WO1992006065A1 - New pyrethrinoid esters of 4-(dihalogenomethyl) 2,3,5,6-tetrafluorobenzylic alcohol, preparation method thereof and application thereof as pesticides - Google Patents

Abstract

The invention relates to compounds of formula (I) wherein Hal1 and Hal2, the same or different from each other, are a halogen atom, X is a hydrogen atom, an alkyl, alkenyl or alkynyl radical having up to 4 carbon atoms or a cyano radical or an aralkynyl radical having up to 10 carbon atoms, and A is the residue of a pyrethrinoid acid, in all the possible diastereoisomer forms thereof and their mixtures. The compounds of formula (I) have interesting pesticide properties.

Description

 New pyrethroid esters of alcohol 4- (dihaloαenoethyl) 2,3,5-6-tétrafluorobenzylicrue- their preparation process and their application as pesticides.

The present invention relates to new pyre¬ thrinoid esters of 4- (dihalomethyl) 2,3,5,6-tetrafluorobenzyl alcohol, their preparation process and their application as pesticides. The subject of the invention is the compounds of formula (I):

in which :

- Hal, ^and Hal ₂ identical or different from each other, represent a halogen atom,

- X represents a hydrogen atom, an alkyl radical, alké- nyle or alkynyl containing up to 4 carbon atoms or a cyano radical or an aralkynyl radical containing up to ₁ 0 carbon atoms,

- And A represents the remainder of a pyrethroid acid, in all their possible diastereoisomeric forms as well as their mixtures.

Hal., And Hal- preferably represent a fluorine, chlorine or bromine atom.

When X represents an alkyl radical, it is preferably a methyl radical. Among the preferred compounds of the invention, mention may be made of the compounds in which Ha 2 and Hal ₂ represent the same halogen atom, for example those in which Hal _j and Ha ₁ , each represent a fluorine atom. We can égalemen _t it _t st as preferred compounds of the invention those in which X represents a hydrogen atom.

A more particular subject of the invention is the compounds of formula (I) as defined above, in which: either A represents a radical:

in which: - Z _j . ^{and z} ₂ - ^ each have a methyl radical,

- or Z _j _ represents a hydrogen atom and

- either Z ₂ represents a radical:

dans lequel Z₃ représente un atome d'hydrogène ou d'halogène et T^ et T₂, identiques ou différents, représentent un atome d'hydrogène, un atome d'halogène, un radical alkyloxy ou alkyle renfermant de 1 à 8 atomes de carbone éventuellement substitués par des halogènes, un radical mono-, di- ou tri- fluorométhyle ou cyano ou un noyau phényle éventuellement substitué par un halogène, ou T₁ et T₂ forment ensemble un radical cycloalkyle renfermant de 3 à 6 atomes de carbone ou un radical :

in which Z ₃ represents a hydrogen or halogen atom and T ^ and T ₂ , which are identical or different, represent a hydrogen atom, a halogen atom, an alkyloxy or alkyl radical containing from 1 to 8 atoms carbon optionally substituted by halogens, a mono-, di- or tri-fluoromethyl or cyano radical or a phenyl ring optionally substituted by a halogen, or T ₁ and T ₂ together form a cycloalkyl radical containing 3 to 6 carbon atoms or a radical:

in which B represents an oxygen or sulfur atom - or Z ₂ represents a radical: \

/ \ cd in which a, b, c and d, identical or different, each represent a halogen atom, - either Z ₂ represents a radical:

\

vs

0 in which D represents a hydrogen or halogen atom, an alkyloxy radical containing from 1 to 8 carbon atoms, G represents an oxygen or sulfur atom and J represents either a linear, branched or cyclic alkyl radical , saturated or unsaturated, containing from 1 to 8 carbon atoms, optionally substituted by one or more functional groups, identical or different, or else an aryl group containing from 6 to 14 carbon atoms, optionally substituted by one or more functional groups identi ¬ that or different, or else a heterocyclic radical possibly substituted by one or more functional groups, identical or different, or else A represents a radical:

dans lequel U, en position quelconque sur le noyau benzénique, représente un atome d'halogène, un radical alkyle renfermant de 1 à 8 atomes de carbone ou un radical alcoxy renfermant de 1 à 8 atomes de carbone, m représentant le nombre 0, 1 ou 2 et quand m est 2, les substituants U peuvent être identiques ou différents.

in which U, in any position on the benzene ring, represents a halogen atom, an alkyl radical containing from 1 to 8 carbon atoms or an alkoxy radical containing from 1 to 8 carbon atoms, m representing the number 0, 1 or 2 and when m is 2, the substituents U can be the same or different.

