CZ611477A3

CZ611477A3 - Insecticidal, acaricidal and nematocidal agent and process for preparing an active component thereof

Info

Publication number: CZ611477A3
Application number: CS776114A
Authority: CZ
Inventors: Jacques Ing Martel; Jean Ing Tessier; Jean-Pierre Demoute
Original assignee: Roussel Uclaf
Priority date: 1977-07-19
Filing date: 1977-09-21
Publication date: 1994-02-16
Also published as: CH630890A5; FR2398041B2; CH630601A5; FR2398041A2; CZ278747B6

Abstract

The new acids correspond to the formula <IMAGE> in which X1 represents hydrogen, fluorine, chlorine or bromine, X2 represents fluorine, chlorine or bromine and X3 represents chlorine, bromine or iodine; the invention also comprises the chlorides of these acids. These acids have antifungal and bactericidal properties; they can thus be used especially in agriculture for controlling parasitic fungi of crops, and as industrial biocides, especially for protecting industrial fillers and adhesives. They can also be used, as well as their chlorides, as intermediates in the synthesis of new esters having insecticidal activity and other products. They can be prepared from 2,2-dimethyl-3-(2'-X1-2'-X2-vinyl)cyclopropane-1-carboxylic acid by chlorination, bromination or iodination, followed by optional conversion to a chloride.

Description

MP-564-77-HO-1-i-

Ui oc

Insecticidal, acaricidal and nematocidal agent and method of preparing its active ingredient

Technical field

The present invention relates to an insecticidal, acaricidal and nematocidal composition and to a process for preparing an active ingredient thereof.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides an insecticidal, acaricidal and non-nematic agent comprising at least one cyclopropanecarboxylic ester with a polyhalogenic group in one of its possible isomeric forms of formula I as active ingredient.

wherein X 1 represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, X 2, which is identical to or different from X 1, represents a fluorine atom, a chlorine atom or a bromine atom, X 1 represents a chlorine atom or a bromine atom and R represents a benzyl group optionally substituted by at least one group comprising alkyl groups having a total number of carbon atoms of 1 to 4, alkenyl groups having a total number of carbon atoms of 2 to 6, alkenyloxy groups having a total number of carbon atoms of 2 to 6, alkanedienyl groups having a total of carbon numbers of 4 to 8, methylenedioxy and benzyl or 2

wherein the substituent is hydrogen or methyl and R 1 is phenyl or 5-benzyl-3-furylmethyl, or

wherein R 1 represents an alkenyl group having 2 to 6 carbon atoms, in particular a vinyl group or a propen-1-yl group, or

H

4 in which is hydrogen, -C = N or -C = CH and R1 is chloro or methyl and n is an integer of 0, 1 or 2, and especially a 3-phenoxybenzyl or alpha-cyano group. 3-phenoxybenzyl, or a group of formula

Wherein S / I denotes an aromatic or analogous dihydro 3 or tetrahydro ring.

In addition, the insecticidal composition of the invention may preferably contain a synergistic agent of pyrethrinoid compounds.

The invention also relates to a process for the preparation of an active compound of the formula I as defined above, wherein the general substituents are as defined above, wherein the ester of the formula II is

> X2 H 'H3C, > cn 3 X 1 / C 2 COR (II) HX wherein X 2 and R are as defined above, wherein said ester is in one of its isomeric forms, acts by a chlorinating or brominating agent capable of binding two chlorine or bromine atoms to a double bond side chain of cyclopropanecarboxylic acid.

Esters of formula I may exist in a number of isomeric forms. The cyclopropanecarboxylic acids forming the acidic moiety of the esters of formula I have three asymmetric carbons, i.e., asymmetric carbons at the 1 and 3 positions of the cyclopropane ring and the asymmetric carbon at position 1 " the polyhalogenated ethyl chain attached to the cyclopropane ring at the 3-position. In the case where all three general substituents, X 2 and X 2 are different from each other, there may be another asymmetric carbon at the 2 'position of the polyhalogenated ethyl side chain.

Also, the alcohol R-OH forming the alcoholic moiety of the esters of formula (I) may contain one or more asymmetric carbons and / or one or more double bonds which make the E / Z isomerism.

The esters of formula I obtained by the process of the invention include, for a given definition of the general substituents X1, X2, X1 and R, all compounds resulting from the combination of an isomer (racemic 4 or optically active) resulting from the existence of different asymmetric carbons in the isomeric acid moiety. (racemic or optically active) corresponding to the existence of asymmetric carbons in the alcohol moiety of the molecule. Where the general substituents α are identical, they may exist for a given steric configuration of asymmetric carbons at the 1 and 3 positions of the cyclopropane ring, as well as for a given alcohol residue structure (which may also contain one or more asymmetric carbons and / or one or more double of the E / Z isomerism) two diastereoisomeric forms of the esters of the formula I or the corresponding acids (K) due to the existence of an asymmetric carbon at the 1-position. In particular, said two diastereoisomeric forms may be characterized by their nuclear magnetic resonance spectra or their migration rates in thin layer chromatography. These isomers may also be separated and isolated in the pure state, in particular by chromatographic procedures, said two diasteroisomeric forms being referred to herein and elsewhere as isomers (A) and (B). Especially those esters whose cyclopropanecarboxylic acids (K), forming the acidic moiety of said esters, have the structure 1R, cis or 1R, trans: acids 2,2-dimethyl-3 will be mentioned from the esters of the formula I prepared according to the process of the invention. - (2 ", 2 " -dibromo-1 "," dichloroethyl) cyclo-propane-1-carboxylic acid, 2,2-dimethyl-3- (1 "," 2 ","" -tetrachloroethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- (2 ' -difluoro-1 ', 2 ' -dichloroethyl) cyclopropane-1-carboxylic acid 2,2-dimethyl -3- (2 ", 2 " -dichloro-1 ", 2 " -dibromoethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- (2 ", 2 " 1 ", 2 " -dibromoethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl- (1 ", 2 "," 2 " -tetrabromethyl) cyclopropane-1-carboxylic acid, 5 2,2-Dimethyl-3- (2 ', 2'-difluoro-2', 1'-diiodoethyl) cyclopropane-1-carboxylic acid 2,2-dimethyl hyl-3- (2'-dichloro-2 ', 1'-diiodoethyl) cyclopropane-1-carboxylic acid 2,2-dimethyl-3- (2'-dibromo-2'); , 1-diiodoethyl) cyclopropane 1-carboxylic acid, 2,2-dimethyl-3- (1 ", 2 ", 2 ' -tribromoethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- ( 1 ', 2 ' -dichloro-2 ' -bromoethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl- (1 ', 2 ', 2 ' -trichloroethyl) cyclopropane-1-carboxylic acid, 2 , 2-dimethyl-3- (1 ', 2 ' -dibromo-2 ' -chloroethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl- (1 ', 2 ' -dichloro-2 ' -fluoroethyl) cyclopropane -1-carboxylic acid, 2,2-dimethyl- (1 ', 2 ' -dibromo-2 ' -fluoroethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- (2 ' -fluor-2 ", 1-diiodoethyl-cyclopropane-1-carboxylic acid 2,2-dimethyl-3- (2-chloro-2-yl) diiodoethyl-cyclopropane-1-carboxylic acid 2,2-dimethyl-3- (2'-bromo-2 ', 1'-diiodoethyl) cyclopropane-1-carboxy 2,2-dimethyl-3- (1 ', 2 " -trichloro-2 ' -fluoroethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- (1 "," 2 " -dibromo-2 " -chloro-2 ' -fluoroethyl) -cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- (1 "," 2 "," -trichloro-2 ' -bromoethyl) cyclopropane-1 carboxylic acid, 2,2-dimethyl-3- (1 ", 2 ", 2 " -tribromo-2 ' -chloroethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- (2 ' -fluoro- 1, 2'-tribromethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- (2-bromo-2-fluoro-1, 2'-dichloroethyl) cyclopropane-1-carboxylic acid; carboxylic acid, 2,2-dimethyl-3- (2'-fluoro-2 ' -chloro-2 ', 1 ' -diiodethyl) cyclopropane-1-carboxylic acid, 6-2,2-dimethyl-3- ( 2 " -fluoro-2 ", 1 ' -diiodethyl) cyclopropane-1-carboxylic acid, 2,2-dimethyl-3- (2 " -chloro-2 " -bromo-2 "," 1 " cyclo-propane-1-carboxylic acid.

