FR2558466A2 - New cyclopropanecarboxylic acid derivatives, process for preparing them and their use for combating parasites - Google Patents

Abstract

The object of the present certificate of addition is to illustrate, using new examples, the general formula 1 of the main patent. It also relates to pesticide compositions containing the products illustrating the new examples.

Description

dans laquelle la copule acide cyclopropanique est de stucture lR,cis ou 1R, trans, X représente un atome d'halogène et R représente un atome d'hydrogène, un radical alcoyle linéaire, ramifié ou cyclisé, saturé ou insaturé, renfermant jusqu'a 12 atomes de carbone ou le reste d'un alcool
R-OH utilisé dans la synthèse des pyréthrinoides, la géométrie de la double liaison portée par le carbone en 3 pouvant être de structure E ou Z.In its main patent application filed in France on August 3, 1983 under the number 83.12858, entitled "New derivatives of cyclopropane carboxylic acid, their preparation process and their application to pest control", the applicant company has described and claimed in all their possible isomeric forms as well as mixtures of these isomers compounds of formula (I)

in which the cyclopropane acid copula is of structure IR, cis or IR, trans, X represents a halogen atom and R represents a hydrogen atom, a linear alkyl radical, branched or cyclized, saturated or unsaturated, containing up to 12 carbon atoms or the rest of an alcohol
R-OH used in the synthesis of pyrethroids, the geometry of the double bond carried by the carbon in 3 can be of structure E or Z.

 In the main patent application, the applicant company has also described and claimed a process for the preparation of the compounds of formula (I).

 In the main patent application, the applicant company has also described and claimed the application of the compounds of formula (a9 to the pest control of plants, premises and warm-blooded animals as well as pesticidal compositions containing at least one compound of formula (I) optionally in combination with other compounds.

 This certificate of addition is now intended to illustrate by new examples the general formula (I) of the main patent.

 The certificate of addition more precisely relates to the compounds corresponding to formula (I) as defined in claim 1 of the main patent application whose names follow - (1R, cis) 2,2-dimethyl acid 3 / (Z) 2-bromo-2-cyanoethylene cyclopropane carboxylic acid, (1R, trans) 2,2-dimethyl 3 / (E + Z) 2-bromo-2-cyanoethenyl / cyclopropane carboxylic acid, 1R, cis 2,2-dimethyl 3 / (E + Z) 2-chloro-2-cyano ethenyl / cyclopropane carboxylate (R, S) cyano 2- (6-phenoxy pyridyl) methyl; 1R, cis 2,2-dimethyl 3 / (Z) 2-chloro-2-cyano ethenyl / cyclopropane carboxylate (R, S) 2- (6-phenoxy pyridyl) ethyl; - 1R, cis 2,2-dimethyl 3 / (E) 2-chloro-2-cyano ethenyli cyclopropane carboxylate (R, S) 2- (6-phenoxy pyridyl) ethyl 9 - 1R, cis 2,2-dimethyl 3 (Z) 2-bromo-2-cyano ethenyl / cyclopropane carboxylate (R, S) cyano 2- (6-phenoxy pyridyl) methyl; 1R, trans 2,2-dimethyl 3 / (E) 2-bromo-2-cyano ethenyl cyclopropane carboxylate (S) cyano (3-phenoxy phenyl) methyl - 1R, trans 2,2-dimethyl 3 / (z) ) (S) cyano (3-phenoxy phenyl) methyl 2-bromo-2-cyanoethenyl / cyclopropane carboxylate; - (S) 2-methyl-4-oxo-3- (2-propenyl) -2-cyclopenten-1-yl 1 R, cis 2,2-dimethyl-3 ((2) -methyl-2-cyanoethylene-cyclopropane carboxylate.