When T, T ₂ or 1- represent a halogen atom, it it is preferably a fluorine, chlorine or bromine atom.

When ^ or T ₂ represents an alkyl or alky¬ loxy radical, it is preferably a methyl, ethyl, propyl, methoxy, ethoxy or propoxy radical. a, b, c and d preferably represent a chlorine or bromine atom.

When D represents a halogen atom, it is preferably a fluorine, chlorine or bromine atom. When J represents an alkyl radical substituted by one or more functional groups, alkyl is preferably understood to mean a radical containing from 1 to 8 carbon atoms such as, for example, the methyl, ethyl, propyl, isopropyl, butyl or isobutyl radical. or tert-butyl and by functional group one of those mentioned in the European application published under the number 50534.

J can also represent an alkyl radical substituted by an aryl radical, in particular an optionally substituted phenyl radical. When J represents an alkyl radical substituted by one or more functional groups, there may be mentioned as preferred values of J, the radicals:

- (CH ₂ ) _n -C (Hal) ₃ in which n ₁ is an integer from 1 to S and Hal άn halogen atom, for example the radical -CH ₂ -CC1 ₃ , -CH ₂ -CF ₃ , - CH ₂ -CH ₂ -CC1 ₃ or CH ₂ -CH ₂ -CF ₃ ;

- (CH ₂ ) _n -CH (Hal) ₂ in which Hal is defined as above and n _{2 is} a number from 0 to 8, for example the radical -CH ₂ -CHC1 ₂ , -CH ₂ -CHF ₂ or -CHF ₂ ; - (CH ₂ ) _n -CH ₂ (Hal) in which n ₁ and Hal are defined as above, for example the radical -CH ₂ -CH ₂ C1 or -CH ₂ -CH ₂ F, -C (CHal ₃ ) ₃ in which Hal is defined as above, for example the radical -C (CF ₃ ) ₃ or -C (CF ₃ ) ₂ ~ CC1 ₃ , -C (CF ₃ ) ₂ -CH ₃ , -C (CH ₃ ) ₂ -CF ₃ or -C (CH ₃ ) (CF ₃ ) -CH ₂ -CK ₃ , -CH (CF ₃ ) -CH ₃ or -CH (CF ₃ ) ₂ , -C (CH ₃ ) ₂ -CN , -CH (CH ₃ ) -CN or - (CH ₂ ) _n -CN in which n is defined as above, -CH (CN) -C (Hal), in which Hal is defined as above, for example the radical: -CH (CN) -CC1 ₃ - (CH ₂ ) _n -0R _a , in which n ^ is defined as above and R represents a hydrogen atom or a linear or branched alkyl radical containing from 1 to 8 carbon atoms, for example the radical -CH ₂ -OCH ₃ , -CH ₂ -CH ₂ -0-CH ₃ , -CH ₂ -CH ₂ -0-CH ₂ -CH ₃ or -CH ₂ -CH ₂ -OH;

in which n ^ and R _a are defined as above and the two radicals R _a can be different from each other, for example the radical:

-CH ₂ -CH ₂ -NH-CH ₃ , -CH ₂ -CH ₂ -N (CH ₃ ) ₂ or -CH ₂ -CH ₂ -N (CH ₃ ) -CH ₂ -CH ₃ ; - (CH ₂ ) _n - ¹

in which ^ is defined as above, for example the radical:

- (CH ₂ ) _n -CH (OH) -CH ₂ -OH

1 in which n ^ is defined as above for example the radical

est défini coi-ime précédemment et THP représente le radical 2-tétrahydropyrannyle, par exemple le radical : -CH₂-O-THP ou -CH₂-CH₂-O-THP ;-CH ₂ -CH (OH) -CH ₂ -OH; "(CH ₂ ) _n -O-THP in which

is defined above and THP represents the 2-tetrahydropyrannyl radical, for example the radical: -CH ₂ -O-THP or -CH ₂ -CH ₂ -O-THP;

1 - = ^/ in which n ^ _^ is defined as above, for example the benzyl or phenethyl radical;

in which n ^ is defined as above, for example the radical:

When J represents an optionally substituted aryl radical, it is preferably the optionally substituted phenyl radical.