Of course, the esters of formula I prepared by the process of the invention can also be derived from cyclopropanecarboxylic acids (K) having the structure 1S, cis or 1S, trans.

Likewise, these esters of the formula I can be derived either from cyclopropanecarboxylic acids (K) of the dl-cis structure (a mixture of 1R, cis and 1S, cis structures) or dl-trans (equimolar mixture of IR, trans and 1S structures) trans) or a mixture of acids of the dl-cis structure and the acids of the dl-trans structure. In particular, the present invention provides a process for the preparation of compounds of formula I wherein the acid moiety has the structure IR, cis or IR, trans, as well as compounds of formula I in which the acid moiety has the structure dl-cis or dl-trans and compounds having Formula I and mixtures of esters whose acid moiety has the structure dl-cis or dl-trans. Among the alcohol-containing alcohols of the esters prepared by the process of the invention, the following may be cited in particular: benzyl alcohol, 2,5-diethyl-4-allylbenzyl alcohol, 5-benzyl-3-fluoromethanol, 5- (propin-2-yl) -2 -methyl-3-furylmethanol (kikuthrol), 5- (propin-2'-yl) -2-furylmethanol (prothrol), 1-oxo-2-allyl-3-methylcyclopent-2-en-4-ol (allethrolone) , 1-oxo-2- (2 ', 4 ' -pentadienyl) -3-methylcyclopent-2-en-4-ol, 1-oxo-2- (2 ' -butenyl) -3-methyl- cyclopent-2-en-4-ol, 3-phenoxybenzyl alcohol, alpha-cyano-3-phenoxybenzyl alcohol, alpha-ethynyl-3-phenoxybenzyl alcohol, 3,4,5,6-tetrahydrophthalimidomethyl alcohol and especially optically active forms of these alcohols that contain asymmetric carbon.

In particular, compounds of formula (I) will be cited in which X 1 is fluorine, chlorine or bromine, X 2 is identical to X 1 and is fluorine, chlorine or bromine and R 1 and R are as defined above, those compounds in which X1 represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, X2 is different from X1 and represents a fluorine atom,

Chlorine or bromine; and R are as defined above, as well as compounds in which X 1 and X 2 are as defined above and R is 5-benzyl-3-furylmethyl alcohol, 1-oxo-2-allyl- The 3-methylcyclopent-2-en-4-yl radical, the 3-phenoxybenzyl alcohol radical and the alpha-cyano-3-phenoxybenzyl alcohol radical, said alcohols being racemic or optically active alcohols, and compounds wherein X 1 is fluorine atom , chlorine or bromine, X2 is identical to X1 and is fluorine, chlorine or bromine, X1 is chlorine, bromine or iodine and R is 5-benzyl-3-furylmethyl alcohol, 1-oxo The 2-allyl-3-methylcyclopent-2-en-4-yl radical, the 3-phenoxybenzyl alcohol radical and the alpha-cyano-3-phenoxybenzyl alcohol radical, said alcohols being racemic or optically active alcohols.

Of particular interest are the compounds of formula I in the form of the isomers A, in the form of B isomers, the existence of which is due to the asymmetric carbon at position 1 " of the formula (I) or in the form of a mixture of said isomers, the following structures: (S) -? - cyano-3-phenoxybenzyl- (1R, cis-2,2-diethyl-3- (1 ', 2,2,2 * -tetrabromethyl) ) cyclopropane-1 / carboxylate, (S) -alpha-cyano-3-phenoxybenzyl (1R, cis-2,2-dimethyl-3- (2,2 " -di-chloro-1 "," dibromoethylcyclopropane ") -1 / carboxylate. Preferred compounds are also those exemplified. The compounds of formula (I) may be in the form of the isomers A or in the form of the isomers B (these isomeric forms being conditioned by the existence of an asymmetric carbon at the 1-position of formula X or as a mixture of said isomers.

The compounds of the present invention may also be used in the form of mixtures of cis stereoisomers and trans configurations represented in the mixture in any desired amount. Particularly suitable are mixtures of cis stereoisomers and trans configurations represented in said mixture in weight ratios of 20:80, 5:50 or 80:20.

In particular, chlorine or bromine is used as the halogenating agent for the halogenation of the esters of the formula II, the halogenation of the esters of the formula II being carried out in an organic solvent which does not react with said chlorine or bromine, such as carbon tetrachloride, chloroform or methylene chloride.

In general, the esters of formula II used as starting materials in the process of the invention are described in particular in FR 1185612 and FR 2240914, or processes analogous to those described in the aforementioned French patents. In the case where the general substituents X 1 and halogen are, wherein x 1 is different from X 2 ', the esters of formula II are described in the dissertation further Gordon Brown (Denton, Texas), December 1974, " Structure-activity studies of halo pyrethroids " or said compounds may be prepared by methods analogous to those described in the present dissertation.