 The products of the addition may be prepared by the method of the main patent.

dans laquelle R conserve la meme signification que précédemment a l'action d'un composé de formule (III) :

dans laquelle X conserve la même signification que précédemment pour obtenir un composé de formule (I) correspondant que l'on soumet, Si désiré, a l'action d'un agent d'estérification si R représente un atome d'hydrogène, ou que l'on soumet, si désiré, a l'action d'un agent de clivage de la fonction ester, puis, si désiré, a l'action d'un agent d'estérification.The process according to the main patent application is characterized in that according to the Wittig reaction a compound of formula (II) is subjected to:

in which R preserves the same meaning as above for the action of a compound of formula (III):

in which X has the same meaning as above to obtain a corresponding compound of formula (I) which is subjected, if desired, to the action of an esterification agent if R represents a hydrogen atom, or if desired, the cleavage agent is subjected to the ester function and, if desired, to the action of an esterification agent.

 The compounds of formula (II) and formula (III) are known products.

 The products of formula (III) can be prepared according to the process described in Helv. Chem. Acta. Flight. 60 (1977) p. 585.

The Wittig reaction generally used to prepare the products of formula (I) provides compounds of formula (I) whose geometry is
E + Z.

 The isomers at the double bond level can be separated, if desired, by physical methods such as chromatography, or at the level of the acids, or at the level of the alkyl esters, or at the level of the final esters.

 The 02R cleavage agent is preferably the heat used with an acidic hydrolysis agent. As acidic hydrolysis agent, p-toluenesulphonic acid may be used.

 Esterification can be carried out in the presence of a tertiary base, such as pyridine. This esterification can be carried out advantageously in the presence of a mixture of pyridine, dicyclohexyl carbodiimide and 4-dimethylaminopyridine or pyridine.

 It goes without saying that the Wittig reaction, cleavages of ester functions, esterification are reactions well known to those skilled in the art and need not be detailed here.

 The compounds of formula (I) of the addition have interesting properties which allow their use in the fight against parasites. This may include, for example, the control of plant pests, house pests and parasites of warm-blooded animals.

 Thus the products of the invention can be used to control insects, nematodes and mites parasitic plants and animals.

 In general, the addition compounds have the same biological properties as the compounds of the main breve application.

 The addition therefore also relates to the application of the compounds as defined above to the control of plant pests, parasites of premises and parasites of warm-blooded animals.

 The products of formula (I) of the addition may be used in particular for controlling insects in the agricultural field, for example to combat aphids, lepidopteran larvae and coleopterans. They are used at doses of between 10 g and 300 g of active ingredient per hectare.

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

 The products of formula (I) of the addition may also be used to control plant-parasitic mites and nematodes.

The compounds of the addition of formula (I) can still be used to fight against parasitic mites of animals, for example to fight against ticks and in particular ticks of the species Boophilus, those of the species Hyalomnia, those of the species Amblyomnia and those of the species
Rhipicephalus or to fight against all kinds of scabies including sarcoptic mange, psoroptic mange and chorioptic mange. They can also be used against lice and helminths.

 The addition therefore also relates to compositions for combating plant pests, parasites of the premises and parasites of warm-blooded animals, characterized in that they contain as active ingredient at least one of the products defined above .

 The subject of the addition is in particular insecticidal compositions containing as active principle at least one of the products defined above.

 The compositions of the addition are prepared according to the usual processes of the agrochemical industry. They may be optionally added with one or more other pesticidal agents. These compositions may be in the form of powders, granules, suspensions, emulsions, solutions, aerosol solutions, combustible strips, baits or other preparations conventionally used for the use of such compounds.

 In addition to the active ingredient, these compositions contain, in general, a vehicle and / or a nonionic surfactant, ensuring, in addition, a uniform dispersion of the constituent substances of the mixture. The vehicle used may be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, mineral, animal or vegetable oil, a powder such as talc, clays, silicates, kieselguhr or a solid fuel.

 The insecticidal compositions according to the addition preferably contain from 0.005% to 10% by weight of active ingredient.

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

 The compositions according to the addition can then advantageously consist, for the non-active part, of a combustible coil, or a non-combustible fibrous substrate. In the latter case, the fumigant obtained after incorporation of the active ingredient is placed on a heating apparatus.

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

 The dose of active ingredient can then be, for example, 0.03 to 1% by weight.

 In the case where a noncombustible 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 addition for use in the premises can also be obtained by preparing a sprayable oil based on the active ingredient, 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 acaricide and nematicide compositions may be in particular in the form of powder, granules, suspensions, emulsions, solutions.

