticides and different mechanisms of action in turn, which slows down the development of resistance or can be completely prevented.

Whether a resistance mechanism responsible for the resistance of a pest to a particular insecticide makes this pest resistant to a new insecticide (cross-resistance) is difficult to predict due to the various mechanisms of resistance. In particular, in cases where the mechanism of action of the novel insecticide is unknown or in which resistance is mediated by mechanisms other than alteration of the binding site, for example by metabolic resistance, it is difficult to predict cross-resistance. There is therefore a great need for methods of controlling animal pests which are resistant to one or more classes of insecticides, in particular cyclodienes, organophosphates, carbamates, formamides, pyrethroids, spinosynes, neonicotinoids, insect growth regulators and antifeedants , which prevent a pest from eating) are resistant.

The object of the present invention was to provide a class of compounds for controlling insecticide-resistant insects, in particular from the family of Culicidae. The problem is solved, as well as other tasks not explicitly mentioned, which can be derived or deduced from the relationships discussed herein, by the use of the compounds of the formula

(I)

wherein

Ri is hydrogen, cyano, alkenyl or alkynyl,

Q is a radical of the formula (L I)

(L I)

stands in which

Y is CH or N,

Z is halogen, n is 0, 1, 2 or 3,

M is oxygen, sulfur, methylene or oxymethylene,

R 2 represents optionally substituted hetaryl, preferably pyridin-2-yl or pyridine-3 or one of the radicals from the series

wherein the arrow denotes the bond to the adjacent ring, X 1, Χι ', X "are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, Alkylthio, haloalkylthio, alkylsulinyl, haloalkylsulfmyl, alkylsulfonyl, haloalkylsulfonyl, halogen, nitro, cyano, amino, alkylamino, dialkylamino, and Yi and Y ₂ are each independently halogen or haloalkyl, preferably halogen is selected from the group of bromine or chlorine, preferably haloalkyl is trifluoromethyl, for controlling insecticide-resistant insects.

Depending on the nature of the substituents, the compounds of the formula (I) can also be present in different compositions as optical isomers or mixtures of isomers, which can optionally be separated in a customary manner.

Possible configuration of the compounds of the formula (I) are described by the formulas (I-a) to (I-d) shown below:

in which the radicals Yi, Y2, Ri and Q have the abovementioned meanings.

The compounds of the formulas (Ia), (Ib), (Ic) or (Id) can be present both as mixtures and in the form of their pure isomers. If appropriate, mixtures of the compounds of the formulas (Ia), (Ib), (Ic) or (Id) can be separated by physical methods, for example by chromatographic methods. Furthermore, the compounds of the formula (I) can be present in the two isomeric forms of the formulas (IA) or (IB), depending on the position of the substituent Ri:

(I-A) (I-B)

For reasons of clarity, only the structural formula (I) without the above-described stereochemistry will be shown in the following. However, this includes that the compound in question may optionally be present as isomer mixture (I-a), (I-b), (I-c) or (I-d) or in the other isomeric form.

Furthermore, it has been found that the novel compounds of the formula (I) can be obtained when compounds of the general formula (III)

in which

Yi and Y2 have the meaning given above, and

LG for an optionally in situ generated nucleofuge leaving group, is, with compounds of the general formula (IV)

(IV) in which R 1, R 2, M, Y, Z and n have the meaning given above, optionally in the presence of a suitable acid binder and optionally in the presence of a suitable diluent.

The compounds of the invention are generally defined by the formula (I).

Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below.

In a preferred embodiment, the compound has the general formula (II)

in which

Y is CH or N,

Z is halogen, n is 0, 1, 2 or 3,

R 2 represents optionally substituted hetaryl, preferably pyridin-2-yl or pyridin-3-yl, or one of the radicals from the series

where the arrow marks the bond to the adjacent ring,

X 1, Χι ', X "are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, Halogenalkylsulfonyl, halogen, nitro, cyano, amino, alkylamino, dialkylamino, and

Yi and Y _{2 are} bromine, chlorine or trifluoromethyl.

In a particularly preferred embodiment, the compounds have the general formula (II.1) or (II.2):

(II I) (II.2) in which

Z is hydrogen or fluorine, n is 1, one of the radicals from the series

in which the arrow marks the bond to the adjacent ring,

X 2, X 2 ', X 2 "independently of one another are C 1 -C -alkyl, C 1 -C -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halogenoalkoxy, C 1 -C 4 -haloalkylthio, C 1 -C 4 -haloalkylsulfmyl, C 1 -C 4 -alkyl C4- Halogenalkylsulfonyl, fluorine, chlorine, bromine, iodine or cyano, preferably trifluoromethyl, trifluoromethoxy, fluorine or chlorine, particularly preferably fluorine and chlorine.

In a preferred embodiment, the compounds have the general formula (Π.3),

wherein

Y is CH or N,

Ri is hydrogen, cyano, alkenyl or alkynyl, preferably cyano, - -

Z is fluorine, chlorine, bromine or iodine, preferably fluorine,

where the arrow marks the bond to the adjacent ring,

X ₂ , X ₂ ', X ₂ "are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl , Halogen, nitro, cyano, amino, alkylamino, dialkylamino, and

Y ₁ and Y ₂ independently of one another are halogen or haloalkyl, preferably halogen is selected from the series bromine or chlorine, preferably haloalkyl is trifluoromethyl.

Further very particularly preferred substituents of the radicals listed in the compounds of the formula (I) are explained in Table 1.

Table 1: Very particularly preferred compounds of the formula (I) - -

Further particularly preferred substituents of the radicals listed in the compounds of the formula (3) are explained in Table 2. Table 2: Very particularly preferred compounds of the formula (Π.3)

Particular preference according to the invention is given to compounds of the formula (I) in which a combination of the meanings listed above as being particularly preferred is present. The compounds of the formula (I) according to the invention can be prepared by customary methods known to the person skilled in the art.

If Y 1, Y 2, Z _n , Y, R 1 and R 2 have the meanings given above and M is oxygen (M = -O-) and n is 0, 1 or 2, then the compounds of the formula (Ia) according to the invention can are prepared according to the reaction steps A to D shown in Reaction Scheme I.

- -

Reaction scheme I

(La)

In the process according to the invention for the preparation of the novel compounds of the formula (Ia) as compound of the formula (IVa-1; n = O; Y = CH; R ² = 4-fluorophenoxy), for example 2- (3- (4- Fluorophenoxy) phenyl) -2-hydroxy-acetonitrile used and as a compound of formula (III), the (1R, 3R) - 3- (2,2-dibromoethyl) -2,2-dimethyl-cyclopropanecarboxylic acid used, so can the manufacturing process (Step D) by Reaction Scheme II:

Reaction scheme II

The determination of the absolute configuration can be made by X-ray structure analysis. - -

By way of example, the determination of the absolute configuration of the (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (S) -cyano [3- (3-fluorophenoxy) phenyl] methyl ester by means of anomalous Dispersion described (see Helfellungsbeispiele, Example 5b).

The compounds which are required as starting materials for preparing the process (stage D) according to the invention are generally defined by the formulas (III) and (IV).

In these formulas and (IV) (III) Yi, Y2, Z _n, Y, Ri and R2 preferably represent those radicals which have already been mentioned in connection with the description of the substances of the general formula (I) according to the invention as preferred substituents.

The compounds of formula (III) may, for. T. commercially or by literature methods according to the reaction scheme I (step C) are obtained from the corresponding 2,2-dimethyl-cyclopropanecarboxylic acids (A-l) (see also Preparation Example 1, step C).

For example, the cyclopropanecarboxylic acids (Al) are known: for Υ ', Υ ² = Br, 3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (DE-OS 2544150), (IR, 3R) -3- (2,2-dibromo-ethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (M. Elliott et al., Pestic., Sci. 1975, 6, 537-542), (1R, 3S) -3- (2,2-) Dibromoethenyl) - 2,2-dimethyl-cyclopropanecarboxylic acid (GB Pat. 1,446,304), (IS, 3S) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropane carboxylic acid (DE-OS 2544150), for Y. ¹ = CF ₃ ; Y ² = Cl, 3- (2-chloro-3,3,3-trifluoro-1-propen-1-yl) -2,2-dimethylcyclopropanecarboxylic acid (GB Pat. 2085000), (IR, 3R) - 3 - [(LZ) -2-chloro-3,3,3-trifluoro-1-propen-1-yl] -2,2-dimethylcyclopropanecarboxylic acid, ira-i'-3- (2-chloro-3, 3,3-trifluoro-1-propen-1-yl) -2,2-dimethyl-cyclopropane-carboxylic acid and (1S, 3S) -3 - (2-chloro-3,3,3-trifluoro-1-propene - 1 -yl) -2,2-dimethyl-cyclopropane-carboxylic acid, (DE-OS 2802962).

In the formulas (III) and LG, LG stands for an in situ generated nucleofuge leaving group ("Leaving Group").

Examples of compounds of the formula (III) having a nucleofugic leaving group LG are known; For example, the cyclopropanecarboxylic acid halides (II): with LG = Cl and Yi, Y2 = Br, 3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanoic acid chloride (DE-OS 2544150), (lR, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanoic acid chloride (U.S. Patent 4,342,770); with LG = Br and Yi, Y2 = Br, (1R-cw) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanoic acid bromide (FR 2407200); with LG = F and Yi, Y2 = Br, (IR-di ') - 3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropane-acid fluoride (FR 2407200); with LG = Cl and _Yi = CF ₃ ; Y ₂ = Cl, 3- (2-chloro-3,3,3-trifluoro-1-propen-1-yl) -2,2-dimethylcyclopropanecarboxylic acid chloride (S.J.Xue et al., Yingyong Huaxue 2004, 21, 319-321; ref CAS 1 3 1: 1 9 0 5 1 6, 2 0 0 4), (1R, 3R) -3 - [(1Z) -2-chloro-3,3,3-trifluoro -l-propen-1-yl] -2,2-dimethylcyclopropanecarboxylic acid chloride (WO 2003/053905). Some of the compounds of the formula (IV, n = 0) are already known or can be obtained by methods known from the literature in accordance with Reaction Scheme I (cf., Preparation Example 1, Steps A and B).

For example, the compounds of the formula (IVa-1) are prepared from optionally Z-substituted 3-aryl (hetaryl) oxybenzaldehydes (A-4) which are obtainable by stage A / method I or stage A / method II, and the compounds of the formula (A-7a) are obtained by means of a suitable carbonyl reaction (see reaction scheme I, step B).

For example, in the compounds where the radical Ri is cyano, it is corresponding substituted 2-hydroxy-acetonitrile (cyanohydrins) (IVa-1), which can be obtained by known preparation methods. Cyanohydrin formation may be carried out in the presence of alkali metal cyanides (eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkaishi 1986, 11, 169-174) or trimethylsilyl cyanide (TMS-CN, see LH McKendry, J. Labeled Comp., Radiopharm., 1984, 21, 401-408; U.S. Patent 4,221,799, see Preparation Example 1, Step B).

For example, 3- (4-bromophenoxy) -a-hydroxybenzene acetonitrile and 3- (3-fluorophenoxy) -α-hydroxybenzene acetonitrile (DE-OS 2,621,433), 4-fluoro-3- (4-fluorophenoxy) are known ) -a-hydroxybenzeneacetonitrile and 4-fluoro-3- (3-fluorophenoxy) -a-hydroxybenzene acetonitrile (German Offenlegungsschrift No. 2,739,854) or 3- (4-chlorophenoxy) -a-hydroxybenzene acetonitrile (EP Pat. A 91208).

Moreover, if, for example, in the compounds of the formulas (IV) the radical R ^{1 is} ethynyl, these are corresponding substituted 2-ethynyl-methanols (IVa-2) which are prepared by known preparation methods from optionally Z-substituted 3-aryl ( hetaryl) oxybenzaldehydes (A-4, Y = CH or N) and the compounds of the formula (A-7b) can be obtained by means of a suitable carbonyl reaction (compare to Reaction Scheme III, Step B / Method III).

- 5 -

Reaction scheme III

LEVEL B TMS-R, (A-7b)

(Method III)

z. TMS = Si (CH ₃ ) ₃ when R, CEC Li

The formation of the 2-ethynylmethanol (IVa-2) in the presence of alkali metal (trimethylsilyl) acetylidene (eg lithium (trimethylsilyl) acetylide, US-A 2010227841, compare method III in preparation example 11 , Stage B).

For example: a-ethynyl-3- (4-fluorophenoxy) -benzenemethanol (DE-OS 2,621,433) or a-ethynyl-4-fluoro-3-phenoxy) -benzenemethanol (WO 9408931) are known.

The optionally Z-substituted 3-aryl (hetaryl) oxybenzaldehydes (A-4) are either from optionally Z-substituted 3-formyl-phenylboronic acid derivatives of the formula (A-2) and (hetero) aromatic hydroxy compounds of the formula (A -3) (compare step A, method I) or from optionally Z-substituted 3-hydroxybenzaldehydes of the formula (A-5) and boronic acid derivatives of the formula (A-6) (compare step A, method II).

The optionally Z-substituted 3-formyl-phenylboronic acid derivatives of the formula (A-2) are known from the literature or accessible by methods known from the literature. For example: 4-ethoxy-3-formylphenylboronic acid (WO 2008/057497) or 4-fluoro-3-formylphenylboronic acid (WO 2003/097576) are known.