It goes without saying that the esters of formula II used in the process of the invention exist in numerous isomeric forms, the existence of these forms being due to the existence of asymmetric carbons at the 1 and 3 positions of the cyclopropane ring, and the possible existence of either one or the other. several asymmetric carbons, or one or more double bonds, conducive to E / Z isomerism in the alcohol moiety.

The compounds of the formula I have remarkable insecticidal properties, in particular an extremely intense lethal effect and very good weathering properties (heat, light and moisture).

In view of the above, the compounds of formula I are suitable for use in the control of insects in agriculture. For example, the compounds can be used to effectively control aphids and larvae of lepidopteran and coleoptera insects. The compounds are preferably used in dosages of between 1 and 100 g of active ingredient per hectare of land. Due to their rapid action, the compounds of the formula I can be used as household insecticides. In particular, the insecticidal activity of the compounds of the invention can be demonstrated by tests for domestic fly, Spodoptera Littoralis insects as well as Epilachna Variavestris and Sito-philus Granarius, Tribolium Castaneum and Blatella Germanica insects. These assays are described in the Examples section below. 9

The compounds of the formula I according to the invention can also be used for the preparation of insecticidal compositions containing as active ingredient at least one compound of the formula I, in particular at least one compound of the formula I in the form of isomer A or isomer B , conditioned by the existence of an asymmetric carbon in the 1 'position of the general formula I or in the form of mixtures of these isomers, the names of which have been mentioned above. The insecticidal composition may contain one or more pesticidal agents in addition to the active ingredient (s). Said insecticidal compositions may be formulated in the form of dusts, granules, suspensions, emulsions, solutions, solutions for aerosols, flammable bands, baits or other types of formulations commonly used for a given kind of compounds. In addition to the active ingredient, the compositions contain a carrier and / or a non-ionic surfactant to ensure, inter alia, uniform dispersion of the individual components of the insecticidal composition. The carrier may be a liquid, for example, water, alcohol, hydrocarbon, or other organic solvents, mineral oils, animal oils, or vegetable oils, powder, for example, talc, clay or silicate, optionally diatomaceous earth, or a solid fuel such as e.g. chamomile residue.

In order to enhance the insecticidal activity of the compounds of the present invention, it is possible to use said compounds in admixture with conventional insecticides used in similar cases such as: 1- (2,5,8-troxydodecyl-2-propyl-4,5-methylenedioxy) benzene (piperonyl butoxide), N- (2-ethylheptyl) bicyclo [2.2.1] -5-heptene-2,3-dicarboximide and piperonyl-bis-2- (2'-n-butoxyethoxy) ethyl acetal ( tropital).

These insecticidal compositions preferably contain from 0.005 to 10% by weight of the active ingredient. Said compositions may preferably contain a synergistic agent, in particular piperonyl butoxide. The compounds of the formula I also possess interesting acaricidal and non-carcinogenic properties. This is proven by tests on Tetranychus Urticae and on Ditylenchus Mycellophagus.

The compounds of formula (I) can thus be used for the preparation of acaricidal and non-particulate compositions containing as active ingredient at least one compound of formula (I) in one of its possible isomeric forms, in particular at least one of the following. compounds: isomers A and B / (S) -alpha-cyano-3-phenoxybenzyl / -1R, cis-2,2-dimethyl-3- (1 ", 2 ", 2 "," tetrabromethyl) cyclopropane -1-carboxylate and isomers A and B / (S) -alpha-cyano-3-phenoxybenzyl / -1R, cis-2,2-dimethyl-3- (2,2 " -dichloro-1 "," -dibromoethyl) cyclopropane-1-carboxylate.

As with the above-mentioned insecticidal compositions, said acaricidal and nematocidal compositions may also be used in admixture with at least one other pesticidally active agent. In particular, said acaricidal and nematocidal compositions may be formulated in the form of powders, granules, suspensions, emulsions and solutions.

For acaricidal application, a wettable powder for foliage dusting preferably contains 1 to 80% by weight of the active ingredient, or a liquid for foliar spray containing 1 to 500 g / l of active ingredient. Foliar powder containing 0.05 to 3% by weight of the active ingredient may also be used. For nematocidal application, a soil spray liquid containing 300 to 500 g / l of active ingredient is preferably used.

The acaricidal and nematocidally active compounds prepared by the process of the invention are preferably used in doses of 1 to 100 g of active ingredient per hectare. The acicicidal properties of the compounds of formula I predetermine these compounds for use in combating flowable parasites of animals. The assays given in the examples below show the efficacy of compounds of formula I on Rhipicephalus Sanguineus in a dog. The compounds of formula (I) may be used in animals to control, in particular, all species of scabies, in particular those causing sarcoptic, psorotic and chorioptic scabies. The compounds of formula (I) may also be used to combat all kinds of ticks such as Boophilus, Hyalomnia species, Amblyoma species, and Rhipicephalus species. The invention therefore also relates to a method for controlling mite parasites of animals using a veterinary composition comprising at least one compound of the formula X as active ingredient.

Said compositions may be used by the mechanism of external application, but also by parenteral or oral administration. The compositions may also be used in admixtures with other active ingredients which exhibit a synergistic effect with the compounds of formula (I). These active substances have already been mentioned above. Said compositions may be prepared by conventional procedures. Finally, it is possible to use compounds of the formula I for veterinary purposes in admixture with feed mixtures for cattle and poultry. For example, it is possible to use a feed mixture containing 0.002 to 0.4% by weight (alpha-cyano-3-phenoxybenzyl) -1R, cis-2,2-dimethyl-3R- (2 ', 2', 1 ', 1'). -tetrabromethyl) cyclopropane-1-carboxylate. These feed compositions are comprised of a feed composition which additionally contains at least one compound of formula I. The invention will now be described in more detail by way of example only, and not by way of limitation. the formulation of the claims. EXAMPLES Example 1

[(S) -alpha-3-phenoxybenzyl] - (1R, cis) -2,2-dimethyl-3- (1 ', 2', 2 ', 2 tetrabromethyl) cyclopropane-1-carboxylate, isomer A and isomer B

7.57 g of ((S) -α-cyano-3-phenoxybenzyl) - (1R, cis) -2,2-dimethyl-3- (2 ', 2'-dibromvinyl) cyclopropane are dissolved in 100 ml of carbon tetrachloride. Bromine (2.4 g) dissolved in carbon tetrachloride (15 ml) was added and the resulting mixture was stirred at 20 ° C for 45 minutes and then concentrated to dryness under reduced pressure. The residue obtained is separated (10 g) by silica gel chromatography. Using a 1: 1 mixture of benzene and petroleum ether (t 35 to 75 ° C) as eluent, first isomer A (4.12 g) and then isomer B (4 g) / (S) -alpha-cyano -3-phenoxybenzyl- (1R, cis) -2,2-dimethyl-3- (1 ', 2', 2 ', 2'-tetrabromethyl) cyclopropanecarboxylate.