 The acaricide and nematicide compositions may be optionally added with one or more other pesticidal agents.

 For acaricidal use, wettable powders containing 1 to 80 l of active ingredient (or foliar spray liquids containing 1 to 500 g / l of active ingredient) are preferably used. foliar powders containing 0.05 to 3% active ingredient.

 For the nematicide use, it is preferable to use soil treatment liquids containing from 300 to 500 g / l of active ingredient.

 The acaricide and nematicide compounds according to the addition are preferably used at doses of between 1 and 100 g of active ingredient per hectare.

 The addition therefore also relates to the acaricide compositions as well as the nematicidal compositions containing as active ingredient at least one of the products defined above.

 The addition also relates to the acaricide compositions containing as active ingredient at least one of the products defined above, characterized in that they are used in the fight against parasites of warm-blooded animals, especially against ticks and ticks. gales.

 When it comes to combating animal parasites, the compositions may be used in the form of a spray, a bath, or according to the "for-on" method.

 When using the method for-one, it is preferable to use solutions containing from 0.5 to 49 active ingredient per 100 cm 3 of solution.

 When it comes to controlling animal parasitic mites, it is possible to incorporate the products of the addition of formula (I) into food compositions in combination with a nutritive mixture suitable for animal feed. The nutrient mixture may vary depending on the animal species; it may contain cereals, sugars and grains, soybean meal, peanut cake and sunflower meal, animal meal, for example, fishmeal, synthetic amino acids, mineral salts, vitamins and antioxidants.

 The addition therefore also relates to the compositions intended for animal feed containing as active ingredient at least one of the products defined above.

 The addition also relates to combinations endowed with insecticidal, acaricidal or nematicidal activity, characterized in that they contain as active ingredient, on the one hand at least one of the products defined above and on the other hand, a at least pyrethroid esters selected from the group consisting of esters of allethrolone, methyl 3,4,5,6-tetrahydrophthalimide alcohol, 5-benzyl-3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and cyano-3-phenoxy benzyl alcohols of chrysanthemic acids, by the 5-benzyl-3-furyl methyl alcohol esters of 2,2-dimethyl-3- (2-oxo-3-tetrahydrothiophenyl) methyl) cyclopropane-1-carboxylic acids, by 3-Phenoxy benzyl alcohol and 3-phenoxy benzyl alcohol-cyano esters of 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylic acids, by esters of 4-cyano 3- alcohols benzyl phenoxy of 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylic acid 3-phenoxy benzyl alcohol esters of 2-parachlorophenyl 2-isopropyl acetic acids, esters of allethrolone, methyl 3,4,5,6-tetrahydrophthalimide alcohol, 5-benzyl alcohol 3- methyl furyl, 3-phenoxy benzyl alcohol and alpha-cyano 3-phenoxy benzyl alcohols of 2,2-dimethyl-3- (1,2-2,2-tetrahaloethyl) cyclopropane-1-carboxylic acids, wherein Halo "represents a fluorine, chlorine or bromine atom, it being understood that the acidic copula and alcohols of the pyrethroid esters above may exist in all their possible stereoisomeric forms.

 The subject of the addition is also the compositions as defined above, characterized in that they contain, in addition, a pyrethroid synergist.

 The following examples illustrate the invention without limiting it.

1R, cis 2,2-dimethyl 3 / (# E + # Z) 2-bromo-2-cyanoethenyl / cyclopropane carboxylic acid and 1R, cis 2,2-dimethyl 3 / (# E + # Z) 2 acid 2-cyano ethenyl / cyclopropane carboxylic acid, used as starting materials, were prepared as follows:
PREPARATION 1: 1R, cis 2,2-dimethyl 3 / (E + Z) 2-bromo-2-cyanoethylene cyclopropane carboxylic acid.