When J represents a heterocyclic radical, they are preferably pyridyl, furyl, thienyl, oxazolyl or thiazolyl radicals.

Among the most interesting compounds of formula (I), there may be mentioned:

- the compounds of formula (I) in which A represents a radical:

- the compounds of formula (I) in which A represents a radical

in which Hal represents a halogen atom and J represents _t an alkyl radical containing from 1 to 8 carbon atoms, linear, branched or cyclized and saturated, optionally substituted by one or more halogen atoms, the double bond having the geometry (E), for example those in which Hal represents a fluorine atom and J a linear or branched alkyl radical containing up to 4 carbon atoms. - the compounds of formula (I) in which A represents a radical:

- the compounds of formula (I) in which A represents a radical:

- the compounds of formula (I) in which A represents a radical:

in which ^ represents a bromine or chlorine atom.

- the compounds of formula (I) in which A represents a radical:

dans lequel Z₁ et Z₂ représentent chacun un radical méthyle. Parmi les composés préférés, on peut citer tout parti- culièrement les produits dans lesquels la copule cyclopropani- que est de structure (IR,cis) .

in which Z ₁ and Z ₂ each represent a methyl radical. Among the preferred compounds, mention may be made of any part especially the products in which the cyclopropanic copula is of structure (IR, cis).

The subject of the invention is of course more particularly of course the compounds the preparation of which is given below in the experimental part, such as the compound of Example 1 or also the compounds of Examples 3, 4 and 5.

A subject of the invention is also a process for preparation, characterized in that an acid of formula (II) is subjected:

AC0 ₂ H (II)

in which A retains its previous meaning, or a functional derivative of this acid, to the action of an alcohol of formula (III):

in which X, Ha ^ and Hal ₂ retain their previous meaning, to obtain the corresponding compound of formula (I).

The functional acid derivative used is preferably an acid chloride.

When the acid of formula (II) is reacted with alcohol, it is preferably carried out in the presence of dicyclohexylcarbodiimide.

The acids of formula (II) used are known products, used in the synthesis of pyrethroid compounds.

The alcohols of formula (III) are new products and are themselves an object of the present invention.

Among the alcohols of formula (III), there may be mentioned as preferred alcohol, the alcohol the preparation of which is given below in the experimental part. The alcohols of formula (III) can be prepared by analogy with the process for the preparation of 4-difluo ~ romethyl 2,3,5,6-tetrafluorobenzyl alcohol described below in the experimental part which can be schematized as follows:

THP-0-CH ₂ -BF reduction> THP-0-CH ₂ -BH

1) BuLi / THF

2) CHF ₂ C1

TsOH J,

HO-CH ₂ -B-CHF ₂ <THP-0-CH ₂ -B-CHF ₂

MeOH

THP = 2-tetrahydropyrannyl;

B ≈ 2,3,5,6-tetrafluoro phenylene

The compounds of formula (I) have interesting properties which allow their use in the fight against parasites. It can be, for example, the fight against plant parasites, whether they are soil parasites or aerial parts, local parasites and parasites of warm-blooded animals.

This is how the products of the invention can be used to fight against insects, nematodes and parasitic mites of plants and animals.

The subject of the invention is in particular the application of the compounds of formula (I) to the fight against plant parasites, local parasites and parasites of warm-blooded animals.

The products of formula (I) can also be used to fight against insects and other soil parasites, for example beetles, such as DIABROTICA, wireworms and white worms, myriapods such as scutigeria and blaniules, and dipterans as cécydoiαiεs and lepidoptera like the ground moths. They are used in doses of between 5 g and 300 g of active ingredient per hectare.

The products of formula (I) can also be used to fight against insects in premises, to fight in particular against flies, mosquitoes and cockroaches.

The products of formula (I) are more photostable.

All of these properties make products of formula (I) products which correspond perfectly to the requirements of the modern agrochemical industry: they make it possible to protect crops while preserving the environment.