Isomer A has the following properties: [alpha] D = -53 [deg.] (C = 0.5%, benzene), elemental analysis: C22H19Br4NO3 (665.037) C (%) H (%) B (%) N (%) calculated 39.73 2.88 48.06 2, 1 1 found 39.9 2.9 48.2 2.1, infrared spectrum: absorption at 1740 cm tester), absorption at 1615, 1588, 1573 and 1488 cm \ t aromatic nuclei, nuclear magnetic resonance spectrum: peaks 1.25-1.33 ppm (hydrogens of methyl group at position 2 of the cyclopropane ring), peaks of 1.75-2.17 ppm (hydrogen at position 1 and at position 3 of the cyclopropane ring) , peaks of 5.19-5.55 ppm (hydrogen at the side chain position), peak at 6.38 ppm (benzylic hydrogen), peaks at 6.91 - 7.59 ppm (hydrogens of aromatic nuclei, isomer A is thin-layer chromatography) jšíΕ = -3 at 224 nm, .C = -4.5 at 237 ηπι, Δ. = -0.05 at 290 nm.

Isomer B has the following properties: [alpha] D = + 111 [deg.] (C = 0.6%, benzene), elemental analysis: C22H19Br4NO3 (665.037) C (%) H (%) Br (%) N (%) calculated 39 73 2.88 48.06 2.1 1 found 39.8 3.0 48.1 2.0, infrared (chloroform): absorption at 1743 cm -1 (ester), absorption at 1615, 1588, 1573 and 1488 cm 1, due to the existence of aromatic nuclei, nuclear magnetic resonance spectrum: peaks 1.24-1.40 ppm (hydrogen of methyl groups at position 2 of the cyclopropane ring), peaks of 1.83-2.25 ppm (hydrogen at position 1 and position 2 cyclopropane ring), peaks of 3.98-5.20 ppm (hydrogen at the 1 'side of the side chain), peak 6.39 (benzylic hydrogen), peaks at 6.92-7.52 ppm (hydrogens of aromatic nuclei), isomer B is in thin-layer chromatography, less mobile, circular dichroism: 13 (dioxane) AE = + 4.7 at 223 nm, AE + 4.2 at 247 nm. Example 2

[(S) -alpha-cyano-3-phenoxybenzyl] - (1R, cis) -2,2-dimethyl-3- (2 ', 2'-dichloro-1', 2'-dibromoethyl) cyclopropane-1-carboxylate isomer A and isomer B

17.07 g of ((S) -alpha-cyano-3-phenoxybenzyl) - (1R, cis) -2,2-dimethyl-3- (2 ', 2'-dichloro-vinyl) -cyclopropane-dissolved in 200 ml of carbon tetrachloride Of 1-carboxylate, followed by the addition of 6.55 g of bromine dissolved in 20 ml of carbon tetrachloride. The bromine solution is added over 10 minutes. The reaction mixture is stirred for 48 hours at 20 DEG C. and then concentrated to dryness under reduced pressure by distillation. The residue obtained is separated into individual components (23.8 g of residue) by chromatography on silica gel using a 7: 3 mixture of benzene and cyclohexane as eluent. 10.4 g of isomer A (this isomer is more mobile in thin layer chromatography) and 10 g of isomer B (which is less mobile in thin layer chromatography) are obtained ((S) -alpha-cyano-3-phenoxybenzyl). (1R, cis) -2,2-dimethyl-3- (2 ', 2'-dichloro-1,2'-dibromoethyl) cyclopropane-1-carboxylate.

Isomer A has the following properties: [alpha] D = -61 [deg.] (C = 0.5%, benzene), elemental analysis: C22H19Br2Cl2NO3 (576.125) C (%) H (%) Br (%) Cl (%) N ( % 45.85 3.3 27.74 12.3 2.4 found 45.8 3.3 27.7 12.3 2.3, infrared spectrum (chloroform): absorption at 1738 cm -1 (ester) absorption at 1485, 1585 and 1610 cm -1, due to the presence of aromatic nuclei, nuclear magnetic resonance spectrum: peaks 1.29-1.37 ppm (hydrogen of methyl groups at position 2 of the cyclopropane ring) peaks of about 2.05 (hydrogen at position 1 and at position 3 of the cyclopropane ring), peaks of 5.20-5.29-5.37-5.45 ppm (hydrogen bound to the asymmetric carbon of the side chain), peak 6.45 ppm (benzyl hydrogen), peaks 7 , 0-7.6 ppm (aromatic nucleus hydrogens), 14 circ.dichroism (dioxane): = = -8 at 221 nm (inflection), & = = 0.14 at 289 nm (max).

Isomer B has the following properties: [alpha] D = + 119 [deg.] (C = 1%, benzene), elemental analysis: C22H19Br2Cl2NO3 (576.125) C (%) H (%) Br (%) Cl (%) N (%) Calculated 45.86 3.3 27.7 12.3 2.4 found 46.2 3.4 27.6 12.2 2.3, infrared absorption at spectrum: 1740 cm @ -1 (ester), absorption at 1610, 1585 and 1485 cm -1 (aromatic nuclei), nuclear magnetic resonance spectrum: peaks 1.25-1.38 ppm (hydrogens of methyl groups at position 2 of the cyclopropane ring), peaks 1.87-2.3 ppm (hydrogens at position 2) and at the 3-position of the cyclopropane ring), the peaks at 4.97-5.01-5.11-5.16 ppm (hydrogen bound to the asymmetric carbon of the side chain), the peak at 6.46 ppm (benzylic hydrogen), the peaks at 7- 7.67 ppm (hydrogens of aromatic nuclei, circ. Dichroism (dioxane): = £ = +9 at 220-221 nm (max.), Δ £ - +0.23 at 289 nm (max.). RS) -α-cyano-3-phenoxybenzyl] - (1R, trans) -2,2-dimethyl-3- (1 ', 2', - 2,2'-tetrabromethyl) cyclopropane-1-carboxylate

This compound was obtained by treatment with bromine on ((RS) -alpha-cyano-3-phenoxybenzyl) - (1R, trans) -2,2-dimethyl-3- (2,2'-dibrominyl) cyclo-propane-1-carboxylate. in the form of isomer A and isomer B.