 3.5 g of bromo cyano methylene triphenyl phosphorane, 30 cm 3 of tetrahydrofuran and 4 cm 3 of dimethylformamide are mixed under an inert atmosphere. 1.3 g of the lactone of 1R acid, cis 2,2-dimethyl dihydroxy methyl cyclopropane carboxylic acid and 10 cm3 of tetrahydrofuran are added to the solution obtained. The mixture is kept at room temperature for 16 hours, brought to dryness; 5.8 g of an oily residue are obtained, which is chromatographed on silica eluting with hexane-ethyl acetate 7/3 to 1% acetic acid. The mixture of the isomers et / Z (F = 132 ° C.) is obtained.

PREPARATION 2: 1R, cis 2,2-dimethyl 3 / (E + Z) 2-chloro-2-cyanoethenyl I cyclopropane carboxylic acid.

 Working as in Preparation 1, from chloro cyano methyl triphenyl phosphorane, the desired product (F # 50 C) is obtained.

EXAMPLE 1 1R, cis 2,2-dimethyl-3 ((Z) 2-bromo-2-cyanoethenyl / cyclopropane carboxylic acid.

STAGE A: 1R, cis-2,2-dimethyl-3 - ((2) -bromo-2-cyano ethenyl / tert-butyl cyclopropane carboxylate and #E isomer.

 7.5 g of bromo cyano methylene triphenyl phosphorane are mixed in 50 cm 3 of tetrahydrofuran and 4 g of tert-butyl 1 R, cis 2,2-dimethyl-3-formyl cyclopropane carboxylate in 50 cm 3 of tetrahydrofuran and the mixture is refluxed for 20 hours. After cooling, the mixture is filtered off with suction, the filtrate is concentrated to dryness under reduced pressure, the residue is taken up in 100 cm 3 of isopropyl ether, the insoluble matter is filtered off and the filtrate obtained is concentrated to dryness. The residue is chromatographed on silica, eluted with a hexane-ethyl acetate mixture (95/5) and gives 1.4 g of isomer (E) F = 102-103 ° C. and 0.4 g of isomer (Z). F <500C and 0.7 g of a mixture of isomer (E) and (Z).

STAGE B: 1R, cis 2,2-dimethyl-3 ((Z) 2-bromo-2-cyanoethenyl / cyclopropane carboxylic acid.

 1.5 g of the isomer (Z) obtained as in Stage A, 50 cm3 of anhydrous toluene and 150 mg of para-toluenesulphonic acid are refluxed for 30 minutes. After cooling to room temperature, the organic phase is washed with water, dried and concentrated to dryness. 1.2 g of expected product is obtained, mp = 139-140 ° C.

EXAMPLE 2: 1 R, trans 2,2-dimethyl-3 - [(E + Z) 2-bromo-2-cyanoethenyl] cyclopropane carboxylic acid.

STAGE A: 1R, trans 2,2-dimethyl 3 - / (E + Z) 2-bromo-2-cyano ethenyl cyclopropane carboxylate terbutyl.

 Stage A of Example 1 is carried out starting from 4 g of 1 R, trans-2,2-dimethyl-3-formyl carboxylate and obtains 2.7 g of expected product F = 88 C.

STAGE B: 1R, trans 2,2-dimethyl-3 - / (E + Z) 2-bromo-2-cyanoethenyl / cyclopropane carboxylic acid.

 The procedure is as in Step B of Example 1 from the 2.7 g of product obtained above and 2.05 g of expected product F = 136 C (slightly net).

EXAMPLE 3: (1 R, cis) 2,2-Dimethyl 3 / (E + Z) 2-chloro-2-cyano ethenyl / cyclopropane carboxylate (R, S) cyano 2- (6-phenoxy pyridyl) methyl.

 In a mixture of 1 g of (R, S) cyano 2- (6-phenoxy pyridyl) methyl alcohol and 5 cm 3 of methylene chloride, 0.9 g of 1 R, cis 2,2-dimethyl acid are introduced. 3 / (E + Z) 2-chloro-2-cyanoethenyl cyclopropanecarboxylic acid dissolved in 2 cm3 of methylene chloride, added at +5 ° C, 50 mg of 4-dimethylamino pyridine, 0.9 g of dicyclohexyl carbodiimide and 5 cm3 methylene chloride, stirred for 16 hours at 200C, filtered, the filtrate concentrated to dryness by distillation under reduced pressure, the residue chromatographed on silica eluting with a mixture of hexane and ethyl acetate (7/3) and obtains 1.46 g of desired product.