The products of formula (I) can also be used to fight against mites and parasitic nematodes of plants. The compounds of formula (I) can also be used to fight against parasitic mites of animals, to fight for example against ticks and in particular ticks of the genus Boophilus, those of the genus Hyalomnia, those of the genus Amblyomnia and those of the genus Rhipicephalus or to fight against all kinds of scabies, in particular sarcoptic scabies, psoroptic scabies and chorioptic scabies.

A subject of the invention is therefore also compositions intended for combating parasites of warm-blooded animals, parasites of premises and plants, characterized in that they contain at least one of the products of the formula ( I) defined above and in particular the product of example 1 or else the products of examples 3, 4 and 5.

The invention particularly relates to insecticide compositions containing as active principle at least one of the products defined above.

The compositions according to the invention are prepared according to the usual methods of the agrochemical industry or of the veterinary industry or of the industry for products intended for animal nutrition. These compositions can be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible strips, baits or other preparations conventionally used for the use of this. kind of compounds.

In addition to the active principle, these compositions generally contain a vehicle and / or a non-ionic surfactant, ensuring, moreover, a uniform dispersion of the constituent substances of the mixture. The vehicle used can be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, a mineral, animal or vegetable oil, a powder such as talc, clays, silicates, kieselguhr or a solid fuel. The insecticide compositions according to the invention preferably contain from 0.005% to 10% by weight of active material.

According to an advantageous procedure, for use in premises, the compositions according to the invention are used in the form of fumigant compositions.

The compositions according to the invention can then advantageously consist, for the non-active part, of a combustible insecticide coil (or coil), or also of an incombustible fibrous substrate. In the latter case, the fu iant obtained after incorporation of the active material is placed on a heating device such as an electric emitter.

In the case where an insecticide coil is used, the inert support can be, for example, composed of pyrethrum marc, Tabu powder (or Machilus Thumbergii leaf powder), pyrethrum stem powder, cedar leaf powder , wood powder (such as sawdust) starch and coconut shell powder.

The dose of active ingredient can then be, for example, from 0.03 to 1% by weight. In the case where an incombusible fibrous support is used, the dose of active material can then be, for example, from 0.03 to 95% by weight.

The compositions according to the invention for use in premises can also be obtained by preparing a sprayable oil based on active principle, this oil soaking the wick of a lamp and then being subjected to combustion.

The concentration of the active ingredient incorporated in the oil is preferably from 0.03 to 95% by weight. The subject of the invention is also the acaricidal compositions containing as active principle at least one of the products of formula (I) defined above.

A subject of the invention is also the nematicide compositions containing as active principle at least one of the products of formula (I) defined above.

The insecticide compositions according to the invention, like the acaricide and nematicide compositions, can optionally be added with one or more other pesticidal agents. The acaricide and nematicide compositions can be in particular in the form of powder, granules, suspen¬ sions, emulsions, solutions.

For acaricide use, wettable powders are preferably used for foliar spraying, containing from 1 to 80% by weight of active ingredient, or liquids for foliar spraying containing from 1 to 500 g / l of active principle. It is also possible to use powders for leaf dusting containing from 0.05 to 3% of active material.

For nematicidal use, liquids are preferably used for treating soils containing 300 to 500 g / l of active ingredient.

The acaricide and nematicide compounds according to the invention are preferably used in doses of between 1 and 100 g of active ingredient per hectare. A subject of the invention is also the acaricide compositions intended for the fight against parasitic mites of warm-blooded animals in particular against ticks and scabies, characterized in that they contain as active principle, at least one of the products of formula (I) defined above.

To enhance the biological activity of the products of the invention, they can be added to conventional synergists used in such cases such as l- (2,5,8-trioxadodecyl) 2-propyl 4,5-methylenedioxy benzene ( or piperonyl butoxide) or N- (2-ethyl heptyl) bicyclo [2.2.l] hept-5-ene-2,3-dicar-boximide, or piperonyl-bis-2- (2 '-n-butoxy ethoxy) ethylacetal (or tropital).

The compounds of formula (I) exhibit excellent general tolerance, and the invention therefore also relates to the products of formula (I), in particular for combating the diseases created by ticks and scabies in humans and animals. The products of the invention are especially used to fight against lice as a preventive or curative and to fight against scabies.