Infrared spectrum (chloroform): -1 -1 absorption at 1740, 1586 and 1485 cm, nuclear magnetic resonance spectrum: peaks 1.20-1.26 ppm (hydrogens of methyl groups at position 2 of the cyclopropane ring), peaks of 4.3-4.48 -4.67 ppm (hydrogen at position 1 'of the side ethyl chain at position 3 of the cyclopropane ring), peak 6.48 ppm (hydrogen bonded to carbon at which C = N is bonded), peaks at 6.97-7, 17 (aromatic ring hydrogens). Example 4 / (RS) -alpha-cyano-3-phenoxybenzyl [1- (1R, trans) -2,2-dimethyl-3- (2,2-dichloro-1, 2'-dibromoethylcyclopropane-1-carboxylate]

This compound was prepared by bromination with ((RS) -alpha-cyano-3-phenoxybenzyl) - (1R, trans) -2,2-dimethyl-3- (2 ', 2'-dichlorvinyl) cyclopropane-1-carboxylate in infrared spectrum (chloroform): absorption at 1743, 1588, and 1487 cm @ 2 nuclear magnetic resonance spectrum: peaks 1.20-1.26-1.32-1.35 ppm (hydrogens of methyl groups in position 2) of the cyclopropane ring), peaks of 1.68-1.77 ppm (hydrogen at position 1 of the cyclopropane ring), peaks of 1.95-2.42 ppm (hydrogen at position 3 of the cyclopropane ring), peaks of 4.23-4.25- 4.40-4.42-4.57 ppm (hydrogen at position 1 * of the ethylene chain at position 3 of the cyclopropane ring), peak 6.48 ppm (hydrogen bonded to carbon at which C = N is bonded), peak 7 , 0-1.67 ppm (hydrogens of aromatic nuclei). Example 5 ((R, S) -alpha-cyano-3-phenoxybenzyl) -1d-cis-trans-2,2-dimethyl-3- (2 ', 2'dichloro-1,2'-dibromoethyl) cyclopropane-1-carboxylate

Use ((R, S) -α-cyano-3-phenoxybenzyl) -1d-cis-trans-2,2-dimethyl-3- (2 ', 2'-dichlorvinyl) cyclopropane-1-carboxylate having the following properties: ultraviolet spectrum (ethanol): inflection at 226 nm (E1 * 522), inflection at 267 nm (e] = 43), inflection at 272 nm (E1 = 47), maximum at 278 nm (Ej = 52), nuclear magnetic resonance spectrum (CDCl3): peaks 1.20-1.30 ppm (hydrogen of methyl groups), peaks of 5.60-5.75 ppm (hydrogen at position Γ of dichlorvinyl chain corresponding to isomer of trans), peaks 6.20-6, 31 ppm (hydrogen at position 1 * of dichlorvinyl, chain corresponding to cis isomer), peaks at 6.41-6.46 ppm (hydrogen bonded to carbon at alpha to function -CN), peaks at 7.0-7.66 ppm ( aromatic nuclei).

6.7 g of ((R, S) -alpha-cyano-3-phenoxybenzyl) -1d-cis-trans-2,2-dimethyl-3- (2 ', 2'-dichlorvinyl) - are added to 30 ml of carbon tetrachloride. The cyclopropane-1-carboxylate of the above properties and a solution of 0.85 ml of bromine in 10 ml of carbon tetrachloride are added over about one hour to the mixture thus formed. The mixture was stirred at 20 ° C for two hours and then concentrated to dryness under reduced pressure to give 10 g of crude product. The crude product is purified by chromatography on silica gel eluting with cyclohexane: ethyl acetate (9: 1) to give 7.5 g of ((R, S) - .alpha.-cyano-3-phenoxybenzyl) -dis-cis. trans-2,2-dimethyl-3- (2 ', 2'-dichloro-1', 2'-dibromoethyl) cyclopropane-1-carboxylate.

Elemental analysis: C22H19O3NCl2Br2 C (%) H (%) N (%) Cl (%) Br (%) calculated 45.86 3.32 2.43 12.30 27.74 Found 46.2 3.6 2 , 4 12.5 27.5, ultraviolet spectrum (ethanol): inflection at 267 nm (EI = 34), inflection at 272 nm (e] = 35), max -1 mum at 277 nm (E1 = 38), nuclear magnetic resonance spectrum: peaks 1.20-1.44 ppm (hydrogens of methyl groups), peaks 1.54-2.40 ppm (hydrogens at position 1 and position 3 of the cyclopropane ring), peaks 4.21-4.51 ppm (hydrogen at the 1-position of the dichlorvinyl chain corresponding to the trans isomer), peaks at 4.97-5.40 ppm (hydrogen at the λ 'position of the dichlorvinyl chain corresponding to the cis isomer), peaks at 6.42-6.50 ppm (hydrogen bonded to carbon at position alpha to the -CN group, peaks of 7.0-7.55 ppm (hydrogens of aromatic nuclei). Example 6

Study of insecticidal properties of isomers A and B / (S) -alpha-cyano-3-phenoxybenzyl- (1R, cis) -2,2-dimethyl-3- (1 ', 2', 2 ', 2'-tetrabromo- ethyl) cyclopropane-1-carboxylate (compounds Y1 and Y4), insecticidal properties of isomers A and B / (S) -alpha-cyano-3-phenoxybenzyl (- (1R, cis) -2,2-dimethyl-3- ( 2 " -dichloro-1 " -dibromoethyl) cyclopropane-1-carboxylate (compound < RTI ID = 0.0 > Y < / RTI > as well as the insecticidal properties of (RS) -alpha-cyano-3-phenoxybenzyl) -dl-trans-2 , 2-dimethyl-3- (2 ', 2'-dichloro-1', 2'-dibromoethyl) cyclopropane-1-carboxylate (compound, {(RS) -alpha-cyano-3-phenoxybenzyl] -1R, trans -2,2-dimethyl-3- (4 ', 2, 2,2' -tetrabromethyl) cyclopropane-1-carboxylate (compound Yg, / (RS) -alpha-cyano-3-phenoxybenzyl / -1R, cis- 2,2-dimethyl-3- (2 ', 2'-dibromo-1', 2'-dichloroethyl) cyclopropane-1-carboxylate (Compound Y1), [(RS) -alpha-cyano-3-phenoxybenzyl] [-1R, trans-2,2-dimethyl-3- (2,2-dichloro-1 ', 2'-dibromoethyl) cyclopropane-1-carboxylate (compound Yg) and [5-benzyl-3-fury] 1-methyl-1R, cis-2,2-dimethyl-3- (1 ', 2', 2 ', 2' -tetrabromethyl) cyclopropane-1-carboxylate.