 / &alpha; / D = + 5 (c = 0.5%, chloroform).

EXAMPLE 4 (1R, cis) 2,2-Dimethyl 3 H (S) -2- (6-phenoxy pyridyl) ethyl and (1R, cis) 2 (2R) cis (2R) -cycloalkenyl-cyclopropane carboxylate (R, S) 2- (6-Phenoxy pyridyl) ethyl, 2-dimethyl-3 ((E) -2-chloro-2-cyanoethenyl cyclopopane carboxylate.

 In a manner analogous to that used for Example 1, (1R, cis) 2,2-dimethyl-3 ((+) -2-chloro-2-cyanoethenyl) cyclopropane carboxylic acid is esterified with alcohol (R, S) 2- (6-phenoxy pyridyl) ethyl, chromatography the ester obtained on silica eluting with a mixture of hexane and ethyl acetate (8/2) and then with a mixture of hexane and acetate of ethyl (7.5 / 2.5), 1.08 g of isomer (E), 2.65 g of a mixture which is purified by chromatography on silica eluting with a hexane-acetate mixture. of ethyl (9-1) and gives 1.20 g of isomer (Z).

Isomer (E) / δ / D = + 52.5 (c = 0.5%, chloroform).

Isomer (Z) / δ / D = + 14.5 (c = 0.5%, chloroform).

EXAMPLE 5: (1 R, cis) 2,2-Dimethyl 3 H (S) -2-bromo-2-cyano ethenyl cyclopropane carboxylate (R, S) cyano 2- (6-phenoxy pyridyl) methyl.

 In a manner analogous to that of Example 2 starting from acid (1R, cis) 2,2-dimethyl 3 / (E + Z) 2-bromo-2-cyano ethenyl / cyclopropane carboxylic acid and alcohol (R, S ) cyano 2- (6-phenoxy pyridyl) methyl, the desired compound is obtained.

 / &alpha; / D = + 3 (c = 1%, toluene).

EXAMPLE 6 (1R, trans) 2,2-Dimethyl 3 / (E) 2-bromo-2-cyano ethenyl cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) methyl and (1R, trans) 2,2-dimethyl (S) cyano (3-phenoxy phenyl) methyl (Z) 2-bromo-2-cyanoethenyl / cyclopropane carboxylate.

 By operating in a manner analogous to that of Example 4, the desired E-isomer F = 118 ° C, λ / δ = + 20 (c = 1.2%, chloroform) and the isomer ZF = 115 is obtained. C.

EXAMPLE 7 ((R) cis) 2,2-Dimethyl 3 / (z) 2-bromo-2-cyano ethenyl / cyclopropane carboxylate (S) 2-methyl-4-oxo-3- (2-propenyl) -2-cyclopenten-1 -yl e.

 By operating in a similar manner to that of Example 4, the desired product is obtained.

NMR spectrum (deuterochloroform).

pics a 5,5-6,2 ppm de l'hydrogène de

pic a 5,7 ppm de l'hydrogène en position 1 de l'alléthrolone pics a 7,3-7,5 ppm de l'hydrogène éthylénique de la double liaison porteuse de CN et de Br.peak at 1.3 ppm hydrogens of geminated methyl peaks at 2.0 ppm of methyl hydrogens at 2 of allethrolone peaks at 4.8-5.25 ppm of methylene hydrogens

peaks at 5.5-6.2 ppm of the hydrogen of

peak at 5.7 ppm of the hydrogen at position 1 of the allethrolone peaks at 7.3-7.5 ppm of the ethylenic hydrogen of the double bond carrying CN and Br.