The (hetero) aromatic hydroxy compounds of the formula (A-3) are known from the literature or can be obtained by methods known from the literature (for example preparation of phenols: see Houben-Weyl, Methoden der Organischen Chemie, Volume VI / 1c). In addition, the optionally Z-substituted 3-hydroxybenzaldehydes of the formula (A-5) are known from the literature or can be obtained by methods known from the literature (for example preparation of aldehydes: see Houben-Weyl, Methoden der Organischen Chemie, Volume VII / 1, 2 Edition, p. 413). Furthermore, the boronic acid derivatives of the formula (A-6) are known from the literature or accessible by methods known from the literature (cf., Coupling Reactions with Boronic Acid Derivatives: Chem. Rev. 1995, 95, 2457-2483; Tetrahedron 2002, 58, 9633-9695, Metal-Catalyzed Cross- Coupling Reactions (Eds .: A. de Meijere, F. Diederich), 2 ^nd ed., Wiley-VCH, Weinheim, 2004).

If Yi, Y _2, Z _n, Y, Ri and R ₂ have the meanings given above and M is a methyl group (M = -CH ₂ -), and n is 0, 1, 2 or 3, can then according to the invention Compounds of formula (Ib) are prepared according to the reaction steps A to D shown in Reaction Scheme IV.

Reaction scheme IV

(Ib)

The compounds required as starting materials for preparing the process (step D) according to the invention are generally defined by the formulas (III) and (IV).

In these formulas (III), (IV) Yi, Y2, Z _n, Y, Ri and R2 preferably represent those radicals which have already been mentioned in connection with the description of the substances of the general formula (I) according to the invention as preferred substituents.

Some of the compounds of the formulas (IVb-1) are known or can be obtained by methods known from the literature in accordance with Reaction Scheme IV (cf., Preparation Example 13, Method IV, Step A). _?

For example, the compounds of the formula (IVb-1) are prepared from optionally Z-substituted 3-aryl (hetaryl) methylbenzaldehydes (A-9) which are obtainable by stage A / method IV, and the compounds of the formula (A-7a ) by means of a suitable carbonyl reaction (compare Reaction Scheme IV, step B). For example, in the compounds where the radical R ^{1 is} cyano, it is corresponding substituted 3- [hetaryl (aryl) methyl] -a-hydroxy-benzeneacetonitrile (cyanohydrins) (IVb-1), which are obtained by known preparation methods can. Cyanohydrin formation can be carried out in the presence of alkali metal cyanides (eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkishi 1986, 11, 169-174) or trimethylsilyl cyanide (TMS-CN, see LH McKendry, J. Biol. Labeled Comp., Radiopharm., 1984, 21, 401-408, U.S. Patent 4,221,799, see Preparation Example 1, Step B).

For example, 3 - [(4-fluorophenyl) methyl] -a-hydroxybenzene acetonitrile (EP-A 18 315) or 4-fluoro-α-hydroxy-3- (phenylmethyl) benzene acetonitrile (EP-A 227 415) are known , EP-A 253 536).

The (hetero) aromatic hydroxy compounds of the formula (A-2) are known from the literature or according to the methods described above, literature accessible. In addition, the optionally Z-substituted halomethyl compounds of the formula (A-8) in which halogen may be chlorine, bromine or iodine are commercially available or obtainable by the methods known from the literature (for example bromomethylation: see Houben-Weyl, Methoden Chemische Chemie, Vol. V / 4, p. 784; chloromethylation of non-activated arenes: see H. Suzuki Bull. Chem. Soc., Japan, 1970, 43, 3299). If Y 1, Y ₂ , Z _n , Y, R 1 and R 2 have the meanings given above and M is an oxyethylene group (M = -O-CH ₂ -) and n is 0, 1, 2 or 3, then the compounds of the formula (Ic) according to the invention are prepared according to the reaction steps A to D shown in Reaction Scheme V.

- -

Reaction scheme V

(Ic)

Some of the compounds of the formula (IVc-1) are known or can be obtained by methods known from the literature in accordance with Reaction Scheme V (cf., Preparation Example 17, Method V, Step A).

For example, the compounds of the formula (IVc-1) are prepared from optionally Z-substituted 3-hydroxybenzaldehydes (A-5) which are obtainable by stage A / method V, and the compounds of formula (A-7a) by means of a suitable carbonyl reaction obtained (see Reaction Scheme V, step B).

If, for example, in the compounds the radical R ^{1 is} cyano, these are corresponding substituted a-hydroxy-3- (phenylmethoxy) -benzeneacetonitriles (cyanohydrins) (IVc-1) which can be obtained by known preparation methods. Cyanohydrin formation may be carried out in the presence of alkali metal cyanides (eg sodium cyanide, see K. Ozawa et al, Nippon Noyaku Gakkaishi 1986, 11, 169-174) or trimethylsilyl cyanide (TMS-CN, see LH McKendry, J. Labeled Comp. Ratiopharm 1984, 21, 401-408, U.S. Patent 4,221,799, see Preparation Example 1, Step B) ,

For example, a-hydroxy-4-methoxy-3- (phenylmethoxy) -benzeneacetonitrile (EP-A 18 315) or a-hydroxy-3-methoxy-5- (phenylmethoxy) -benzeneacetonitrile are known (S. Weist et al. , J. Amer. Chem. Soc., 2004, 126, 5942-5943).

The optionally Z-substituted 3-hydroxybenzaldehydes of the formula (A-5) are known from the literature or can be obtained according to the methods described above, which are known from the literature.

In addition, the optionally Z-substituted halomethyl compounds of the formula (A-8), in which halogen may be chlorine, bromine or iodine, are commercially available or obtainable in accordance with the methods described above and known from the literature.

Alternatively, the reaction of compounds of the formula (IV) with the compounds of the formula (III) can also be carried out in the presence of a coupling agent for the carboxylic acid and optionally in the presence of a basic reaction auxiliary in one of the diluents given below. Suitable coupling agents for carrying out the preparation process are all those which are suitable for the preparation of an amide bond (cf., for example, Houben-Weyl, Methods of Organic Chemistry, Volume 15/2; Bodansky et al., Peptide Synthesis 2nd ed. (Wiley & Sons, New York 1976) or Gross, Meierhofer, The Peptides: Analysis, Synthesis, Biology (Academic Press, New York 1979).

In general, it is advantageous to carry out the preparation process according to the invention in the presence of diluents. Diluents are advantageously used in such an amount that the reaction mixture remains easy to stir throughout the process. Suitable diluents for carrying out the process according to the invention are all inert organic solvents.

Examples include: halogenated hydrocarbons, especially chlorinated hydrocarbons such as tetraethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene; Alcohols, such as methanol, ethanol, isopropanol, butanol; Ethers such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, anisole, phenol, cyclohexyl methyl ether, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dichlorodiethyl ether and Polyethers of ethylene oxide and / or propylene oxide; Amines such as trimethyl, triethyl, tripropyl, tributylamine, N-methylmorpholine, pyridine and tetramethylenediamine; Nitrohydrocarbons such as nitromethane, nitroethane, nitropropane, nitrobenzene, chloronitrobenzene, o-nitrotoluene; Nitriles such as acetone nitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile and compounds such as tetrahydrothiophene dioxide and dimethyl sulfoxide, tetramethylene sulfoxide, dipropyl sulfoxide, benzyl methyl sulfoxide, diisobutyl sulfoxide, dibutyl sulfoxide, diisoamyl sulfoxide; Sulfones such as dimethyl, diethyl, dipropyl, dibutyl, diphenyl, dihexyl, methylethyl, ethylpropyl, ethylisobutyl and pentamethylene sulfone; aliphatic, cycloaliphatic or aromatic hydrocarbons, such as pentane, hexane, heptane, octane, nonane and technical hydrocarbons; For example, so-called white spirits with components with boiling points in the range, for example, from 40 ° C to 250 ° C, cymene, gasoline fractions within a boiling interval of 70 ° C to 190 ° C, cyclohexane, methylcyclohexane, petroleum ether, ligroin, octane, benzene, toluene, chlorobenzene , Bromobenzene, nitrobenzene, xylene; Esters such as methyl, ethyl, butyl, isobutyl acetate, as well as dimethyl, dibutyl, ethylene carbonate; Amides such as hexamethylene phosphoric acid diamide, formamide, N-methylformamide, Ν, Ν-dimethylformamide, NN-dipropylformamide, N, N-dibutylformamide, N-methylpyrrolidine, N-methylcaprolactam, l, 3 Dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidine, octylpyrrolidone, octyl-caprolactam, 1,3-dimethyl-2-imidazolinedione, N-formyl-piperidine, N, N'-1,4-diformyl-piperazine; Ketones such as acetone, acetophenone, methyl ethyl ketone, methyl butyl ketone.

Mixtures of the solvents and diluents mentioned can also be used for the process according to the invention.

Preferred diluents for carrying out the process according to the invention are ethers, such as methyl tert-butyl ether, tetrahydrofuran or dioxane, in particular tetrahydrofuran.

The preparation of compounds of the formula (I) according to the preparation process is carried out by reacting compounds of the formula (IV) in the presence of compounds of the formula (III), if appropriate in the presence of an acid binder and, if appropriate, in one of the diluents mentioned.

The reaction time is generally 10 minutes to 48 hours. The reaction takes place at temperatures between -10.degree. C. and + 200.degree. C., preferably between + 10.degree. C. and 120.degree. C., more preferably at room temperature.

It can be worked under normal pressure in principle. Preference is given to working at atmospheric pressure or at pressures up to 15 bar and optionally under a protective gas atmosphere (nitrogen, helium or argon).

For carrying out the process according to the invention, in general from 0.5 to 4.0 mol, preferably from 0.7 to 3.0 mol, more preferably from 1.0 to 2.0 mol, of the compound of the formula ## STR3 ## per mole of compound of the general formula (IV) (III) used.

Furthermore, it is advantageous to carry out the preparation process in the presence of basic reaction auxiliaries (acid binders). As basic reaction auxiliaries for carrying out the process according to the invention, it is possible to use all suitable acid binders, such as amines, in particular tertiary amines and also alkali metal and alkaline earth metal compounds.

By way of example, mention may be made of the hydroxides, hydrides, oxides and carbonates of lithium, sodium, potassium, magnesium, calcium and barium, as well as other basic compounds such as amidine or guanine dinb as ene 7-methyl-l, 5,7-triaza bicyclo (4.4.0) dec-5-ene (MTBD); Diazabicyclo (4.3.0) nonene (DBN), diazabicyclo (2.2.2) octane (DABCO), 1,8-diazabicyclo (5.4.0) undecene (DBU), cyclohexyltetrabutyl-guanidine (CyTBG), cyclohexyltetramethylguanidine (CyTMG) , Ν, Ν, Ν, Ν-tetramethyl-l, 8-naphthalenediamine, pentamethylpiperidine, tertiary amines such as triethylamine, trimethylamine, tribenzylamine, triisopropylamine, tributylamine, tricyclohexylamine, triamylamine, trihexylamine, Ν, Ν-dimethylaniline, N, N- Dimethyl-to-luidin, N, N-dimethyl-p-aminopyridine, N-methyl-pyrrolidine, N-methyl-p ip e ri din, N-methyl-imidazole, N-methyl-pyrazole, N-methyl-morpholine, N-methyl-hexamethylenediamine, pyridine, 4-pyrrolidinopyridine, 4-dimethylaminopyridine, quinoline, α-picoline, β-picoline, isoquinoline, pyrimidine, acridine, Ν, Ν, Ν ', Ν'-tetramethylenediamine, Ν, Ν' , Ν'-tetraethylenediamine, quinoxaline, N-propyl-diisopropylamine, N-ethyl-diisopropylamine, N, N'-dimethyl-cyclohexylamine, 2,6-lutidine, 2,4-lutidine or triethyldiamine.

Tertiary amines such as trimethylamine, triethylamine or N-ethyl-N, N-diisopropylamine are preferably used.

After completion of the reaction, the entire reaction mixture is concentrated. The products obtained after work-up can be purified in the usual way by recrystallization, vacuum distillation or column chromatography (see also the Preparation Examples).

Depending on the nature of the substituents, the compounds according to the invention can be present as geometrical and / or as optically active isomers or corresponding isomer mixtures in different compositions. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. The invention thus comprises pure stereoisomers as well as any mixtures of these isomers.

The active compounds according to the invention are suitable for plant protection, favorable warm-blooded toxicity and good environmental compatibility for protecting plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and mollusks found in agriculture, horticulture, livestock, forestry, gardens and recreational facilities, supplies and materials, and the sanitary sector. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include: Pests of the genus Arthropoda, in particular of the class Arachnida eg Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia graminum , Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp. Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp., Metatetranychus spp., Neutrombicula autumnalis, Nuphersa spp., Oligonychus spp., Ornithodorus spp., Ornithonyssus spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psorop - Spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., Tetranychus spp., Trombicula alfreddugesi, Vae jovis spp., Vasates lycopersici.

From the genus of Chilopoda, e.g. Geophilus spp., Scutigera spp.

From the order or class of collembola e.g. Onychiurus armatus.

From the class of Diplopoda e.g. Blaniulus guttulatus.

From the class of Insecta, e.g. from the order of the Blattodea e.g. Blattella asahinai, Blattella germanica, Blatta orientalis, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta spp., Supella longipalpa.