Study of Lethal Effect of Compound Y ^ on Housefly 1) Stidium Activity of Compounds Y1, Y2, Y3 and Y4

The insects used in this test are four-day-old female flies. Using an Arnold micromanipulator, these females are topically applied with 1 µl of acetone solution to dorsal thorax. 50 individuals are used for this assay. Mortality is assessed 24 hours after administration. The test is performed using only the compounds of the invention and using these compounds in admixture with piperonyl butoxide (10 parts of the synergistically active compound per part of test compound). The results shown in Table 1 below are expressed as DL ^ q (in nanograms), the dose necessary to kill 50% of the insects.

Table 1

Compound Y- DLjq (nanograms) Compound Y- Compound Y-, Compound Y. 2 3 4 isomer A isoner B isomer A isomer B No use synergistically active substance 1.13 1.0 1.25 0.60 Using a synergistically active substance 0.24 0.55 0.83 0.46

Compounds Y1, Y2, Yg and Y4 have extremely high lethal activity on the house fly. This activity may be enhanced by combination with piperonyl butoxide. 18 2) Study of compound efficacy

The conditions of this assay are the same as those given in the above assay, giving the results shown in Table 2 below.

Table 2 Dose of active substance (mg / l) Mortality in% after 24 hours DL50 (ng / insect) Compound Y_ 5 83.3 alone 3.75 76.7 2.50 63.3 1.25 26.6 2.03 Compound Y_5 100 together with 2 5 93.3 synergistically reactive 1.0 46.6 0.99 0.5 16.7

The compound exhibits very pronounced insecticidal activity against domestic flies. B) Study of the flying effect on Spodoptera littoralis larvae 1) In this test, a topical application of the acetone solution is carried out using an Arnold micromanipulator to the dorsal thorax of the larvae. 10-15 larvae per dose of test product are used. The larvae used are larvae in the fourth larval stage, i. larvae about 10 days old. The larvae were kept in a heat environment at 24 ° C and 65% relative humidity. After application, the larvae are placed on an artificial medium (Poitoit medium). Mortality is evaluated 48 hours after administration. The results obtained are shown in Table 3 below.

Table 3

Compound Y 1 (isomer 3 ° (ng) Compound (Isomer B) 0.32 0.68 19

The compounds and the present invention show extremely high lethal activity on Spodoptera littoralis larvae. 2) Insecticidal activity of a substantially equimolar mixture of compound Y 1 and compound Y 1 in a substantially equimolar mixture of compound Y 1 and compound Y 1, compound Y7 and compound Y 1 on Spodoptera Littoralis caterpillar. 1 µL of test product acetone solution is applied to each individual's dorsal thorax. For each dose used, 15 Spodoptera Littoralis caterpillars are used in the fourth larval stage. After said application, the caterpillars are placed on an artificial medium (Poitoit's broth). At 24 hours and 48 hours after administration, efficacy control (percent mortality relative to the control group of caterpillars to which no active compounds were applied) was performed and the lethal dose of DL, -q in nanograms per bead was determined. The results obtained are shown in Table 4 below.

Table 4

Compound Dose Effective Effectiveness in% after DL ^ q after 48 hours of substance (mg / l) 24 h 48 h (ng (bead) Essentially equimolar-0.5 80.0 66.7 spherical mixture of compound Y ^ (isorner A) and Compounds Y ~ (iso- 0.375 53.3 40.0 0.25 33.3 33.3 mer B) 0.125 0 0 0.38 Essentially equimolar-0.5 100 100 bead mixture 0.375 76.7 73 Y, (isomer A) and Y. (iso- 0.25 40.0 40.0 mer B) 0.125 49.3 20.0 0.31 Compound Y-, 2.5 100 1.25 66 , 6 0.625 53.3 0.312 40.0 0.51 - 20 -

Table 4 (continued)

Compound Yg 1 93.2 0.75 66.6 0.50 46.6 0.25 13.3 0.51

Control group of caterpillars: no mortality.

The test compounds show high potency against Spo-doptera littoralis. C) Study of time dependence of insecticidal activity of compounds of the invention

The tested insects are 4-day-old female flies. Sprays were used in Keans and March's chambers using a mixture of equal volumes of acetone and kerosene (amount of solution used: 2 x 0.2 mL) as solvent. About 50 insect individuals are used per application. An insect mortality check is performed every minute up to 10 minutes and then after 15 minutes, determining the q -q value by the usual method. The results obtained are shown in Table 5 below.

Table 5 KT ^ q in minutes (for 1 g / l) Compound Y1 Compound Y2 Compound Y ^ Compound (isomer A) (isomer B) (isomer A) (isomer B) 3.5 6.5 4.5 4.2

KT5Q (" knock-time ") means the time that 50% of insects die at a given dose of test product. This time is inversely proportional to the rate of action of the test product.

The compounds Y 1, Y 2, Y 1 and Y 4 of the invention have a rapid lethal effect on flies. D) Study of insecticidal efficacy of compound Y 1 (isomer A) and Y 4 21 (isomer B) as well as Yg, Yg, Y 1 and Yg on larvae of Epilachna Vari-vestris This test performs topical application in the same manner as it was performed in the previous case at lareb spo-doptera. Larvae larvae are used for larvae and after application the larvae feed on bean leaves. 72 hours after dosing, larval mortality is evaluated. The results obtained are shown in Table 6 below.

Table 6

Compound Dose (mg / l) Mortality (%) D150 (ng / insect Compound Yg 1.25 100 (isomer A) 1 90 0.625 60 0.312 50 0.37 Compound Y ^ 1 90 (isomer B) 0.625 80 0.312 70 0.156 40 0.20 Compound Yg 5 100 2.5 80 1.25 70 0.625 50 0.53 Compound Yg 2.5 90 1.25 80 0.625 60 0.312 40 0.44 Compound Y ^ 5 100 2.5 90 1.25 50 0.625 40 0.93 Compound Yg 5 100 2.5 80 1.25 60 22

Table 6 (continued) 22 0.625 0.312 40 20 0.88 E) Study of insecticidal activity of a substantially equimolar mixture of compound Y (isomer A) and compound (isomer B) and a substantially equimolar mixture of compound Y (isomer A) and compound Y4 (isomer B) to Sitophilus Granarius and Tribolium Castaneum

This test is carried out by direct dusting of the contaminated grain.