EXAMPLE 8 Preparation of a sluble concentrate

Homogeneous mixing of the product of Example 3 is carried out ................................ 0.25 9 - piperonyl butoxide ................................... 1 g - tween 80 ...... ........................................... 0,25 g - topanol A ................................................ 0, 1 g - water .............................................. ........ 98.4 g
EXAMPLE 9 Preparation of an Emulsifiable Concentrate

The product of Example 4 (Z isomer) is intimately mixed ....................... 0.015 g - Piperonyl butoxide ....... ............................ 0.5 g - topanol A ............... ................................ 0.1 g - xylene ............ ...................................... 95.885 g - tween 80 ....... ......................................... 3.5 g
EXAMPLE 10 Preparation of an Emulsifiable Concentrate

A homogeneous mixture of the product of Example 4 (isomer E) is carried out ..................... 1.5 g - tween 80 .... ............................................ 20 g - topanol A 4 0.1 g - xylene 78.4 g
EXAMPLE 11 Preparation of a Smoke Composition

 Homogeneously mixed product of Example 5 (Z isomer) 0.25 g - tabu powder ........................ .................. 25 g - cedar leaf powder ........................ ...... 40 g - pine wood powder .................................... 33 , 75 g - bright green ................................................ 0 , 5 g - paranitrophenol ......................................... 0,5 g .

BIOLOGICAL STUDY OF COMPOUNDS FROM ADDITION
A) Study of the slaughter effect on houseflies
Test insects are 4-day-old female houseflies. It is carried out by direct spraying at the concentration of 0.25 g / l in Kearns and March chamber using as solvent a mixture of acetone (5%) and Isopar L (petroleum solvent) (amount of solvent uses 2 ml in one second). 53 insects are used per treatment. The controls are carried out every minute until 10 minutes, then 15 minutes and the KT 50 is determined by the usual methods.

<SEP> COMPOUNDS <SEP> KT <SEP> 50 <SEP> in <SEP> mn
<tb> of <SEP> the example <SEP> 3 <SEP> 2,3
<tb> of <SEP> the example <SEP> 4 <SEP> (isomer <SEP> E) <SEP> 2,7
<tb> of <SEP> the example <SEP> 4 <SEP> (isomer <SEP> Z) <SEP> 3,3
<tb> of <SEP> example <SEP> 5 <SEP> (isomer <SEP> Z) <SEP> 2,2
<tb> of <SEP> the example <SEP> 6 <SEP> (isomer <SEP> E) <SEP> 4.1
<tb> of <SEP> the example <SEP> 6 <SEP> (isomer <SEP> Z) <SEP> 4,8
<Tb>
B) Study of the lethal effect on cockroach
The tests are performed by contact on glass film, by pipetting, acetone solutions of different concentrations on the bottom of glass Petri dish whose edges have been previously talcated to prevent the escape of insects. lethal concentration 50 (LC 50), a dose that can kill half cockroaches.

<tb><SEP> COMPOUNDS <SEP> CL <SEP> 50 <SEP> in <SEP> mg / m2
<tb> of <SEP> the example <SEP> 3 <SEP> 1,3
<tb> of <SEP> the example <SEP> 4 <SEP> (isomer <SEP> E) <SEP> 1.05
<tb> of <SEP> the example <SEP> 4 <SEP> (isomer <SEP> Z) <SEP> 1.07
<tb> of <SEP> example <SEP> 5 <SEP> (isomer <SEP> Z) <SEP> 2.0
<Tb>

C) Acaricidal study of the compounds of the invention
Bean plants with 2 infested leaves of 25 female Tetranychus Urticae per leaf were used and placed under an airy voucher under a constant luminous ceiling.

 The plants are treated with the Fisher pistol: 4 ml of solution to be tested, containing the pyrethrinide, per plant of an equal volume mixture of water and acetone. Allow to dry for 12 hours and then proceed to infestation. The mortality checks are carried out 80 hours later.

The LC 50 is determined in mg / hl, that is the concentration at which 50% mortality is obtained.

The experimental results obtained are summarized in the following table

<tb><SEP> COMPOUNDS <SEP> CL <SEP> 50 <SEP> in <SEP> mg / hl
<tb> of <SEP> the example <SEP> 4 <SEP> (isomere <SEP> E) <SEP> 2303
<tb> of <SEP> the example <SEP> 4 <SEP> (isomer <SEP> Z) <SEP> 3420
<Tb>
D) Conclusion
The compounds of the invention are endowed with good biological activity with respect to the parasites tested.