From the order of Coleoptera e.g. Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agestlastica alni, Agriotes spp., Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apion spp., Apogonia spp., Atomaria spp , Attagenus spp., Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Cinticerica spp., Curculio spp , Cryptolestes ferruginus, Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Dicladispa armigera, Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus spp., Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decemlineata, Leucoptera spp., Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp., Megascelis spp., Melanotus spp., Meligethes aeneus, Melolontha spp., Migdus spp., Monochamus spp., Naupactus xanthographus , Necrobia spp., Niptus hololeucus, Oryctes rhinooceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus spp., Oxycetonia jucunda, Phedelon cochleariae, Phyllophaga spp., Phyllophaga helleri, Phyllotreta spp., Popillia japonica, Premnotrypes spp., Prostephanus truncatus, Psylliodes spp., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sitophilus oryzae, Sphenophorus spp., Stegobium paniceum, Starchus spp., Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.

From the order of Diptera, for example, Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis - capitata, Chironomus spp., Chrysomyia spp., Chrysops spp., Chrysozona pluvialis, Cochliomyia spp., Contarinia spp., Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp., Culicoides spp., Culiseta spp., Cuterebra spp., Dacus oleae, Dasyneura spp., Delia spp., Dermatobia hominis, Drosophila spp., Echinocnemus spp., Fannia spp., Gasterophilus spp., Glossina spp., Haematopota spp., Hydrellia spp., Hydrellia griseola, Hylemya spp., Hippobosca spp ., Hypoderma spp., Liriomyza spp. Lucilla spp., Lutzomyia spp., Mansonia spp., Musca spp., Oestrus spp., Oscinella frit, Paratanytarsus spp., Paralauterbordiella subcincta, Pegomyia spp., Phlebotomus spp , Phorbia spp., Phormia spp., Piophila casei, Prodiplosis spp., Psila rosae, Rhagoletis spp., Sarcophaga spp., Simulium spp, Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp. ,

From the order of Heteroptera, e.g. Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocris spp., Campylomma livida, Cavelerius spp., Cimex spp., Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp , Eusystus spp., Eurygaster spp., Helipeltis spp., Horcias nobilellus, Leptocorisa spp., Leptocorisa varicornis, Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Monaionion atratum, Nezara spp., Oebalus spp., Pentomidae Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.

From the order of Homoptera, for example, Acizzia acaciaebaileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp., Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp , Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Arytainilla spp., Aspidiela spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, Bo- reioglycaspis melaleucae, Brachycaudus helichrysi, Brachycolus spp., Brevicoryne brassicae, Cacopsylla spp., Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chondracris rosea, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Cryptoneossa spp., Ctenarytaina spp., Dalbulus spp., Dialeurodes citri, D iaphorina citri ,, Diaspis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Eucalyptolyma spp., Euphyllura spp., Euscelis bilobatus, Ferrisia spp., Geococcus coffeae, Glycaspis spp., Heteropsylla cubana, Heteropsylla spinulosa, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Macrosteles facifrons, Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisigri, Nephotettix spp., Nettigoniclla spectra, Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Oxya chinensis, Pachypsylla spp , Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Prosopidopsyl la flava, Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psyllopsis spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp. - -

Scaphoideus titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella forcifera, Sogatodes spp., Stictocephala festina, Siphoninus phillyreae, Tenalaphara malayensis, Tetragonocephela spp., Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum Trioza spp. Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.

From the order of Hymenoptera e.g. Acromyrmex spp., Athalia spp., Atta spp., Diprion spp., Hoplo- campa spp., Lasius spp., Monomorium pharaonis, Sirex spp., Solenopsis invicta, Tapinoma spp., Uracus spp., Vespa spp., Xeris spp ..

From the order of isopods e.g. Armadillidium vulgare, Oniscus asellus, Porcellio scaber.

From the order of Isoptera e.g. Coptotermes spp., Cornitermes cumulans, Cryptotermes spp., Incisperses spp., Microtermes obesi, Odontotermes spp., Reticulitermes spp.

From the order of Lepidoptera e.g. Achroia grisella, Acronica major, Adoxophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyelois transitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cecececia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheima- tobia brumata, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Conopomorpha Spp., Conotrachelus spp., Copitarsia spp., Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignocellus, Eidana saccharina, Ephestia spp., Epinotia spp., Epiphyas postvittana , Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., Hedylepta spp., Helicoverpa spp., Heliothis spp. , Hofmannophila pseudospretella, Homoeos oma spp., Homona spp., Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia mestela, Leucinodes orbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antennata, Lobesia spp., Loxagrotis albicosta, Lymantria spp., Lyonetia spp , Malacosoma neustria, Maruca testulalis, Mamstra brassicae, Melanitis leda, Mocis spp., Monopis obviella, Mythimna separata, Nemapogon cloacellus, Nymphula spp., Oiketicus spp., Oria spp., Orthaga spp., Ostrinia spp., Oulema oryzae, Panolis flammea, Parnara spp., Pectinophora spp., Perileucoptera spp., Phthorimaea spp., Phyllocnistis citrella, Phyllonorcter spp., Pieris spp., Platynota stultana, Plodia interpunctella, Plusia spp., Plutella xylostella, Prays spp., Prodenia Spp., Protoparce spp., Pseudaletia spp., Pseudaletia unipuncta, Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Scirpophaga innotata, Scotia segetum, Sesamia spp., Sesamia inferens, Sparganothis spp., Spodoptera spp ., Spodoptera praefica, Stathmopoda spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thermesia gemmata lis, Tinea cloacella, Tinea pellionella, Tineola bisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., Tryporyza incertulas, Tuta absoluta, Virachola spp ..

From the order of Orthoptera or Saltatoria e.g. Acheta domesticus, Dichroplus spp., Gryllotalpa spp., Hieroglyphus spp., Locusta spp., Melanoplus spp., Schistocerca gregaria.

From the order of Phthiraptera e.g. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloera vastatrix, Phtirus pubis, Trichodectes spp.

From the order of Psocoptera eg Lepinotus spp., Liposcelis spp. - 5 -

From the order of siphonaptera e.g. Ceratophyllus spp., Ctenocephalides spp., Pulex irritans, Tunga penetrans, Xenopsylla cheopsis.

From the order of Thysanoptera e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips hevens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp.

From the order of Zygentoma (= Thysanura), z. Ctenolepisma spp., Lepisma saccharina, Lepismo-inquilinus, Thermobia domestica.

From the class of Symphyla e.g. Scutigerella spp ..

Pests of the Mollusca strain, in particular of the bivalve class, e.g. Dreissena spp., As well as from the class Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.

Animal parasites from the strains of Plathelminthes and Nematoda, e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocollus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., On- chocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosome spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp. , Trichuris trichuria, Wuchereria bancrofti.

Plant pests from the strain of Nematoda, i. plant parasitic nematodes, in particular Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus spp., Trichodorus spp., Tylenchulus spp, Xiphinema Spp., Helicotylenchus spp., Tylenchorhynchus spp., Scutellonema spp., Paratrichodorus spp., Meloinema spp., Paraphelenchus spp., Aglenchus spp., Belonolaimus spp., Nacobbus spp, Rotylenchulus spp., Rotylenchus spp., Neotylenchus spp. Paraphelenchus spp., Dolichodorus spp., Hoplolaimus spp., Punctodera spp., Criconemella spp., Quinisulcius spp., Hemicycliophora spp., Anguina spp., Subanguina spp., Hemicriconemoides spp., Psilenchus spp., Pseudohalenchus spp., Criconemoides spp ., Cacopaurus spp.

Furthermore, from the sub-kingdom of protozoa, the order of coccidia can be determined, e.g. Fight Eimeria spp.

The active compounds according to the invention are particularly suitable for controlling pyrethroid-resistant insects. Preference is given to pyrethroid-resistant insects which originate from the family of Culicidae, Muscidae or Blattidae. Particularly preferred are those insects which originate from the family of Culicidae. Most preferred are the insects selected from the genera group - -

Aedes aegypti, Aedes albopictus, Anopheles stephensi, Culex quinquefasciatus, Anopheles albimanus, Anopheles funestus, Anopheles gambiae, Culex pipiens pallens, Anopheles minimus, Anopheles arabiensis and Anopheles sacharovi. Particularly preferred are the insects are selected from the group of the genera Culex quinquefasciatus and Anopheles gambiae. The compounds according to the invention can also be used in certain concentrations or application rates as herbicides, safeners, growth regulators or agents for improving plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including anti-viral agents) or as anti-MLO agents (Mycoplasma -like-organism) and RLO (Rickettsia-like-organism). They can also be used as intermediates or precursors for the synthesis of other active ingredients.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural products, active ingredient impregnated synthetic materials, fertilizers and microencapsules in polymeric materials.

These formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. The preparation of the formulations is carried out either in suitable systems or before or during use.

Excipients which can be used are those which are suitable for imparting special properties to the composition itself and / or preparations derived therefrom (for example spray liquor, seed dressing), such as certain technical properties and / or specific biological properties. Typical auxiliaries are: extenders, solvents and carriers. As extender, e.g. Water, polar and non-polar organic chemical liquids e.g. from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone ), Esters (including fats and oils) and (poly) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).

In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as _?

Cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethyl sulfoxide, and water.

Suitable solid carriers are: e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules are suitable: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are non-ionic and / or ionic substances, e.g. from the classes of alcohol POE and / or POP ethers, acid and / or POP-POE esters, alkyl-aryl and / or POP-POE ethers, fatty and / or POP-POE adducts, POE and / or POP polyol derivatives, POE and / or POP sorbitol or sugar adducts, alkyl or aryl sulfates, sulfonates and phosphates or the corresponding PO ether adducts. Further suitable oligo- or polymers, e.g. starting from vinylic monomers, from acrylic acid, from EO and / or PO alone or in combination with e.g. (poly) alcohols or (poly) amines. Furthermore, find use lignin and its sulfonic acid derivatives, simple and modified celluloses, aromatic and / or aliphatic sulfonic acids and their adducts with formaldehyde.

Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-like polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Other additives may be fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Stabilizers, such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve the chemical and / or physical stability, may furthermore be present. The formulations generally contain between 0.01 and 98% by weight of active ingredient, preferably between 0.5 and 90%.

The active ingredient according to the invention may be present in its commercial formulations as well as in the formulations prepared from these formulations in admixture with other active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals.

A mixture with other known active ingredients, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or with agents for improving the plant properties is possible. The active compounds according to the invention may also be present in the form of insecticides in their commercial formulations and in the forms prepared from these formulations in admixture with synergists. Synergists are compounds which increase the effect of the active ingredients without the added synergist itself having to be active.

The active compounds according to the invention may furthermore, when used as insecticides in their commercial formulations and in the forms of use prepared from these formulations, be present in mixtures with inhibitors which reduce degradation of the active ingredient after application in the environment of the plant, on the surface of plant parts or in plant tissues ,

The active ingredient content of the application forms prepared from the commercial formulations can vary widely. The active ingredient concentration of the application forms can be from 0.00000001 up to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.

The application is done in a custom forms adapted to the application.

According to the invention, all plants and parts of plants can be treated. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant breeders' rights. Plant parts are understood to mean all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, as well as roots, tubers and rhizomes become. The plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds. The treatment according to the invention of the plants and parts of plants with the active ingredients takes place directly or by acting on their environment, habitat or storage space according to the usual treatment methods, eg by dipping, spraying, evaporating, atomizing, spreading, brushing, injecting and in propagation material, in particular in seed, furthermore by single-layer or multi-layer encapsulation.

As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, wild-type or plant species obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and plant cultivars and their parts are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms "parts" or "parts of plants" or "plant parts" have been explained above.

It is particularly preferred according to the invention to treat plants of the respective commercially available or in use plant cultivars. Plant varieties are plants with new traits that have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also give rise to superadditive ("synergistic") effects. For example, reduced application rates and / or extents of the spectrum of action and / or enhancement of the effect of the substances and agents that can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering efficiency, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products possible, which exceed the actual expected effects.

The preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits"). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products. Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance the plants against certain herbicidal active ingredients. Examples of transgenic plants are the important crops such as cereals (wheat, rice), corn, soybeans, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and Grapes), with special emphasis on maize, soya, potato, cotton, tobacco and oilseed rape. Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins formed in the plants, in particular those produced by the genetic material from Bacillus thuringiensis (for example by the genes CrylA (cf. a), CrylA (b), CrylA (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) are produced in the plants (hereinafter "Bt plants"). Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are also particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene). The genes which confer the desired properties ("traits") can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD ^® (for example maize, cotton, soya beans), KnockOut ^® (for example maize), StarLink ^® (for example maize), Bollgard ^® ( cotton), NuCOTN ^® (cotton) and NewLeaf ^® (KAR toffel) are sold. Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties may be mentioned, under the trade names Roundup Ready ^® (tolerance to Gly phosate example maize, cotton, soya bean), Liberty Link ^® (tolerance to phosphinotricin, for example oilseed rape), IMI ^® (Tolerance to imidazolinone) and STS ^® (tolerance to sulfonylureas eg corn). As herbicide-resistant (conventionally grown on herbicide tolerance) plants are also sold under the name Clearfield ^® varieties (eg corn). Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.