The products of the invention can be administered externally, by spraying, by shampooing, by bathing or brushing.

The products of the invention for veterinary use can also be administered by brushing the backbone according to the method known as the "pour-on" method.

It may also be indicated that the products of the invention can be used as biocides or as growth regulators.

The invention also relates to associations with insecticidal, acaricidal or nematicidal activity, characterized in that they contain as active material, on the one hand at least one of the compounds of general formula (I), and on the other hand, at least one of the pyrethroid esters chosen from the group consisting of esters of ¹ allethrolone, of 3,4,5,6-tetrahydrophthalimidomethyl alcohol, of 5-benzyl 3-furyl methyl alcohol, of 3-phenoxy benzyl alcohol and alpha-cyano 3-phenoxy benzyl alcohol of chrysanthemic acids, by 5-benzyl 3-furyl methyl alcohol esters of 2,2-dimethyl 3- (2-oxo 3-tetrahydrothiophenylidene acids) methyl) cyclopropanecarboxylic, by esters of 3-phenoxy benzyl alcohol and alpha-cyano 3-phenoxy benzyl alcohol esters of 2,2-dimethyl 3- (2,2-dichlorovinyl) cyclopropanecarboxylic acids, by esters of 2,2-dimethyl 3- (2,2-dibromovinyl) alpha-cyano 3-phenoxy benzy¬ alcohol cyclopro¬ panecarboxyliques, with 3-phenoxy benzyli¬ alcohol esters as 2-parachlorophenyl 2-isopropyl acetic acids, with allethrolone esters, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, d 5-benzyl 3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and alpha-cyano 3-phenoxy benzy¬ alcohol of 2,2-dimethyl 3- (1,2,2,2-tetrahaloethyl) acids cyclopropanecarboxyliques, in which "halo" represents a fluorine, chlorine or bromine atom, it being understood that the compounds of formula (I) can exist in all their possible stereoisomeric forms as well as the acid and alcohol copulas of the pyrethroid esters above.

The following examples illustrate the invention without, however, limiting it.

EXAMPLE 1: [1R, (lalpha, 3alpha)] -3 - [(Z) -2-chloro 3,3,3- (tri-fluoro 1-propenyl] 2,2-dimethyl cyclopropanecarboxylate of 4- (difluoromethyl) 2 , 3,5,6-tetrafluoro benzyl.

1.52 g of 3- [(Z) -2-chloro 3,3,3-trifluoro-1-propenyl] 2,2-dimethyl cyclopropanecarboxylic acid are introduced into 30 cm ³ of methylene chloride. 1.44 g of 4- (difluoromethyl) 2,3,5,6-tetrafluoro benzyl alcohol are added. The mixture is cooled to 5 "C. and 1.29 g of dicyclohexylcarbodiimide and 105 mg of dimethylaminopyridine in solution in 15 cm ³ of methylene chloride are added. The reaction mixture is kept under stirring for 1 hour. 3 g of crude sought product, which is purified by chromatography on silica eluting with a hexane-isopropyl ether mixture (95-5), thus obtaining 2.53 g of sought product, melting at 58 ° C. [ alpha] _D = + 15.5 ° ± 1 ° (C = 0.55%, CHC1 ₃ )

By operating as above from the appropriate acids and alcohols, the products of formula (I) corresponding to the following examples were obtained.

EXAMPLE 2: [1R, (lalpha, 3alpha)] -3- [(E) -3-tert-butoxy 2- fluoro 3-oxo l-propenyl] 2,2-dimethyl cyclopropanecarboxylate of 4- (difluoromethyl) 2,3 , 5,6-tetrafluoro benzyl. [alpha] _D ≈ + 22 ° ± 1 ° (C = 1%, CHC1 ₃ )