Claims (10)

1) The compounds whose names follow - (1R, cis) 2,2-dimethyl-3 ({Z) 2-bromo-2-cyanoethylene / cyclopropane carboxylic acid, - (1R, trans) 2,2-acid dimethyl 3 / (E + Z) 2-bromo-2-cyano ethenyl / cyclopropane carboxylic acid, - 1R, cis 2,2-dimethyl 3 / (E + Z) 2-chloro-2-cyanoethylene cyclopropane carboxylate (R) S) cyano 2- (6-phenoxy pyridyl) methyl; 1R, cis 2,2-dimethyl 3 / (Z) 2-chloro-2-cyano ethenyl / cyclopropane carboxylate (R, S) 2- (6-phenoxy pyridyl) ethyl - 1R, cis 2,2-dimethyl 3 ((E) 2-chloro-2-cyano ethenyl / cyclopropane carboxylate (R, S) 2- (6-phenoxy pyridyl) ethyl; - (R, S) -cyano 2- (6-phenoxy pyridyl) methyl 1R, cis 2,2-dimethyl 3 / (Z) 2-bromo-2-cyano ethenyl cyclopropanecarboxylate; 1R, trans 2,2-dimethyl 3 / (E) 2-bromo-2-cyano ethenyl / cyclopropane carboxylate (S) cyano (3-phenoxy phenyl) methyl - 1R, trans 2,2-dimethyl 3 / ( Z) 2-bromo-2-cyano ethenyl / cyclopropane carboxylate (S) cyano (3-phenoxyphenyl) methyl; - (S) 2-methyl-4-oxo-3- (2-propenyl) -2-cyclopenten-1-yl 1R, cis 2,2-dimethyl 3 / (Z) 2-bromo-2-cyano ethenyl / cyclopropane carboxylate. 2) Application of the compounds as defined in claim 1 to the control of plant pests, parasites of premises and parasites of warm-blooded animals. 3) Compositions for the control of plant pests, parasites of premises and parasites of warm-blooded animals, characterized in that they contain as active ingredient at least one of the products defined in claim 1. 4) The insecticidal compositions containing as active principle at least one of the products defined in claim 1. 5) The acaricide compositions containing as active principle at least one of the products defined in claim 1. 6) nematicide compositions containing as active ingredient at least one of the products defined in claim 1. 7) The acaricide compositions containing as active ingredient at least one of the products defined in claim 1, characterized in that they are used in the fight against parasites of warm-blooded animals, especially against ticks and scabies. 8) The compositions intended for animal feed containing as active ingredient at least one of the products defined in claim 1. 9) The associations endowed with insecticidal, acaricidal or nematicidal activity, characterized in that they contain as active ingredient, on the one hand at least one of the products defined in claim 1 and on the other hand, at least one of the esters pyrethroids selected 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 o-alcohols (- 3-phenoxy benzyl cyano chrysanthemic acids, by the esters of 5-benzyl 3-furyl methyl alcohol 2,2-dimethyl-3- (2-oxo-3-tetrahydrothiophenylidene methyl) cyclopropane-1-carboxylic acids, esters of 3-phenoxybenzyl alcohol and 3-phenoxybenzyl alcohols of 2,2dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylic acids, by the esters of 3-phenano-benzyl alcohol-benzyl alcohols; 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropane-1-carboxylic acids, by the esters of al 3-phenyl-2-isopropyl-acetic acid 2-parachl-2-parachl orophenyl, by esters of allethrolone, 3,4,5,6-tetrahydrophthalimido methyl alcohol, 5-benzyl 3-furyl methyl alcohol, alcohol 3 benzyl phenoxy and 3-phenoxybenzyl-1-cyanoalcohol 2,2dimethyl 3- (1,2-2,2-tetrahaloethyl) cyclopropane-1-carboxylic acids, in which "halo represents a fluorine, chlorine atom or or bromine, it being understood that the acidic copula and alcohols of the above pyrethrin esters can exist in all their possible stereoisomeric forms. 10) The compositions according to any one of claims 3 to 9, characterized in that they contain, in addition, a synergist pyrethrin noides.