The listed plants can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active substance mixtures according to the invention. The preferred ranges given above for the active compounds or mixtures also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the compounds or mixtures specifically mentioned in the present text. - - Production examples

Example 1 (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [3- (4-fluorophenoxy) phenyl] methyl ester

Step A (Method I): 3- (4-fluorophenoxy) benzaldehyde (cf also DE-OS 2 615 435)

To a mixture of 2.25 g (15 mmol) of 3-formylphenylboronic acid (cf., also EP 1 167 371 A2) and 1.12 g (10 mmol) of 4-fluorophenol in 100 ml of anhydrous dichloromethane were successively freshly dried 4A molecular sieves , 1.81 g (10 mmol) of copper (II) acetate and 7, 0 mL (50 mmol) of triethylamine. Subsequently, the reaction mixture was stirred for 24 hours at room temperature and filtered through silica gel. Thereafter, the organic phase was separated in vacuo and the remaining crude product by flash chromatography (silica gel, eluent: 10% ethyl acetate: hexanes). This gives 1.25 g (58% of theory) of 3- (4-fluorophenoxy) benzaldehyde as a pure product.

Step B: 2- (3- (4-fluoropheno

0.19 g (0.9 mmol) of 3- (4-fluorophenoxy) benzaldehyde (step A) were stirred in 5 ml of dry dichloromethane under an inert gas atmosphere (nitrogen). Thereafter, 0.34 ml (2.7 mmol) of trimethylsilyl cyanide and 0.013 ml (0.09 mmol) of triethylamine were added, and the reaction mixture was stirred at room temperature for 2 hours. Subsequently, the reaction mixture was dissolved in 2 ml of THF. After addition of 2 ml of 2N hydrochloric acid was stirred for a further two hours at room temperature. The THF was distilled off in vacuo and the remaining residue was diluted with water. After extraction with ethyl acetate, the combined organic phases were dried over magnesium sulfate and concentrated in vacuo. The remaining crude product was purified by flash chromatography (silica gel eluent: 30% ethyl acetate: hexane). This gives 208 mg (95% of theory) of pure 2- (3- (4-fluorophenoxy) phenyl) -2-hydroxy-acetonitrile. - -

Step C: (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid chloride (also see

US Pat. 4,342,770)

1.19 g (4.0 mmol) of (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropane carboxylic acid (compare also M. Eliott et al., Pesticide Sci., 6, 537 -542, 1975) were dissolved in 10 ml of dry dichloromethane and 4.0 ml (8.0 mmol) of oxalyl chloride and a catalytic amount (2 drops) of DMF were added under an inert gas atmosphere (nitrogen). After stirring for two hours at room temperature, the solvent was removed in vacuo and the crude (IR, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride used for the next reaction step (Step D).

Step D: (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid cyano [3- (4-fluorophenoxy) phenyl] methyl ester 327 mg (1.1 mmol) of the product obtained in step C (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride was stirred under inert gas atmosphere in 2 ml of THF and added dropwise at 0 ° C with a solution of 243 mg (1.0 mmol ) 2- (3- (4-fluorophenoxy) phenyl) -2-hydroxy-acetonitrile in 3 mL of anhydrous THF and then with 153 mL (1.1 mmol) of triethylamine. Thereafter, the reaction mixture was stirred for 2 hours at room temperature, then treated with saturated brine and extracted with ethyl acetate. The organic extracts were combined and washed successively with 1N hydrochloric acid, saturated sodium bicarbonate solution and saturated brine. Subsequently, the separated organic phase was dried over magnesium sulfate, and after filtration from filtered under reduced pressure. A yellow oil is obtained which is purified by column chromatography (silica gel, eluent: 5% ethyl acetate: hexane) 460 mg (80% of theory) (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl- cyclopropanecarboxylic acid cyano [3- (4-fluorophenoxy) phenyl] methyl ester as a colorless oil.

Mixture of diastereomers I and II

ES HRMS: m / z found: 543.9561, 545.9510, 547.9536 (MNa ⁺ ).

C22Hi8FN0 ₃ Br ₂ (MNa ⁺⁾ calculated: 543.9535, 545.9515, 547.9494.

lH NMR (400 MHz, CDC1 ₃ ) δ 7.29 (t, J = 8.0 Hz, 1H), 7.14 (d, J = 7.8 Hz, 1H), 7.02 (dt, J = 8.4 Hz, 1H), 6.99 - 6.86 ( m, 5H), 6.61 (d, J = 6.3 Hz, 1H), 6.59 (d, J = 6.4 Hz, 1H), 6.28 (s, 1H), 6.23 (s, 1H), 1.98 (t, J = 8.4 Hz, 1H), 1.95 (t, J = 8.4 Hz, 1H), (1.82 (d, J = 8.4 Hz, 1H), 1.21 (s, 3H), 1.19 (s, 3H), 1.15 (s, 3H) , 1.10 (s, 3H) ppm.

1 ³ C NMR (100 MHz, CDCl 3) δ 168.91, 168.87, 160.85, 158.96, 158.92, 158.44, 152.36, 152.34, 152.32, 134.24, 133.97, 132.94, 132.79, 131.16, 122.56, 122.47, 121.57, 121.55, 121.49, 121.46 , 119.98, 1 19.95, - -

117.63, 117.50, 117.17, 1694, 116.46, 16.32, 91.32, 91.10, 62.79, 62.72, 36.89, 36.85, 31.49, 31.42, 29.38, 29.19, 28.55, 28.53, 15.38, 15.36 ppm.

The (1: 1) mixture of diastereomers can be separated by preparative HPLC (column Knauer, normal phase, dimension: 250 × 20 mm, filling: Eurosper 100-5 Si, detection of the wavelength at 254 nm). The column was eluted with 8% ethyl acetate / hexane at a flow rate of 5 mL / min.

Example la -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (R) -cyan [3- (4-

Retention time (prep HPLC): 35-38 min.

ES HRMS: m / z found: 543.9561, 545.9510, 547.9536 (MNa ⁺ )

C22Hi8FN0 ₃ Br ₂ (MNa ⁺⁾ calculated: 543.9535, 545.9515, 547.9494.

1H NMR (400 MHz, CDCl ₃ ) δ 7.41 (t, J = 8.0 Hz, 2H), 7.29 - 7.21 (m, 1H), 7.16 - 6.96 (m, 5H), 6.68 (d, J = 8.4 Hz), 6.32 (s, 1H), 2.05 (t, J = 8.4Hz, 1H), 1.91 (d, J = 8.4Hz, 1H), 1.31 (s, 3H), 1.29 (s, 3H) ppm. ¹³ C NMR (100 MHz, CDCl3) δ 168.89, 160.86, 158.94, 158.45, 152.30, 133.92, 132.86, 131.13, 122.52, 121.54, 119.96, 117.60, 117.16, 116.93, 116.43, 91.07, 62.74, 36.86, 31.48, 29.39, 28.57, 15.34 ppm.

Example Ib (10A, 3A) -3- (2,2-dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid (5) cyanogen [3- (4-fluorophenoxy) phenyl] methyl ester

Retention time (prep HPLC): 40-42 min.

ES HRMS: m / z found: 543.9561, 545.9510, 547.9536 (MNa ⁺ ).

C22Hi8FN0 ₃ Br ₂ (MNa ⁺⁾ calculated: 543.9535, 545.9515, 547.9494.

1H, 7.11 (t, J = 5.6Hz, 1H), 7.01-6.84 (m, 6H), 6.57 (d, J = 8.3Hz) , 1H), 6.24 (s, 1H), 1.95 (t, J = 8.4Hz, 1H), 1.78 (d, J = 8.4Hz, 1H), 1.12 (s, 3H), 1.07 (s, 3H) ppm.

¹³ C NMR (100 MHz, CDCl 3) δ 168.87, 160.88, 158.97, 158.46, 152.30, 152.28, 134.19, 132.70, 131.15, 122.44, 121.56, 121.48, 119.93, 117.47, 117.16, 116.93, 116.30, 91.33, 62.68, 36.90, 31.40, 29.20, 28.55, 15.37 ppm. In an analogous manner, Examples 2 to 5 were obtained.

Example 2b (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (S) -cyano [3- (4-chlorophenoxy) phenyl] methyl ester

ES HRMS: m / z found: 559.9224, 561.9194, 563.9201 (MNa ⁺ ).

C22Hi8ClN0 ₃ Br ₂ (MNa ⁺ ) calcd: 559.9420, 561.9210, 563.9199.

lH NMR (400 MHz, CDC1 ₃₎ δ 7:41 (t, J = 8.0 Hz, 1H), 7:32 (d, J = 8.8 Hz, 2H), 7.27 (d, J = 7.8 Hz, 1H), 7.14 (s, 1H), 7.05 (d, J = 8.2 Hz, 1H), 6.96 (d, J = 8.8 Hz, 2H), 6.70 (d, J = 8.3 Hz, 1H), 6.38 (s, 1H), 2.08 (t, J = 8.4 Hz, 1H), 1.92 (d, J = 8.4 Hz, 1H), 1.25 (s, 3H), 1.20 (s, 3H) ppm. ¹³ C NMR (100 MHz, CDCl3) δ 168.86, 158.21, 155.35, 134.31, 132.74, 131.25, 130.44, 129.57, 122.94, 121.03, 120.60, 118.11, 116.28, 91.36, 62.66, 36.92, 31.41, 29.23, 28.56, 15.39 ppm ,

Example 3b (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (S) -cyan [3- (4-fluorophenoxy) phenyl] methyl ester

ES HRMS: m / z found: 490.0790 (MNa ⁺ ). C23H18CIF4NO3 (MNa ⁺ ) calculates: 490.0809.

'H NMR (400 MHz, CDCl3) δ 7.27 (t, J = 8.0 Hz, 1H), 7.11 (t, J = 6.3 Hz, 1H), 7.01-6.83 (m, 5H), 6.70 (d, J = 9.2 Hz, 1H), 6.25 (s, 1H), 2.16 (t, J = 8.7 Hz, 1H), 1.91 (d, J = 8.3 Hz, 1H), 1.17 (s, 3H), 1.09 (s, 3H) ppm , ¹³ C NMR (100 MHz, CDCl 3) δ 168.74, 160.91, 159.01, 158.49, 152.27, 152.24, 134.03, 131.16, 129.23, 129.18, 122.43, 121.57, 121.49, 1 19.97, 1 17.45, 1 17.16, 1 16.93, 1 16.16 , 62.84, 32.38, 32.10, 30.18, 28.52, 15.18 ppm.

Example 4a (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (R) -cyan [3- (3-fluorophenoxy) phenyl] methyl ester - 5 -

ES HRMS: m / z found: 490.0797 (MNa ⁺ ). C23H18CIF4NO3 (MNa ⁺ ) calculates: 490.0809. ¹ H NMR (400 MHz, CDCl 3) δ 7.39 (d, J = 6.8 Hz, 1H), 7.36 - 7.26 (m, 2H), 7.17 (dd, J = 11.4, 4.9 Hz, 1H), 7.06 (s, 1H ), 6.96 (d, J = 8.1 Hz, 1H), 6.74-6.68 (m, 1H), 6.66 (d, J = 8.2 Hz, 1H), 6.59 (d, J = 10.0 Hz, 1H), 6.29 (s , 1H), 6.20 (s, 1H), 2.16-2.10 (m, 1H), 1.92 (d, J = 8.3 Hz, 1H), 1.20 (s, 6H) ppm.

¹³ C NMR (100 MHz, CDCl3) δ 166.95, 166.93, 163.29, 160.83, 156.38, 156.27, 155.78, 131.99, 130.37, 129.37, 129.35, 129.25, 128.97, 127.80, 127.51, 127.47, 127.46, 127.44, 126.39, 121.49, 119.35, 116.91, 114.52, 114.36, 112.98, 112.95, 109.40, 109.18, 105.30, 105.05, 61.43, 60.97, 30.56, 30.16, 30.13, 26.62, 13.28, 13.26 ppm.

Example 4b (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethylcyclopropanecarboxylic acid (S) -cyan [3- (3-fluorophenoxy) phenyl] methyl ester

ES HRMS: m / z found: 490.0797 (MNa ⁺ ). C23H18CIF4NO3 (MNa ⁺ ) calculates: 490.0809.

'H NMR (400 MHz, CDCl3) δ 7.31 (t, J = 8.0 Hz, 1H), 7.17 (t, J = 7.3 Hz, 1H), 7.05 (s, 1H), 6.98 (d, J = 8.2 Hz, 1H), 6.76-6.66 (m, 3H), 6.59 (d, J = 10.0 Hz, 1H), 6.27 (s, 1H), 2.16 (t, J = 8.7 Hz, 1H), 1.92 (d, J = 8.3 Hz, 1H), 1.17 (s, 3H), 1.09 (s, 3H) ppm.

¹³ C NMR (100 MHz, CDCl3) δ 166.83, 163.28, 160.82, 156.35, 156.25, 155.80, 132.30, 129.39, 129.36, 129.26, 127.30, 127.25, 121.41, 119.34, 116.80, 114.20, 113.03, 113.00, 109.43, 109.22, 105.29, 105.05, 60.89, 30.47, 30.22, 28.30, 26.63, 13.27 ppm.