EXAMPLE 3: [1R, (lalpha, 3alpha)] -3- [2-chloro 2-fluoro ethenyl) 2,2-dimethyl cyclopropanecarboxylate of 4- (difluoro¬ methyl) 2,3,5,6-tetrafluoro benzyl . [alpha] _D = + 6.5 ° ± 1 ° (C = 0.8%, CHC1 ₃ ) EXAMPLE 4: [1R, (lalpha, 3alpha)] -3- [(E) -2-fluoro 3-methoxy 3- oxo l-propenyl] 2,2-dimethyl cyclopropanecarboxylate of 4- (ifluoromethyl) 2,3,5,6-tetrafluoro benzyl. [lpha] _D = + 11.5 ° ± 1 ° (C = 1%, CHC1 ₃ ) EXAMPLE 5: [1R, (lalpha, 3alpha)] - 3 - [(E) -2-cyano 2-fluoro όthényl] 2,2-dimethyl cyclopropanecarboxylate of 4- (difluoro¬ methyl) 2,3,5,6- όtrafluoro benzyl.

[alpha] _D = + 41.5 ° ± 1 ° (C = 0.7%, CHC1 ₃ ) Preparation of alcohol 4- (difluoromethyl) 2 -3.5-6-tetrafluoro benzylifjue

Stage A: 2 - [[[4- (difluoromethyl) 2,3,5,6-tetrafluoro phenyl] ethyl] oxy] tetrahydropyran

6 g of 2 - [[(2,3, 5,6-tetrafluorophenyl) methyl] oxy] tetrahydropyran in 100 cm ³ of tetrahydrofuran are added to -60-0.6 g. 15.6 cm ³ of butyllithium in hexane are added. It is stirred for one hour at -45 "C. Then a stream of chlorodifluoromethane is bubbled for one hour. It is stirred for one hour from -45" C to -10 "C. It is poured onto sodium acid phosphate, extracted with ethyl acetate and dried, 6.7 g of crude product are obtained which is chromatographed on silica eluting with a hexane-isopropyl ether mixture (9-1), 3 g of sought product is obtained.

Stage B: alcohol 4- (difluoromethyl) 2,3,5,6-tetrafluoro benzyl

A mixture of 2.9 g of product prepared in stage A, 40 cm ³ of methanol and 150 mg of para-toluenesulfonic acid is stirred at 20 ° C. for 1 hour. Poured into ice water, extracted with isopropyl ether, washed with water, dried and concentrated. 2.9 g of sought product is obtained, after chromatography on silica (eluent: hexane-ethyl acetate (8-2)). Mp 30 ° C.

EXAMPLE 6 Preparation of a soluble concentrate A homogeneous mixture of: Product of Example 3: 0.25 g Piperonyl butoxide: 1.00 g

Tween 80: 0.25 g

Topanol A: 0.1 g

Water: 98.4 g EXAMPLE 7: Preparation of an emulsifiable concentrate Intimately mixed:

Product of Example 4: 0.015 g Piperonyl Butoxide: 0.5 g Topanol A 0.1 g Tween 80 3.5 g Xylene 95.885 g EXAMPLE 8 Preparation of an emulsifiable concentrate A homogeneous mixture of

Product of Example 5: 1.5 g Tween 80: 20.00 g

Topanol A: 0.1 g

Xylene: 78.4 g EXAMPLE 9: Preparation of a smoke-producing composition The following are mixed in a homogeneous manner:

Product of Example 3 0.25 g Tabu powder 25.00 g Cedar leaf powder 40.00 g Pine wood powder 33.75 g Brilliant green 0.5 g p-Nitrophenol 0.5 g

BIOLOGICAL STUDY A. Study of the effect of slaughter on houseflies

The test insects are 4-day-old female house flies. The operation is carried out by direct spraying at a concentration of 0.10 g / l in a Kearns and March chamber using as solvent a mixture of acetone (5%) and Isopa: L (petroleum solvent) (amount of solvent used 2 cm ³ in one second). 50 insects are used per treatment. The checks are carried out every minute up to 10 minutes, then at 15 minutes and the KT ₅₀ is determined by the usual methods. The experimental results obtained are summarized in the following table:

KT ₅₀ compounds in minutes

I Example 3 7.9 | Example 4 2.2 [Example 5 6.1 B. Study of the lethal effect of the compounds of the invention on various insect worms a) Study of the lethal effect on larvae of Spodoptera Littoralis The tests are carried out by topical application of an acetone solution using the micro Arnold's manipulator on the dorsal thorax of the larvae. 15 larvae are used per back of product to be tested. The larvae used are fourth instar larvae, that is to say about 10 days old when raised at 24 ° C and 65% relative humidity. After treatment, the individuals are placed on artificial nutrient medium (Poitout medium).