Spray 5 ml of the test product acetone solution and 0,1 ml water per 100 g of grain contained in a one liter rotary flask (on the move). An infestation is carried out with 50 insect individuals (Sitophilus or Tribolium). For each dose at the end of the seventh day, the percent mortality with respect to the control group of insects to which the active ingredient is not applied and the lethal concentration of CL ^ q is determined. The results obtained are shown in Table 7 below.

Table 7

Compound Dose Efficacy after 7 d (%)

Sitophilus Tribolium Sitophilus Tribolium Granarius Castaneum Granarius Castaneum Essentially equimolar mixture of compound Y1 (isomer A) and compound Y ^ (isomer B) 1 67,0 0,5 28,7 0,25 4,0 100,0 92,0 0, 75 24.3 0.32 Essentially equimolar mixture of compound Y, (isomer A) and compound Y4 (isomer B) 1 62.5 0.5 18.4 0.25 2.0 100 99.0 62.6 0, 85 0.22 23 Insect control mortality: Sitophilus Granarius 1.0%, Castolium Castaneum 4.0%.

The tested mixtures have a very strong insect activity, Tribolium Castaneum. Their insecticidal activity against Sitophilus Granarius is somewhat lower. F) Insecticidal Activity Study of the Compounds of the Invention against Blatella Germanica In this test, adult male insects and essentially equimolar mixtures of Y1 (isomer A) and Y2 (isomer B) as well as substantially equimolar mixtures of Y ^ (isomer) are used. A) and Y4 (isomer B). This test is performed in a film deposited on glass. 2 ml of acetone containing 10 mg / l of test product is poured into a 154 cm 2 petri dish and allowed to evaporate. The film thus obtained contains 1.3 mg of active ingredient per m. Insects are placed on the film. After 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 40 minutes, 50 minutes and 60 minutes, the number of paralyzed insects is evaluated. Then the insects are transferred to clean containers. Insect mortality was evaluated 24 hours, 48 hours, and 72 hours (the percentage of paralyzed insects and the percentage of dead insects calculated on the control group of insects). The results obtained are shown in Table 8 below. 24 a

Compound Active substance Percentage of paralyzed insects after Percentage mortality CN P- oo sr rr O) t o < T > omoo o VO r- o tn o o o • 6 MGc tn oooo o t o - o 09 o t o o t o o o o o mo o c t > - 40 06 09 tn 1— o 70 30 o * - o tn o tn ooo cn 00 cn o * 04 tn ooo tn o o 04 co m * “< y Ol quot " 04 1 co tn tn o t o tn or * θ 'cn x: ou' «4J 40 oo 45 ooo 3 C • 3 o tn t e CN CN cn rH 3 3 N > n 14 c 1 Sl 1 5 0 't8 H 0 QNQNN • iH 3 N * * H H o * * (U 04 S * > · tn ί · > · > 1 CC -i-í c * cc > 8 > 8 8 8

0) * S 2? 2 c • Η C C C C C C C C C C C C &&&&& 8 8 8 lt lt lt lt lt lt lt lt lt lt lt lt lt lt lt lt lt lt lt lt < with

Substantially equimolar mixtures of compound Y1 and compound Y2, as well as substantially equimolar mixtures of compound Y1 and compound Y1, have remarkable insect activity Blatella Germanica Example 7

Study of acaricidal activity of compound Y1, mixture of compound Y1 (isomer A) and compound Y4 (isomer B), as well as compounds Y1 (isomer A) and compound Y4 (isomer B) A) Activity on Tetranychus Urticae Test with eggs and larvae This test uses bean leaves infested with 10 female Tetranychus Urticae on one leaf at a time. The leaves are coated with glue on the perimeter. The females are allowed to lay eggs for 24 hours. The females are then removed from the leaf and the leaves of the infested egg are divided into two groups. a) a test merger is applied to the first group of leaves. This is done by spraying 0.5 ml of an aqueous solution each sheet using concentrations of 50 and 25 g of test compound per hectare. b) The active group is not applied to the second group of leaves and this group of leaves serves as the control group. The number of live eggs and live larvae is evaluated in days after administration. The results, expressed as a percentage of egg and larval mortality (relative to the control group), are shown in Table 9 below.

Table 9

Compound

Grams effective Number can withstand mortality (%) of substance per hectare egg egg larvae Essentially equimolecules 50 103 25.2 33.8 refractive mixture of compound Yj (isomer A) and longitudinal component Y ^ (isomer B) 25 161 22, 4 22.4 Essentially equimolecules 50 85 45.9 23.9 fracture mixture of compound Y ^ (isomer A) and compound 25 61 19.7 21.5 runes Y ^ (ison B) Control group 0 181 7.7 2.4 26 A substantially equimolar mixture of compounds Y1a and as a substantially equimolar mixture of compounds and Y4 have ovicidal and larvicidal activity against Tetranychus Urticae. B) Effectiveness on Panochynus Ulmi

This test was performed using Compound Y2, applied to grapevine " Sirah ". The test was repeated for each dose four times by the block method. A single control was applied to each block without active compound administration. Each plot includes 10 vines. The application of the active ingredient is carried out by spraying at a rate of 1000 liters of spray solution per hectare using a Van de Weij sprayer operated at constant pressure. After 7 days, 16 days and 26 days after administration, the numbers of mobile forms (larvae and adults) present on 15 leaves are evaluated by separating these forms from the leaves with a brush and adding them to the control experiment. The results obtained are summarized in Table 10 below.

Table 10

Number of mobile forms on 15 sheets after Dose 7 days 16 days 26 days 2.5 g / h compounds Y2 338 453 356 Trial 492 967 696

Compound Y2 exhibits good acaricidal activity against Panochynus Ulmi larvae and adults. Example 8

Study of nematocidal efficacy of a mixture of compound Y (isomer A) and compound Y (isomer B) and mixtures of compound Y (isomer B) and compound Y ^ (isomer A) on Ditylenchus Myceliophagus

0.5 ml of water containing about 2000 nematodes is added to a tube containing 10 ml of the test aqueous acaricide solution to be tested. Mortality is assessed by binocular magnification 24 hours after application, with three replicates corresponding to 1 ml of 27 test solution each. The experimental results obtained are shown in Table 11 below, which are based on the control experiment.