Example 5b (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid (S) -cyano [3- (3-fluorophenoxy) phenyl] methyl ester -

ES HRMS: m / z found: 543.9561, 545.9510, 547.9536 (MNa ⁺ ). C22Hi8FN0 ₃ Br ₂ (MNa ⁺⁾ calculated: 543.9535, 545.9515, 547.9494. ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.44 (t, J = 8.0 Hz, 1H, Ar-H), 7.32-7.29 (m, 2H, Ar-H), 7.18 (t, J = 2.0 Hz, 1H , Ar-H), 7.10 (d, J = 8.1 Hz, 1H, Ar-H), 6.85 (td, J = 8.3, 2.4 Hz, 1H, Ar-H), 6.80 (dd, J = 8.2, 2.3 Hz , 1H, Ar-H), 6.74 (t, J = 2.4 Hz, 1H, Ar-H), 6.70 (d, J = 8.4 Hz, 1H, -CH = CCBr ₂ ), 6.40 (s, 1H, -CH - CN), 2.08 (t, J = 8.4 Hz, 1H, CH), 1.92 (d, J = 8.4 Hz, 1H, CH), 1.25 (s, 3H, CH ₃ ), 1.21 (s, 3H, CH ₃ ) ppm.

¹³ C NMR (100 MHz, CDCl 3) δ 168.85, 165.17, 162.71, 158.28, 158.18, 157.65, 134.35, 132.67, 131.26, 131.15, 123.32, 121.19, 1 18.71, 1 16.23, 1 14.91, 1 14.88, 1 1 1.30, 1 1 1.09, 107.18, 106.94, 91.35, 62.62, 36.92, 31.40, 29.22, 28.54, 15.35 ppm.

Determination of the absolute configuration by means of anomalous dispersion (X-ray determination):

The X-ray structure determination of a suitable single crystal of example 5b was carried out with a Bruker D8 diffractometer with APEX CCD detector and a 1.5 kW graphite monochromatic Mo radiation. Structure resolution was performed using X-SEED (Barbour, LJ "X-Seed - A Software tool for supramolecular crystallography" J. Supramol. Chem., 2001, 1, 1 89-191), a graphical interface to SHELX97 (G. Sheldrick, SHELX-97 Programs for Solving and Refining Crystal Structures, Institute of Inorganic Chemistry, University of Tammanstrasse 4, D-3400 Gottingen, Germany, 1997). The value of the absolute structure parameters (0.01 (1)) confirms the absolute configuration of Example 5b.

Crystal data:

C22Hi80 ₃ Br ₂ FN (523.19 g / mol) colorless platelets, 0.50 x 0.3 x 0.3 mnr

Space group: orthorhombic, 2i2i2i (No. 12549 reflections collected, 4452 unique

6.2327 (19) Ä R _in t = 0.0216 12.196 (4) Ä Final GooF = 1.011 c = 12.460 (3) Ä Rl = 0.0256

V = 2054.1 (1 1) Ä ^; wR2 = 0.0634 _?

Z = 4 279 parameters, 2 restraints μ = 3,979 mm ^"1

D _c = 1.692 g / cm ³ T = 100 (2) K

Example 6 (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [4-fluoro-3- (4-fluorophenoxy) phenyl] methyl ester

Step A (Method II): 4-fluoro-3- (4-fluorophenoxy) benzaldehyde (cf also DE-OS 2,739,854)

To a mixture of 280 mg (2 mmol) of 4-fluoro-3-hydroxybenzaldehyde and 560 mg (4 mmol) of 4-fluorophenylboronic acid in 20 mL of anhydrous dimethylene chloride were successively freshly activated 4A molecular sieves, 364 mg (2 mmol) Copper (II) acetate and 1.39 mL (10 mmol) of triethylamine. The entire reaction mixture was stirred for 24 hours at room temperature. Thereafter, the reaction mixture was filtered through silica gel and the solvent was removed in vacuo. The residual crude product was purified by flash chromatography (silica gel, eluent: 10% ethyl acetate / hexane). This gives 230 mg (49% of theory) of pure 4-fluoro-3- (4-fluorophenoxy) benzaldehyde, which can be reacted further in accordance with Example 1 (see stages B-D). Mixture of diastereomers I and II

ES HRMS: m / z found: 561.9464, 563.9412, 565.9372 (MNa ⁺ ).

C22Hi ₇ F ₂ N03Br2 (MNa ⁺⁾ calculated: 561.9441, 563.9420, 565.9400. ¹ H NMR (400 MHz, CDC1 ₃ ) δ 7.36-2.24 (m, 3H), 7.18 (t, J = 7.3 Hz, 1H), 7.12-7.03 (m, 1H), 7.00 (dd, J = 9.0, 4.3 Hz, 1H), 6.70 (d, J = 6.5 Hz, 1H), 6.68 (d, J = 6.5 Hz, 1H), 6.35 (s, 1H), 6.30 (s, 1H), 2.12-2.05 (m, 1H ), 1.92 (d, J = 8.4 Hz, 1H), 1.32 (s, 3H), 1.30 (s, 3H), 1.26 (s, 3H), 1.20 (s, 3H) ppm.

¹³ C NMR (100 MHz, CDCl 3) δ 168.82, 168.80, 160.71, 160.70, 158.30, 158.29, 156.52, 156.47, 154.00, 153.95, 152.66, 152.64, 152.62, 145.60, 145.55, 145.49, 145.43, 132.85, 132.68, 129.32, 129.29, 129.03, 128.99, 124.54, 124.46, 124.45, 124.37, 120.75, 120.74, 120.63, 120.61, 119.92, 119.88, 119.84, 119.79, 118.50, 1 18.31, 117.12, 1 16.88, 116.29, 1 16.14, 91.37, 91.13, 62.29, 62.24, 36.91, 36.88, 31.43, 31.35, 29.46, 29.24, 28.51, 28.48, 15.32, 15.30 ppm.

Example 6b (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid (S) -cyan [4-fluoro-3- (4-fluorophenoxy) phenyl] methyl ester

ES HRMS: m / z found: 561.9464, 563.9412, 565.9372 (MNa ⁺ ).

C22Hi ₇ F ₂ N03Br2 (MNa ⁺⁾ calculated: 561.9441, 563.9420, 565.9400. ¹ H NMR (400 MHz, CDC1 ₃ ) δ 7.33-2.22 (m, 1H), 7.14 (d, J = 7.5 Hz, 1H), 7.09-6.95 (m, 2H), 6.67 (d, J = 8.3 Hz, 1H), 6.32 (s, 1H), 2.08 (t, J = 8.4Hz, 1H), 1.89 (d, J = 8.4Hz, 1H), 1.24 (s, 3H), 1.18 (s, 3H) ppm.

¹³ C NMR (100 MHz, CDCl3) δ 168.78, 160.73, 158.32, 156.49, 153.97, 152.63, 152.61, 145.63, 145.51, 132.61, 129.30, 129.26, 124.42, 124.34, 120.61, 120.60, 119.91, 119.83, 118.50, 118.31, 117.11, 116.88, 116.11, 91.41, 62.22, 36.93, 31.35, 29.23, 28.50, 15.32 ppm.

In an analogous manner, Examples 7 to 10 were obtained. Example 7b (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid (S) -cyano [4-fluoro-3- (4-chlorophenoxy) phenyl] methyl ester

ES HRMS: m / z found: 577.9155, 579.9106, 581.9090 (MNa ⁺ ).

C22Hi ₇ ClFN0 ₃ Br2 (MNa ⁺ ) calcd: 577.9145, 579.9116, 581.9095. ¹ H NMR (400 MHz, CDCl 3) δ 7.37-7.16 (m, 5H), 6.93 (dd, J = 7.1, 5.2 Hz, 1H), 6.67 (d, J = 8.3 Hz, 1H), 6.34 (s, 1H ), 2.08 (t, J = 8.4 Hz, 1H), 1.89 (d, J = 8.4 Hz, 1H), 1.25 (s, 3H), 1.19 (s, 3H) ppm.

¹³ C NMR (100 MHz, CDCl 3) δ 168.78, 156.73, 155.60, 154.20, 144.76, 144.65, 132.58, 130.35, 129.42, 129.38, 124.98, 124.91, 121.45, 121.44, 1 19.31, 1 18.62, 1 18.43, 1 16.08, 91.46, 62.17, 36.95, 31.35, 29.27, 28.52, 15.33 ppm. - -

Example 8b (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (S) -cyano [4-fluoro-3- (4-fluorophenoxy) phenyl] methyl ester

ES HRMS: m / z found: 508.0703 (MNa ⁺ ). C23H17F5NO3CI (MNa ⁺ ) calcd: 508.0715. ¹ H NMR (400 MHz, CDCl 3) δ 7.34-2.27 (m, 2H), 7.16 (d, J = 9.6 Hz, 1H), 7.12-6.97 (m, 4H), 6.82 (d, J = 9.2 Hz, 1H ), 6.35 (s, 1H), 2.29 (dt, J = 13.5, 8.7 Hz, 1H), 2.07 - 1.98 (m, 1H), 1.32 (s, 3H), 1.22 (s, 3H) ppm.

¹³ C NMR (100 MHz, CDCl 3): δ 168.6, 159.5 (J = 242Hz), 155.6 (J = 254Hz), 152.5, 145.6 (J = 12.1Hz), 129.1 (J = 4.0Hz), 128.9, 124.4 (J = 7.6Hz), 123.4, 120.5, 119.9 (J = 9.0Hz), 1 18.4 (J = 9.2Hz), 1 17.0 (J = 23.3Hz), 1 15.9, 62.3, 32.3, 32.1, 30.2, 28.5, 15.1ppm ,

Example 9b (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (S) -cyano [4-fluoro-3- (3-fluorophenoxy) phenyl] methyl ester

ES HRMS: m / z found: 508.0698 (MNa ⁺ ).

C23H17F5NO3CI (MNa ⁺ ) calcd: 508.0715.

'H NMR (400 MHz, CDCl3) δ 7.27-7.10 (m, 4H), 6.73-6.57 (m, 3H), 6.56 (d, J = 9.9 Hz, 1H), 6.23 (s, 1H), 2.16 (t , J = 8.7 Hz, 1H), 1.90 (d, J = 8.3 Hz, 1H), 1.17 (s, 3H), 1.08 (s, 3H) ppm.

¹³ C NMR (100 MHz, CDCl 3): δ 168.6, 162.4 (J = 248 Hz), 156.6 (J = 259 Hz), 152.8, 144.1, 131.2 (J = 10 Hz), 129.0, 128.9, 125.4 (J = 8.0 Hz), 123.3, 122.2, 1 18.6 (J = 19.2Hz), 116.2, 1 13.2 (J = 3.2Hz), 1 1 1.1 (J = 21.4Hz), 105.5 (J = 26.5Hz), 62.3, 32.2, 32.1, 30.2, 28.5, 15.1 ppm.

Example 10b (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid (S) -cyano [4-fluoro-3- (4-chlorophenoxy) phenyl] methyl ester - -

ES HRMS: m / z found: 524.0429, 526.0436 (MNa ⁺ ). C23H17F4NO3Cl2 (MNa ⁺ ) calcd: 524.0419, 526.0436. ¹ H NMR (400 MHz, CDCl 3) δ 7.31-7.16 (m, 4H), 7.12 (d, J = 7.4 Hz, 1H), 6.86 (d, J = 8.9 Hz, 2H), 6.72 (d, J = 9.2 Hz, 1H), 6.26 (s, 1H), 2.21 (t, J = 8.7 Hz, 1H), 1.94 (d, J = 8.3 Hz, 1H), 1.22 (s, 3H), 1.13 (s, 3H) ppm ,

¹³ C NMR (100 MHz, CDCl 3) δ 168.64, 156.78, 155.58, 154.26, 144.83, 144.71, 130.35, 129.48, 129.27, 129.23, 129.06, 129.01, 124.98, 124.91, 121.44, 1 19.31, 1 18.64, 118.45, 1 15.93 , 62.32, 32.29, 32.15, 30.23, 28.50, 15.14 ppm. Example 11 (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid ethynyl [4-fluoro-3-

(4-fluorophenoxy) phenyl] methylester

Step A: It is 4-fluoro-3- (4-fluorophenoxy) benzaldehyde (see also DE-OS 2,739,854) g

Example 6, Step A (Method II).

Step B (Method III): 3- (4-Fluorophenoxy) phenyl) -a-ethynyl-4-fluorobenzenemethanol

0.59 g (2.53 mmol) of 3- (fluorophenoxy) benzaldehyde (Step A, Method II) were stirred in 10 ml of dry tetrahydrofuran under an inert gas atmosphere (nitrogen). Thereafter, with stirring, 7.6 ml (3.8 mmol) of lithium tetramethylsilyl-acetylene (as a 0.5 M solution in THF) was added at a temperature of -78 ° C and heated to 0 ° C within 3 hours. Subsequently, the reaction mixture was treated with a saturated ammonium chloride solution and extracted with ethyl acetate. The organic phase was dried over magnesium sulfate and concentrated in vacuo. After that it became - - Remaining crude product dissolved in 2 ml of THF, the solution at -20 ° C with 3.8 ml (3.8 mmol) of IM solution tetra-n-butylammonium fluoride (TBAF) and stirred for 30 minutes. Subsequently, the entire reaction mixture was mixed with water and then extracted with ethyl acetate. The organic phase was dried over magnesium sulfate and concentrated after filtration in vacuo. The remaining crude product was purified by flash chromatography (silica gel eluent: 30% ethyl acetate: hexane). This gives 395 mg (60% of theory) of pure 3- (4-fluorophenoxy) phenyl) -a-ethynyl-4-fluorobenzenemethanol which, according to stage D (method I), is reacted with (IR, 3R) -3- ( 2,2-dibromethenyl) -2,2-dimethyl-cyclopropane-carboxylic acid chloride can be reacted.