Mortality checks are carried out 48 hours after treatment. The experimental results obtained are summarized in the following table:

b) Study of activity on Diabrotica

The test insects are last instar larvae of

Diabrotica.

A washer of filter paper 9 cm in diameter, placed at the bottom of a Petri dish, is treated with 2 cm ³ of acetone solution. After drying, 10 larvae are deposited per dose and the mortality control is carried out 24 hours after treatment.

The lethal dose 100 (DL _1Q0 ) expressed in mg / liter is determined.

The results obtained are as follows: Product of Example 3: 0.6

Product of Example 4: 5.0

Product of Example 1: 0.3

Product of Example 5: 10 C) STUDY OF THE ACTIVITY ON APHIS CRACCIVORA

2 cm ³ of hydro-acetone solution (50/50) are sprayed - onto bean leaves (vicia fabae) until runoff. After drying, 15 wingless females of Aphis craccivora are deposited. The whole is kept on wet filter paper inside a Petri dish. 24 hours after the start of contact, the number of dead insects is determined.

Claims

1) The compounds of formula (I):

in which : - Hal _{j ^} and Hal ₂ identical or different from each other, represent a halogen atom, X represents a hydrogen atom, an alkyl, alkenyl or alkynyl radical containing up to 4 carbon atoms or a cyano radical or an aralkynyl radical containing up to 10 carbon atoms, - And A represents the remainder of a pyrethroid acid, in all their possible diastereoisomeric forms as well as their mixtures. 2) The compounds of formula (I) as defined in the claims 1 in which H ^ and Hal ₂ represent the same halogen atom. 3) The compounds of formula (I) as defined in claim 2, in which Hal 4 and Hal ₂ each represent a fluorine atom. 4) The compounds of formula (I) as defined in any one of claims 1 to 3 in which X represents a hydrogen atom. 5) The compounds of formula (I) as defined in any one of claims 1 to 4 in which: either A represents a radical:

in which : Z ₁ and Z ₂ each represent a methyl radical, - or Z _χ represents a hydrogen atom and - either Z ₂ represents a radical:

in which Z ₃ represents a hydrogen or halogen atom and T _χ and T ₂ , which are identical or different, represent a hydrogen atom, a halogen atom, an alkyloxy or alkyl radical containing from 1 to 8 atoms carbon optionally substituted by halogens, a mono-, di- or tri-fluoromethyl or cyano radical or a phenyl ring optionally substituted by a halogen, or T _χ and T ₂ together form a cycloalkyl radical containing 3 to 6 carbon atoms or a radical:

in which B represents an oxygen or sulfur atom - or Z ₂ represents a radical:

in which a, b, c and d, identical or different, each represent a halogen atom, - or Z ₂ represents a radical:

in which D represents a hydrogen or halogen atom, an alkyloxy radical containing from 1 to 8 carbon atoms, G represents an oxygen or sulfur atom and J represents either a linear, branched or cyclic, saturated or unsaturated alkyl radical containing from 1 to 8 carbon atoms, optionally substituted by one or more functional groups, identical or different, or else an aryl group containing from 6 to 14 carbon atoms, optionally substituted by one or more identical or different functional groups, or else a heterocyclic radical optionally substituted by one or more functional groups, identical or different, or else A represents a radical:

in which U, in any position on the benzene ring, represents a halogen atom, an alkyl radical containing from 1 to 8 carbon atoms or an alkoxy radical containing from 1 to 8 carbon atoms, m representing the number 0, 1 or 2 and when m is 2, the substituents U can be the same or different. 6) The compounds of formula (I) as defined in claim 5 in which A represents a radical:

7) The compounds of formula (I) as defined in the resale! cation 5 in which A represents a radical:

0 — J in which Hal represents a halogen atom and J represents an alkyl radical containing from 1 to 8 carbon atoms, linear, branched or cyclized and saturated, optionally substituted by one or more halogen atoms, the double bond having the geometry (E). 8) The compounds of formula (I) as defined in claims 7 in which Hal represents a fluorine atom and J a linear or branched alkyl radical containing up to 4 carbon atoms. 9) The compounds of formula (I) as defined in claim 5 in which A represents a radical:

10) The compounds of formula (I) as defined in claims 5 in which A represents a radical:

11) The compounds of formula (I) as defined in claim 5 in which A represents a radical:

in which - ^ represents a bromine or chlorine atom. 12) The compounds of formula (I) as defined in claims 5 in which A represents a radical 5 in which Z ^ and Z ₂

a methyl radical. 13) The compounds of formula (I) defined in any one of claims 6 to 12 in which the cyclopropanic copula is of structure (1R, cis). 14) [1R, (lalpha, 3alpha)] -3- [(Z) -2-chloro 3,3,3- (trifluoro 10 l-propenyl] 2,2-dimethyl cyclopropanecarboxylate 4- (difluo¬ romethyl) 2,3,5,6-tetrafluoro benzyl. 15) Process for preparing the compounds of formula (I) as defined in any one of claims 1 to 14, characterized in that an acid of formula (II) is subjected: 15 AC0 ₂ H (II) in which A retains its previous meaning, or a functional derivative of this acid, to the action of an alcohol of formula (III):

30 in which X, Hal _χ and Hal ₂ retain their previous meaning, to obtain the corresponding compound of formula (I). 16) As new industrial products, the compounds of formula (III), defined in claim 15. 17) As new industrial product as defined in claim 16, alcohol 4- (difluoromethyl) 2, 3,5,6-tetra- benzyl fluoro. 18) Application of the compounds of formula (I) as defined * to any one of claims 1 to 14 in the fight against plant parasites, local parasites and parasites of warm-blooded animals. 19) The compositions intended for the fight against plant parasites, local parasites and parasites of warm-blooded animals, characterized in that they contain as active principle at least one of the products defined in any one of the claims 1 to 13. 20) The compositions intended for the fight against plant parasites, local parasites and parasites of warm-blooded animals, characterized in that they contain at least one of the products defined in claim 14 as active principle. 21) The insecticide compositions containing as active principle at least one of the products defined in any one of claims 1 to 14. 22) The acaricidal compositions containing as active principle at least one of the products defined in any one of Claims 1 to 14. 23) The nematicide compositions containing as active principle at least one of the products defined in any one of Claims 1 to 14. 24) The acaricide compositions intended for the fight against parasites of warm-blooded animals, in particular against ticks and scabs, characterized in that they contain as active ingredient, at least one of the products defined in any one of claims 1 to 14. 25) Associations endowed with insecticide, acaricide or nematicide activity, characterized in that that they contain as active material, on the one hand at least one of compounds of general formula (I) as defined in claim 1, and on the other hand, at least one of the pyrethroid esters chosen from the group consisting of esters of allethrolone, 3,4,5,6-tetrahydrophthalimido methyl alcohol, 5-benzyl 3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and alpha-cyano 3-phenoxy benzyl alcohol acids chrysan- thematic, by 5-benzyl 3-furyl methyl esters of 2,2-dimethyl 3- (2-oxo 3-tetrahydrothiophenylidene-methyl) cyclopropanecarboxylic acids, by esters of 3-phenoxy benzyl alcohol and alcohol alpha-cyano 3-phenoxy benzy-lics of 2,2-dimethyl 3- (2,2-dichlorovinyl) cyclopro-panecarboxylic acids, by alpha-cyano 3-phenoxy benzyl alcohol esters of 2,2-dimethyl acids 3- (2,2-dibromovinyl) cyclopropanecarboxylic, by 3-phenoxy benzyl alcohol esters of 2-parachlorophenyl 2-isopropyl acetic acids by allethrolone esters, 3,4,5,6-tetrahydrophthalimido methyl esters , methyl 5-benzyl 3-furyl alcohol, 3-phenoxy benzyl alcohol and alpha-cyano 3-phenoxybenzyl alcohol of 2,2-dimethyl 3- (1,2,2,2-tetrahaloethyl) cyclopropanecarboxylic acids , in which "halo" represents a fluorine, chlorine or bromine atom, it being understood that the acid and alcohol copulas of the pyrethroid esters s above can exist in all their possible stereoisomeric forms. 26) The compositions as defined in one of claims 19 to 25, characterized in that they additionally contain a synergist of the pyrethroids.