Table 11

Compound Active substance (mg / 1) Mortality (%) Essentially equimolar 10 99 mixture of compound (isomer 1 23.5 A) and compound Y2 (isomer B) Substantially equimolar 10 99.3 mixture of compound Y ^ (isomer 1 41, 5 A) and Y 1 (isomer B)

The test mixtures have a pronounced nematocidal activity. Example 9 A homogeneous mixture was prepared comprising: ((S) -alpha-cyano-3-phenoxybenzyl) - (1R, cis) -2,2-dimethyl-3- (1 ', 2 ', 2 ', 2 '- tetrabromethyl) cyclopropane-1-carboxylate (isomer A) 0.25 g piperonyl butoxide 1 g Tween 80 0.25 g Topanol 0.1 g water 98.4 g ·

This mixture is an emulsifiable concentrate. Example 10 A perfect blend is prepared comprising: ((3) -alpha-cyano-3-phenoxybenzyl) - (1R, cis) -2,2-dimethyl-3- (1,2,2,2 " -tetrabromethyl) cyclic -propane-1-carboxylate (isomer A) 0.015 g piperonyl butoxide 0.5 g 28

Topanol A 0.1 g xylene 99.385g.

This mixture is an emulsifiable concentrate. Example 11 A homogeneous mixture is prepared comprising: ((S) -alpha-cyano-3-benoxybenzyl- (1R, cis) -2,2-dimethyl-3- (1 ', 2 *, 2 *, 2 " -tetrabromethyl) cyclopropane-1-carboxylate (isomer A) 1.5 g Tween 80 20 g Topanol A 0.1 g xylene 78.4 g Example 12 Preparation of Smoke Preparation A homogeneous mixture is prepared comprising: ((S) -alpha-cyano) -3-phenoxybenzyl (- (1R, cis) -2,2-dimethyl-3- (1 ', 2', 2 ', 2' - tetrabromoethyl) cyclopropane-1-carboxylate (isomer A) 0,25 g cedar powder 40 g pine wood powder 33.75 g brilliant green 0.5 g p-nitrophenol 0.5 g Example 13

Preparation of an insecticidal composition containing a compound of formula (I) A mixture comprising: ((RS) -alpha-cyano-3-phenoxybenzyl) -1d, cis-trans-2,2-dimethyl-3- (2,2-dichloro-1) is prepared. 1,2-dibromoethyl) cyclo-1-carboxylate 1 g piperonyl butoxide 8 g Tween 80 1 g Topanol A 0.1 g water 89.9 g Example 14 29

Compound feed containing a compound of formula I

As basic balanced feed ingredients, feed containing corn, dehydrated alfalfa, cereal straw, melamine cuts, urea and mineral vitamin spice are used. This feed contains at least 11% crude protein material (of which 2.8% is supplied with urea), 2.5% fat and a maximum of 15% cellulose, 6% mineral and 13% moisture. The feed used corresponds to 82 feed units per 100 kg and in 100 kg it contains: 910 000 UI of vitamin A, 91 000 UI of vitamin D, 15 mg of vitamin E and 150 mg of vitamin C. 0,04 kg (alpha) -cyano-3-phenoxy-benzyl) -1R, cis-2,2-dimethyl-3- (2 ', 2', 2 ', 1'-tetrabromoethyl) cyclopropane-1-carboxylate (mixture of Y1 and Y ^). Example 15 A solution is prepared containing: (S) -α-cyano-3-phenoxybenzyl (-1R, cis-2,2-dimethyl-3- (1, 2, 2 ', 2' - (RS) -tetrabromethyl) ) - cyclopropane-1-carboxylate 50 g Emcol H 300 B + 80 g xylene 870 g +) mixture of calcium salt of alkylbenzene sulfonate (anionic moiety) and polyoxyethylene ether (nonionic moiety).

Claims

1. An insecticidal, acaricidal and nematocidal composition comprising, as active ingredient, at least one cyclopropanecarboxylic ester with a polyhalogen group in one of its isomeric forms of the formula (I).

wherein is hydrogen, fluorine, chlorine or bromine,% 2, which is identical to or different from X, is fluorine, chlorine or bromine, X1 is chlorine or bromine and R is benzyl a group optionally substituted by at least one group comprising alkyl groups having a total number of carbon atoms of 1 to 4, alkenyl groups having a total number of carbon atoms of 2 to 6, alkenyloxy groups having a total number of carbon atoms of 2 to β, alkanedienyl groups having a total number of carbon atoms of 4 to 8, methylenedioxy and benzyl, or a group of formula

wherein the substituent is hydrogen or methyl and R2 is phenyl or 5-benzyl-3-furylmethyl or the group of general formula 31

wherein is alkenyl having 2 to 6 carbon atoms, in particular vinyl or propen-1-yl or a group of formula

-CsCH and Rj are chlorine or methyl and n is an integer equal to 0.1 or 2, and especially 3-phenoxybenzyl or alpha-cyano-3-phenoxybenzyl or a group of formula

wherein S / I denotes an aromatic or analogous dihydro- or tetrahydro-ring.

An insecticidal composition according to claim 1, characterized in that it contains at least one cyclopropanecarboxylic acid ester with a polyhalogen group in all its possible isomeric forms of the formula I as active substance.

is a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom which is identical to or different from X 1, is a fluorine atom, a chlorine atom or a bromine atom, is a chlorine atom or a bromine atom and is a benzyl group optionally substituted by at least one alkyl group groups having a total number of carbon atoms of 1 to 4, alkenyl groups having a total number of carbon atoms of 2 to 6, alkenyloxy groups having a total number of carbon atoms of 2 to 6, alkanedienyl groups having a total number of carbon atoms of 4 to 8, methylenedioxy and benzyl groups or a group of formula

wherein R 1 is hydrogen or methyl and the substituent is phenyl or 5-benzyl-3-furylmethyl, or

wherein the alkenyl group contains from 2 to 6 carbon atoms, in particular a vinyl group or a propen-1-yl group, or a group of the formula H

4 in which is hydrogen, -C = N or -C = CH and Rj is chlorine or methyl and 33 is an integer equal to 0, 1 or 2, and especially 3-phenoxybenzyl or alpha-cyano A 3-phenoxybenzyl group, or a group of the formula

wherein S / I denotes an aromatic or analogous dihydro- or tetrahydro-ring.

3. Insecticidal composition according to claim 2, characterized in that it contains a substance having a synergistic effect with pyrethrinoid compounds.

4. A process for the preparation of an active compound of the formula I according to claim 1, wherein the ester of the formula II is

wherein and R are as defined above and which is in one of its isomeric forms, act with a chlorinating or brominating agent capable of binding two chlorine atoms or two bromine atoms to the cyclopropanecarboxylic acid side chain double bond.