Mixture of diastereomers I and II ES HRMS: m / z found: 560.9465, 562.9460, 564.9470 (MNa ⁺ ).

C23H18 F ₂ O ₃ Br ₂ Na (MNa ⁺ ) calcd: 560.9488, 562.9468, 564.9448. ¹ H NMR (400 MHz, CDCl 3) δ 7.25-7.05 (m, 3H), 7.01-6.82 (m, 4H), 6.63 (t, J = 8.4 Hz, 1H), 6.28 (d, J = 2.2 Hz, 1H ), 6.24 (d, J = 2.2 Hz, 1H), 2.57 (dd, J = 5.0, 2.3 Hz, 1H), 1.98 - 1.72 (m, 2H), 1.19 (s, 3H), 1.16 (s, 3H) , 1.12 (s, 3H), 1.09 (s, 3H) ppm. ¹³ C NMR (100 MHz, CDCl3) δ 168.01, 158.99, 156.59, 156.57, 154.43, 154.39, 151.94, 151.89, 151.69, 143.29, 143.22, 143.17, 143.1 1, 132.51, 132.47, 132.29, 132.25, 131.99, 131.97, 123.05 , 122.97, 122.96, 122.88, 119.61, 119.48, 118.04, 117.99, 117.96, 117.91, 116.37, 116.35, 116.19, 116.16, 115.44, 115.20, 88.95, 88.91, 76.04, 75.72, 75.00, 74.84, 63.26, 63.22, 34.89, 34.85 , 30.53, 27.19, 27.16, 27.12, 26.99, 13.97, 13.95 ppm. In an analogous manner, Example 12 was obtained.

Example 12 (1R, 3R) -3- (2-Chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid ethynyl [4-fluoro-3- (4-fluorophenoxy) phenyl] methyl ester

Mixture of diastereomers I and II ES HRMS: m / z found: 507.0756 (MNa ⁺ ).

C24H18 F ₅ 0 ₃ ClNa (MNa ⁺ ) calcd: 507.0762. ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.23-7.04 (m, 4H), 6.95-6.82 (m, 4H), 6.78 (d, J = 9.3 Hz, 1H), 6.27 (d, J = 2.2 Hz, 1H), 6.23 (d, J = 2.2 Hz, 1H), 2.55 (d, J = 3.0 Hz, 1H), 2.14 - 2.03 (m, 1H), 1.91 (dt, J = 8.3, 4.3 Hz, 1H), 1.20 (s, 3H), 1.20 (s, 3H), 1.16 (s, 3H), 1.10 (s, 3H) ppm.

¹³ C NMR (100 MHz, CDCl 3) δ 167.92, 167.87, 159.06, 156.65, 154.54, 154.49, 152.04, 151.99, 151.73, 143.37, 143.31, 143.25, 143.19, 132.40, 132.36, 132.14, 132.1 1, 128.65, 128.61, 128.57 , 123.1 1, 123.03, 123.00, 122.93, 120.71, 1 19.66, 119.52, 118.07, 117.99, 1 17.92, 116.39, 116.20, 115.44, 1 15.20, 78.60, 78.38, 76.34, 76.02, 75.70, 75.10, 74.95, 63.56, 63.48 , 31.62, 30.56, 30.14, 30.10, 28.22, 28.03, 27.16, 27.11, 21.62, 13.80, 13.78, 13.06 ppm.

Example 13 (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [3- (4-fluorobenzyl) phenyl] methyl ester

0.50 g (3.3 mmol) of 4-formylphenylboronic acid (see also EP 1 167 371 A2) are successively added under a protective gas atmosphere (nitrogen) to a mixture of 1.38 g (10 mmol) of potassium carbonate in 10 ml of tetrahydrofuran and 5 ml of water, Added 0.37 ml (3.0 mmol) of 4-fluorobenzylbromide and 0.089 g (0.075 mmol) of tetrakis (triphenylphosphine) palladium (0). Thereafter, the reaction mixture is stirred at 80 ° C for 16 hours. Subsequently, the reaction mixture is mixed with 50 ml of 1N hydrochloric acid and extracted three times with 30 ml of ethyl acetate. The combined organic phases are dried over magnesium sulfate, filtered and concentrated in vacuo. The remaining crude product was purified by flash chromatography (silica gel, eluent: 10% ethyl acetate: hexane). This gives 0.5 g (80% of theory) of pure 3 - [(4-fluorophenyl) methyl] benzaldehyde which can be reacted further in accordance with Example 1 (see stages BD). - -

Mixture of diastereomers I and II

ES HRMS: m / z rounded: 541.9755, 543.9747, 545.9738 (MNa ⁺ ). C ₂ 3H ₂ oFNO ₂ Br ₂ (MNa ⁺ ): 541.9742, 543.9722, 545.9702. ^l H NMR (400 MHz, CDC1 ₃₎ δ 7:37 (d, J = 5.0 Hz, 1H), 7:32 (s, 1H), 7:26 to 7:23 (m, 1H), 7.12 (dd, J = 7.7, 5.4 Hz, 2H), 6.97 (t, J = 8.7 Hz, 1H), 6.71 (d, J = 4.1 Hz, 1H), 6.69 (d, J = 4.2 Hz, 1H), 6.37 (s, 1H), 6.33 (s, 1H), 3.98 (s, 2H), 2.04 (t, J = 8.4 Hz, 1H), 1.90 (d, J = 8.4 Hz, 1H), 1.30 (s, 3H), 1.27 (s, 3H), 1.22 ( s, 3H), 1.17 (s, 3H) ppm.

¹³ C NMR (100 MHz, CDCl 3) δ 169.02, 168.98, 163.20, 160.77, 142.77, 136.30, 136.27, 133.03, 132.86, 132.68, 132.37, 131.30, 130.83, 130.75, 129.94, 128.63, 128.60, 126.21, 126.19, 116.70, 116.58, 115.99, 115.77, 91.24, 91.00, 63.16, 63.12, 41.26, 36.82, 31.57, 31.48, 29.33, 29.11, 28.58, 28.55, 15.37 ppm.

In an analogous manner, Examples 14 to 16 were obtained.

Example 14 (1R, 3R) -3- (2-Chloro-2-trifluoromethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [4-fluoro-3- (4-fluorobenzyl) phenyl] methyl ester

Mixture of diastereomers I and II

ES HRMS: m / z found: 506.0899 (MNa ⁺ ). C24H19CIF5NO2 (MNa ⁺ ) calculates: 506.0922. ¹ H NMR (400 MHz, CDCl 3): δ 7.39 (1H, m), 7.30 (1H, dd, J = 2.1, 7.1Hz), 7.19 (1H, m), 7.15 (2H, m) 6.99 (2H, m ), 6.80 (1H, d, J = 9.2Hz), 6.36 (1H, s), 6.29 (1H, s), 4.02 (2H, s), 2.27 (1H, t, J = 8.4Hz), 2.24 (1H , t, J = 8.5Hz), 2.01 (1H, d, J = 8.4Hz), 1.35 (3H, s), 1.33 (3H, s), 1.28 (3H, s), 1.17 (3H, s) ppm.

¹³ C NMR (100 MHz, CDCl 3): δ 168.7, 162.3 (J = 245Hz), 162.2 (J = 249Hz), 134.9, 132.9 (J = 3.2Hz), 131.1 (J = 4.7Hz), 130.9 (J = 7.4 Hz), 129.8 (J = 16.9Hz), 129.1 (J = 9.1Hz), 128.4, 116.9 (J = 23.3Hz), 115.9 (J = 20.1Hz), 62.7, 62.6, 34.4, 32.4, 32.3, 30.3, 28.5 , 15.1 ppm.

Example 15 (1R, 3R) -3- (2-Chloro-2-trifluoromethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [3- (thien-3-ylmethyl) phenyl] methyl ester - -

Mixture of diastereomers I and II

ES HRMS: m / z rounded: 476.0664 (MNa ⁺ ).

C22H19CIF3NO2S (MNa ⁺ ) calculates: 476.0675. 1H NMR (400 MHz, CDCl 3): δ 7.38 (3H, m), 7.28 (2H, m), 6.94 (1H, m), 6.90 (1H, m), 6.85 (1H, d, J = 0.9Hz), 6.83 (1H, d, J = 0.9Hz), 6.39 (1H, s), 6.33 (1H, s), 4.02 (2H, s), 2.28 (1H, t, J = 8.5Hz), 2.24 (1H, t , J = 8.5Hz), 2.04 (1H, d, J = 8.3Hz), 2.02 (1H, d, J = 1.5Hz), 1.34 (6H, s), 1.29 (3H, s), 1.21 (3H, s ) ppm.

¹³ C NMR (100 MHz, CDCl 3): δ 166.8, 142.4, 140, 140.7, 132.4, 132.0, 131.3, 131.2, 129.8, 129.4 (J = 4.6Hz), 129.2 (J = 4.6Hz), 128.5, 128.4, 126.4 , 126.2, 126.1, 122.0, 116.5, 116.4, 63.3, 63.2, 36.7, 36.6, 32.5, 32.4, 32.1, 32.0, 30.3, 30.1, 28.6, 15.2 ppm.

Example 16 (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid cyano [3- (thien-2-ylmethyl) phenyl] methyl ester

ES HRMS: m / z found: 529.9393, 531.9338, 533.9364 (MNa ⁺ ). C2iHi9N0 ₂ Br ₂ S (MNa ⁺ ) calcd: 529.9401, 531.9380, 533.9360.

'H NMR (400 MHz, CDCl3): δ 7.40 (4H, m), 7.35 (1H, m), 7.17 (1H, m), 6.93 (1H, m), 6.81 (2H, m), 6.72 (1H, d, J = 8.4Hz), 6.69 (1H, d, J = 8.4Hz), 6.39 (1H, s), 6.35 (1H, s), 4.19 (2H, s), 2.07 (1H, t, J = 8.4 Hz), 2.03 (1H, t, J = 8.4Hz), 1.90 (1H, d, J = 8.4Hz), 1.32 (3H, s), 1.29 (3H, s), 1.25 (3H, s), 1.18 ( 3H, s) ppm.

¹³ C NMR (100 MHz, CDCl 3): δ 169.0, 168.9, 143.2, 142.1, 132.9, 132.8, 132.6, 132.3, 131.1, 131.0, 129.9, 128.4, 128.3, 127.4, 126.4, 125.9, 124.8, 116.6, 116.5, 91.2 , 90.9, 63.1, 63.0, 36.8, 36.2, 31.5, 31.4, 30.2, 29.3, 28.6, 28.5, 15.4 ppm. - 5 -

Example 17 (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [3- (4-fluorophenylmethoxy) phenyl] methyl ester

Step A (Method V): 4-Fluoro-3- (4-fluorophenylmethoxy) -benzaldehyde

To a mixture of 0.70 g (50 mmol) 4-fluoro-3-hydroxybenzaldehyde, 1.10 mL (9.0 mmol) 4-fluorobenzylbromide in 20 mL acetone was added 1.25 mg (9.0 mmol). Given potassium carbonate. Thereafter, the reaction mixture was stirred at reflux temperature for 2 hours. After cooling to room temperature, the reaction mixture was filtered and the filtrate was concentrated in vacuo. The remaining crude product was purified by column chromatography (eluent: 5% ethyl acetate: hexane). This gives 1.16 g (90% of theory) of 4-fluoro-3- (4-fluorophenylmethoxy) -benzaldehyde as a yellow solid, which can be reacted further in accordance with Example 1 (see stages B-D).

Mixture of diastereomers I and II

ES HRMS: m / z found: 575.9572, 577.9587, 579.9600 (MNa ⁺ ). C23Hi9N03F ₂ Br ₂ (MNa ⁺ ) calcd: 575.9597, 577.9577, 579.9556. ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.44 (2H, m), 7.18 (1H, m), 7.16 (1H, m), 7.14 (1H, m), 7.09 (2H, m), 6.74 (1H, d, J = 8.5Hz), 6.68 (1H, d, J = 8.5Hz), 6.35 (1H, s), 6.33 (1H, s), 5.12 (2H, s), 2.09 (1H, t , J = 8.3Hz), 2.04 (1H, t, J = 8.3Hz), 1.89 (1H, d, J = 8.3Hz), 1.86 (1H, d, J = 8.3Hz), 1.32 (3H, s), 1.29 (3H, s), 1.27 (3H, s), 1.21 (3H, s) ppm. ¹³ C NMR (100 MHz, CDCl 3): δ 168.9, 161.3 (J = 245 Hz), 155.2 (J = 249 Hz), 147.9 (J = 1 1.5 Hz), 133.5, 131.9, 130.0 (J = 8.4 Hz), 129.9 ( J = 8.3Hz), 128.7 (J = 3.9Hz), 128.4 (J = 3.9Hz), 121.9 (J = 8.2Hz), 121.7 (J = 8.2Hz), 1 17.4 (J = 20.1Hz), 1 16.4, 1 16.3, 1 16.0 (J = 22.3Hz), 1 15.6 (J = 3.4Hz), 1 15.5 (J = 3.4Hz), 91.3, 91.1, 71.3, 62.6, 36.8, 36.7, 31.9, 29.4, 29.1, 28.8, 15.6 ppm.

In an analogous manner, Example 18 was obtained. - -

Example 18 (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyan [3

(4-fluorphenylmethoxy) phenyl] methylester

Mixture of diastereomers I and II ES HRMS: m / z found: 522.0850 (MNa ⁺ ). C24H19CIF5NO3 (MNa ⁺ ) calcd: 522.0871. ¹ H NMR (400 MHz, CDCl 3): δ 7.43 (2H, m), 7.18 (1H, m), 7.16 (1H, m), 7.14 (1H, m), 7.09 (2H, m), 6.86 (1H, d, J = 9.3Hz), 6.83 (1H, d, J = 9.1Hz), 6.36 (1H, s), 6.31 (1H, s), 5.12 (2H, s), 2.29 (1H, t, J = 8.6Hz), 2.24 (1H, t, J = 8.6Hz), 2.02 (1H, d, J = 8.5Hz), 2.00 (1H, d, J = 8.6Hz), 1.35 (3H, s), 1.32 (3H, s), 1.29 (3H, s), 1.21 (3H, s) ppm.

¹³ C NMR (100 MHz, CDCl 3): δ 166.8, 160.9 (J = 245Hz), 155.1 (J = 249Hz), 147.9 (J = 1 1.5Hz), 129.8, 127.9 (J = 8.3Hz), 127.8 (J = 3.9Hz), 127.7, 127.2 (J = 4.9Hz), 127.1 (J = 4.9Hz), 126.1 (J = 4.9Hz), 126.0 (J = 4.9Hz), 121.1, 121.9 (J = 8.2Hz), 121.7 ( J = 8.2Hz), 1 15.3 (J = 20.1Hz), 1 14.1, 1 13.9 (J = 22.3Hz), 1 13.6 (J = 3.4Hz), 113.5 (J = 3.4Hz), 69.2, 60.7, 30.7, 29.8, 28.2, 28.0, 26.7, 13.0 ppm. Example 19 -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [6- (4-fluoro)

Step A: 2-bromo-6- (4-fluorophenoxy) pyridine (see also J.W. Street et al., Neth. Recueil des

Travaux Chimiques des Pays-Bas 88, 1391 -412, 1969)

0.57 g (16.9 mmol) of sodium hydride was washed in a 100 ml flask under an inert gas atmosphere (nitrogen) with 15 ml of hexane. Subsequently, 15 ml of N, N-dimethylformamide (DMF) and 1.42 g (12.7 mmol) of 4-fluorophenol dissolved in 5 ml of DMF were added at room temperature. Once the gas - 7 -

Winding (foaming), 2.0 g (8.44 mmol) of 2,6-dibromopyridine were added and the reaction mixture was stirred at 100 ° C for 16 hours. Thereafter, the reaction mixture was mixed with 15 ml of 5% sodium bicarbonate solution. The DMF was removed in vacuo and the remaining residue was dissolved in 100 ml of ethyl acetate. It was then washed with 50 ml of water and 50 ml of saturated brine. The organic phase was dried over magnesium sulfate, and concentrated by filtration in vacuo. A clear oil is obtained, which gives by column chromatography (eluent: 20% ethyl acetate: hexanes) 1.62 g (72% of theory) of 2-bromo-6- (4-fluorophenoxy) pyridine as a clear oil.

Step B: 6- (4-fluorophenoxy) -2-pyridine-carboxaldehyde (see also US 4,281,133)

In a 100 ml flask, 1.67 g (6.23 mmol) of 2-phenyl-6-bromopyridine were admixed with 50 ml of dry tetrahydrofuran (THF) and cooled to -78 ° C. under an inert gas atmosphere (nitrogen). Subsequently, 4.3 ml of (6.85 mmol of 1.6 M n-butyllithium solution was added dropwise and the resulting pale brown solution was stirred for an additional hour at -78 ° C. After addition of 0.55 ml (6.85 mmol) of DMF, the reaction mixture became The mixture was stirred for a further 30 minutes at -78 ° C. and then gradually warmed to room temperature, then 50 ml of 5% sodium bicarbonate solution were added to the weakly orange solution and the mixture was extracted three times with 50 ml of ethyl acetate were then washed with 50 ml of saturated brine, then the separated organic phase was dried over magnesium sulfate and concentrated by evaporation in vacuo to give a clear oil which was purified by column chromatography (eluent: 15% ethyl acetate: hexanes) 0.86 g (64 % of theory) gives 6- (4-fluorophenoxy) -2-pyridine-carboxaldehyde as a clear oil.

Step C: 2- (6- (4-Fluoro-phenoxy) -2-pyridinyl) -2-hydroxy-acetonitrile (see also US-P 4,221,799)

0.76 g (3.50 mmol) of 6- (4-fluorophenoxy) -2-pyridine-carboxaldehyde were stirred in 50 ml of dry dichloromethane under an inert gas atmosphere (nitrogen). Thereafter, 1.40 ml (10.50 mmol) of trimethylsilyl cyanide and 0.05 ml (0.35 mmol) of triethylamine were added and the reaction mixture was stirred for 2 hours at room temperature. Subsequently, the solvent was removed under reduced pressure and the remaining residue was dissolved in 30 ml of THF. After addition of 20 ml of 2M hydrochloric acid was still stirred for two more hours at room temperature. The reaction solution was made alkaline with about 20 ml of saturated aqueous sodium bicarbonate solution (pH 8) and extracted three times with 50 ml of ethyl acetate. The combined organic phases were washed with 50 ml of saturated brine. Subsequently, the separated organic phase was dried over magnesium sulfate, and concentrated after filtering in vacuo. A clear oil is obtained, which is purified by column chromatography (eluent: 25% ethyl acetate: hexanes) 0.50 g (59% of theory) of 2- (6- (4-fluorophenoxy) -2-pyridinyl) -2-hydroxy-acetonitrile clear oil results.

Step D: (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethylcyclopropanecarboxylic acid chloride (also see

US-P 4,342,770)

0.44 g (1.48 mmol) of (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropane carboxylic acid (see also M. Eliott et al., Pesticide Sci., 6, 537-542 , 1975) were dissolved in 30 ml of dry dichloromethane and treated under inert gas atmosphere (nitrogen) with 2 drops of DMF. After dropwise addition of 1.5 ml (2.96 mmol) of oxalyl chloride, the reaction mixture was stirred at room temperature for two hours. Thereafter, the solvent was removed in vacuo and the crude (IR, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride dried under vacuum for one hour.

Step E: (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [6- (4-fluoro-phenoxy-2-pyridinyl) methyl ester

The (1R, 3R) -3- (2,2-dibromoethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride obtained in step D was stirred under inert gas atmosphere in 30 ml of THF. Thereafter, with a solution of 0.30 g (1.23 mmol) of 2- (6- (4-fluorophenoxy) -2-pyridinyl) -2-hydroxy-acetonitrile (see step C), in 5.0 ml of THF and 0.21 ml (1.48 mmol) of triethylamine. After two hours of stirring at room temperature, the entire reaction mixture was mixed with 50 ml of ethyl acetate. It was then washed successively with 50 ml of water, 20 ml of 1N hydrochloric acid, 20 ml of saturated sodium bicarbonate solution and 30 ml of saturated brine. Subsequently, the separated organic phase was dried over magnesium sulfate, and concentrated after filtering in vacuo. A yellow oil is obtained which is purified by column chromatography (eluent: 15% ethyl acetate: hexanes) 0.36 g (56% of theory) (1R, 3R) -3- (2,2-dibromethenyl) -2,2-dimethyl- cyclopropanecarboxylic acid cyano [6- (4-fluoro-phenoxy-2-pyridinyl) methyl ester as a pale yellow oil. The (l: l) mixture of diastereomers can be separated by column chromatography.

Diastereomer I: ES HRMS: m / z found: 544.9523 C2iHi ₇ N ₂ 03F ²³ Na ⁷⁹ Br2 calculates: 544.9488.

'H-NMR (400MHZ, CDC1 ₃ ): δ 7.79 (1H, t, J = 7.4Hz), 7.24 (1H, t, J = 7.4Hz), 7.17-7.07 (4H, m), 6.94 (1H, d , J = 8.3Hz), 6.66 (1H, d, J = 8.3Hz), 6.28 (1H, s), 2.06 (1H, t, J = 8.4Hz), 1.93 (1H, d, J = 8.4Hz), 1.29 (6H, s) ppm. ¹³ C-NMR (100 MHz, CDCl 3): 168.6, 163.8, 161.4, 159.0, 149.5, 149.4, 141.3, 132.8, 130.1, 123.2, 123.1, 116.7, 116.5, 116.4, 115.8, 112.8, 91.1, 63.6, 36.9, 31.4 , 29.4, 28.6, 15.3 ppm.

Diastereomer II:

ES HRMS: m / z found: 544.9523 C2iHi ₇ N ₂ 03F ²³ Na ⁷⁹ Br2 calculates: 544.9488.

'H NMR (400MHZ, CDCl3): δ 7.79 (1H, t, J = 7.4Hz), 7.24 (1H, t, J = 7.4Hz), 7.17-7.06 (4H, m), 6.94 (1H, d, J = 8.3Hz), 6.66 (1H, d, J = 8.3Hz), 6.28 (1H, s), 2.08 (1H, t, J = 8.4Hz), 1.94 (1H, d, J = 8.4Hz), 1.26 (3H, s), 1.20 (3H, s) ppm.

¹³ C NMR (100 MHz, CDCl 3): 168.6, 163.8, 161.4, 158.9, 149.6, 149.5, 141.3, 132.8, 130.1, 123.2, 123.1, 116.7, 116.5, 116.4, 115.7, 112.8, 91.3, 63.5, 36.9, 31.4, 29.2, 28.6, 15.3 ppm.

In an analogous manner, Examples 20 to 24 can be obtained. Example 20 (1R, 3R) -3- (2,2-Dibromoethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [6- (2-fluoro-phenoxy-2-pyridinyl) methyl ester

Diastereomer I:

ES HRMS: m / z found: 544.9500 C2iHi ₇ N ₂ 03F ²³ Na ⁷⁹ Br2 calculates: 544.9488. 'H NMR (400MHZ, CDCl3): δ 7.81 (1H, t, J = 7.4Hz), 7.25 (1H, t, J = 7.4Hz), 7.16-7.06 (4H, m), 7.03 (1H, d, J = 8.3Hz), 6.66 (1H, d, J = 8.3Hz), 6.25 (1H, s), 2.05 (1H, t, J = 8.4Hz), 1.91 (1H, d, J = 8.4Hz), 1.28 (3H, s), 1.27 (3H, s) ppm.

¹³ C-NMR (100 MHz, CDCl 3): 168.6, 163.0, 156.3, 153.9, 149.2, 141.2, 140.8, 140.7, 132.9, 130.1, 126.9, 126.8, 125.0, 124.9, 124.2, 117.3, 117.1, 116.6, 115.7, 112.4 , 91.0, 63.5, 45.0, 36.8, 31.3, 29.3, 28.6, 15.3 ppm.

Diastereomer II: ₅

ES HRMS: m / z found: 544.9500 C2iHi ₇ N ₂ 03F ²³ Na ⁷⁹ Br2 calculates: 544.9488.

'H-NMR (400MHZ, CDC1 ₃ ): δ 7.81 (1H, t, J = 7.4Hz), 7.26 (1H, t, J = 7.4Hz), 7.16-7.06 (4H, m), 7.03 (1H, d , J = 8.3Hz), 6.66 (1H, d, J = 8.3Hz), 6.26 (1H, s), 2.07 (1H, t, J = 8.4Hz), 1.91 (1H, d, J = 8.4Hz), 1.26 (3H, s), 1.18 (3H, s) ppm. ¹³ C-NMR (100 MHz, CDCl 3): 168.6, 163.0, 156.3, 153.9, 149.4, 141.6, 141.2, 140.8, 140.7, 132.9, 130.1, 126.8, 126.7, 125.0, 124.9, 124.2, 1 17.3, 117.1, 1 16.7 , 1 15.6, 1 12.6, 91.2, 63.5, 45.0, 36.9, 31.3, 29.2, 28.6, 15.4 ppm.

Example 21 (1R, 3R) -3- (2-Chloro-2-trifluoromethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [6- (2-fluorophenoxy-2-pyridinyl) methyl ester

Diastereomer I:

ES HRMS: m / z found: 491.0743 C22Hi ₇ N ₂ 03F4 ²³ Na ³⁵ Cl calculated: 491.0762.

'H-NMR (400MHZ, CDCl3): δ 7.81 (1H, t, J = 8.0Hz), 7.27-7.14 (5H, m), 7.03 (1H, d, J = 8.0Hz), 6.79 (1H, d, J = 9.2Hz), 6.25 (1H, s), 2.24 (1H, t, J = 8.8Hz), 2.03 (1H, d, J = 8.4Hz), 1.34 (3H, s), 1.30 (3H, s) ppm.

¹³ C-NMR (100 MHz, CDCl 3): 168.5, 163.0, 156.3, 153.9, 149.0, 141.2, 140.7, 129.4, 126.9, 126.8, 125.0, 123.2, 117.3, 117.1, 116.7, 115.6, 112.5, 63.6, 32.3, 32.0 , 30.4, 28.6, 15.2 ppm.

Diastereomer II:

ES HRMS: m / z found: 491.0743 C22Hi ₇ N ₂ 03F4 ²³ Na ³⁵ Cl calculated: 491.0762. 'H-NMR (400MHZ, CDCl3): δ 7.81 (1H, t, J = 8.0Hz), 7.27-7.14 (5H, m), 7.04 (1H, d, J = 8.4Hz), 6.80 (1H, d, J = 9.2Hz), 6.27 (1H, s), 2.27 (1H, t, J = 8.8Hz), 2.04 (1H, d, J = 8.4Hz), 1.31 (3H, s), 1.20 (3H, s) ppm.

¹³ C NMR (100 MHz, CDCl 3): 168.5, 163.1, 156.3, 153.9, 149.2, 141.2, 140.7, 129.2, 126.9, 126.8, 125.0, 124.2, 117.3, 117.1, 116.8, 115.4, 112.5, 100.0, 63.6, 32.3, 32.1, 30.2, 28.6, 15.2 ppm.

Example 22 (1R, 3R) -3- (2-Chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid cyano [6- (3-fluorophenoxy-2-pyridinyl) methyl ester - 5 -

Diastereomer I:

ES HRMS: m / z found: 491.0744 C ₂₂ Hi ₇ N ₂ 0 ₃ F ₄ ²³ Na ³⁵ Cl calculated: 491.0762.

'H-NMR (400MHZ, CDC1 ₃ ): δ 7.81 (1H, t, J = 8.0Hz), 7.41-7.31 (2H, m), 7.02-6.91 (4H, m), 6.80 (1H, d, J = 9.2Hz), 6.30 (1H, s), 2.26 (1H, t, J = 8.8Hz), 2.07 (1H, d, J = 8.4Hz), 1.34 (3H, s), 1.32 (3H, s) ppm.

¹³ C-NMR (100 MHz, CDCl 3): 168.6, 163.0, 156.3, 153.9, 149.3, 141.4, 140.9, 129.4, 126.9, 126.8, 125.0, 123.0, 117.3, 117.1, 116.9, 115.7, 112.5, 63.6, 32.3, 32.0 , 30.4, 28.6, 15.2 ppm.

Diastereomer II:

ES HRMS: m / z found: 491.0744 C ₂₂ Hi ₇ N ₂ 0 ₃ F ₄ ²³ Na ³⁵ Cl calculated: 491.0762. 'H-NMR (400MHZ, CDCl3): δ 7.83 (1H, dd, J = 15.4, 7.6Hz), 7.43-7.33 (2H, m), 7.01-6.91 (4H, m), 6.81 (1H, d, J = 9.2Hz), 6.32 (1H, s), 2.29 (1H, t, J = 8.8Hz), 2.06 (1H, d, J = 8.4Hz), 1.31 (3H, s), 1.21 (3H, s) ppm ,

¹³ C NMR (100 MHz, CDCl 3): 168.6, 163.0, 156.3, 153.9, 149.3, 141.4, 140.9, 129.4, 126.9, 126.8, 125.0, 123.0, 117.3, 117.1, 116.9, 115.7, 112.5, 63.6, 32.3, 32.0, 30.4, 28.6, 15.2 ppm. Example 23 (1R, 3R) -3- (2-chloro-2-trifluoromethenyl) -2,2-dimethylcyclopropanecarboxylic acid cyano [6- (2,6-difluoro-phenoxy-2-pyridinyl) methyl ester

-5 -

Diastereomer I:

ES HRMS: m / z found: 509.0679 C22Hi6N ₂ 03F ₅ ²³ Na ³⁵ Cl calculated: 509.0667.

'H NMR (400MHZ, CDC1 ₃ ): δ 7.84 (1H, t, J = 7.4Hz), 7.28 (1H, d, J = 7.4Hz), 7.22-7.12 (2H, m), 7.00 (2H, m ), 6.79 (1H, d, J = 7.8Hz), 6.24 (1H, s), 2.25 (1H, t, J = 8.8Hz), 2.03 (1H, d, J = 8.3Hz), 1.34 (3H, s ), 1.29 (3H, s) ppm.

¹³ CNMR (100 MHz, CDCl3): 168.2, 161.9, 157.4, 148.6, 141.1, 129.2, 129.1, 125.9, 116.9, 115.1, 112.3, 112.2, 112.1, 63.3, 32, 31, 8, 30, 1.30, 15.0 ppm.

Diastereomer II:

ES HRMS: m / z found: 509.0679 C22Hi6N ₂ 03F ₅ ²³ Na ³⁵ Cl calculated: 509.0667. ¹ H NMR (400MHz, CDCl 3): δ 7.84 (1H, t, J = 7.4Hz), 7.28 (1H, d, J = 7.4Hz), 7.22-7.13 (2H, m), 7.00 (2H, m), 6.79 (1H, d, J = 7.8Hz), 6.26 (1H, s), 2.27 (1H, t, J = 8.8Hz), 2.03 (1H, d, J = 8.3Hz), 1.31 (3H, s), 1.19 (3H, s) ppm.

¹³ CNMR (100 MHz, CDCl3): 168.4, 162.2, 157.6, 155.2, 149.0, 141.4, 129.2, 129.1, 126.0, 123.1, 117.2, 115.2, 112.6, 112.5, 112.4, 63.5, 32.3, 32.30, 1.28, 15.2 ppm. Example 24 (1R, 3R) -3- (2-Chloro-2-trifluoromethenyl) -2,2-dimethyl-cyclopropanecarboxylic acid cyano [6- (2,4,6-trifluoro-phenoxy-2-pyridinyl) methyl ester

Diastereomer I:

ES HRMS: m / z found: 527.0558 C22Hi ₅ N ₂ 03F6 ²³ Na ³⁵ Cl calculated: 527.0573. 'H-NMR (400MHZ, CDCl3): δ 8.07 (1H, dd, J = 5.0, 1.9Hz), 7.76 (1H, t, J = 7.7Hz), 7.12-7.04 (2H, m), 6.93 (1H, t, J = 9.5Hz), 6.79 (1H, d, J = 9.2Hz), 6.68 (1H, s), 2.26 (1H, t, J = 8.8Hz), 2.03 (1H, d, J = 8.0Hz) , 1.35 (3H, s), 1.33 (3H, s) ppm.

¹³ C-NMR (100 MHz, CDCl3): 168.4, 161.8, 147.5, 140.4, 130.1, 129.1, 129.0, 120.0, 114.5, 111.1, 102.2, 102.0, 52.7, 32.7, 32.2, 30.4, 28.5, 15.2 ppm. - 5 -

Diastereomer II:

ES HRMS: m / z found: 527.0558 C22Hi ₅ N ₂ 03F6 ²³ Na ³⁵ Cl calculated: 527.0573.

'H-NMR (400MHz, CDC1 ₃ ): δ 8.09 (1H, dd, J = 5.0, 1.9Hz), 7.78 (1H, t, J = 7.6Hz), 7.13-7.06 (2H, m), 6.95 (1H , m), 6.83 (1H, d, J = 9.2Hz), 6.72 (1H, s), 2.30 (1H, t, J = 8.8Hz), 2.05 (1H, d, J = 8.0Hz), 1.32 (3H , s), 1.25 (3H, s) ppm.

¹³ C NMR (100 MHz, CDCl 3): 168.4, 161.8, 147.5, 140.4, 130.1, 129.1, 129.0, 120.0, 114.5, 111.1, 102.2, 102.0, 52.7, 32.7, 32.2, 30.4, 28.5, 15.2 ppm.

- 5 -

Biological examples

Mosquito test [Anopheles funestus FANG (sensitive) and Anopheles funestus FUMOZ-R (resistant)] Solvent 1: acetone

Solvent 2: Dow Corning 556 Silicone Fluid To prepare the active compound preparations according to the invention, the amount of active compound required for the desired concentration (%> m / v) is dissolved in 0.7 ml of solvent 1 and then mixed with 0.7 ml of solvent 2.

Each 1.4 ml of a drug solution are dropped onto a filter paper and the soaked papers dried overnight. Each 20 non-blood-fed, 3-5 day old female mosquitoes [Anopheles funestus FANG (sensitive) or Anopheles funestus FUMOZ (resistant)] are brought into contact with one of the soaked filter papers for 60 minutes. Subsequently, the mosquitoes are removed from the filter paper and supplied with sugar water.

After 24 hours, the effect is determined in%. 100% means that all mosquitoes have been killed. 0% means that no mosquitoes have been killed.

The determined effect in% is plotted as a function of the active substance concentration and the LC50 is determined from the resulting curves (LC50 = mean lethal concentration.) The mean lethal concentration LC50 is the statistically calculated concentration of a substance that is expected to be 50% of the exposed animals within the study period afterwards leads to death.). The quotient "LC50 (FUMOZ-R) / LC50 (FANG)" represents the resistance ratio RR and is then determined accordingly from the LC50 values.

In this test, z. B. the following compounds of the preparation examples a significantly reduced RR value compared to the standard deltamethrin and thus an improved Resistenzbrechung: DELTAMETHRIN LC50 RR

FANG Concentration 0.3 0.15 0.075 0.037 0.019 0.009 0.005 0.002 0.001 0.0006 0.00045%

(%)

Mortality (%) 100 100 100 100 99 100 100 100 93.4 70.5

1000

FUMOZ concentration 0.6 0.3 0.15 0.075 0.032 0.016 0.008 0.004 0.002 0.45%

R (%)

Mortality (%) 63 38 13 3 3 0 1 0 2

Example lb LC50 RR

FANG Concentration 0.27 0.09 0.03 0.01 0.003 0.001 0.0004 0.0001 0.00004 0.001 1%

(%)

Mortality (%) 100 100 100 100 100 36 4 0

164

FUMOZ Concentration 1, 2 0.6 0.4 0.3 0.2 0.1 0.08 0.04 0.02 0.18% R (%)

Mortality (%) 98 90 90 75 41 34 10 7 1

Example 7 b LC50 RR

FANG Concentration 0.27 0.09 0.03 0.01 0.003 0.001 0.0004 0.0001 0.00004 0.0012%

(%)

Mortality (%) 100 99 99 67 63 9 3 1

165

FUMOZ Concentration 1, 2 0.6 0.4 0.3 0.2 0.1 0.05 0.025 0.013 0.20% R (%)

Mortality (%) 100 98 87 73 37 10 7 4 3

Example 2b LC50 RR

FANG Concentration 0.27 0.09 0.03 0.01 0.003 0.001 0.0004 0.0001 0.00004 0.001%

(%)

Mortality (%) 100 100 100 98 97 44 33 1 1 3

1 10

FUMOZ Concentration 1, 2 0.6 0.3 0.15 0.08 0.04 0.02 0.01 0.005 0.1 1% R (%)

Mortality (%) 100 100 93 65 24 10 0 5 0 - 5 -

Example 8b LC50 RR

FANG Concentration 0.27 0.09 0.03 0.01 0.003 0.001 0.0004 0.0001 0.00004 0.0006%

(%)

Mortality (%) 100 100 98 99 98 77 18 13 5

550

FUMOZ concentration 0.6 0.3 0.15 0.08 0.04 0.02 0.01 0.005 0.33% R (%)

Mortality (%) 83 48 6 2 1 1 2 0

Example 9b LC50 RR

(%)

Mortality (%) 100 100 100 96 81 54 8 5 0

133

FUMOZ concentration 0.6 0.3 0.15 0.08 0.04 0.02 0.01 0.005 0.16% R (%)

Mortality (%) 88 88 47 4 17 0 1 0

Claims

claims

1. Use of the compounds of the formula (I),

wherein

Ri is hydrogen, cyano, alkenyl or alkynyl,

Q is a radical of the formula (LI)

stands in which

Y is CH or N,

Z for halogen,

n is 0, 1, 2 or 3,

M is oxygen, sulfur, methylene or oxymethylene,

R2 represents optionally substituted hetaryl or one of the radicals from the series

where the arrow marks the bond to the adjacent ring,

Xi, Χι ', X "are independently alkyl, haloalkyl, cycloalkyl, halogenocycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkoxyalkyl, haloalkoxyalkyl, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, Halogenalkylsulfonyl, halogen, nitro, cyano, amino, alkylamino, dialkylamino, and

Yi and Y ₂ independently represent halogen or haloalkyl for controlling insecticide-resistant insects.

Use of the compounds according to claim 1 for the control of pyrethroid-resistant insects.

Use of the compounds according to claim 1 or 2, characterized in that the insects are from the family of Culicidae, Muscidae or Blattidae.

Use according to claim 3, characterized in that the insects are from the family of Culicidae.

Use according to claim 4, characterized in that the insects are selected from the genera Aedes aegypti, Aedes albopictus, Anopheles stephensi, Culex quinque fasciatus, Anopheles albimanus, Anopheles funestus, Anopheles gambiae, Culex pipiens pallens, Anopheles minimus, Anopheles arabiensis and Anopheles sacharovi.

Use according to claim 5, characterized in that the insects are selected from the group of the genera Culex quinquefasciatus and Anopheles gambiae.